JP2012082326A - Master batch containing high heat-resistant heat ray shielding component, production method of the master batch, high heat-resistant heat ray shielding transparent resin molded article, and high heat-resistant heat ray shielding transparent laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a master batch relating to a heat ray shielding transparent resin molded article in various shapes having transmitting property for visible rays and a heat ray shielding function, the master batch containing a high heat-resistant heat ray shielding component, from which a transparent resin molded article having good transmitting property for visible rays, a superior heat ray shielding function and high heat resistance can be obtained.SOLUTION: The master batch containing the high heat-resistant heat ray shielding component contains: composite tungsten oxide fine particles having a hexagonal crystalline structure expressed by general formula MWO, the particles subjected to an oxidation exposure treatment at 50°C or higher and 400°C or lower in an oxygen-containing atmosphere; and at least one kind of thermoplastic resin selected from an acrylic resin, a polycarbonate resin, a polyether imide resin, a polystyrene resin, a polyether sulfonic resin, a fluororesin, a polyolefin resin and a polyester resin. The master batch is used for producing a heat ray shielding transparent resin molded article.

Description

  The present invention is used for the manufacture of heat ray shielding moldings widely used for window materials, arcades, ceiling domes, carports, etc. used for building roofing materials and wall materials, automobiles, trains, airplanes, etc. The present invention relates to a masterbatch containing a high heat resistance heat ray shielding component and a production method thereof, a high heat resistance heat ray shielding transparent resin molding produced using the master batch, and a high heat resistance heat ray shielding transparent laminate.

  In addition to visible light, ultraviolet rays and infrared rays are included in the sunlight that enters through so-called openings such as windows and doors of various buildings and vehicles. Near infrared rays having a wavelength of 800 to 2500 nm among infrared rays contained in the sunlight are called heat rays, and cause the indoor temperature to rise by entering from the opening. In order to solve this problem, in recent years, in various fields of buildings and vehicle window materials, heat ray shielding molding that shields heat rays while taking in enough visible light, and suppresses temperature rise while maintaining brightness. The demand for the body has increased rapidly, and many proposals have been made regarding the heat ray shielding molded body.

  For example, a heat ray shielding plate has been proposed in which a heat ray reflective film obtained by vapor-depositing a metal or metal oxide on a transparent resin film is bonded to a transparent molded body such as glass, an acrylic plate, or a polycarbonate plate. However, this heat ray reflective film itself is very expensive. In addition, since a complicated process such as an adhesion process is required, the cost is increased. Moreover, since the adhesiveness of a transparent molded object and a reflective film is not favorable, it has the fault that peeling of a film arises by a time-dependent change.

  Many heat ray shielding plates formed by directly depositing metal or metal oxide on the surface of the transparent molded body have been proposed. In manufacturing the heat-ray shielding plate, an apparatus that requires high-vacuum and high-precision atmosphere control is required, which has a problem that mass productivity is poor and versatility is poor.

In addition, for example, a heat ray shielding plate in which an organic near-infrared absorber typified by a phthalocyanine compound or an anthraquinone compound is incorporated into a thermoplastic transparent resin such as polyethylene terephthalate resin, polycarbonate resin, acrylic resin, polyethylene resin, or polystyrene resin. And films have been proposed (see Patent Documents 1 and 2, etc.).
Furthermore, for example, a heat ray shielding plate in which inorganic particles such as mica coated with titanium oxide or titanium oxide having heat ray reflectivity are kneaded as heat ray reflective particles in a transparent resin such as acrylic resin and polycarbonate resin has been proposed. (See Patent Documents 3 and 4).

  On the other hand, the present applicant pays attention to hexaboride fine particles having a large amount of free electrons as a component having a heat ray shielding effect, and hexaboride fine particles are dispersed in polycarbonate resin or acrylic resin, or hexaboride. A heat ray shielding resin sheet material in which fine particles and ITO fine particles and / or ATO fine particles are dispersed is disclosed (see Patent Document 5).

The optical properties of the heat ray shielding resin sheet material in which hexaboride fine particles alone or hexaboride fine particles, ITO fine particles and / or ATO fine particles are dispersed have a maximum of visible light transmittance in the visible light region. It exhibits a strong absorption in the near infrared region and has a minimum solar radiation transmittance. As a result, the optical characteristics of visible light transmittance of 70% or more and solar radiation transmittance in the range of 50% are exhibited.
The present applicant has disclosed in Patent Document 6 a thermoplastic resin and a heat ray shielding component hexaboride (XB ₆ , where X is La, Ce, Pr, Nd, Gd, Tb, Dy, Ho, Y, Sm, Eu. , Er, Tm, Yb, Lu, Sr and Ca) as a main component, and a heat ray-shielding transparent resin molded article and heat ray-shielding transparent laminate to which the masterbatch is applied. Disclosed the body. And, by applying the masterbatch, heat-shielding transparent resin moldings of various shapes having a high heat-ray shielding function while maintaining excellent visible light transmission ability, using a high-cost physical film-forming method, etc. It was disclosed that it was prepared by a simple method without any problem.

  Further, in the patent document 7, the applicant of the present invention is represented by the general formula WyOz (where W is tungsten, O is oxygen, 2.0 <z / y <3.0) as fine particles having a solar radiation shielding function. Tungsten oxide fine particles and / or general formula MxWyOz (W is tungsten, O is oxygen, 0.001 ≦ x / y ≦ 1, 2.0 <z / y ≦ 3.0) By applying fine particles of composite tungsten oxide, it is disclosed that a solar radiation shielding laminated structure having high solar radiation shielding characteristics, a low haze value, and low production costs can be manufactured.

JP-A-6-256541 JP-A-6-264050 JP-A-2-173060 JP-A-5-78544 JP 2003-327717 A JP 2004-59875 A International Publication No. WO2005 / 87680A1 Pamphlet

  According to the study by the present inventors, in the heat ray shielding plates and films described in Patent Documents 1 and 2, a large amount of near infrared absorber must be blended in order to sufficiently shield the heat rays. However, when a large amount of the near-infrared absorber is blended, there is a problem that the visible light transmission ability is lowered. Furthermore, since organic compounds are used as near-infrared absorbers, application to buildings and vehicle window materials that are constantly exposed to direct sunlight has difficulty in weather resistance and is not necessarily appropriate. It was.

In addition, in the heat ray shielding plates described in Patent Documents 3 and 4, it is necessary to add a large amount of the heat ray reflective particles in order to enhance the heat ray shielding ability, and the visible light transmission ability is increased as the blending amount of the heat ray reflective particles is increased. There is a problem that the physical properties of the transparent resin as a molded body, particularly the impact strength and toughness, are lowered.
On the other hand, the heat ray shielding sheet materials described in Patent Documents 5 to 7 are not sufficiently satisfactory with respect to heat resistance, and there is still room for improvement.

  The present invention has been made paying attention to the above-mentioned problems, and the problem is that the visible light transmittance of various shapes of the heat ray-shielding transparent resin moldings having a visible ray transmission ability and a heat ray shielding function. Provided a masterbatch containing a high heat resistance heat ray shielding component having a good and excellent heat ray shielding function, and further obtaining a highly heat resistant transparent resin molded product, and a method for producing the same, and using this master batch together An object of the present invention is to provide a manufactured high heat resistant heat ray shielding transparent resin molding and a high heat resistant heat ray shielding transparent laminate.

  In order to solve the above-mentioned problems, the present inventors have conducted extensive research. As a result, the general formula MyWOz (where M is Cs, Rb, K, Na, Ba, Ca, Sr, Mg, Nb, Ge, In, Tl). One or more elements selected from the above, W is tungsten, O is oxygen, 0.1 ≦ y ≦ 0.5, 2.2 ≦ z ≦ 3.0) Although the composite tungsten oxide fine particles are already oxides, the heat-shielding material fine particles obtained by subjecting the composite tungsten oxide fine particles to an oxidation exposure treatment in an oxygen-containing atmosphere are found to have excellent heat resistance. In addition, it has been found that the masterbatch in which the heat ray shielding material fine particles are dispersed, the heat ray shielding transparent resin molding, and the heat ray shielding transparent laminate are also excellent in heat resistance. The present invention has been completed based on such technical knowledge.

That is, the first configuration for solving the above-described problem is:
Formula _M y WO _z (where, M is Cs, Rb, K, Na, Ba, Ca, Sr, Mg, Nb, Ge, In, 1 or more elements selected from among Tl, W is tungsten, O is a composite tungsten oxide fine particle having a hexagonal crystal structure represented by oxygen, 0.1 ≦ y ≦ 0.5, 2.2 ≦ z ≦ 3.0), and further in an oxygen-containing atmosphere. Composite tungsten oxide fine particles treated by oxidation exposure at 50 ° C. or higher and 400 ° C. or lower;
And one or more thermoplastic resins selected from acrylic resins, polycarbonate resins, polyetherimide resins, polystyrene resins, polyethersulfone resins, fluororesins, polyolefin resins and polyester resins,
A masterbatch containing a high heat resistance heat ray shielding component, which is used for producing a heat ray shielding transparent resin molded article.
The second configuration is
2. The high heat-resistant heat ray shielding component-containing masterbatch according to claim 1, wherein the composite tungsten oxide fine particles obtained by the oxidation exposure treatment are fine particles having a dispersed particle diameter of 800 nm or less.
The third configuration is
The high heat-resistant heat ray shielding component-containing masterbatch described in the first or second configuration is made of the same kind of thermoplastic resin molding material as the thermoplastic resin of the masterbatch or a different type of thermoplastic resin molding material having compatibility. A highly heat-resistant heat ray-shielding transparent resin molded article that is diluted and molded into a predetermined shape.
The fourth configuration is
A high heat resistant heat ray shielding transparent laminate, wherein the high heat resistant heat ray shielding transparent resin molding described in the third configuration is laminated on another transparent molding.
The fifth configuration is
A method for producing a heat-shielding heat ray shielding component-containing masterbatch used for producing a heat ray shielding transparent resin molded article,
A composite tungsten oxide fine particle represented by the general formula MyWOz (where 0.1 ≦ Y ≦ 0.5, 2.2 ≦ Z ≦ 3.0) and having a hexagonal crystal structure is obtained in an oxygen-containing atmosphere. A step of oxidizing exposure treatment at a temperature of from ℃ to 400 ℃,
A step of adding the composite tungsten oxide fine particles subjected to the oxidation exposure treatment and a dispersing agent to a solvent and performing pulverization / dispersion treatment to obtain a fine particle dispersion;
After obtaining the fine particle dispersion, removing the solvent to obtain the fine particle dispersion; and
A method for producing a masterbatch containing a high heat resistance heat ray shielding component, comprising: mixing, melting and kneading and molding the fine particle dispersed powder and a thermoplastic resin pellet.
The sixth configuration is
It is a manufacturing method of the manufacturing method of the high heat resistant heat ray shielding component containing masterbatch as described in the 5th structure characterized by the oxygen concentration of the said oxygen containing atmosphere being 0.1 volume% or more and 25 volume% or less. .

  A masterbatch containing a high heat-resistant heat ray shielding component according to the present invention is diluted and kneaded with a thermoplastic resin molding material, and further, a plate shape, a film shape, a spherical shape, etc. by a known method such as extrusion molding, injection molding, compression molding, etc. By forming into an arbitrary shape, it is possible to produce a heat ray shielding transparent resin molding and a heat ray shielding transparent laminate having a maximum transmittance in the visible light region and strong absorption in the near infrared region and having high heat resistance. It has become possible.

Hereinafter, embodiments of the present invention will be specifically described.
The masterbatch containing a high heat resistance heat ray shielding component for the heat ray shielding transparent resin molded article of the present embodiment is composed of a thermoplastic resin and a general formula M _y WO _z (where M is Cs, Rb, K, Na, Ba, Ca). , Sr, Mg, Nb, Ge, In, Tl, one or more elements selected from W, tungsten, O is oxygen, 0.1 ≦ y ≦ 0.5, 2.2 ≦ z ≦ 3. The main component is composite tungsten oxide fine particles having a hexagonal crystal structure represented by (0). The thermoplastic resin is at least one selected from an acrylic resin, a polycarbonate resin, a polyetherimide resin, a polystyrene resin, a polyethersulfone resin, a fluororesin, a polyolefin resin, and a polyester resin, and the composite tungsten oxide. A masterbatch containing a highly heat-resistant heat ray shielding component, characterized in that the surface of fine particles is subjected to an oxidation exposure treatment.

  Hereinafter, the composite tungsten oxide fine particles, the high heat resistant dispersant, and the thermoplastic resin constituting the high heat resistant heat ray shielding component-containing master batch will be described in this order, and further, the fine particles having a heat ray shielding function to the thermoplastic resin will be described. A dispersion method and a method for producing a high heat-resistant heat ray shielding component-containing masterbatch will be described, and finally, a heat ray shielding transparent resin molded product will be described.

1) Composite tungsten oxide fine particles The composite tungsten oxide fine particles absorb a large amount of light in the near-infrared region, particularly in the vicinity of a wavelength of 1000 nm. Therefore, the transmitted color tone often has a blue color tone. Moreover, the particle diameter of the said heat ray shielding material can be suitably selected according to the use purpose.

  First, when used for applications that maintain transparency, the composite tungsten oxide fine particles preferably have a dispersed particle diameter of 800 nm or less. This is because a dispersed particle size of less than 800 nm does not completely block light by scattering, can maintain visibility in the visible light region, and at the same time can efficiently maintain transparency. In particular, when importance is attached to transparency in the visible light region, it is preferable to further consider scattering by particles.

  When importance is attached to the reduction of scattering by the particles, the dispersed particle diameter of the composite tungsten oxide fine particles is 200 nm or less, preferably 100 nm or less. The reason is that if the dispersed particle diameter of the dispersed particles is small, the scattering of light in the visible light region having a wavelength of 400 nm to 780 nm due to geometric scattering or Mie scattering is reduced. This is because, as a result of the light scattering being reduced, it can be avoided that the heat ray shielding film becomes like frosted glass and clear transparency cannot be obtained. That is, when the dispersed particle diameter of the dispersed particles is 200 nm or less, the geometric scattering or Mie scattering is reduced and a Rayleigh scattering region is obtained. This is because in the Rayleigh scattering region, the scattered light is reduced in inverse proportion to the sixth power of the particle diameter, so that the scattering is reduced and the transparency is improved as the dispersed particle diameter is reduced. Furthermore, when the dispersed particle size is 100 nm or less, the scattered light is preferably extremely small. From the viewpoint of avoiding light scattering, it is preferable that the dispersed particle size is small. If the dispersed particle size is 1 nm or more, industrial production is easy.

The composite oxide fine particles are composite tungsten represented by the general formula M _y WO _z (where 0.1 ≦ y ≦ 0.5, 2.2 ≦ z ≦ 3.0) and having a hexagonal crystal structure. Oxide fine particles. Here, the composite tungsten oxide in which the M element includes one or more selected from, for example, Cs, Rb, K, Tl, Na, Ba, Ca, Sr, Mg, Nb, Ge, In, and Tl. Fine particles are mentioned. The addition amount y of the additive element M is preferably 0.1 or more and 0.5 or less, and more preferably around 0.33. This is because the value of y theoretically calculated from the hexagonal crystal structure is 0.33, and preferable optical characteristics can be obtained with addition amounts around this value. Moreover, about the range of z, 2.2 <= z <= 3.0 is preferable.

The composite tungsten oxide fine particles according to the present invention are obtained by subjecting the composite tungsten oxide fine particles to oxidation treatment by exposure in an oxygen-containing atmosphere even though the composite tungsten oxide fine particles having the above-described configuration are already oxides. It was obtained.
The exact mechanism by which the heat resistance of the final heat-resistant heat-shielding transparent resin molded product or laminate is improved by the oxidation treatment by the exposure is still unclear. However, the present inventors have a result that a new oxide film is further formed on the surface of the composite tungsten oxide fine particles having the above-described structure by the oxidation treatment by the exposure, and the oxide film becomes a barrier layer of external oxygen. It is considered that the heat resistance of the composite tungsten oxide fine particles according to the present invention is improved, and the heat resistance of the high heat resistant heat ray shielding transparent resin molded product or the laminate as the final product is improved.

2) Method for producing composite tungsten oxide fine particles General formula M _y WO _{z according} to the present invention (where M is the M element, W is tungsten, O is oxygen, 0.1 ≦ y ≦ 0.5, 2.2) A method for producing the composite tungsten oxide fine particles represented by ≦ z ≦ 3.0) will be described.
The composite tungsten oxide fine particles for forming a high heat-resistant heat ray shield according to the present invention are a mixed powder obtained by mixing tungstic acid (H ₂ WO ₄ ) and an oxide or / and hydroxide of M element, or trioxide. Mixed powder in which tungsten fine particles and oxide or / and hydroxide of M element are mixed, or mixture of tungstic acid (H ₂ WO ₄ ) and tungsten trioxide fine particles, oxide of M element and / or water A mixed powder in which an oxide is mixed, or tungstic acid (H ₂ WO ₄ ) and / or tungsten trioxide fine particles, an aqueous solution of a metal salt of an M element, a colloidal solution of a metal oxide, or an alkoxy solution. The dried powder obtained by mixing and drying one or more of the above is calcined in an inert gas or a mixed gas atmosphere of an inert gas and a reducing gas to obtain a general formula My A composite tungsten oxide particle represented by Oz (where M is the M element, W is tungsten, O is oxygen, 0.1 ≦ y ≦ 0.5, 2.2 ≦ z ≦ 3.0) is generated. Then, the composite tungsten oxide fine particles obtained by wet pulverization. Then, the composite tungsten oxide fine particles obtained by the above-mentioned formula pulverization are again subjected to an oxidation exposure treatment in an oxygen-containing atmosphere to obtain the composite tungsten oxide fine particles for forming a high heat resistant heat ray shield according to the present invention.

The tungstic acid (H ₂ WO ₄ ) used as a raw material is not particularly limited as long as it becomes an oxide by firing. As the tungsten trioxide used as a raw material, tungsten trioxide fine particles obtained by firing the tungstic acid (H ₂ WO ₄ ) may be used, or commercially available products may be used. Here, from the viewpoint of the optical characteristics of the composite tungsten oxide fine particles for heat ray shielding to be produced, it is preferable to use an oxide obtained by firing tungstic acid (H ₂ WO ₄ ) used as a raw material. From the viewpoint of productivity, tungsten trioxide fine particles such as commercially available products can be used. From the same viewpoint, a mixture of both may be used.

When the tungstic acid (H ₂ WO ₄ ) is fired and used as tungsten trioxide fine particles, the treatment temperature during firing is preferably 200 ° C. or higher from the viewpoint of the desired properties and optical properties of the tungsten trioxide fine particles. On the other hand, if the treatment temperature during firing exceeds 1000 ° C., the effect of firing is saturated, and if it is 1000 ° C. or less, grain growth that causes a decrease in optical properties can be avoided, and therefore 1000 ° C. or less is preferable. The treatment time during firing may be appropriately selected according to the treatment temperature, but may be 10 minutes or more and 5 hours or less.

The kind of the raw material when added is preferably an oxide or / and a hydroxide. The M element oxide and hydroxide are mixed with tungstic acid (H ₂ WO ₄ ) and / or tungsten trioxide fine particles. What is necessary is just to perform a mixing process with a commercially available crusher, a kneader, a ball mill, a sand mill, a paint shaker, etc.

Further, tungstic acid (H ₂ WO ₄ ) or / and tungsten trioxide fine particles are mixed with one or more selected from an aqueous solution of a metal salt of the M element, a colloidal solution of a metal oxide, and an alkoxy solution. When the dried powder is produced, the partner ion for forming the salt with the element M is not particularly limited, and examples thereof include nitrate ion, sulfate ion, chloride ion, carbonate ion and the like. . The drying temperature and time are not particularly limited.

Next, the mixture or the dried powder is fired in a mixed gas atmosphere of an inert gas and a reducing gas in order to generate oxygen vacancies. As the atmosphere for the firing, a mixed gas of an inert gas such as nitrogen, argon, or helium and a reducing gas such as hydrogen, alcohol, or ammonia can be used. As described above, when firing in a mixed gas atmosphere of an inert gas and a reducing gas, the concentration of the reducing gas in the inert gas may be appropriately selected according to the firing temperature, and is not particularly limited. For example, it is 20 vol% or less, preferably 10 vol% or less, more preferably 7 vol% or less. This is because if the concentration of the reducing gas is 20 vol% or less, the production of WO ₂ having no heat ray shielding function due to rapid reduction can be avoided.

The treatment temperature during firing may be appropriately selected according to the reducing gas concentration, but may be appropriately selected at a temperature at which WO ₂ is not generated due to the presence of the reducing gas.
Moreover, although the said baking may be implemented under the process temperature of 1 step as mentioned above, it is good also as multiple steps which change atmosphere and baking temperature in the middle of baking. For example, in the first step, firing is performed at 100 ° C. or more and 650 ° C. or less in a mixed gas atmosphere of an inert gas and a reducing gas, and in the second step, firing is performed at 650 ° C. or more and 1200 ° C. or less in an inert gas atmosphere. By doing so, a heat ray shielding fine particle having excellent heat ray shielding properties can be obtained, which is a preferable configuration.

  The firing treatment time may be appropriately selected depending on the temperature, but may be 5 minutes or more and 5 hours or less. The composite tungsten oxide particles thus obtained are wet pulverized together with an appropriate solvent, for example, with a bead mill, a ball mill, a sand mill, a paint shaker, an ultrasonic homogenizer, etc., to make the composite tungsten oxide particles finer.

Next, in order to collect the wet-pulverized composite tungsten oxide fine particles and impart a heat resistance function, the composite tungsten oxide fine particles are subjected to an oxidation exposure treatment in an oxygen-containing atmosphere. However, if the oxygen concentration in the oxygen-containing atmosphere is too high, the surface of the fine particles is excessively oxidized and the oxide film becomes thicker. If the oxide film on the surface of the fine particles is excessively thick, the amount of filler used is increased in the subsequent process, resulting in an increase in cost.
On the other hand, if the oxygen concentration in the oxygen-containing atmosphere is too low, the oxide film on the surface of the fine particles becomes excessively thin and the effect on heat resistance is reduced.
From the above, the oxygen concentration in the oxygen-containing atmosphere is preferably 0.1 vol% or more and 25 vol% or less. Therefore, even when the oxidation exposure treatment is performed in the atmosphere (oxygen concentration of about 21% by volume), the composite tungsten oxide fine particles for forming a high heat resistant heat ray shield according to the present invention can be obtained.
The treatment temperature may be appropriately selected according to the oxygen concentration, but is preferably 20 ° C. or higher and 400 ° C. or lower from the viewpoint of the heat resistance effect. The oxidation exposure treatment time may be appropriately selected according to the treatment temperature. Specifically, for example, if the treatment temperature is 50 ° C. or more and less than 100 ° C., the treatment time is 10 hours or more and 72 hours or less, 100 ° C. If it is 400 degreeC or less, 1 hour or more and 72 hours or less are preferable. The obtained composite tungsten oxide fine particles exhibit a sufficient heat resistance function.

3) High heat-resistant dispersant Conventionally, a dispersant generally used for coating is used for the purpose of uniformly dispersing various oxide fine particles in an organic solvent. However, according to studies by the present inventors, these dispersants are not designed on the assumption that they are used at a high temperature of 200 ° C. or higher. Specifically, in this embodiment, when a heat-shielding fine particle and a thermoplastic resin are melt-kneaded, if a dispersant having low heat resistance is used, the functional group in the dispersant is decomposed by heat, and the dispersibility This caused problems such as yellowing to browning as the color decreased.

  On the other hand, in this embodiment, as the high heat resistant dispersant, one having a thermal decomposition temperature measured by TG-DTA of 230 ° C. or higher, preferably 250 ° C. or higher is used. As a specific structural example of the high heat resistant dispersant, there is a dispersant having an acrylic main chain as a main chain and a hydroxyl group or an epoxy group as a functional group. A dispersant having this structure is preferable because of its high heat resistance.

And if the thermal decomposition temperature of a dispersing agent is 230 degreeC or more, it will not discolor from yellow to brown itself while maintaining the dispersibility without the said dispersing agent thermally decomposing at the time of shaping | molding. As a result, in the molded article to be produced, the heat ray shielding fine particles are sufficiently dispersed, so that the visible light transmittance is ensured well and the original optical characteristics can be obtained, and the molded article is colored yellow. There is no need to
Specifically, when a test for kneading the dispersant of the present invention and a polycarbonate resin at a general kneading setting temperature (290 ° C.) of polycarbonate is performed, the kneaded product has exactly the same appearance as when only the polycarbonate is kneaded. Was confirmed to be colorless and transparent and not colored at all. On the other hand, for example, when a similar test was performed using a dispersant having low heat resistance described in Comparative Example 1 described later, it was confirmed that the kneaded material was colored brown.

As described above, the high heat resistant dispersant used in the present embodiment has an acrylic main chain, but at the same time, a dispersant having a hydroxyl group or an epoxy group as a functional group is preferable. This is because these functional groups are adsorbed on the surface of the composite tungsten oxide fine particles to prevent the aggregation of the composite tungsten oxide fine particles and have an effect of uniformly dispersing the composite tungsten oxide fine particles in the molded body. .
Specifically, an acrylic dispersant having an epoxy group as a functional group and an acrylic dispersant having a hydroxyl group as a functional group are preferable examples. Such a dispersant may be selected from a commercially available dispersant product by performing the TG-DTA measurement described above.

  In particular, when a resin having a high melt kneading temperature such as a polycarbonate resin or an acrylic resin is used as the thermoplastic resin, it has a high heat resistance having an acrylic main chain having a thermal decomposition temperature of 250 ° C. or more and a hydroxyl group or an epoxy group. The effect of using the dispersant is remarkably exhibited.

  The weight ratio of the high heat resistant dispersant to the composite tungsten oxide fine particles is preferably in the range of 10 ≧ [weight of the high heat resistant dispersant / weight of the composite tungsten oxide fine particles] ≧ 0.5. If the weight ratio is 0.5 or more, the composite tungsten oxide fine particles can be sufficiently dispersed, so that the fine particles do not aggregate and sufficient optical characteristics are obtained. Moreover, if the said weight ratio is 10 or less, the mechanical characteristics (bending strength, surface height) of heat ray shielding transparent resin molding itself will not be impaired.

4) Thermoplastic resin Next, the thermoplastic resin used in the present embodiment is not particularly limited as long as it is a transparent thermoplastic resin having a high light transmittance in the visible light region. For example, it is preferable that the visible light transmittance described in JIS R3106 is 50% or more and the haze described in JISK7105 is 30% or less when a plate-like molded body having a thickness of 3 mm is used.
Specific examples include acrylic resins, polycarbonate resins, polyetherimide resins, polyester resins, polystyrene resins, polyethersulfone resins, fluorine resins, and polyolefin resins. When heat-shielding transparent resin moldings are applied to various building and vehicle window materials, acrylic resin, polycarbonate resin, polyetherimide resin are considered in consideration of transparency, impact resistance, weather resistance, etc. Fluorine resin is more preferable.

  As acrylic resin, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate as main raw materials, acrylic acid ester having vinyl group having 1 to 8 carbon atoms as required, vinyl acetate, styrene, acrylonitrile, methacrylonitrile, etc. A polymer or copolymer using as a copolymerization component. Furthermore, an acrylic resin polymerized in multiple stages can also be used.

  The polycarbonate resin is preferably an aromatic polycarbonate. As the aromatic polycarbonate, one or more divalent phenolic compounds represented by 2,2-bis (4-hydroxyphenyl) propane and 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane And a polymer obtained by a known method such as interfacial polymerization, melt polymerization, or solid phase polymerization from a carbonate precursor typified by phosgene or diphenyl carbonate.

  In addition, as the fluororesin, polyfluorinated ethylene, polydifluorinated ethylene, polytetrafluoroethylene, ethylene-2 fluoroethylene copolymer, ethylene-4 fluoroethylene copolymer, tetrafluoroethylene-par Examples include fluoroalkoxyethylene copolymers.

5) Dispersion method of fine particles having heat ray shielding function in thermoplastic resin The dispersion method of the composite tungsten oxide fine particles, which are fine particles having a heat ray shielding function, in the thermoplastic resin may be a method in which the fine particles can be uniformly dispersed in the resin. Can be arbitrarily selected. As an example, first, a dispersion in which the composite tungsten oxide fine particles are dispersed in an arbitrary solvent is prepared using a method such as a bead mill, a ball mill, a sand mill, or an ultrasonic dispersion. Next, the dispersion, dispersant, thermoplastic resin granules or pellets, and other additives as necessary are added to a ribbon blender, tumbler, nauter mixer, Henschel mixer, super mixer, planetar. Using a kneader such as a Lee mixer, and a Banbury mixer, kneader, roll, kneader ruder, single screw extruder, twin screw extruder, etc., uniformly melt and mix while removing the solvent from the dispersion. Thus, a mixture in which the composite tungsten oxide fine particles are uniformly dispersed in the thermoplastic resin can be prepared. The kneading temperature is maintained at a temperature at which the thermoplastic resin used does not decompose.

As another method, a high heat-resistant dispersant is added to a dispersion of composite tungsten oxide fine particles having a heat ray shielding function, the solvent is removed by a known method, and the obtained powder and thermoplastic resin particles It is also possible to prepare a mixture in which composite tungsten oxide fine particles are uniformly dispersed in a thermoplastic resin by uniformly melting and mixing the body or pellets and, if necessary, other additives.
In addition, it is also possible to use a method in which a powder of composite tungsten oxide fine particles not subjected to dispersion treatment and a dispersant are directly added to a thermoplastic resin and uniformly melt-mixed.
The dispersion method is not limited to these methods as long as the composite tungsten oxide fine particles are uniformly dispersed in the thermoplastic resin.

6) Manufacturing method of masterbatch containing high heat-resistant heat ray shielding component By kneading a thermoplastic resin in which composite tungsten oxide fine particles are uniformly dispersed with a vent type uniaxial or biaxial extruder, and processing into a pellet form And the high heat resistant heat ray shielding component containing masterbatch which concerns on this embodiment can be obtained.
The high heat-resistant heat ray shielding component-containing masterbatch pellets can be obtained by a method of cutting the most general melt-extruded strand. Accordingly, examples of the shape include a cylindrical shape and a prismatic shape. It is also possible to adopt a so-called hot cut method in which the molten extrudate is directly cut. When adopting the hot cut method, it is common to take a shape close to a sphere.

  The high heat-resistant heat ray shielding component-containing masterbatch according to the present invention can take any form or shape. However, when the heat ray-shielding transparent resin molded product is molded, it is preferable to have the same form and shape as the thermoplastic resin molding material used for dilution of the high heat-resistant heat ray shielding component-containing masterbatch.

  Furthermore, it is also possible to mix | blend a general additive further to the high heat-resistant heat ray shielding component containing masterbatch which concerns on this invention. For example, azo dyes, cyanine dyes, quinoline dyes, perylene dyes, carbon black, and other dyes and pigments commonly used for coloring thermoplastic resins in order to give any color tone as necessary An effective expression level may be blended. In addition, hindered phenol and phosphorus stabilizers, release agents, hydroxybenzophenone, salicylic acid, HALS, triazole and triazine UV absorbers, coupling agents, surfactants and antistatic agents An effective expression amount such as

7) High heat-resistant heat ray shielding transparent resin molded product The high heat resistant heat ray shielding transparent resin molded product according to the present invention comprises the above-mentioned high heat resistant heat ray shielding component-containing masterbatch and the same kind of thermoplastic resin as the masterbatch thermoplastic resin. It is obtained by diluting and kneading with a resin molding material or a different kind of thermoplastic resin molding material having compatibility with the thermoplastic resin of the masterbatch and molding into a predetermined shape.

Since the high heat resistant heat ray shielding transparent resin molding according to the present invention is manufactured using a master batch containing a high heat resistance heat ray shielding component, there is very little thermal deterioration during molding. For this reason, the heat ray shielding fine particles, which are composite tungsten oxide fine particles, are sufficiently dispersed in the transparent resin molded product, and as a result, good visible light transmittance is secured.
The shape of the high heat-resistant heat ray shielding transparent resin molding can be molded into an arbitrary shape as necessary, and can be molded into a flat shape and a curved shape. Moreover, the thickness of the high heat-resistant heat ray shielding transparent resin molding can be adjusted to an arbitrary thickness as necessary from a plate shape to a film shape. Furthermore, the resin sheet formed in a planar shape can be formed into an arbitrary shape such as a spherical shape by post-processing.

  Examples of the molding method of the high heat-resistant heat ray shielding transparent resin molded product include any methods such as injection molding, extrusion molding, compression molding, and rotational molding. In particular, a method of obtaining a molded product by injection molding and a method of obtaining a molded product by extrusion molding are preferably employed. As a method for obtaining a plate-like or film-like molded article by extrusion molding, the molded thermoplastic resin is produced by a method in which a molten thermoplastic resin extruded using an extruder such as a T-die is taken out while being cooled by a cooling roll. The injection-molded product is suitably used for a vehicle body such as an automobile window glass or a roof, and the plate-like or film-like product obtained by extrusion molding is suitably used for a building such as an arcade or a carport. The

  The above high heat-resistant heat ray shielding transparent resin molded product can be used for structural materials such as window glass and arcade as well as other transparent molded products such as inorganic glass, resin glass and resin film. It can also be used for a structural material as a highly heat-resistant heat ray shielding transparent laminate laminated and integrated by the above method. For example, a highly heat-resistant heat ray shielding transparent laminate having a heat ray shielding function and a scattering prevention function can be obtained by laminating and integrating a high heat resistant heat ray shielding transparent resin molded body previously formed into a film shape onto an inorganic glass by a heat lamination method. Obtainable.

  In addition, by heat lamination method, co-extrusion method, press molding method, injection molding method, etc., high heat resistant heat ray is formed by laminating and integrating with other transparent molded body at the same time as molding of high heat resistant heat ray shielding transparent resin molded body. It is also possible to obtain a shielding transparent laminate. The high heat-resistant heat ray shielding transparent laminate can be used as a more useful structural material by complementing each other's drawbacks while effectively exhibiting the advantages of the mutual molded bodies.

  As described above in detail, by using the masterbatch containing the high heat resistance heat ray shielding component of the present embodiment in which the composite tungsten oxide fine particles are uniformly dispersed in the thermoplastic resin using a dispersant as the heat ray shielding component. The heat-shielding transparent resin molded body and the heat-ray-shielding transparent body having a heat-ray shielding function and a high transmission performance in the visible light range without using a high-cost physical film-forming method or a complicated process. A laminated body can be provided.

Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to the following examples.
In each Example, the visible light transmittance and the heat ray transmittance of the heat ray shielding transparent resin molding were measured using a spectrophotometer U-4000 manufactured by Hitachi, Ltd. This heat ray transmittance is an index indicating heat ray shielding performance. The haze value was measured based on JIS K 7105 using HR-200 manufactured by Murakami Color Research Laboratory Co., Ltd.

[Example 1]
After adding an aqueous solution prepared by dissolving 7.43 kg of cesium carbonate in 6.70 kg of water to 34.57 kg of tungstic acid (H ₂ WO ₄ ), moisture was removed while stirring at 100 ° C. to obtain a dry powder. It was. Next, the dry powder is heated while supplying 5% H ₂ gas with N ₂ gas as a carrier, and heat-treated at a temperature of 800 ° C. for 5.5 hours to obtain Cs _0.33 WO ₃ particles (a )
Next, 5 wt% of the Cs _0.33 WO ₃ particles (a), 5 wt% of the high heat resistant dispersant (S), and 90 wt% of toluene were weighed, and 6 with a paint shaker containing 0.3 mmφZrO ₂ beads. A composite tungsten oxide fine particle dispersion (liquid A) was prepared by time pulverization and dispersion treatment. And the high heat resistant dispersing agent (b) was further added to the said (A liquid), and it was set as the ratio of high heat resistant dispersing agent (S): composite tungsten oxide microparticles | fine-particles = 3: 1 (weight ratio).
(A liquid) was loaded into a vacuum crusher, and toluene was removed while vacuum crushing to obtain a composite tungsten oxide fine particle dispersed powder (A powder).
The resulting (A flour), N ₂ gas in the distribution of a 5 vol% O ₂ gas as a carrier, and 24-hour oxidation exposure process at a temperature of 100 ° C., oxidation exposure process powder according to Example 1 ( Treatment A powder) was obtained.
The obtained (treated A powder) and polycarbonate resin pellets which are thermoplastic resins were mixed so that the Cs _0.33 WO ₃ concentration was 2.0% by weight and mixed uniformly using a blender.
The mixture is melt-kneaded at 290 ° C. with a twin-screw extruder, and the extruded strand is cut into pellets to obtain a masterbatch (masterbatch A) containing a high heat-resistant heat ray shielding component for a heat ray shielding transparent resin molding. It was.
The obtained (Masterbatch A) was diluted with polycarbonate resin pellets (diameter 2.5 mm, length 3 mm) to adjust the Cs _0.33 WO ₃ concentration to 0.03% by weight. An example in which the polycarbonate resin dilution of the master batch A was uniformly mixed with a tumbler and then extruded to a thickness of 1 mm, 2 mm and 3 mm using a T-die, and the composite tungsten oxide fine particles were uniformly dispersed throughout the resin. Each heat ray shielding transparent resin molded product according to 1 (molded product A) was obtained.
The optical characteristics of (Form A) according to Example 1 were measured, and the heat ray transmittance and haze value when the visible light transmittance was 75% were determined from a three-point plot.

As shown in Table 1, the heat ray transmittance of (Form A) was 38.7% and the haze value was 1.1%.
Next, in order to investigate the heat resistance of (Form A), the following accelerated test was performed.
(Formed product A) was exposed at a temperature of 120 ° C. for 72 hours, and the change rate of visible light transmittance before and after the exposure (denoted as ΔVLT) was examined. As a result, (ΔVLT) after 168 hours was 0.95%, and an improvement in heat resistance was confirmed as compared with the case where no baking treatment was performed in an oxygen-containing atmosphere (see Comparative Example 1 below).

[Example 2]
The (A powder) obtained in Example 1 was heated in an air atmosphere and subjected to an oxidation exposure treatment at a temperature of 100 ° C. for 1 hour to obtain an oxidation exposure treatment powder (treatment B powder) according to Example 2.
Thereafter, the same operation as in Example 1 was performed except that (Processing A powder) was replaced with (Processing B powder) to obtain a heat ray shielding transparent resin molded product (molded product B) according to Example 2.

As shown in Table 1, the heat ray transmittance was 38.8% and the haze value was 0.9% when the visible light transmittance of the molded body B was 75%.
Moreover, (ΔVLT) after exposure for 168 hours at a temperature of 120 ° C. was 1.30%, and an improvement in heat resistance was confirmed as compared with Comparative Example 1 below, which was not treated in an oxygen-containing atmosphere.

[Example 3]
A heat ray shielding transparent resin molded product (molded product C) according to Example 3 was obtained in the same manner as in Example 1 except that an acrylic resin was used as the thermoplastic resin.

As shown in Table 1, the heat ray transmittance was 39.3% and the haze value was 2.1% when the visible light transmittance of the molded body C was 75%.
Moreover, (ΔVLT) after exposure for 168 hours at a temperature of 120 ° C. was 0.98%, confirming an improvement in heat resistance as compared with Comparative Example 1 below, which was not treated in an oxygen-containing atmosphere.

[Example 4]
A heat ray shielding transparent resin molded product (molded product D) according to Example 4 was obtained in the same manner as in Example 1 except that polyethylene terephthalate resin was used as the thermoplastic resin.

As shown in Table 1, the heat ray transmittance of the (molded product D) when the visible light transmittance was 75% was 38.6%, and the haze value was 0.55%.
In addition, (ΔVLT) after exposure for 72 hours at a temperature of 120 ° C. was 0.95%, and an improvement in heat resistance was confirmed as compared with Comparative Example 1 below, which was not treated in an oxygen-containing atmosphere.

[Example 5]
A heat ray shielding transparent resin molded product (molded product E) according to Example 5 was obtained in the same manner as Example 1 except that ethylene-tetrafluoroethylene resin was used as the thermoplastic resin.

As shown in Table 1, the heat ray transmittance of (molded product E) when the visible light transmittance was 75% was 39.5%, and the haze value was 22.7%.
Moreover, (ΔVLT) after exposure for 168 hours at a temperature of 120 ° C. was 0.98%, confirming an improvement in heat resistance as compared with Comparative Example 1 below, which was not treated in an oxygen-containing atmosphere.
The haze value was as high as 22.7%. This is because the haze was increased because the ethylene-tetrafluoroethylene resin itself was cloudy.

[Example 6]
A heat ray shielding transparent resin molded product (molded product F) according to Example 6 was obtained in the same manner as Example 1 except that a polyethylene resin was used as the thermoplastic resin.

As shown in Table 1, the heat ray transmittance of (molded product F) when the visible light transmittance was 75% was 40.1%, and the haze value was 12.8%.
Further, (ΔVLT) after exposure for 168 hours at a temperature of 120 ° C. was 0.99%, and an improvement in heat resistance was confirmed as compared with Comparative Example 1 below, which was not treated in an oxygen-containing atmosphere.
The haze value was as high as 12.8%. This is because the haze was increased because the polyethylene resin itself was cloudy.

[Example 7]
Except for replacing cesium carbonate with rubidium carbonate and mixing tungstic acid (H ₂ WO ₄ ) and an aqueous solution of rubidium carbonate so that Rb / W = 0.33 (molar ratio), the same as in Example 1. Thus, Rb _0.33 WO ₃ fine particles (b) were obtained.
Thereafter, the same operation as in Example 1 was performed except that the fine particles (a) were replaced with the fine particles (b) to obtain a heat ray shielding transparent resin molded product (molded product G) according to Example 7.

As shown in Table 1, the heat ray transmittance of (molded product G) when the visible light transmittance was 75% was 46.5%, and the haze value was 1.1%.
Moreover, (ΔVLT) after exposure for 168 hours at a temperature of 120 ° C. was 1.14%, and an improvement in heat resistance was confirmed as compared with Comparative Example 1 below, which was not treated in an oxygen-containing atmosphere.

[Example 8]
Except that cesium carbonate was replaced with indium nitrate and tungstic acid (H ₂ WO ₄ ) and an indium nitrate aqueous solution were mixed so that In / W = 0.3 (molar ratio), the same as in Example 1. Thus, In _0.3 WO ₃ fine particles (c) were obtained.
Thereafter, a heat ray shielding transparent resin molded product (molded product H) according to Example 8 was obtained by performing the same operation as in Example 1 except that the fine particles (a) were replaced with the fine particles (c).

As shown in Table 1, the heat ray transmittance was 50.7% and the haze value was 1.0% when the visible light transmittance of the molded body H was 75%.
In addition, (ΔVLT) after 168 hours of oxidation exposure at a temperature of 120 ° C. was 1.24%, and an improvement in heat resistance was confirmed as compared with Comparative Example 1 below, which was not treated in an oxygen-containing atmosphere.

[Example 9]
Except that cesium carbonate was replaced with thallium formate and tungstic acid (H ₂ WO ₄ ) and thallium formate aqueous solution were mixed so that Tl / W = 0.33 (molar ratio), the same as in Example 1. Thus, Tl _0.33 WO ₃ fine particles (d) were obtained.
Thereafter, the same operation as in Example 1 was performed except that the fine particles (a) were replaced with the fine particles (d) to obtain a heat ray shielding transparent resin molded product (molded product I) according to Example 9.

As shown in Table 1, the heat ray transmittance was 44.3% and the haze value was 1.1% when the (molded product I) had a visible light transmittance of 75%.
In addition, (ΔVLT) after exposure for 168 hours at a temperature of 120 ° C. was 1.09%, and an improvement in heat resistance was confirmed as compared with Comparative Example 1 below which was not treated in an oxygen-containing atmosphere.

[Example 10]
Except that cesium carbonate was replaced with potassium chloride, and tungstic acid (H ₂ WO ₄ ) and an aqueous potassium chloride solution were mixed so that K / W = 0.33 (molar ratio), the same as in Example 1. Thus, K _0.33 WO ₃ fine particles (e) were obtained.
Thereafter, the same operation as in Example 1 was performed except that the fine particles (a) were replaced with the fine particles (e) to obtain a heat ray shielding transparent resin molded product (molded product J) according to Example 10.

As shown in Table 1, the heat ray transmittance of the (molded product J) when the visible light transmittance was 75% was 47.4%, and the haze value was 1.1%.
In addition, (ΔVLT) after exposure for 168 hours at a temperature of 120 ° C. was 1.16%, and an improvement in heat resistance was confirmed as compared with Comparative Example 1 below, which was not treated in an oxygen-containing atmosphere.

[Example 11]
Except that cesium carbonate was replaced with barium hydroxide octahydrate and tungstic acid (H ₂ WO ₄ ) and barium hydroxide aqueous solution were mixed so that Ba / W = 0.33 (molar ratio), In the same manner as in Example 1, Ba _0.33 WO ₃ fine particles (f) were obtained.
Thereafter, the same operation as in Example 1 was performed except that the fine particles (a) were replaced with the fine particles (f) to obtain a heat ray shielding transparent resin molded product (molded product K) according to Example 10.

As shown in Table 1, the heat ray transmittance of the (molded product K) when the visible light transmittance was 75% was 53.5%, and the haze value was 1.1%.
In addition, (ΔVLT) after exposure for 168 hours at a temperature of 120 ° C. was 1.31%, and an improvement in heat resistance was confirmed as compared with Comparative Example 1 below, which was not treated in an oxygen-containing atmosphere.

[Example 12]
The (A powder) obtained in Example 1 was heated in a mixed gas atmosphere of 5 volume% oxygen and 95 volume% nitrogen, and subjected to an oxidation exposure treatment at a temperature of 200 ° C. for 24 hours. A treated powder (treated C powder) was obtained.
Thereafter, the same operation as in Example 1 was performed except that (Processing A powder) was replaced with (Processing C powder) to obtain a heat ray shielding transparent resin molded product (molded product L) according to Example 12.

As shown in Table 1, the heat ray transmittance of the (formed product L) when the visible light transmittance was 75% was 38.5%, and the haze value was 1.1%.
Further, (ΔVLT) after exposure for 72 hours at a temperature of 120 ° C. was 0.27%, and an improvement in heat resistance was confirmed as compared with Comparative Example 1 below, which was not treated in an oxygen-containing atmosphere.

[Example 13]
The (A powder) obtained in Example 1 was heated in a mixed gas atmosphere of 1 vol% oxygen and 99 vol% nitrogen, and subjected to an oxidation exposure treatment at a temperature of 100 ° C. for 24 hours. A treated powder (treated D powder) was obtained.
Thereafter, the same operation as in Example 1 was performed except that (Processing A powder) was replaced with (Processing D powder) to obtain a heat ray shielding transparent resin molded product (molded product M) according to Example 13.

As shown in Table 1, the heat ray transmittance of the (Molded product M) when the visible light transmittance was 75% was 38.6%, and the haze value was 1.0%.
In addition, (ΔVLT) after exposure for 72 hours at a temperature of 120 ° C. was 1.15%, and an improvement in heat resistance was confirmed as compared with Comparative Example 1 below which was not treated in an oxygen-containing atmosphere.

[Comparative Example 1]
The same operation as in Example 1 was performed except that (A powder) obtained in Example 1 was replaced with (A powder) without subjecting the (A powder) to oxidation exposure treatment. The heat ray shielding transparent resin molding (molded body N) was obtained.

As shown in Table 1, the heat ray transmittance was 38.8% and the haze value was 1.0% when the visible light transmittance of the molded body N was 75%.
Moreover, (ΔVLT) after exposure for 72 hours at a temperature of 120 ° C. was 1.46%, and it was confirmed that the heat resistance was inferior to those of Examples 1 to 13.

Claims (6)

Formula _M y WO _z (where, M is Cs, Rb, K, Na, Ba, Ca, Sr, Mg, Nb, Ge, In, 1 or more elements selected from among Tl, W is tungsten, O is a composite tungsten oxide fine particle having a hexagonal crystal structure represented by oxygen, 0.1 ≦ y ≦ 0.5, 2.2 ≦ z ≦ 3.0), and further in an oxygen-containing atmosphere. Composite tungsten oxide fine particles treated by oxidation exposure at 50 ° C. or higher and 400 ° C. or lower;
And one or more thermoplastic resins selected from acrylic resins, polycarbonate resins, polyetherimide resins, polystyrene resins, polyethersulfone resins, fluororesins, polyolefin resins and polyester resins,
A masterbatch containing a high heat resistance heat ray shielding component, which is used for producing a heat ray shielding transparent resin molding.   2. The high heat-resistant heat ray shielding component-containing masterbatch according to claim 1, wherein the composite tungsten oxide fine particles obtained by the oxidation exposure treatment are fine particles having a dispersed particle diameter of 800 nm or less.   The high heat-resistant heat ray shielding component-containing masterbatch according to claim 1 or 2 is diluted with a thermoplastic resin molding material of the same type as the thermoplastic resin of the masterbatch or a different type of thermoplastic resin molding material having compatibility, And the high heat resistant heat ray shielding transparent resin molding characterized by being shape | molded by the predetermined | prescribed shape.   4. A high heat resistant heat ray shielding transparent laminate, wherein the high heat resistant heat ray shielding transparent resin molding according to claim 3 is laminated on another transparent molding. A method for producing a heat-shielding heat ray shielding component-containing masterbatch used for producing a heat ray shielding transparent resin molded article,
A composite tungsten oxide fine particle represented by the general formula MyWOz (where 0.1 ≦ Y ≦ 0.5, 2.2 ≦ Z ≦ 3.0) and having a hexagonal crystal structure is obtained in an oxygen-containing atmosphere. A step of oxidizing exposure treatment at a temperature of from ℃ to 400 ℃,
A step of adding the composite tungsten oxide fine particles subjected to the oxidation exposure treatment and a dispersing agent to a solvent and performing pulverization / dispersion treatment to obtain a fine particle dispersion;
After obtaining the fine particle dispersion, removing the solvent to obtain the fine particle dispersion; and
A method for producing a masterbatch containing a high heat resistance heat ray shielding component, comprising: mixing, melting and kneading and molding the fine particle dispersed powder and a thermoplastic resin pellet.   The method for producing a masterbatch containing a high heat resistance heat ray shielding component according to claim 5, wherein the oxygen concentration in the oxygen-containing atmosphere is 0.1 vol% or more and 25 vol% or less.