JP2018118463A - Heat ray-shielding transparent resin laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide excellent barrier property, scratch resistance and heat dissipation property to a heat ray-shielding transparent resin molding having high visible light transmittance and heat ray-shielding property.SOLUTION: A heat ray-shielding transparent resin laminate is provided which comprises: a heat ray-shielding transparent resin molding containing a heat ray-shielding fine particle and a thermoplastic resin; and a barrier film that is formed at least one surface of the molding and has visible light transmittance, and in which the barrier film is formed of at least one of SiO, AlOand diamond-like carbon and has a film thickness of 0.1 μm-5 μm, and the laminate has light transmittance at wavelengths of 400 nm to 800 nm according to JIS R 3106 of 70% or more, oxygen permeability measured based on MOCON method according to JIS K 7126-2 of less than 0.1 cm/m/day/atm, and water vapor permeability at a temperature of 40°C and relative humidity of 90% measured based on the MOCON method according to JIS K 7129B of less than 0.01 g/m/day.SELECTED DRAWING: None

Description

  The present invention is widely used for window materials used for openings of buildings and vehicles, or roof materials and wall materials of buildings, and has high visible light permeability and heat ray shielding transparency excellent in heat ray shielding properties. The present invention relates to improvement of a resin molded body.

  As building materials such as windows and doors, and window materials used in the openings of vehicles such as automobiles, trains, and aircraft, or roof materials and wall materials of buildings such as arcades, ceiling domes, and carports, A transparent glass material such as a glass plate or a resin material such as a resin film, a resin sheet, or a resin plate is used for taking in sunlight. However, solar rays include ultraviolet rays and infrared rays in addition to visible rays, and among infrared rays, near infrared rays having a wavelength in the range of 800 nm to 2500 nm are also called heat rays, and these glass materials or resin materials are used. This approach causes the temperature inside the structure such as the room to rise.

  In recent years, in order to prevent such near-infrared light from entering, there has been a rapid increase in demand for a heat ray-shielding transparent resin molded article that can shield heat rays while allowing sufficient passage of visible light. Many proposals have been made regarding shielding transparent resin moldings.

  For example, Japanese Patent Laid-Open No. 61-277437 discloses a heat ray shielding plate in which a heat ray reflective film obtained by depositing a metal on a transparent resin film is bonded to a transparent substrate such as a glass plate, an acrylic plate, or a polycarbonate plate. ing. However, since the heat ray reflective film itself is very expensive and requires a complicated process such as an adhesion process, the heat ray shielding plate is expensive. Moreover, since the adhesiveness of a transparent base material and a heat ray reflective film is not good, there exists a problem that peeling of a heat ray reflective film arises by a time-dependent change.

  In addition, in Japanese Patent Application Laid-Open Nos. H05-075544 and H2-173060, a heat ray shielding plate formed by kneading mica coated with titanium oxide as heat ray reflective particles in a transparent resin such as an acrylic resin or a polycarbonate resin. Has been proposed. However, in this heat ray shielding plate, it is necessary to add a large amount of heat ray reflective particles in order to enhance the heat ray shielding ability, and the visible light transmission ability is lowered as the blending amount of the heat ray reflective particles is increased. If the addition amount of the heat ray reflective particles is decreased, the visible light transmission ability is increased, but the heat ray shielding ability is lowered. Therefore, with this heat ray shielding plate, it is difficult to satisfy the heat ray shielding ability and the visible light transmission ability at the same time. Further, when a large amount of heat ray reflective particles are blended, there is a problem in strength that the physical properties of the transparent resin constituting the molded body, particularly impact resistance strength and toughness are lowered.

  In JP-A-2003-327717, focusing on hexaboride fine particles having a large amount of free electrons as a component having a heat ray shielding effect, hexaboride fine particles or hexaboride in polycarbonate resin or acrylic resin. A heat ray shielding resin sheet material formed by dispersing fine particles and ITO (tin-containing indium oxide) fine particles and / or ATO (antimony-containing tin oxide) fine particles is disclosed.

Japanese Patent Application Laid-Open No. 2006-219661 discloses a tungsten oxide fine particle represented by a general formula: WO _X (2.45 ≦ X ≦ 2.999) and / or a general formula as a component having a heat ray shielding function. : _M Y _WO indicated by Z (0.1 ≦ Y ≦ 0.5,2.2 ≦ Z ≦ 3.0), and a transparent resin substrate composite tungsten oxide fine particles having a hexagonal crystal structure The heat ray shielding resin sheet material formed by including in is disclosed.

  On the other hand, JP-A-61-277437 discloses forming a hard coat film such as epoxy resin, acrylic resin, amino resin, polysiloxane on the surface of a transparent resin film. JP-A-2005-344006 discloses a transparent resin film prepared from a polycarbonate resin, a heat ray shielding inorganic compound composed of a metal oxide such as ATO and ITO, and a transparent resin composition composed of an additive. A heat ray shielding transparent resin film having a surface coated with a silicone resin hard coat agent or an organic resin hard coat agent is disclosed. However, these hard coat films are only formed for the purpose of imparting higher hardness than the resin film and improving the weather resistance.

  JP-A-61-277437 and JP-A-2005-344006 disclose that a primer layer is provided between a transparent resin film and a hard coat film. In particular, JP-A-2005-344006 discloses that a primer layer contains an ultraviolet absorber or the like. However, the formation of the primer layer is only for the purpose of improving the adhesion, and the addition of an ultraviolet absorber or the like is only for the purpose of improving the durability against the adhesion.

JP-A 61-277437 Japanese Patent Application Laid-Open No. H05-075544 JP-A-2-173060 JP 2003-327717 A Japanese Patent Laid-Open No. 2006-219661 JP 2005-344006 A

  Among conventional heat ray shielding transparent resin moldings, in the structure in which a metal thin film is formed on the surface of the transparent resin molding, or in the structure in which oxide fine particles having heat ray reflectivity and heat ray shielding properties are dispersed in the transparent resin molding If the product is exposed to the outside air for a long period of time or installed in a place with high humidity, the metal thin film may be oxidized, or the oxide particles and resin may be altered or deteriorated, preventing the original performance from being maintained. There is. Moreover, the actual situation is that sufficient consideration has not been given to measures for preventing damage caused by human hands, stepping stones, etc., and means for radiating absorbed heat.

  In addition, even in the structure in which a hard coat film and a primer layer are provided on the surface of the transparent resin molded body, absorption of oxygen and moisture from the atmosphere is not taken into consideration, and similarly, a heat ray shielding transparent resin molded body is used. Sufficient barrier properties, scratch resistance, and heat dissipation properties are not sufficiently imparted.

  Accordingly, an object of the present invention is to provide excellent barrier properties, scratch resistance, and heat dissipation for a heat ray shielding transparent resin molded product that can exhibit high heat ray shielding properties while maintaining visible light transmittance. It is to grant.

  As a result of intensive studies to achieve the above object, the present inventor has made visible on at least one surface of a heat ray shielding transparent resin molding containing heat ray shielding fine particles and a thermoplastic resin by PVD method or CVD method. By forming and laminating a light-transmitting barrier film to form a heat ray-shielding transparent resin laminate, it is superior to a heat ray-shielding transparent resin molded article having high visible light permeability and heat ray shielding properties. The present inventors have found that barrier properties, scratch resistance, and heat dissipation properties can be imparted, and have reached the present invention.

  That is, the heat ray shielding transparent resin laminate of the present invention includes a heat ray shielding transparent resin molded product containing heat ray shielding fine particles and a thermoplastic resin, and visible light formed on at least one surface of the heat ray shielding transparent resin molded product. And a barrier film having permeability.

  The heat ray shielding transparent resin laminate of the present invention preferably has a light transmittance of 70% or more from a wavelength of 400 nm to a wavelength of 800 nm based on JIS R 3106.

Moreover, it is preferable that the oxygen permeability measured based on the MOCON method prescribed | regulated to JISK7126-2 of the said heat ray shielding transparent resin laminated body is less than 0.1 cm < ³ > / m < ² > / day / atm.

Furthermore, the water vapor permeability of the heat ray-shielding transparent resin laminate at a temperature of 40 ° C. and a relative humidity of 90%, measured based on the MOCON method defined in JIS K 7129B, is less than 0.01 g / m ² / day. It is preferable.

The barrier film is preferably composed of a thin film made of at least one selected from SiO ₂ , Al ₂ O ₃ , and DLC (diamond-like carbon) and having a thickness of 0.1 μm to 5 μm. The barrier film can be formed by a PVD method or a CVD method.

  The heat ray shielding fine particles are composed of at least one selected from heat ray absorbing fine particles and heat ray reflective fine particles.

  Examples of the heat ray-absorbing fine particles include fine particles comprising at least one selected from antimony-containing tin oxide, tin-containing indium oxide, tungsten oxide, composite tungsten oxide, and hexaboride. Examples of the heat ray reflective fine particles include metal fine particles composed of one or more selected from Au, Ag, Pd, Cu, Ni, and Al.

  The thermoplastic resin is composed of at least one selected from acrylic resin, polycarbonate resin, polyetherimide resin, polystyrene resin, polyethersulfone resin, fluorine-based resin, polyolefin resin, and polyester resin.

  The heat ray shielding transparent resin laminate of the present invention comprises a heat ray shielding transparent resin molded product containing heat ray shielding fine particles and a thermoplastic resin, and a visible light transmissive property formed on at least one surface of the heat ray shielding transparent resin molded product. It has excellent barrier properties, scratch resistance, and heat dissipation, and even if it is exposed to the outside air for a long time or installed in a place with high humidity, the heat ray shielding fine particles are deteriorated and deteriorated. Therefore, the heat ray shielding performance can be maintained and secured over a long period of time, the heat ray shielding transparent resin molded product is prevented from being damaged, and the heat dissipation of the absorbed heat is improved. The use of the transparent resin molded product can be expanded.

  Hereinafter, embodiments of the present invention will be described in detail, but the present invention is not limited thereto.

  The heat ray shielding transparent resin laminate of the present invention comprises a heat ray shielding transparent resin molding containing heat ray shielding fine particles and a thermoplastic resin, and a visible light transmissive property formed on at least one surface of the heat ray shielding transparent resin molding. A barrier film.

  The heat ray shielding transparent resin laminate of the present invention has a high visible light transmittance and a heat ray shielding transparent resin molded article excellent in heat ray shielding properties, and is excellent while having high visible light transparency and heat ray shielding properties. As long as it has barrier properties, scratch resistance, and heat dissipation, there is no particular limitation on its shape. It can be used for parts. Furthermore, it can be formed into an arbitrary shape as necessary, and can be formed into a flat shape and a curved surface. Moreover, the thickness of the heat ray shielding transparent resin laminate can be adjusted to an arbitrary thickness as necessary from a plate shape, a sheet shape to a film shape. Furthermore, the plate-shaped heat ray shielding transparent resin laminate formed in a planar shape can be formed into an arbitrary shape such as a spherical shape by post-processing.

1. Heat ray shielding transparent resin laminate The heat ray shielding transparent resin laminate of the present invention has a barrier film having visible light permeability formed on at least one surface of a heat ray shielding transparent resin molding containing heat ray shielding fine particles and a thermoplastic resin. Has been. This barrier film is formed by a PVD method (physical vapor deposition method) or a CVD method (chemical vapor deposition method).

  The light transmittance from a wavelength of 400 nm to a wavelength of 800 nm of the heat ray shielding transparent resin laminate based on JIS R 3106 is preferably 70% or more, and more preferably 75% or more. By maintaining the light transmittance in this way, the high visible light transmittance of the heat ray shielding transparent resin molded product is maintained.

In particular, the oxygen permeability of the heat ray shielding transparent resin laminate measured based on the MOCON method defined in JIS K 716-2 is preferably less than 0.1 cm ³ / m ² / day / atm. It is more preferably less than 08 cm ³ / m ² / day / atm, and even more preferably less than 0.05 cm ³ / m ² / day / atm. The oxygen permeability can be measured using an oxygen permeability measuring device or the like.

In addition, the water vapor permeability of the heat ray shielding transparent resin laminate at a temperature of 40 ° C. and a relative humidity of 90% measured based on the MOCON method defined in JIS K 7129B is less than 0.01 g / m ² / day. are preferred, more preferably less than 0.009g ^/ m 2 ^/ day, more preferably less than 0.008g ^/ m 2 ^/ day. The water vapor permeability can be measured using a water vapor permeability measuring device or the like.

When the oxygen permeability is 0.1 cm ³ / m ² / day / atm or more, or the water vapor permeability is 0.01 g / m ² / day or more, the barrier property becomes insufficient, and the outside air is used for a long time. If it is touched or placed in a place with high humidity, the heat ray shielding fine particles and the thermoplastic resin may be deteriorated and deteriorated due to absorption of oxygen and moisture from the atmosphere.

  As described above, in the heat ray shielding transparent resin laminate of the present invention, a barrier film having visible light permeability is formed on at least one surface of the heat ray shielding transparent resin molding containing the heat ray shielding fine particles and the thermoplastic resin. Yes. By laminating a barrier film having visible light permeability on at least one surface of the heat ray-shielding transparent resin molding by PVD or CVD, an effect of suppressing permeation of oxygen and water vapor is obtained. It is done.

  Hereinafter, for the heat ray shielding transparent resin molding and the barrier film constituting the heat ray shielding transparent resin laminate, (1) a barrier film, (2) a method for forming the barrier film, (3) a heat ray shielding transparent resin molding, and (4) The manufacturing method of the heat ray shielding transparent resin molded product will be described in this order.

(1) Barrier film The heat ray shielding transparent resin laminate of the present invention has a visible light transmissive barrier film on at least one surface of a plate-like heat ray shielding transparent resin molding such as a resin film, a resin sheet, or a resin plate. The main feature is that

The barrier film has an effect of suppressing permeation of predetermined oxygen and permeation of water vapor, and has a predetermined visible light permeability, and is constituted by a thin film formed by a PVD method or a CVD method, The effect of suppressing the permeation of oxygen and the permeation of water vapor, ie, having at least one selected from SiO ₂ (silica), Al ₂ O ₃ (alumina), and DLC (diamond-like carbon), which has a high gas barrier property. Is preferred.

  Of the materials constituting the barrier film, DLC, in particular, can provide not only high gas barrier properties but also high heat dissipation to the barrier film, and it is easy to ensure transparency of the barrier film.

  By using DLC as a gas barrier film having a heat dissipation property, not only a heat dissipation property and a gas barrier property can be compatible, but also transparency can be easily secured. DLC refers to a carbon material similar to diamond and has an intermediate crystal structure between diamond and graphite. More specifically, it has an amorphous structure in which carbon is the main component and contains some hydrogen and includes both diamond bonds (SP3 bonds) and graphite bonds (SP2 bonds). DLC is a material that exhibits a predetermined gas barrier property and a predetermined heat dissipation property, and also has an electrical insulation property.

  From the viewpoint of sufficiently ensuring the heat dissipation of the barrier film, the thermal conductivity of the barrier film is preferably 30 W / mK or more, more preferably 35 W / mK or more, and 40 W / mK or more. Further preferred. The higher the thermal conductivity, the better the heat dissipation, which is preferable. However, the upper limit of the thermal conductivity of DLC is usually 2000 W / mK or less, which is the thermal conductivity of diamond.

  The thermal conductivity of the barrier film can be measured using an optical alternating current method. For example, the thermal conductivity can be measured using an optical AC method thermal diffusivity measuring apparatus (Laser PIT-1 manufactured by Advance Riko Co., Ltd.) with a diode laser as the heat source and the measurement environment as atmospheric pressure (20 ° C.).

  When heat dissipation is imparted to the barrier film using DLC, the thermal conductivity of the barrier film can be controlled by the composition of DLC. Specifically, DLC usually contains a predetermined amount of hydrogen, and this hydrogen may cause the thermal conductivity to be lower than 30 W / mK. For this reason, it is preferable to adjust the hydrogen content in order to control the thermal conductivity of the barrier film satisfactorily. On the other hand, when an appropriate amount of hydrogen gas is added, there is an advantage that it is easy to ensure the denseness due to the ashing effect.

In addition, the barrier film constituting the heat ray shielding transparent resin laminate of the present invention includes a barrier film in which an additive element is added to a main constituent material such as SiO ₂ , Al ₂ O ₃ , and DLC. In particular, when heat dissipation is imparted to the barrier film using DLC, the thermal conductivity of the barrier film depends on the composition of the DLC, and the carbon that is the main component of the DLC contains a predetermined amount of a predetermined additive element. It is also possible to control by. Examples of such additive elements include silicon (Si), titanium (Ti), aluminum (Al), phosphorus (P), sulfur (S), and chlorine (Cl). From the viewpoint that the bond structure is similar to carbon, silicon is preferred. It is also effective to add nitrogen (N) or oxygen (O) in order to impart transparency and structural flexibility. From the viewpoint of improving the denseness of the barrier film, sulfur and chlorine are preferable. The content of such additive elements is more than 0 atomic% and 4.5 atomic% or less, preferably 0.1 atomic% or more and 2.5 atomic% or less. When silicon is used as the additive element, the atomic ratio of carbon to silicon in the heat-dissipating gas barrier film is C: Si = 1000: 0 to 1000: 40 (Si exceeds 4.0 atomic% and 4.0 atoms) % Or less), and more preferably C: Si = 1000: 1 to 1000: 20 (Si is 0.1 atomic% or more and 2.0 atomic% or less). The content of such additive elements can be usually measured by XPS (X-ray photoelectron spectroscopy).

  The film thickness of the barrier film is arbitrary as long as it can exhibit a predetermined gas barrier property and additionally a predetermined heat dissipation property, but is preferably in the range of 0.1 μm to 5 μm, and in the range of 0.5 μm to 2 μm. More preferably, it is more preferably in the range of 0.5 μm to 1 μm. When the film thickness is less than 0.1 μm, predetermined characteristics as a barrier film cannot be exhibited, while when it exceeds 5 μm, it is difficult to ensure high transparency.

  The refractive index of the barrier film using DLC is 1.4 or more and 2.2 or less, preferably 1.42 or more and 2.1 or less, more preferably 1.44 or more and 2.0 or less, and still more preferably 1. 5 or more and 1.7 or less. Thereby, it becomes easy to ensure transparency as a barrier film having heat dissipation, and as a result, a highly transparent heat ray shielding transparent resin laminate can be obtained. In addition, the refractive index in this range is almost the same as the refractive index of the heat ray-shielding transparent resin molded article, there is no reflection at the interface with the molded article, and without reducing the visible light transmittance and the heat ray shielding function, It is possible to add barrier properties and scratch resistance to the heat ray shielding transparent resin molding.

(2) Manufacturing method of barrier film A barrier film having visible light permeability is formed by PVD or CVD on at least one surface of the heat ray-shielding transparent resin molding constituting the heat ray-shielding transparent resin laminate. Can do.

  That is, the barrier film can be formed using a compact PVD film forming apparatus (physical vapor deposition apparatus) or CVD film forming apparatus (chemical vapor deposition apparatus) without using a large-scale hard coat facility. Film formation is possible.

  The PVD method is a method in which a material for forming a thin film is prepared as a target, and the target is vaporized with heat, or is struck out with Ar ions to form a film. Examples of the PVD method include a vacuum deposition method, an ion plating method, an ion beam deposition method, a sputtering method, and an ion beam sputtering method. On the other hand, the CVD method is a method in which a compound gas containing atoms constituting a thin film is introduced as a raw material, excited by plasma or heat, and a chemical reaction is used to form a thin film on a substrate. Examples of the CVD method include a thermal CVD method and a plasma CVD method. Any film forming method can be selected based on the performance and film quality of the thin film to be formed.

As a method for forming the SiO ₂ film and the Al ₂ O ₃ film, a vacuum deposition method in which a vapor deposition material is dissolved by an electron beam or the like and vaporized, and atoms from SiO ₂ and Al ₂ O ₃ targets by Ar ions are used. There is a sputtering method in which it is ejected and deposited on a sheet. The sputtering method tends to increase the film formation time, but is suitable for obtaining a dense film and a smooth film or a film having better adhesion. The vacuum deposition method is suitable for improving the barrier property by thickening the barrier film. Therefore, the film forming method is selected in consideration of the required performance and cost according to these characteristics.

  On the other hand, for the DLC film, film formation using a plasma CVD method is suitable. In the plasma CVD method, acetylene gas is introduced as a compound gas and the acetylene gas is decomposed by plasma, whereby a DLC film is formed on the surface of the heat ray-shielding transparent resin molded body. In the plasma CVD method, since the compound gas is activated using plasma, the film can be formed at a low temperature, so that it is particularly suitable for film formation on a resin sheet.

(3) Heat ray shielding transparent resin molded body The heat ray shielding transparent resin molded body which is the base material of the heat ray shielding transparent resin laminate of the present invention mainly contains heat ray shielding fine particles and a thermoplastic resin.

  The content of the heat ray shielding fine particles with respect to the thermoplastic resin is preferably 0.01 parts by mass or more and less than 20 parts by mass, and more preferably 0.1 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the thermoplastic resin. When the content of the heat ray shielding fine particles is larger than this range, the heat ray shielding fine particles are aggregated, the dispersion in the resin becomes insufficient, and the haze (cloudiness value) of the molded heat ray shielding transparent resin molding is increased. May end up. In addition, dilution dilution may occur when the masterbatch containing heat ray shielding fine particles is diluted and kneaded with a thermoplastic resin molding material. On the other hand, when the content of the heat ray shielding fine particles is less than the above range, it depends on the thickness of the heat ray shielding transparent resin molding to be molded, but particularly when the heat ray shielding transparent resin molding is a film having a thickness of 400 μm or less. However, sufficient heat ray shielding ability may not be obtained.

  The shape of the heat ray-shielding transparent resin molded product can be formed into an arbitrary shape as necessary, and can be formed into a flat shape and a curved shape. Moreover, the thickness of the heat ray shielding transparent resin molded product can be adjusted to an arbitrary thickness as necessary from a plate shape, a sheet shape to a film shape. Furthermore, the resin sheet formed into a flat shape can be formed into an arbitrary shape such as a spherical shape by post-processing.

  For example, when the heat ray shielding transparent resin molding is formed into a sheet shape, the thickness of the resin sheet is not particularly limited, but is preferably in the range of 0.2 mm to 5.0 mm, and 0.5 mm to 4.0 mm. The range of is more preferable. If the thickness of the resin sheet is less than 0.2 mm, it is necessary to increase the content of the heat ray shielding fine particles in order to increase the heat ray shielding effect. As a result, the thermal decomposition occurs during melting and kneading of the transparent resin and the heat ray shielding fine particles. May be promoted, which is undesirable. A sheet having a film thickness exceeding 5.0 mm becomes heavier, the product becomes expensive, and its use is also limited.

  Moreover, when the heat ray shielding transparent resin molding is formed into a film, the thickness of the resin film is not particularly limited, but is preferably in the range of 10 μm to 400 μm, and more preferably in the range of 20 μm to 200 μm. When the thickness of the resin film is less than 10 μm, it is necessary to increase the content of the heat ray shielding fine particles in order to exhibit practical heat ray shielding properties. As a result, the wear strength and impact resistance of the heat ray shielding transparent resin molded product are required. This is not desirable because it can reduce the performance. A film having a film thickness exceeding 400 μm is inferior in processability and handling properties, and the product becomes expensive and its use is limited.

  Furthermore, when the heat ray shielding transparent resin molding is formed into a plate shape, the thickness of the plate material is not particularly limited, but a range of 1 mm to 15 mm is preferable. If the thickness of the resin plate is less than 1 mm, the use as a plate material is limited, and it is necessary to increase the content of the heat ray shielding fine particles in order to increase the heat ray shielding effect, and as a result, the resin plate becomes expensive. Is not desirable. When the thickness of the plate material exceeds 15 mm, the weight becomes heavy, the product becomes expensive, and its use is also limited.

  However, the shape of the heat ray-shielding transparent resin molding of the present invention is not limited to these, and any shape can be adopted as long as the visible light permeability and the heat ray shielding property can be ensured depending on the application.

(3-1) Heat ray shielding fine particles The heat ray shielding fine particles include heat ray absorbing fine particles having excellent heat ray absorbing performance and heat ray reflecting fine particles having excellent heat ray reflecting performance, which are appropriately selected according to the use of the heat ray shielding transparent resin laminate. The

(A) Heat-absorbing fine particles Examples of heat-ray-absorbing fine particles include fine particles of ATO (antimony-containing tin oxide), ITO (tin-containing indium oxide), tungsten oxide, composite tungsten oxide, and hexaboride.

(A-1) ATO fine particles and ITO fine particles The ATO fine particles and the ITO fine particles hardly absorb or reflect light in the visible light region, and have a large reflection and absorption derived from plasma resonance in a wavelength region of 1000 nm or more. In the transmission profile of ATO fine particles and ITO fine particles, the transmittance decreases toward the longer wavelength side in the near infrared region. In the transmission profile of hexaboride fine particles, which will be described later, the transmittance has a minimum value near a wavelength of 1000 nm, and the transmittance gradually increases on the longer wavelength side. For this reason, by using hexaboride fine particles in combination with ITO fine particles or ATO fine particles, it becomes possible to shield the heat rays in the near infrared region without reducing the visible light transmittance, and each can be used alone. The heat ray shielding characteristic is improved as compared with this.

  The size of the ATO fine particles and the ITO fine particles is preferably 200 nm or less in average particle diameter, more preferably 100 nm or less, and particularly preferably in the range of 40 nm to 80 nm. When the average particle diameter is larger than 200 nm, the aggregation of the fine particles becomes strong in the dispersion and causes the fine particles to settle. In addition, the resin becomes a light scattering source, for example, a resin sheet that requires transparency. In this case, the resin sheet will appear cloudy. Also, for translucent roofing materials, etc., in applications that require light transparency that is more opaque than transparency, it is desirable to increase the particle size to promote scattering, but if the particle size is too large, In this case, the average particle diameter of the ATO fine particles and the ITO fine particles is preferably set to 200 nm or less because the external absorption itself is also attenuated.

  In addition, by controlling the content of ITO fine particles and ATO fine particles in the heat ray-shielding transparent resin molding and the content of hexaboride fine particles used in combination to improve heat ray shielding properties, absorption in the visible light region is free. It can be controlled and applied to brightness adjustment and privacy protection.

(A-2) Tungsten oxide fine particles and composite tungsten oxide fine particles Tungsten oxide fine particles have a composition represented by the general formula: WO _X (2.45 ≦ X ≦ 2.999). Further, the composite tungsten oxide fine particles have a general formula M _Y WO _Z (where M is H, He, alkali metal, alkaline earth metal, rare earth element, Mg, 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, One or more elements selected from Te, Ti, Nb, V, Mo, Ta, Re, Be, Hf, Os, Bi, and I, W is tungsten, O is oxygen, 0.1 ≦ Y ≦ 0 .5, 2.2 ≦ Z ≦ 3.0) and a hexagonal crystal structure.

  Since the tungsten oxide fine particles and 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, the transmitted color tone often has a bluish color tone. The particle diameters of the tungsten oxide fine particles and the composite tungsten oxide fine particles are appropriately selected according to the purpose of use. For example, when used for applications that maintain transparency, the dispersed particle diameter is preferably 800 nm or less. In this case, since light is not completely shielded by scattering, visibility in the visible light region is maintained, and at the same time, transparency is efficiently maintained. In particular, when importance is attached to the transparency in the visible light region, it is preferable to select the particle diameters of the tungsten oxide fine particles and the composite tungsten oxide fine particles in consideration of scattering by particles.

  When emphasizing the reduction of scattering by the tungsten oxide fine particles or the composite tungsten oxide fine particles, it is preferable to reduce the dispersed particle diameter to 200 nm or less, preferably 100 nm or less. As a result, the scattering of light in the visible light region having a wavelength of 400 nm to 780 nm due to geometrical scattering or Mie scattering is reduced, and as a result, the infrared shielding film becomes like a frosted glass and clear transparency cannot be obtained. Is avoided. Specifically, when the dispersed particle diameter is 200 nm or less, geometrical scattering or Mie scattering is reduced to form a Rayleigh-scattering region. In this Rayleigh-scattering region, scattered light is inversely proportional to the sixth power of the particle size. Therefore, the scattering is reduced as the dispersed particle size is reduced, and the transparency is improved. 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.

Examples of tungsten oxide fine particles having a composition represented by the general formula: WO _X (2.45 ≦ X ≦ 2.999) include W ₁₈ O ₄₉ , W ₂₀ O ₅₈ , and W ₄ O ₁₁ . If the value of X is 2.45 or more, it is possible to completely avoid the appearance of an undesired WO ₂ crystal phase in the infrared shielding material and to obtain the chemical stability of the material. . On the other hand, if the value of X is 2.999 or less, a sufficient amount of free electrons is generated and an efficient infrared shielding material is obtained, but if it is 2.95 or less, the infrared shielding material is more preferable. A WO _X compound in which the range of X is 2.45 ≦ X ≦ 2.999 is included in a compound called a so-called magnetic phase.

In addition, general formula: M _Y WO _Z (where M is H, He, alkali metal, alkaline earth metal, rare earth element, Mg, 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, One or more elements selected from V, Mo, Ta, Re, Be, Hf, Os, Bi, and I, W is tungsten, O is oxygen, 0.1 ≦ Y ≦ 0.5, 2.2 ≦ Z ≦ 3.0) and the composite tungsten oxide fine particles having a hexagonal crystal structure, the element M is particularly Cs, Rb, K, Tl, In, Ba, Composite tan that contains one or more of Li, Ca, Sr, Fe, Sn, Al, Cu Examples include gusten oxide fine particles. The addition amount of the additive element M is preferably 0.1 or more and 0.5 or less in terms of atomic ratio, and more preferably in the vicinity of 0.33 (approximately in the range of atomic ratio 0.30 to 0.35). This is because the value of the atomic ratio theoretically calculated from the hexagonal crystal structure is 0.33, and preferable optical characteristics can be obtained with the addition amount before and after this. Moreover, about the range of Z, 2.2 <= Z <= 3.0 is preferable. This is also in the composite tungsten oxide material expressed by M _Y WO _Z, in addition to a mechanism similar tungsten oxide material expressed by WO _X works, even in Z ≦ 3.0, the element M This is because free electrons are supplied by addition. From the viewpoint of optical characteristics, the range of Z is more preferably 2.2 ≦ Z ≦ 2.99, and further preferably 2.45 ≦ Z ≦ 2.99.

Here, typical examples of the composite tungsten oxide material include Cs _0.33 WO ₃ (CWO: cesium tungsten oxide), Rb _0.33 WO ₃ , K _0.33 WO ₃ , Ba _0.33 WO _3. As long as Y and Z fall within the above ranges, useful heat ray shielding characteristics can be obtained.

  In addition, it is preferable from a viewpoint of a weather resistance improvement that the surface of tungsten oxide microparticles | fine-particles or composite tungsten oxide microparticles | fine-particles is coat | covered with the oxide containing 1 or more types of Si, Ti, Zr, and Al.

In addition, in order to obtain a desired heat ray shielding resin molded product, the powder color of the tungsten oxide fine particles and / or the composite tungsten oxide fine particles is L ^* recommended by the International Lighting Commission (CIE) ^. In the powder color in the a ^* b ^* color system (JISZ8729), it is desirable to satisfy the conditions that L ^* is 25 to 80, a ^* is −10 to 10 and b ^* is −15 to 15.

  Furthermore, when using tungsten oxide fine particles and / or composite tungsten oxide fine particles as heat ray absorbing fine particles, in addition to these, Sb, V, Nb, Ta, Zr, F, Zn, Al, Ti, Pb, A group consisting of Ga, Re, Ru, P, Ge, In, Sn, La, Ce, Pr, Nd, Gd, Tb, Dy, Ho, Y, Sm, Eu, Er, Tm, Tb, Lu, Sr, and Ca It is also possible to further contain at least one kind of fine particles selected from oxide fine particles, composite oxide fine particles, and boride fine particles comprising at least two elements selected from

  A mixture of the tungsten oxide fine particles and / or the composite tungsten oxide fine particles and the fine particles described above, in which the mixing ratio is set in the range of 95: 5 to 5:95 by mass ratio also has a heat ray shielding function. Preferred as fine particles.

  If the mixing ratio of the tungsten oxide fine particles and / or the composite tungsten oxide fine particles is 5:95 or more, a sufficient heat ray shielding function can be expected. On the other hand, if the mixing ratio of the tungsten oxide fine particles and / or the composite tungsten oxide fine particles is 95: 5 or less, the use amount of the tungsten oxide fine particles and / or the composite tungsten oxide fine particles should be reduced. Cost reduction effect can be expected.

(A-3) hexaboride particles hexaboride fine particles are those of the general formula expressed by the XB _6. Here, the element X is at least one selected from La, Ce, Pr, Nd, Gd, Tb, Dy, Ho, Y, Sm, Eu, Er, Tm, Yb, Lu, Sr, and Ca. Preferably there is. Specifically, lanthanum hexaboride (LaB ₆ ), cerium hexaboride (CeB ₆ ), praseodymium hexaboride (PrB ₆ ), neodymium hexaboride (NdB ₆ ), gadolinium hexaboride (GdB ₆ ), hexaboride terbium _(TbB 6), hexaboride dysprosium _(DyB 6), hexaboride holmium _(HoB 6), hexaboride yttrium _(YB 6), hexaboride samarium _(SmB 6), hexaboride Europium (EuB ₆ ), erbium hexaboride (ErB ₆ ), thulium hexaboride (TmB ₆ ), ytterbium hexaboride (YbB ₆ ), lutetium hexaboride (LuB ₆ ), lanthanum cerium hexaboride ((La) , _{Ce) B 6),} hexaboride strontium _(SrB 6), as such hexaboride calcium (CaB ₆₎ is a representative It is below.

  For the same reason as the ATO fine particles and ITO fine particles, the hexaboride fine particles are preferably 200 nm or less in average particle size, more preferably 100 nm or less, and in the range of 40 nm to 80 nm. Particularly preferred. When the average particle diameter is larger than 200 nm, the aggregation of the fine particles becomes strong in the dispersion and causes the fine particles to settle. In addition, the resin becomes a light scattering source, for example, a resin sheet that requires transparency. In this case, the resin sheet will appear cloudy.

  As for the hexaboride fine particles, it is preferable that the surface is not oxidized, but usually the surface is often slightly oxidized, and it is inevitable that the surface is oxidized to some extent during the fine particle dispersion process. However, even in that case, the effectiveness of developing the heat ray shielding effect is not changed, and therefore, hexaboride fine particles having an oxidized surface can be used.

  Moreover, the higher the completeness as a crystal, the larger the hexaboride fine particle, the larger the heat ray shielding effect can be obtained, but even if the crystallinity is low and a broad diffraction peak is generated by X-ray diffraction, If the internal basic bond is composed of a bond between each metal and boron, such a hexaboride fine particle can also be applied in the present invention in order to exhibit a heat ray shielding effect. .

  The hexaboride microparticles are colored powders such as gray black, brown black, and green black, but are dispersed in heat ray-shielding transparent resin molding materials such as acrylic resin with a particle size sufficiently smaller than the visible light wavelength. If it is made into the state, visible-light transmittance is produced in the heat ray shielding transparent resin molding obtained, but infrared light shielding ability can fully be maintained. The reason for this has not been elucidated in detail, but the amount of free electrons in the hexaboride fine particles is large, and the absorption energy of indirect interband transition due to free electrons inside and on the surface of the fine particles is in the vicinity of visible to near infrared. Therefore, it is considered that the heat rays in this wavelength region are selectively reflected and absorbed.

(A-4) Content of heat ray absorbing fine particles Since the heat ray shielding performance is determined by the content of the heat ray shielding component per unit area of the heat ray shielding transparent resin molded product, the location of the heat ray shielding component per unit area of the molded product. If the fixed amount is dispersed, the desired heat ray shielding performance corresponding to the content of the heat ray shielding component is exhibited regardless of the thickness of the molded body. Accordingly, the content of the heat ray shielding component with respect to the resin is preferably determined in accordance with required optical characteristics, mechanical characteristics of the molded body, and the like. Even if the heat ray shielding component content per unit area that satisfies the heat ray shielding characteristics, the content per unit volume increases as the molded body becomes thinner, and the wear strength and impact resistance of the resin sheet decrease. . Further, the heat ray shielding component may be raised on the surface of the molded body, which may impair the appearance. Therefore, when the molded body is thin, it is necessary to adjust the content of the heat ray shielding component so that the above-described disadvantage does not occur.

  It is necessary to select the content of the heat ray shielding fine particles with respect to the thermoplastic resin in the heat ray shielding transparent resin molding containing the heat ray shielding fine particles and the thermoplastic resin on the premise that the above conditions are satisfied.

(B) Heat ray reflective fine particles: Metal fine particles Examples of the heat ray reflective fine particles include one or more metal fine particles selected from Au, Ag, Pd, Cu, Ni, and Al. Preferably, at least one selected from Au, Ag, Pd, Cu, and Ni, more preferably at least one selected from Ag and Pd, and still more preferably, Ag metal fine particles are used. These metals may be used alone or in combination of two or more. An alloy containing these metals can also be used.

  When using Ag fine particles which are the optimum elements as the heat ray reflective fine particles, the content of silver fine particles contained in all metal fine particles in the heat ray shielding transparent resin molded product is preferably 30% by mass or more, particularly It is more preferably 50% by mass or more, further preferably 70% by mass or more, and particularly preferably 80% by mass or more. In order to increase the infrared reflectance, it is preferable that all the metal fine particles are silver fine particles. When there is too little content of silver fine particles, solar reflectance may fall and heat ray shielding may become inadequate. At the same time, the transmitted light in the visible region is excessively colored, which may increase the visible light absorption rate.

  The average particle diameter of the heat ray reflective fine particles is preferably 1 to 100 nm. On the other hand, it is difficult to produce fine particles having a heat ray reflective particle of less than 1 nm. On the other hand, if the heat ray reflective fine particle is larger than 100 nm, a metallic luster caused by a decrease in transparency or an increase in visible light reflectance, so-called “glare” The increase is a problem.

  When heat ray reflecting fine particles are used as the heat ray shielding fine particles, it is preferable to use a resin film as the heat ray shielding transparent resin molding containing the heat ray reflective fine particles, and the thickness is preferably 5 μm or more and 100 μm or less, more preferably. Is 15 μm or more and 70 μm or less. If the thickness of the heat ray shielding transparent resin molding containing the heat ray reflective fine particles is too thin, not only a sufficient heat ray shielding property can be obtained, but also a film defect is likely to occur and the durability may be deteriorated. On the other hand, if the thickness of the heat ray-shielding transparent resin molding containing the heat ray reflective fine particles is too thick, there is a problem of an increase in so-called “glare” due to a decrease in transparency and an increase in visible light reflectance. Become.

  In the heat ray shielding transparent resin molding containing the heat ray reflective fine particles, a reflection mechanism based on a physical phenomenon called plasma vibration is used. Therefore, it is preferable that the heat-shielding transparent resin molded body has a porous structure in which metal fine particles form a conductive path and reflect light by plasma vibration. In such a porous structure, by controlling the formation of the conductive path appropriately, the movement of free electrons is suppressed, thereby suppressing plasma vibration and transmitting light in the visible light region, and in the near infrared region. It is thought that the characteristic which reflects strongly is expressed.

  When the entire heat-shielding transparent resin molded body is densely filled with metal fine particles and the metal fine particles are more closely connected, the surface resistivity decreases, the conductivity increases, and the visible to infrared range Since the reflectance increases over time, the glare increases and the transparency decreases.

(3-2) Thermoplastic resin The thermoplastic resin used for the heat ray-shielding transparent resin molding is not particularly limited as long as it is a transparent thermoplastic resin having a high light transmittance in the visible light region. In the case of a plate-like molded product, the visible light transmittance based on JIS R 3106 is 50% or more and the haze based on JIS K 7105 is 30% or less. Specific examples include acrylic resins, polycarbonate resins, polyetherimide resins, polystyrene resins, polyethersulfone resins, fluorine resins, polyolefin resins, and polyester resins.

  When heat-shielding transparent resin laminates are used for applications such as building or vehicle window materials, acrylic resin, polycarbonate resin, polyetherimide are considered in consideration of transparency, impact resistance, weather resistance, etc. A resin and a fluorine resin are more preferable.

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

  As acrylic resins, methyl methacrylate, ethyl methacrylate, propyl methacrylate, and butyl methacrylate are used as main raw materials, and acrylic acid esters having 1 to 8 carbon atoms, vinyl acetate, styrene, acrylonitrile, methacrylate, as necessary. Examples thereof include a polymer or copolymer using nitrile as a copolymerization component. Furthermore, an acrylic resin polymerized in multiple stages can also be used.

  Examples of fluororesins include polyfluorinated ethylene, polydifluorinated ethylene, polytetrafluoroethylene, ethylene-2 fluoroethylene copolymer, ethylene-4 fluoroethylene copolymer, tetrafluoroethylene-perfluoroalkoxy. An ethylene copolymer etc. are mentioned.

  Such a thermoplastic resin can contain an ultraviolet absorber, a light stabilizer, an antioxidant, a heat stabilizer, an antistatic agent, a flame retardant, a lubricant, a dye, a pigment, a filler and the like in addition to the heat ray shielding fine particles. .

  Furthermore, a hard coat layer cured by known thermosetting or active energy rays can be laminated on the surface of the heat ray-shielding transparent resin molding.

(4) Manufacturing method of heat ray shielding transparent resin molding Next, a manufacturing method of a heat ray shielding transparent resin molding mainly containing heat ray shielding fine particles and a thermoplastic resin will be described.

  The heat ray shielding fine particle dispersion according to the present invention can be obtained by adding the above-mentioned heat ray shielding fine particles and, if desired, an appropriate amount of a dispersant, a coupling agent, a surfactant, and the like to the solvent for dispersion treatment. The solvent of the heat ray shielding fine particle dispersion is required to have a function for maintaining the dispersibility of the heat ray shielding fine particles and a function that does not cause defects when forming a molded body using the heat ray shielding fine particle dispersion.

  As the solvent, water, an organic solvent, an oil or fat, a liquid resin, a liquid plasticizer for plastics, or a mixture thereof can be selected to produce a heat ray shielding dispersion. Various organic solvents such as alcohols, ketones, hydrocarbons, glycols, and water can be selected as organic solvents that satisfy the above requirements. Specifically, alcohol solvents such as methanol, ethanol, 1-propanol, isopropanol, butanol, pentanol, benzyl alcohol and diacetone alcohol; ketones such as acetone, methyl ethyl ketone, methyl propyl ketone, methyl isobutyl ketone, cyclohexanone and isophorone Solvents such as 3-methyl-methoxy-propionate; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol isopropyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol methyl ether acetate, propylene Glycol derivatives such as glycol ethyl ether acetate; Amides such as N-methylformamide, dimethylformamide, dimethylacetamide and N-methyl-2-pyrrolidone; aromatic hydrocarbons such as toluene and xylene; halogenated hydrocarbons such as ethylene chloride and chlorobenzene Can be mentioned. Among these, organic solvents having low polarity are preferable, and isopropyl alcohol, ethanol, 1-methoxy-2-propanol, dimethyl ketone, methyl ethyl ketone, methyl isobutyl ketone, toluene, propylene glycol monomethyl ether acetate, n-butyl acetate and the like are more preferable. preferable. These solvents can be used alone or in combination of two or more.

  As the liquid resin, methyl methacrylate and the like are preferable. Liquid plasticizers include plasticizers that are compounds of monohydric alcohols and organic acid esters, ester plasticizers such as polyhydric alcohol organic acid ester compounds, and phosphorus compounds such as organic phosphate plasticizers. A preferable example is an acid plasticizer. Among these, triethylene glycol di-2-ethyl hexaonate, triethylene glycol di-2-ethyl butyrate, and tetraethylene glycol di-2-ethyl hexaonate are more preferable because of low hydrolyzability. .

  The dispersant, coupling agent, and surfactant can be selected according to the use, but preferably have an amine-containing group, a hydroxyl group, a carboxyl group, or an epoxy group as a functional group. These functional groups are adsorbed on the surface of the heat ray shielding fine particles, prevent aggregation of the heat ray shielding fine particles, and have a function of uniformly dispersing the heat ray shielding fine particles in the heat ray shielding transparent resin molded body.

  Dispersants that can be suitably used include phosphate ester compounds, polymer dispersants, silane coupling agents, titanate coupling agents, aluminum coupling agents, but are not limited thereto. is not. Examples of the polymer dispersant include an acrylic polymer dispersant, a urethane polymer dispersant, an acrylic block copolymer polymer dispersant, a polyether dispersant, and a polyester polymer dispersant.

  The addition amount of the dispersant is desirably in the range of 10 parts by mass to 1000 parts by mass, and more preferably in the range of 20 parts by mass to 200 parts by mass with respect to 100 parts by mass of the heat ray shielding fine particles. When the added amount of the dispersant is within this range, the heat ray shielding fine particles do not aggregate in the liquid, and dispersion stability is maintained.

  The method for producing the heat ray shielding fine particle dispersion is arbitrarily selected as long as the heat ray shielding fine particles are uniformly dispersed in the resin. For example, using a means such as a bead mill, ball mill, sand mill, ultrasonic dispersion, etc., the prepared heat ray shielding fine particles and an appropriately selected dispersant are mixed and dispersed in an arbitrary solvent to prepare a heat ray shielding fine particle dispersion. To do.

  Next, heat ray shielding fine particle dispersion, thermoplastic resin granules or pellets, and other additives as necessary, ribbon blender, tumbler, nauter mixer, Henschel mixer, super mixer, planetary mixer, etc. Using a kneading machine such as a Banbury mixer, kneader, roll, kneader, single screw extruder, twin screw extruder, etc., uniformly melt and mix while removing the solvent to heat the thermoplastic resin. A mixture in which the shielding fine particles are uniformly dispersed can be prepared.

  Alternatively, a powder obtained by removing the solvent of the heat ray shielding fine particle dispersion by a known means, a granular material or pellet of a thermoplastic resin, and other additives as necessary, are used in the same way. Thus, by uniformly melting and mixing, a mixture in which the heat ray shielding fine particles are uniformly dispersed in the thermoplastic resin can be prepared.

  In addition, it is also possible to add heat ray shielding fine particles not subjected to dispersion treatment directly to the thermoplastic resin and uniformly melt and mix them. Therefore, as long as the heat ray shielding fine particles are uniformly dispersed in the thermoplastic resin, it is not limited to these means, and any other known means can be used.

  The mixture thus obtained is kneaded with a vented uniaxial or biaxial extruder and processed into a pellet form, whereby a heat-shielding fine particle-containing master batch can be obtained.

  A master batch containing pellets of heat ray shielding fine particles can be obtained by a method of cutting the most general melt-extruded strand. Accordingly, examples of the shape include a columnar 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. In this case, the master batch generally has a nearly spherical shape.

  The obtained heat ray shielding fine particle component-containing masterbatch can take any form or shape, but is used for diluting the heat ray shielding fine particle-containing masterbatch when forming a heat ray shielding transparent resin molded product. It is preferable that it is the same form and shape as a thermoplastic resin material.

  Moreover, it is also possible to mix | blend a general additive with a heat ray shielding fine particle containing masterbatch. For example, azo dyes, cyanine dyes, quinoline dyes, perylene dyes, carbon black, and other dyes and pigments commonly used for coloring thermoplastic resins to give any color tone as needed , Hindered phenol and phosphorus stabilizers, mold release agents, hydroxybenzophenone, salicylic acid, HALS, triazole and triazine UV absorbers, coupling agents, surfactants, antistatic agents, etc. Can be used as additives.

  The heat ray shielding transparent resin molded article is obtained by diluting and kneading the heat ray shielding fine particle-containing master batch with the same kind of thermoplastic resin material or a different kind of thermoplastic resin material compatible with the thermoplastic resin constituting the master batch. It is obtained by molding into

  Examples of the method for molding the heat ray-shielding transparent resin molded article include any means such as injection molding, extrusion molding, compression molding, and rotational molding. In particular, a method of obtaining a molded body by injection molding and a method of obtaining a molded body by extrusion molding are preferably employed. As a method for obtaining a sheet-like or film-like molded product by extrusion molding, there is a method of taking out a molten thermoplastic resin extruded using an extruder such as a T-die while cooling with a cooling roll. The injection-molded body is suitably applied to automobile bodies such as window glass and roofs of automobiles, and the sheet-like or film-like molded body obtained by extrusion molding is suitably used for buildings such as arcades and carports. Is done.

  By laminating the barrier film of the present invention on the surface of the heat ray shielding transparent resin molding, a heat ray shielding transparent resin laminate can be obtained. As described above, the heat ray-shielding transparent resin laminate can be formed into an arbitrary shape as necessary, for example, a flat shape or a curved shape. Moreover, the thickness of the heat ray shielding transparent resin laminate can be adjusted to an arbitrary thickness as necessary from a plate shape, a sheet shape to a film shape.

  The heat ray-shielding transparent resin laminate of the present invention can be used for structural materials such as window glass and arcade, and the heat ray-shielding transparent resin laminate can be used for other transparent molded products such as inorganic glass, resin glass, and resin films. It can also be used for a structural material as a heat ray shielding transparent laminated molded body laminated and integrated by an arbitrary method. For example, a heat ray-shielding transparent laminated molded product having a heat ray shielding function and a scattering prevention function can be obtained by laminating and integrating the film-like heat ray shielding transparent resin laminate of the present invention on inorganic glass by a heat laminating method. . This heat ray shielding transparent laminate molded body is more useful by complementing each other's drawbacks while effectively exhibiting the advantages of the heat ray shielding transparent resin laminate of the present invention and the advantages of the molded body to be laminated. It can be used as a structural material.

Example 1
Using a master batch obtained by dispersing and mixing ATO fine particles (average particle size: 55 nm) in polycarbonate (PC) resin as a thermoplastic resin and cutting, a heat ray-shielding transparent resin molded product (thickness 50 μm, size 20 cm) Corner). This heat ray shielding transparent resin molded product is set in a sputtering apparatus (CFS-4ES, manufactured by Shibaura Mechatronics Co., Ltd.), and a barrier film (SiO ₂ film) is formed on this molded product, and a heat ray shielding transparent resin laminate is formed. The body was made.

Specifically, a Si 99.9% 3 inch diameter disk target is used as the target, the ultimate vacuum is 6.5 × 10 ⁻³ Pa, the RF (high frequency) output is 200 W, and the reaction Argon gas: 15 sccm and oxygen gas: 20 sccm were mixed and introduced as gases to form a film for 15 minutes, and a 0.5 μm thick SiO ₂ film was laminated on the heat ray-shielding transparent resin molded body.

  The obtained heat ray-shielding transparent resin laminate was exposed to a constant temperature and humidity chamber having a temperature of 40 ° C. and a relative humidity of 85% for 96 hours, and a weather resistance test was performed.

Moreover, the oxygen transmission rate of the heat ray-shielding transparent resin laminate was measured based on the MOCON method defined in JIS K 716-2, using an oxygen transmission measuring device (manufactured by MOCON, OX-TRAN 2/21). The oxygen permeability is 5.5 × 10 ⁻² cm ³ / m ² / day / atm, and is specified in JIS K 7129B using a water vapor permeability measuring device (manufactured by MOCON, PERMATRAN-W3 / 31). When the water vapor transmission rate was measured under the conditions of a temperature of 40 ° C. and a relative humidity of 90% based on the MOCON method, the water vapor transmission rate was 8.6 × 10 ⁻³ g / m ² / day.

(Example 2)
Using a masterbatch obtained by dispersing and cutting ITO fine particles (average particle size: 80 nm) into a PET resin as a thermoplastic resin, a heat ray shielding transparent resin molded product (thickness 100 μm, size 20 cm square) Produced. This heat ray-shielding transparent resin molded product is set in a sputtering apparatus (CFS-4ES, manufactured by Shibaura Mechatronics Co., Ltd.), and a barrier film (Al ₂ O ₃ film) is formed on this molded product, so that the heat-ray shielding transparent A resin laminate was produced.

Specifically, a 3 inch diameter disk target of Al 99.9% is used as the target, the ultimate vacuum is 4.5 × 10 ⁻³ Pa, the RF output is 200 W, and the reaction gas is: Argon gas: 15 sccm and oxygen gas: 20 sccm were mixed and introduced to form a film for 17 minutes, and an Al ₂ O ₃ film having a thickness of 0.6 μm was laminated.

  The obtained heat ray-shielding transparent resin laminate was exposed to a constant temperature and humidity chamber having a temperature of 40 ° C. and a relative humidity of 85% for 96 hours, and a weather resistance test was conducted.

Moreover, when the oxygen permeability was similarly measured about the heat ray shielding transparent resin laminated body, oxygen permeability was 3.4 * 10 ^<-2 > cm ^{< 3} > / m ^{< 2} > / day / atm, and water vapor permeability was similarly measured. When measured, the water vapor transmission rate was 7.4 × 10 ⁻³ g / m ² / day.

(Example 3)
Using a master batch obtained by dispersing and mixing ATO fine particles (average particle size: 60 nm) in polycarbonate (PC) resin as a thermoplastic resin, a heat ray-shielding transparent resin molded product (thickness 50 μm, size 20 cm) Corner). This heat ray shielding transparent resin molding is set in a plasma CVD apparatus (manufactured by Samco Co., Ltd., PD-100D), and a barrier film (DLC film) is formed on the molding to form a heat ray shielding transparent resin laminate. Was made.

Specifically, the degree of vacuum was set to 2 × 10 ⁻² Pa, acetylene gas was introduced at 10 L / min, a high frequency of 13.56 MHz was applied, excited and ionized, and the film formation rate was set to 630 nm / min. A DLC film having a thickness of 0.5 μm was formed and laminated.

  The film hardness of the DLC film was 2100 Hv in terms of Vickers hardness. The film hardness measurement was performed on a DLC film formed on a silicon substrate at the same time because the DLC film formed on a substrate such as a resin film cannot be accurately measured due to deformation of the base substrate.

  Moreover, when the thermal conductivity of the DLC film was measured by a laser flash method thermal constant measuring device (TC-9000, manufactured by Advance Riko Co., Ltd.), the thermal conductivity was 0.002 W / mK.

  The obtained heat ray-shielding transparent resin laminate was exposed to a constant temperature and humidity chamber having a temperature of 40 ° C. and a relative humidity of 85% for 96 hours, and a weather resistance test was conducted.

Further, when the oxygen transmission rate was measured in the same manner for the heat ray shielding transparent resin laminate, the oxygen transmission rate was 1.8 × 10 ⁻² cm ³ / m ² / day / atm, and the water vapor transmission rate was similarly determined. When measured, the water vapor transmission rate was 4.4 × 10 ⁻³ g / m ² / day.

Example 4
Using a master batch obtained by dispersing and cutting Cs _0.33 WO ₃ (CWO) fine particles (dispersed particle size: 80 nm) in polycarbonate (PC) resin as a thermoplastic resin, heat ray shielding transparent resin molding A body (thickness 50 μm, size 20 cm square) was prepared. This heat ray shielding transparent resin molding is set in a plasma CVD apparatus (manufactured by Samco Co., Ltd., PD-100D), and a barrier film (DLC film) is formed on the molding to form a heat ray shielding transparent resin laminate. Was made.

Specifically, the degree of vacuum is 2 × 10 ⁻² Pa, acetylene gas is introduced at 10 L / min, a high frequency of 13.56 MHz is applied, excitation and ionization are performed, and the film formation rate is 600 nm / min. A DLC film having a thickness of 0.8 μm was formed and laminated.

  The film hardness and thermal conductivity of the DLC film were measured in the same manner as in Example 3. The film hardness of the DLC film was 2200 Hv in terms of Vickers hardness. The thermal conductivity of the DLC film was 0.0015 W / mK.

  The obtained heat ray-shielding transparent resin laminate was exposed to a constant temperature and humidity chamber having a temperature of 40 ° C. and a relative humidity of 85% for 96 hours, and a weather resistance test was conducted.

Moreover, when the oxygen permeability was similarly measured about the heat ray shielding transparent resin laminated body, oxygen permeability was 1.6 * 10 ^<-2 > cm ^{< 3} > / m ^{< 2} > / day / atm, and water vapor permeability was similarly measured. When measured, the water vapor transmission rate was 4.0 × 10 ⁻³ g / m ² / day.

(Comparative Example 1)
Evaluation similar to Example 1 was performed with respect to this molded object, without laminating | stacking a barrier layer on the heat ray shielding transparent resin molded object used in Example 1. FIG.

  When the obtained heat ray shielding transparent resin molded product was exposed to a constant temperature and humidity chamber having a temperature of 40 ° C. and a relative humidity of 85% for 96 hours and a weather resistance test was conducted, the molded product had a mass change of 2%.

Further, when the oxygen permeability was measured in the same manner for the heat ray-shielding transparent resin molded article, the oxygen permeability was 2.5 cm ³ / m ² / day / atm. Similarly, when the water vapor permeability was measured, The transmittance was 15 g / m ² / day.

Claims (6)

A heat ray shielding transparent resin molding containing heat ray shielding fine particles and a thermoplastic resin; and
A barrier film having visible light permeability formed on at least one surface of the heat ray shielding transparent resin molding,
Based on JIS R 3106, the light transmittance from a wavelength of 400 nm to a wavelength of 800 nm is 70% or more, and the oxygen permeability measured based on the MOCON method defined in JIS K 716-2 is 0.1 cm ³ / m ² / less than day / atm,
And the water vapor permeability at a temperature of 40 ° C. and a relative humidity of 90%, measured based on the MOCON method defined in JIS K 7129B, is less than 0.01 g / m ² / day,
Heat ray shielding transparent resin laminate. A heat ray shielding transparent resin molding containing heat ray shielding fine particles and a thermoplastic resin; and
A barrier film having visible light permeability formed on at least one surface of the heat ray shielding transparent resin molding,
The barrier film is made of at least one selected from SiO ₂ , Al ₂ O ₃ , and diamond-like carbon, and has a thickness in the range of 0.1 μm to 5 μm.
Heat ray shielding transparent resin laminate.   The heat ray shielding transparent resin laminate according to claim 1 or 2, wherein the heat ray shielding fine particles are composed of at least one selected from heat ray absorbing fine particles and heat ray reflective fine particles.   The heat ray shielding transparent resin according to claim 3, wherein the heat ray absorbing fine particles are fine particles comprising at least one selected from antimony-containing tin oxide, tin-containing indium oxide, tungsten oxide, composite tungsten oxide, and hexaboride. Laminated body.   The heat ray shielding transparent resin laminate according to claim 3, wherein the heat ray reflective fine particles are metal fine particles composed of one or more selected from Au, Ag, Pd, Cu, Ni, and Al.   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 fluorine resin, a polyolefin resin, and a polyester resin. The heat ray shielding transparent resin laminate according to any one of the above.