TW201439140A - Heat-ray shielding film, heat-ray shielding laminated transparent base material, automobile and building - Google Patents

Abstract

A heat-ray-shielding film which exhibits excellent heat-shielding properties while having a polyvinyl acetal resin as a main component thereof; a heat-ray-shielding transparent substrate using said heat-ray-shielding film; a vehicle in which the heat-ray-shielding transparent substrate is provided as a window material; and a building in which the heat-ray-shielding transparent substrate is used as a window material. Provided is a heat-ray-shielding film which includes: composite tungsten oxide fine particles which are represented by the general formula MyWOz, and which have a hexagonal crystal structure; a selective-wavelength absorbing material; a polyvinyl acetal resin; and a plasticizing agent. The selective-wavelength absorbing material is provided with a transmission profile in which the transmittance of light having a wavelength of 550 nm is at least 90%, and the transmittance of light having a wavelength of 420 nm, when the transmittance of light having a wavelength of 460 nm is at least 90%, is not more than 40%. The weight ratio (the composite tungsten oxide fine particles/the selective-wavelength absorbing material) of the composite tungsten oxide fine particles to the selective-wavelength absorbing material is in the range 100/2 to 100/800. Also provided is a heat-ray-shielding transparent substrate using said heat-ray-shielding film.

Description

Heat ray shielding film, heat ray shielding laminated transparent substrate, automobile and construction

The present invention relates to a heat ray shielding film having excellent visible light transmittance and excellent heat ray shielding function, a heat ray shielding laminated transparent substrate, and a vehicle equipped with the heat ray shielding laminated transparent substrate as a window material, and The heat ray shielding laminated transparent substrate was used as a construction of a window material.

A safety glass used for a window material such as a car or a building material is formed by sandwiching an intermediate layer containing a polyvinyl acetal resin or the like between a plurality of opposing sheets (for example, two sheets) of sheet glass to form a transparent base of the laminated glass. material. Further, it has been proposed to prevent the incident solar energy from being blocked by the heat ray shielding function of the intermediate layer, and to achieve a transparent substrate for the purpose of reducing the load on the cold room and the thermal sensation of the human body.

For example, the laminated glass disclosed in Patent Document 1 is a soft resin in which a heat ray shielding metal oxide composed of tin oxide or indium oxide having a fine particle diameter of 0.1 μm or less is interposed between two opposing plate glasses. Floor.

Further, the laminated glass disclosed in Patent Document 2 is interposed between at least two opposed glass sheets, such as Sn, Ti, Si, Zn, Zr, Fe, Al, Cr, Co, Ce, and the like. In, Ni, Ag, Cu, Pt, Mn, Ta, W, V, Mo metal; oxide of the metal, hydride of the metal, sulfide of the metal, Sb, F in the metal An intermediate layer of dopants, or even such composites.

Further, in the glazing for automobiles disclosed in Patent Document 3, fine particles composed of TiO ₂ , ZrO ₂ , SnO ₂ , and In ₂ O ₃ and glass components composed of an organic cerium or an organic cerium compound are sandwiched in the opposite direction. Between transparent plate members.

Further, the laminated glass disclosed in Patent Document 4 is provided with an intermediate layer composed of three layers between at least two opposed transparent glass plate-like bodies, and the second layer of the intermediate layer is dispersed: Sn , Ti, Si, Zn, Zr, Fe, Al, Cr, Co, In, Ni, Ag, Cu, Pt, Mn, Ta, W, V, Mo metal, oxide of the metal, nitride of the metal, The sulfide of the metal, the dopant of Sb and F in the metal, or the composite of the metal is provided with a resin layer in the intermediate layer between the first layer and the third layer.

However, the conventional laminated glass disclosed in Patent Documents 1 to 4 is likely to have a problem that the heat ray shielding function is insufficient when high visible light transmittance is required.

Further, as a method of improving the heat ray shielding function of the laminated glass, Patent Document 5 discloses an ultraviolet ray shielding body in which a metal oxide semiconductor, a near-infrared absorbing agent, and an ultraviolet absorbing agent are mixed in a transparent synthetic resin, and formed. It is formed on a film.

On the other hand, Patent Document 6 discloses that a laminated glass for heat ray shielding has an intermediate layer having a heat ray shielding function interposed between two sheets of glass, and the intermediate layer is composed of hexabos alone. a fine particle or a heat ray shielding film containing hexaboride microparticles, ITO microparticles and/or ATO microparticles, and an ethylene resin; or the intermediate layer is formed on a surface facing at least one of the glass plates The heat ray shielding film which forms and contains the said microparticles, and the heat ray shielding film which consist of the ethylene-type resin inter

As described in Patent Document 6, the hexaboride microparticles are contained alone or With hexaboride microparticles, ITO microparticles and/or ATO microparticles, the optical properties of the laminated glass for heat ray shielding have a high transmittance in the visible light region and strong absorption in the near-infrared region, and have a very small Penetration rate. As a result, the laminated glass for heat ray shielding has been improved to 50% of the sunlight transmittance when the visible light transmittance is 70% or more, compared with the conventional laminated glass described in Patent Documents 1 to 4. about.

In the laminated glass for heat ray shielding disclosed in Patent Document 7, the polyvinyl acetal resin is replaced by an ultraviolet curable resin, and the heat of the composite tungsten compound is contained in the ultraviolet curable resin. The ray shielding film serves as an intermediate layer.

As described in Patent Document 7, the laminated glass for heat ray shielding has been improved to a conventional one of the conventional laminated glass described in Patent Documents 1 to 4 and Patent Document 6 to a sunlight having a visible light transmittance of 70% or more. The penetration rate is around 35%.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. Hei 8-217500

[Patent Document 2] Japanese Patent Laid-Open No. Hei 8-259279

[Patent Document 3] Japanese Patent Laid-Open No. 4-16041

[Patent Document 4] Japanese Patent Laid-Open No. Hei 10-297945

[Patent Document 5] Japanese Patent Laid-Open Publication No. 2004-37768

[Patent Document 6] Japanese Patent Laid-Open Publication No. 2001-89202

[Patent Document 7] Japanese Patent Laid-Open Publication No. 2010-202495

However, the inventors and the like have further reviewed and found the following problem.

The first problem is in the laminated glass of the prior art described in Patent Documents 1 to 5, and as described above, the heat ray shielding function is insufficient when high visible light transmittance is required.

Furthermore, in the market, the energy efficiency improvement from the improvement of the comfort in the car or the building, or the reduction of the air-conditioning load of the automobile, and the reduction of the cold air load in the building are further advanced. The call for higher performance of heat shields is expected to increase. From this point of view, there is still room for improvement in the laminated glass for heat ray shielding described in Patent Documents 6 and 7.

In order to solve the above problems, it is conceivable to combine the ATO microparticles, the ITO microparticles, the hexaboride microparticles and/or the composite tungsten oxide microparticles, and other selective wavelength absorbing materials in the heat ray shielding film. However, the selection of visible light absorption by the wavelength absorbing material changes the color tone of the heat ray shielding film, and when laminated as a laminated glass, there is a problem that the color tone is inappropriate.

The present invention has been made in view of the above problems. Further, the problem to be solved is to provide a heat ray shielding film which exhibits excellent heat shielding properties with a polyvinyl acetal resin as a main component and which has a suitable color tone, and a heat ray shielding laminate which is transparent using the heat ray shielding film. A substrate, an automobile assembled by using the heat ray shielding laminated transparent substrate as a window material, and a structure used for shielding the transparent substrate with the heat ray as a window material.

In order to solve the above problems, the inventors of the present invention first conducted intensive studies on a method of improving heat ray shielding characteristics while maintaining high visible light transmittance.

The inventors of the present invention have focused on the wavelength distribution of the weighting coefficient used in the calculation of the visible light transmittance described in JIS R 3106. Specifically, the wavelength distribution of the weighting coefficient used in the calculation of the visible light transmittance and the solar energy in the short-wavelength region are studied in detail. Research. Further, by obtaining a short-wavelength region in which visible light rays are appropriately shielded, it is possible to reduce the solar radiation transmittance only when the visible light transmittance is maintained high.

Specifically, at least to prevent the reduction of visible light transmittance, although the conventional technique uses the common knowledge of an ultraviolet shielding agent that does not block the visible light region as much as possible, it is assumed to be ultraviolet light having a wavelength of 300 nm to 380 nm and a wavelength of 380 nm to 480 nm. The visible light energy is strongly absorbed, and on the other hand, in the vicinity of the wavelength of 550 nm which greatly contributes to the calculation of the visible light transmittance, the non-absorbed selective wavelength absorbing material and the composite tungsten oxide fine particles coexist.

However, by coexisting a selective wavelength absorbing material that absorbs visible light, it is predicted that the color tone of the laminated transparent substrate changes. Therefore, the inventors of the present invention then measured the tone value calculated according to JIS Z 8701 from the spectral transmittance of the laminated transparent substrate, and the plastic yellowness calculated from the tone value according to JIS K 7373 (in the present invention) There are various cases in which "YI" is described as an indicator. As a result, it is conceivable that the new concept is not absorbed in the vicinity of the wavelength of 550 nm in the region where the visible light transmittance has a large contribution, and that there is no absorption in the vicinity of the wavelength of 460 nm which has a large influence on the YI of the laminated transparent substrate. The present invention has been completed by a structure in which a selective wavelength absorbing material having a large absorption near a wavelength of 420 nm and a composite tungsten oxide fine particle coexist.

In other words, the heat ray shielding film according to the first aspect of the invention of the present invention contains a composite tungsten oxide fine particle, a selective wavelength absorbing material, a polyvinyl acetal resin, and a heat ray shielding film of a plasticizer, and the composite tungsten oxide is oxidized. The fine particles are of the general formula M _y WO _z (however, M is one or more elements selected from the group consisting of Cs, Rb, K, Tl, In, Ba, Li, Ca, Sr, Fe, Sn, Al, and Cu. And having a hexagonal crystal structure as shown in 0.1 ≦ y ≦ 0.5, 2.2 ≦ z ≦ 3.0), wherein the selective wavelength absorbing material has a transmittance of light of 90% or more at a wavelength of 550 nm, and When the transmittance of light having a wavelength of 460 nm is 90% or more, a transmittance of light having a wavelength of 420 nm is 40% or less; a weight ratio of the composite tungsten oxide fine particles to the selective wavelength absorption material is a composite Tungsten oxide microparticles / selective wavelength absorbing material) = 100/2~100/800 range.

In the heat ray shielding film according to the first aspect of the invention, the composite tungsten oxide fine particles are at least one selected from the group consisting of Cs _0.33 WO ₃ and Rb _0.33 WO ₃ .

In the heat ray shielding film according to the first aspect of the invention, the composite tungsten oxide fine particles are fine particles having a particle diameter of 40 nm or less.

The heat ray shielding film according to any one of the first to third aspects of the present invention, wherein the selective wavelength absorbing material is a benzotriazole compound, a diphenyl ketone compound, or a hydroxyphenyl group At least one selected from the group consisting of a compound, an anthraquinone compound, a methylimine compound, a benzotriazole-based compound, and a benzamidine compound.

The heat ray shielding film according to any one of the first to third aspects of the present invention, wherein the selective wavelength absorbing material is a ruthenium compound.

The heat ray shielding film according to any one of the first to third aspects of the present invention, wherein the selective wavelength absorbing material is a ruthenium compound represented by the formula (Chemical Formula 1), wherein the R-based carbon number is 1 An alkyl group of ~10 or an aralkyl group having a carbon number of 7-10.

The heat ray shielding film according to any one of the first to third aspects of the present invention, wherein the fluorene compound represented by the selective wavelength absorbing material (Chemical Formula 1) has a formula A compound of methyl.

The heat ray shielding film according to any one of the first to seventh aspects of the invention, wherein the heat ray shielding film further contains an ultraviolet absorbing agent.

The ninth aspect of the invention is the heat ray shielding film according to the eighth aspect of the invention, wherein the ultraviolet ray absorbing agent is at least one selected from the group consisting of a benzotriazole compound and a diphenyl ketone compound.

The heat ray shielding film according to the eighth aspect of the invention, wherein the content of the ultraviolet ray absorbing agent in the heat ray shielding film is 0.1% by weight or more and 5.0% by weight or less.

The heat ray shielding film according to any one of the first to tenth aspects of the present invention, wherein the selective wavelength absorbing material has a transmittance of light having a wavelength of 550 nm of 90% or more and a wavelength of 460 nm. When the transmittance is 90% or more, the transmittance of light having a wavelength of 420 nm is a penetration distribution of 15% or less.

The heat ray shielding film according to any one of the first to eleventh aspects of the present invention, wherein the heat ray shielding film further contains an infrared absorbing organic compound.

The heat ray shielding film according to the twelfth aspect of the invention, wherein the infrared absorbing organic compound is a phthalocyanine compound, a naphthoquinone compound, an iminium compound, a diimonium compound, a polymethine compound, or a second At least one selected from the group consisting of a benzene methane compound, a triphenylmethane compound, an anthraquinone compound, an azo compound, a pentadiene compound, a methylimine compound, a squarylium compound, an organometallic complex, and a cyanine compound Kind.

According to a fourth aspect of the invention, the infrared ray-absorbing organic compound is at least one selected from the group consisting of a phthalocyanine compound and a diimmonium compound.

The heat ray shielding film according to any one of the invention, wherein the weight ratio of the infrared absorbing organic compound to the composite tungsten oxide fine particles is (composite tungsten oxide fine particles/infrared rays). Absorbent organic compound) = 100/5~100/100 range.

The heat ray-shielding laminated transparent substrate according to the sixteenth aspect of the invention is the heat ray shielding film according to any one of the first to fifteenth aspects of the invention.

The heat ray shielding laminated transparent substrate according to the sixteenth aspect of the invention, wherein the yellowness (YI) calculated according to JIS K 7373 is -20.0 or more and 10.0 or less.

The heat ray shielding laminated transparent substrate according to the sixteenth aspect of the invention, wherein the yellowness (YI) calculated according to JIS K 7373 is -20.0 or more and 5.0 or less.

The heat ray shielding laminated transparent substrate according to any one of the sixteenth to eighteenth aspects, wherein the visible light transmittance is 88% or more between the plurality of transparent substrates An infrared reflective film having a solar reflectance of 21% or more.

The heat ray shielding laminated transparent substrate according to any one of the sixteenth to nineteenth aspects, wherein the transparent substrate has at least one glass.

The heat ray-shielding laminated transparent substrate according to any one of the sixteenth to twenty-ninth aspects, wherein the visible light transmittance calculated according to JIS R 3106 is 70% or more, and is visible The solar transmittance at a light transmittance of 70% is 32.5% or less.

The automobile of the invention of claim 22, wherein the heat ray-shielding laminated transparent substrate according to any one of the sixteenth to twenty-firstth inventions is assembled as a window material.

The heat ray shielding laminated transparent substrate according to any one of the sixteenth to twenty-first aspects of the present invention is used as a window material.

According to the present invention, by using a polyvinyl acetal resin as a main component and using a composite tungsten oxide fine particle and a selective wavelength absorbing material in combination, a heat ray capable of exhibiting excellent optical characteristics and high weather resistance and having a natural color tone can be obtained. Masking film. Further, by using the above-described heat ray shielding film, a heat ray shielding laminated transparent substrate capable of exhibiting excellent optical characteristics, high weather resistance, and excellent mechanical properties can be obtained. Further, by attaching the laminated transparent substrate as a window material with the heat ray, it is possible to suppress an increase in the temperature inside the vehicle in summer. Moreover, by using the heat ray to shield the laminated transparent substrate as a window material and using it in the opening of the structure, it is possible to realize a structure capable of suppressing an increase in temperature in the summer building.

Hereinafter, embodiments of the present invention will be described in detail.

The heat ray shielding film of the present invention comprises: composite tungsten oxide fine particles, a dispersing agent, a selective wavelength absorbing material, an infrared absorbing organic compound as required, a polyvinyl acetal resin, a plasticizer, and an optional adhesion force. Conditioning agents, as well as other additives as needed.

The heat ray shielding film of the present invention is a composite tungsten oxide fine particle and a minute a powder dispersed in a part of the plasticizer added to the polyvinyl acetal resin to obtain a fine particle dispersion of the composite tungsten oxide, and then the obtained dispersion, the selective wavelength absorbing material, and the polyethylene are condensed After the aldehyde resin and the plasticizer are kneaded, they can be produced by molding into a film shape by a known method such as an extrusion molding method or a roll forming method.

Further, the heat ray shielding film of the present invention is obtained by dispersing a dispersion of the composite tungsten oxide fine particles and a dispersing agent in a general organic solvent, and then dispersing the solid solvent in the solid dispersant. The fine particle dispersion of the composite tungsten oxide in the form of a composite tungsten oxide fine particle, and the obtained dispersion, the selective wavelength absorbing material, the polyvinyl acetal resin, and the plasticizer are kneaded, and then extruded, A known method such as a roll forming method can be produced by molding into a film shape.

Hereinafter, the constituent components of the heat ray shielding film of the present invention, the heat ray shielding film, and the heat ray shielding laminated transparent substrate using the heat ray shielding film will be described in detail.

[1]Composition of heat ray shielding film

The heat ray shielding film of the present invention is first composed of a composite tungsten oxide fine particle, a dispersing agent, a selective wavelength absorbing material, an ultraviolet absorber, an infrared absorbing organic compound, a polyvinyl acetal resin, a plasticizer, and the like, which are constituent components thereof. The force adjuster and other additive materials will be described.

(1) Composite tungsten oxide

The composite tungsten oxide fine particles are preferably of the general formula M _y WO _z (however, the M system is selected from the group consisting of Cs, Rb, K, Tl, In, Ba, Li, Ca, Sr, Fe, Sn, Al, and Cu. One or more types of elements, as shown in 0.1 ≦ y ≦ 0.5, 2.2 ≦ z ≦ 3.0), have a hexagonal crystal structure.

Among the composite tungsten oxide fine particles, examples of preferable composite tungsten oxide fine particles include Cs _0.33 WO ₃ and Rb _0.33 WO ₃ . Among them, if the values of y and z are converged within the above range, useful heat ray shielding characteristics can be obtained. The addition amount of the additive element M is preferably 0.1 or more and 0.5 or less, more preferably 0.33 or so. The reason is that the theoretically calculated value from the crystal structure of the hexagonal crystal is 0.33, and preferable optical characteristics can be obtained depending on the amount of addition before and after. Further, the range of z is preferably 2.2 ≦ z ≦ 3.0. Reason based composite tungsten oxide material represented by M _y WO _z, the same mechanism also play a role in addition to the materials shown in the above-described tungsten oxide WO _x outside, z ≦ 3.0 by the addition of the element M will be supplied free of electronic. In particular, from the viewpoint of optical characteristics, it is more preferably 2.45 ≦ z ≦ 3.00.

The particle size of the composite tungsten oxide fine particles can be appropriately selected in accordance with the purpose of use of the heat ray shielding film. For example, when the heat ray shielding film is used for transparency, the volume average diameter (hereinafter referred to as "dispersion particle diameter" or "dispersion average particle diameter") of the composite tungsten oxide fine particles measured by dynamic light scattering light is preferably used. It is 40 nm or less. The reason is that if the composite tungsten oxide fine particles have a dispersed particle diameter of less than 40 nm, scattering can be utilized without completely shielding the light, and the visibility in the visible light region can be maintained, and the transparency can be maintained efficiently.

When the heat ray shielding film or the heat ray shielding laminated transparent substrate of the present invention is applied to, for example, a windshield such as an automobile, the use of the composite tungsten oxide fine particles is particularly preferable. The resulting scattering is reduced. When further scattering reduction scattering is considered, the dispersed particle diameter of the composite tungsten oxide fine particles can be 30 nm or less, preferably 25 nm or less.

The reason is that if the dispersed particle diameter of the composite tungsten oxide fine particles is small, geometric scattering or Mie scattering can be used to reduce the visible light region in the wavelength range of 400 nm to 780 nm. Light scattering. By reducing the scattering of the light at this wavelength, it is possible to avoid the situation in which the heat ray shielding film has a fog-like appearance when the strong light is irradiated, and the clear transparency is lost.

The reason is that if the dispersed particle diameter of the composite tungsten oxide fine particles is 40 nm or less, the above-described geometric scattering or Mie scattering is lowered to become a Rayleigh scattering region. In the Rayleigh scattering region, since the scattered light system is inversely proportional to the sixth power of the particle diameter, the scattering is improved as the dispersed particle diameter is reduced to improve transparency. Further, when the dispersed particle diameter of the composite tungsten oxide fine particles is 25 nm or less, the scattered light is extremely small, which is preferable.

As described above, from the viewpoint of avoiding light scattering, it is preferred that the dispersed tungsten oxide fine particles have a smaller dispersed particle diameter. On the other hand, when the dispersed particle diameter of the composite tungsten oxide fine particles is 1 nm or more, it can be industrially produced.

Further, the amount of the composite tungsten fine particles contained in the heat ray shielding film is preferably 0.2 g/m ² to 2.5 g/m ² per unit area.

(2) Dispersant

The dispersant of the present invention is used by uniformly dispersing the above-mentioned composite tungsten oxide fine particles of the present invention in a polyvinyl acetal resin to be described later.

The dispersant of the present invention has a thermal decomposition temperature of 200 ° C or higher as measured by a thermogravimetric differential thermal scanning analyzer (hereinafter referred to as "TG-DTA"), and preferably has urethane, acrylic acid, or the like. A dispersant for the styrene backbone. Here, the "thermal decomposition temperature" means a temperature at which the weight starts to decrease due to thermal decomposition of the dispersant in the TG-DTA measurement.

The reason is that if the thermal decomposition temperature is 200 ° C or more, the dispersant does not decompose when it is kneaded with the polyvinyl acetal resin. Thereby, it is possible to avoid the brown coloration of the heat ray shielding film for heat ray shielding laminated glass caused by the decomposition of the dispersant, the decrease in the visible light transmittance, and the inability to obtain the original optical characteristics.

Further, the dispersant preferably has a dispersing agent having a functional group containing an amine group, a hydroxyl group, a carboxyl group or an epoxy group. These functional groups are adsorbed on the surface of the composite tungsten oxide fine particles, and the aggregation of the composite tungsten oxide fine particles is prevented, and even in the heat ray shielding film, the fine particles can be uniformly dispersed. Specific examples thereof include a dispersing agent having an acrylic acid-styrene copolymerization system having a carboxyl group as a functional group, and an acrylic dispersing agent having a functional group containing an amine as an example. The dispersing agent having an amine group in the functional group preferably has a molecular weight of Mw 2000 to 200,000 and an amine value of 5 to 100 mg KOH / g. Further, the dispersing agent having a carboxyl group preferably has a molecular weight of Mw 2000 to 200,000 and an acid value of 1 to 50 mg KOH/g.

The amount of the dispersant added is preferably in the range of 10 parts by weight to 1000 parts by weight, more preferably 30 parts by weight to 400 parts by weight, based on 100 parts by weight of the composite tungsten oxide fine particles. The reason is that if the amount of the dispersant added is within the above range, the composite tungsten oxide fine particles can be uniformly dispersed in the polyvinyl acetal resin without adversely affecting the physical properties of the obtained heat ray shielding film.

(3) Selective wavelength absorbing materials

The selective wavelength absorbing material of the present invention is a material which selectively only absorbs light of a certain wavelength region.

As described above, the present inventors have considered the wavelength distribution of the weighting coefficient used in the calculation of the visible light transmittance described in JIS R 3106, and further reviewed the YI calculation method of the plastic described in JIS Z 8701 and JIS K 7373. . Further, as a result of the review, it is assumed that light having a wavelength of around 420 nm which is not sufficiently shielded when the composite tungsten oxide fine particles are not contained, and which has a large contribution to the calculation of visible light transmittance, has no absorption near the wavelength of 550 nm. And a selective wavelength absorbing material having no absorption near the wavelength of 460 nm, which has a large influence on YI, and a composite of composite tungsten oxide fine particles to make. Further, by using a selective wavelength absorbing material which strongly absorbs light in the vicinity of the wavelength of 420 nm and does not absorb in the vicinity of the wavelength of 460 nm and the wavelength of around 550 nm, the composite tungsten oxide fine particles are used in combination, and the composite is used alone. In the case of the tungsten oxide fine particles, it is possible to obtain a lower solar light transmittance without increasing the YI of the laminated transparent substrate.

Further, for example, when a heat-shielding laminated transparent substrate is used as a member requiring high visibility as in an automobile windshield, when a strong light such as direct sunlight or a headlight is irradiated onto the heat ray shielding laminated transparent substrate, The fine particles such as the composite tungsten oxide fine particles contained therein strongly scatter the short-wavelength region of visible light, and the heat ray shielding laminated transparent substrate becomes a problem of a blue-white matte phenomenon.

Here, the inventors of the present invention have conceived that the selective wavelength absorbing material absorbs scattered light in a short-wavelength region of visible light generated by scattering of fine particles such as composite tungsten oxide fine particles, thereby suppressing the blue-white matte surface. When it occurs, the effect of improving the transparency of the heat ray shielding film of the present invention and the heat ray shielding laminated transparent substrate can be exhibited.

The optical characteristic of the selective wavelength absorbing material in the present invention is a selective wavelength absorbing material other than the absorption of the medium and the substrate. The transmittance of the light having a wavelength of 550 nm of 90 nm or more and the transmittance of light having a wavelength of 460 nm. When it is 90% or more, the transmittance of light having a wavelength of 420 nm is preferably 40% or less. Further, it is more preferable that when the transmittance of light having a wavelength of 550 nm is 90% or more and the transmittance of light having a wavelength of 460 nm is 90% or more, the transmittance of light having a wavelength of 420 nm is 15% or less.

The reason for this is that if the selective wavelength absorbing material has a transmittance of 90% or more of light at a wavelength of 550 nm and a transmittance of 90% or more of light at a wavelength of 460 nm, the transmittance of light at a wavelength of 420 nm is 40% or less. When the selective wavelength absorbing material is used in combination with the composite tungsten oxide fine particles, the visible light transmittance is not lowered, and the YI of the substrate is not greatly increased, and the light near the wavelength of 420 nm can be sufficiently obtained. Absorption. its As a result, compared with the case where the above composite tungsten oxide fine particles are used alone, the color tone is not greatly changed, the solar light transmittance is lowered, and the heat shielding property is improved.

Specific selective wavelength absorbing materials used in the present invention are exemplified by a benzotriazole compound, a diphenyl ketone compound, and a hydroxyphenyl group. a compound, an anthracene compound, a methylimine compound, a benzotriazole-based compound, a benzamidine compound or the like. Among them, a ruthenium compound or a azomethine compound which is sufficiently absorbed by a concentration having a high absorption coefficient of light at a wavelength of 420 nm and which does not affect the strength of the heat ray shielding film is preferably used. In particular, the ruthenium compound has a clear effect even if it is added in a small amount.

When the selective wavelength absorbing material in the present invention is a ruthenium compound, a compound represented by (Chemical Formula 1) is preferably used. Here, R in the formula is an alkyl group having 1 to 10 carbon atoms or an aralkyl group having 7 to 10 carbon atoms. Examples of the alkyl group having 1 to 10 carbon atoms include a methyl group, an ethyl group, a butyl group, and a 2-ethylhexyl group. Examples of the aralkyl group having 7 to 10 carbon atoms include a phenylmethyl group. Among them, among the anthracene compounds represented by (Chemical Formula 1), the compound in which R is a methyl group is particularly preferably a selective wavelength absorbing material of the present invention.

However, even if it is not a ruthenium compound represented by (Chemical Formula 1), the transmittance of light having a krypton skeleton other than the absorption of the ruthenium skeleton and the medium or the substrate is 90% or more at a wavelength of 550 nm. Further, when the transmittance of light having a wavelength of 460 nm is 90% or more, the ruthenium compound having a transmittance of light having a wavelength of 420 nm of 40% or less can be suitably used as the selective wavelength absorbing material of the present invention.

[Chemical 1]

The mixing ratio of the composite tungsten oxide fine particles to the selective wavelength absorbing material, preferably the weight ratio (composite tungsten oxide fine particles/selective wavelength absorbing material) is in the range of 100/2 to 100/800. Better 100/5~100/800, especially good 100/10~100/400. When the mixing ratio of the selective wavelength absorbing material is 100/800 or less, the absorption in the visible light region by the selective wavelength absorbing material does not become excessively strong, and the visible light transmittance is maintained. As a result, compared with the case where the above composite tungsten oxide fine particles are used alone, the solar transmittance can be maintained and the heat shielding property can be maintained. In addition, when the mixing ratio of the selective wavelength absorbing material is 100/800 or less, the absorption of the short-wavelength region of visible light which greatly affects YI is not excessively strong, and the YI does not rise significantly. The color tone of the heat ray shielding film is maintained.

In particular, when the selective wavelength absorbing material has a high absorption coefficient of light having a wavelength of 420 nm, for example, in the case of using a ruthenium compound or a methylimine compound, the addition ratio of the selective wavelength absorbing material is even if the ratio of the above weight ratio is 100/ When it is 100 or less and 100/2 or more, compared with the case of using the above composite tungsten oxide fine particles alone, the color tone does not change much, and the solar transmittance is lowered and the heat shielding property is improved.

When the heat ray-shielding laminated transparent substrate of the present invention is used as a window material for automobiles and construction materials, it is preferably a natural color tone (transparent or achromatic). Special department If the heat ray shielding laminated transparent substrate of the present invention is used in a windshield or the like of an automobile, it is preferable to normally identify the color of the fluoroscopic image in order to secure safety during driving.

From this point of view, it is preferable in the color discrimination test performed on the heat ray-shielding laminated transparent substrate of the present invention, for example, JIS R 3211 and JIS R 3212 which are required for the performance of laminated glass for automobiles. The system can normally identify the color of the fluoroscopic image.

Here, when the YI system of the heat ray shielding laminated transparent substrate of the present invention has a YI of -20 or more and 10 or less, the color of the fluoroscopic image can be normally identified. Further, by adopting the mixing ratio of the composite tungsten oxide fine particles of the present invention and the selective wavelength absorbing material, the YI value of the heat ray shielding laminated transparent substrate of the present invention can be -20 or more and 10 or less. Further, when the YI of the laminated transparent substrate is -20 or more and 5 or less, the color of the fluoroscopic image can be more easily recognized, which is more preferable.

The method of adding the selective wavelength absorbing material to the heat ray shielding film may be any method. For example, the selective wavelength absorbing material can be simply added directly to the polyvinyl acetal resin and the plasticizer. Alternatively, a selective wavelength absorbing material may be added to the plasticizer in which the composite tungsten oxide fine particles have been dispersed, and then mixed with a polyvinyl acetal resin and a plasticizer in an appropriate ratio. Alternatively, the selective wavelength absorbing material may be dispersed or dissolved in a plasticizer and then added to the polyvinyl acetal resin. Alternatively, the selective wavelength absorbing material may be dispersed in a solid dispersant and added to the polyvinyl acetal resin and the plasticizer.

In any case, if the selective wavelength absorbing material can be uniformly dispersed in the heat ray shielding film, it can be suitably used as long as it does not impair the transparency of the obtained heat ray shielding film.

(4) UV absorber

In the heat ray shielding film of the present invention, when the selective wavelength absorbing material has a high absorption coefficient of light having a wavelength of 420 nm, for example, when a ruthenium compound or a carbamide compound is used, a preferred embodiment is to add an ultraviolet absorber.

The first reason why the ultraviolet absorber is further added to the heat ray shielding film of the present invention is that the ruthenium compound and the carbamide compound can efficiently absorb short-wavelength visible light, but by adding an ultraviolet absorber, even Effective absorption is still obtained in the ultraviolet region.

By sufficiently blocking the light in the ultraviolet region, a higher temperature rise suppressing effect can be obtained. Further, it is possible to sufficiently prevent the person or the contents inside the automobile interior or the structure in which the heat ray-shielding laminated transparent substrate of the present invention is mounted, from being affected by ultraviolet rays, sunburn, or deterioration of furniture or interior.

The second reason is to suppress photodegradation of the selective wavelength absorbing material due to sunlight or the like by adding an ultraviolet absorber.

As a result, the heat ray-shielding laminated transparent substrate of the present invention is further provided with a UV absorbing agent in the heat ray shielding film of the present invention even when a window material for an automobile or a building is used for a long period of time. It can suppress photodegradation of selective wavelength absorbing materials caused by sunlight or the like.

The ultraviolet shielding agent may, for example, be a diphenyl ketone compound, a salicylic acid compound, a HALS compound, a benzotriazole compound, or the like. An organic ultraviolet absorber such as a compound, a benzotriazole-based compound or a benzamidine compound; an inorganic ultraviolet absorber such as zinc oxide, titanium oxide or cerium oxide; and a benzotriazole compound or a diphenyl ketone compound. The reason for this is that the benzotriazole compound and the diphenyl ketone compound have a high visible light transmittance and a high durability against long-term exposure to strong ultraviolet rays even when the concentration of ultraviolet rays is sufficiently absorbed.

The content of the ultraviolet absorber in the heat ray shielding film is preferably 0.1 weight. % or more and 5.0% by weight or less. When the content ratio is 0.1% by weight or more, ultraviolet light which cannot be absorbed by the selective wavelength absorbing material can be sufficiently absorbed, and photodegradation of the selective wavelength absorbing material can be sufficiently prevented. Moreover, when the content rate is 5.0% by weight or less, the ultraviolet ray absorbing agent is not precipitated in the heat ray shielding film, and the film strength, adhesion, and penetration resistance are not greatly affected.

On the other hand, such as benzotriazole compounds, diphenyl ketone compounds, three A compound such as a compound, a benzotriazole-based compound or a benzamidine compound has a light absorption coefficient at a wavelength of 420 nm, although it is lower than that of the ruthenium compound or the azomethine compound. Therefore, by adding a considerable amount of the compound to the heat ray shielding film, when the transmittance of the light having the wavelength of 550 nm is 90% or more and the transmittance of the light having the wavelength of 460 nm is 90% or more, The transmittance of light having a wavelength of 420 nm is 40% or less. According to this configuration, the compounds have the effects of both the selective wavelength absorbing material and the ultraviolet absorber.

(5) Infrared absorbing organic compounds

In the present invention, an infrared absorbing organic compound having strong absorption in the near-infrared region may be further added to the heat ray shielding film as needed.

For the infrared absorbing organic compound used for this purpose, an indigo compound, a naphthoquinone compound, an iminium compound, a diimmonium compound, a polymethine compound, a diphenylmethane compound, a triphenylmethane compound, or an anthracene can be used. A compound, an azo compound, a pentadiene compound, a methylimine compound, a squaraine compound, an organometallic complex, a cyanine compound, or the like.

When the infrared absorbing organic compound is selected to be soluble in the plasticizer constituting the heat ray shielding film, the transparency of the obtained heat ray shielding film is not impaired. Preferably.

The infrared absorbing organic compound is more preferably a material capable of strongly absorbing light having a wavelength ranging from 650 nm to 1000 nm from a long wavelength region of visible light to a region near the near infrared ray. The reason is that when the infrared absorbing organic compound having the optical property is used in combination with the composite tungsten oxide fine particles having strong absorption in a wavelength region of 800 nm or more, the multiplication effect is large, and the composite tungsten oxide is used alone. In the case of microparticles, high heat shielding properties can be obtained.

From this point of view, the infrared absorbing organic compound used in the present invention is particularly preferably a diimonium compound or an indigo compound.

The weight ratio of the infrared absorbing organic compound to the composite tungsten oxide fine particles is preferably in the range of [composite tungsten oxide fine particles/infrared absorbing organic compound]=100/5 to 100/100.

When the amount of the infrared absorbing organic compound added is more than 100/5, it is possible to obtain an effect of strongly absorbing light having a wavelength ranging from 650 nm to 1000 nm from the visible long wavelength region to the near infrared region by the infrared absorbing organic compound. Therefore, it is better. In addition, when the weight ratio of the infrared absorbing organic compound is 100/100 or less, the infrared absorbing organic compound can be avoided and absorbed into a wavelength region having a large contribution to the calculation of the visible light transmittance. Light near 550 nm can avoid the reduction of visible light transmittance. Therefore, even if the total visible light transmittance can guarantee the heat shielding property, it is preferable.

(6) Polyvinyl acetal resin

The polyvinyl acetal resin used in the heat ray shielding film of the present invention is preferably a polyvinyl butyral resin. Moreover, the degree of acetalization may be different depending on the physical properties of the heat ray shielding film. A plurality of polyvinyl acetal resins. Further, a copolyvinyl acetal resin obtained by combining a plurality of aldehydes at the time of acetalization can also be preferably used.

From this point of view, the degree of acetalization of the polyvinyl acetal resin is preferably 60% and the upper limit is 75%.

The polyvinyl acetal resin can be produced by acetalizing polyvinyl alcohol with an aldehyde.

The above polyvinyl alcohol is usually obtained by saponifying polyvinyl acetate, and a polyvinyl alcohol having a degree of saponification of 80 to 99.8 mol% is generally used.

Further, the polymerization degree of the polyvinyl alcohol is preferably at a lower limit of 200 and an upper limit of 3,000. When the degree of polymerization is 200 or more, the durability of the heat ray-shielding laminated transparent substrate to be penetrated can be maintained, and the safety can be maintained. On the other hand, when it is 3,000 or less, the moldability of the resin film can be maintained, and the rigidity of the resin film can be maintained in a preferable range, and the workability can be maintained.

The aldehyde is not particularly limited, and generally, an aldehyde having 1 to 10 carbon atoms such as n-butyraldehyde, isobutyraldehyde, 2-ethylbutyraldehyde, n-hexanal, n-octanal or acetaldehyde is used. Among them, n-butyraldehyde, n-hexanal, and n-pentanal are preferred, and butanaldehyde having a carbon number of 4 is more preferred.

(7) Plasticizer

The plasticizer used in the heat ray shielding film containing a polyvinyl acetal resin as a main component of the present invention may, for example, be a plasticizer belonging to a compound of a monohydric alcohol and an organic acid ester, or an organic acid ester compound of a polyol, which is an ester system. A plasticizer such as a plasticizer or an organic phosphate plasticizer is a phosphate-based plasticizer. Any of the plasticizers is preferably liquid at room temperature. It is a plasticizer belonging to an ester compound synthesized from a polyol and a fatty acid.

The ester compound synthesized from a polyhydric alcohol and a fatty acid is not particularly limited, and examples thereof include a diol such as triethylene glycol, tetraethylene glycol or tripropylene glycol, and butyric acid. a diol system obtained by reacting a monobasic organic acid such as isobutyric acid, caproic acid, 2-ethylbutyric acid, heptanoic acid, n-octanoic acid, 2-ethylhexanoic acid, decanoic acid (n-decanoic acid) or citric acid Ester compound. Further, examples thereof include tetraethylene glycol or tripropylene glycol, and the above-mentioned monobasic organic ester compound.

Among them, preferred are triethylene glycol dihexanoate, triethylene glycol di-2-ethylbutyrate, triethylene glycol dicaprylate, triethylene glycol di-2-ethylhexanoate A fatty acid ester of triethylene glycol. The fatty acid ester of triethylene glycol has a good balance of various properties such as compatibility with a polyethylene acetal and cold resistance, and is excellent in workability and solvent property.

When selecting a plasticizer, it is necessary to pay attention to the lower hydrolyzability. From this point of view, preferred is triethylene glycol di-2-ethylhexanoate, triethylene glycol di-2-ethylbutyrate, tetraethylene glycol di-2-ethylhexanoic acid ester.

(8) Adhesion regulator

In the heat ray shielding film of the present invention, it is also preferable to further contain an adhesion adjusting agent as needed.

The adhesion adjusting agent is not particularly limited, and an alkali metal salt and/or an alkaline earth metal salt can be suitably used. The acid constituting the metal salt is not particularly limited, and examples thereof include carboxylic acids such as caprylic acid, caproic acid, butyric acid, acetic acid, and formic acid; and inorganic acids such as hydrochloric acid and nitric acid. Among the alkali metal salts and/or alkaline earth metal salts, preferred are magnesium carboxylate salts having 2 to 16 carbon atoms and potassium carboxylates having 2 to 16 carbon atoms.

The magnesium carboxylate and potassium salt of the organic acid having 2 to 16 carbon atoms are not particularly limited, and for example, magnesium acetate, potassium acetate, magnesium propionate, potassium propionate or magnesium 2-ethylbutyrate can be suitably used. , potassium 2-ethylbutyrate, magnesium 2-ethylhexanoate, potassium 2-ethylhexanoate, and the like.

These adhesion modifiers may be used alone or in combination of two or more.

Moreover, when the binder is a carboxylate of sodium, potassium, magnesium, calcium or strontium, It can have both the effect as an adhesion modifier and the effect of improving the weather resistance of the composite tungsten oxide fine particles.

(9) Other additives

In the heat ray shielding film of the present invention, a general additive may be further blended as needed. For example, an azo dye, an anthocyanin dye, a quinoline dye, an anthraquinone dye, or a carbon black may be added to a dye compound or a pigment compound generally used for coloring a thermoplastic resin. . In particular, the present invention absorbs light on the short-wavelength side of visible light, and thus the transmitted light color is slightly yellowish. Therefore, it is preferred to add a compound such as a dye or a pigment to adjust the color tone of the heat ray shielding film.

Further, a coupling agent, a surfactant, an antistatic agent, or the like may be added to other additives.

[2] Heat ray shielding film

In order to manufacture the heat ray shielding film of the present invention, it is possible to: (i) disperse the above-mentioned composite tungsten oxide fine particles and a dispersing agent in a part of a plasticizer added to the polyvinyl acetal resin, and Producing a composite tungsten oxide fine particle dispersion; or (ii) after obtaining a dispersion in which a composite tungsten oxide fine particle and a dispersing agent are dispersed in a general organic solvent, by removing the organic solvent to produce a solid dispersant A composite tungsten oxide fine particle dispersion in which a composite tungsten oxide fine particle state is dispersed.

Then, the prepared composite tungsten oxide fine particle plasticizer dispersion, or the composite tungsten oxide fine particle dispersion produced, and a selective wavelength absorbing material, a polyvinyl acetal resin, a plasticizer, and a preferred ultraviolet absorber Mixing with other additives and pressure modifiers required, and after kneading, using extrusion molding and rolling A known method such as a shape method can be produced, for example, by forming into a film shape. Further, if an infrared absorbing organic compound is added to the heat ray shielding film as needed, higher heat ray shielding properties can be obtained.

Hereinafter, a method for producing a plasticizer dispersion liquid of composite tungsten oxide fine particles and a method for producing a composite tungsten oxide fine particle dispersion will be described.

(1) Method for producing plasticizer dispersion liquid of composite tungsten oxide fine particles

The composite tungsten oxide fine particles and the dispersing agent are added and mixed in a plasticizer, and a plasticizer dispersion of the composite tungsten oxide fine particles can be obtained by a general dispersion method. Specifically, a dispersion method such as bead milling, ball milling, sanding, or ultrasonic dispersion can be used.

Further, when the composite tungsten oxide fine particles are dispersed in the plasticizer, an organic solvent having a boiling point of 120 ° C or less may be further added as needed.

The organic solvent is preferably one having a boiling point of 120 ° C or lower. If the boiling point is below 120 ° C, it can be easily removed by drying in a subsequent step, especially under reduced pressure. As a result, the removal by the step of drying under reduced pressure proceeds rapidly, and contributes to the productivity of the composition containing the composite tungsten oxide fine particles. Further, since the step of drying under reduced pressure can be easily and sufficiently carried out, it is possible to avoid the residual organic solvent remaining in the composition containing the composite tungsten oxide fine particles of the present invention. As a result, problems such as generation of bubbles can be avoided during the formation of the heat ray shielding film. Specifically, for example, toluene, methyl ethyl ketone, methyl isobutyl ketone, butyl acetate, isopropyl alcohol, or ethanol can be arbitrarily selected as long as the boiling point is 120 ° C or lower and the composite tungsten oxide fine particles can be uniformly dispersed.

A method of uniformly dispersing the composite tungsten oxide fine particles in an organic solvent can be arbitrarily selected in a usual manner. Specific examples may be a method of bead milling, ball milling, sanding, ultrasonic dispersion, or the like.

Further, a method of removing an organic solvent from a dispersion containing composite tungsten oxide fine particles is preferably a method of drying under reduced pressure. Specifically, the dispersion containing the composite tungsten oxide fine particles is dried under reduced pressure while being stirred, and separated into a composition containing the composite tungsten oxide fine particles and an organic solvent component. The apparatus used for the vacuum drying is a vacuum agitation type dryer, but it is not particularly limited as long as it has the above-described function. Further, the pressure reduction pressure in the drying step can be appropriately selected.

By using the reduced-pressure drying method, the composition containing the composite tungsten oxide fine particles is not exposed to a high temperature for a long period of time due to the improvement of the solvent removal efficiency, and thus it is preferable that the dispersed fine particles are not aggregated. Further, the productivity is also improved, and the evaporated organic solvent can be easily recovered, which is also preferable in terms of environmental concerns.

(2) Method for producing composite tungsten oxide fine particle dispersion

The plasticizer dispersion liquid of the composite tungsten oxide fine particles or the composite tungsten oxide fine particles, the dispersant and the plasticizer are added and mixed in the above organic solvent having a boiling point of 120 ° C or less, and then a general dispersion method is used. A composite tungsten oxide fine particle dispersion having a concentration of the composite tungsten oxide fine particles of 50% by mass or less can be produced.

The concentration of the composite tungsten oxide fine particles in the plasticizer is preferably 50% by mass or less. When the concentration of the composite tungsten oxide fine particles in the plasticizer is 50% by mass or less, the formation of fine particles is less likely to occur, and the dispersion can be easily dispersed, and the viscosity can be prevented from increasing rapidly, which is easy to handle.

The method of uniformly dispersing the composite tungsten oxide fine particles in the plasticizer can be arbitrarily selected from the general methods. In a specific example, after the dispersion containing the composite tungsten oxide fine particles is obtained, the composite tungsten oxide fine particle dispersion in which the composite tungsten oxide fine particles are dispersed in the solid dispersant can be obtained by removing the organic solvent by a known method. .

[3] Heat ray shielding laminated transparent substrate

The heat ray shielding laminated transparent substrate using the heat ray shielding film of the present invention has various forms.

For example, the transparent substrate is a heat ray shielding laminated inorganic glass using inorganic glass, and a plurality of inorganic glasses which are opposed to each other are sandwiched by the heat ray shielding film of the present invention, and are laminated by a known method. It can be obtained. The obtained heat ray shielding laminated inorganic glass can be mainly used as a window for inorganic glass or construction used for the front of automobiles.

Further, the heat ray shielding film of the present invention and the heat ray shielding film which is used in combination with the infrared ray reflecting film described later are preferably formed into a heat ray shielding laminated transparent substrate. In the case of this configuration, the infrared reflecting film is laminated and integrated with the transparent PVB resin film by the heat ray shielding film to form a multilayer film. The obtained multilayer film is sandwiched between a plurality of opposing inorganic glasses, and then laminated by lamination by a known method to obtain a heat ray shielding laminated inorganic glass.

When the heat ray shielding laminated inorganic glass is used in an automobile, it is preferable to use the infrared ray reflecting film in the heat ray shielding film of the present invention in consideration of the temperature increase suppressing effect in the automobile. The composition of the outside of the car.

The heat shielding property of the heat ray shielding laminated transparent substrate of the present invention is expressed by the transmittance of visible light according to the transmittance of visible light. The lower the solar transmittance, the lower the solar transmittance, and the more excellent the heat shielding property, the heat ray shielding laminated transparent substrate. Specifically, when the visible light transmittance is 70%, the solar light transmittance is preferably 32.5% or less, more preferably 31% or less, and particularly preferably 30% or less.

In particular, when the heat ray shielding laminated transparent substrate of the present invention is used for a window material such as a windshield of an automobile, it is necessary to satisfy the penetration rate prescribed by the road transport vehicle law. More than 70% of the previous mention, showing a higher heat ray shielding ability. That is, if the solar radiation transmittance of the heat ray shielding laminated transparent substrate is 32.5% or less, the power consumption of the air conditioner when the external temperature is 30 ° C or higher can be reduced by 5 compared with the case of assembling the ordinary laminated glass. %the above. As a result, in particular, a vehicle that uses a battery for a hybrid electric vehicle or an electric vehicle can exhibit an effective effect such as a prolonged cruising distance in terms of suppressing battery consumption. Therefore, it is expected to contribute to the improvement of fuel efficiency and greenhouse gas emission reduction of automobiles, and it is predicted that the future will become an essential component in automobile design.

In the transparent substrate, a transparent resin is used, and the inorganic glass is used in the same manner as in the above-mentioned inorganic glass, and a heat ray shielding laminated transparent substrate can be obtained even if a heat ray shielding film is interposed between the opposing transparent substrates. The use of the heat ray shielding laminated transparent substrate is the same as that of the above-described heat ray shielding laminated inorganic glass.

Moreover, it is needless to say that the heat ray shielding film monomer of the present invention and the heat ray shielding film of the present invention are present on one surface or both surfaces of a transparent substrate such as inorganic glass or transparent resin as needed.

Here, the infrared reflective film used in combination with the heat ray shielding film of the present invention will be described.

When the infrared reflecting film of the present invention is considered to have optical characteristics when used in combination with the heat ray shielding film of the present invention, it is preferable that in the visible light region, there is almost no absorption of sunlight, and only visible light is used in view of the heat ray shielding function. The long wavelength region to the near infrared region, specifically, is reflected in the range of 700 nm to 1200 nm.

Specifically, the infrared film preferably has an optical transmittance of 85% or more and a solar reflectance of 18% or more, more preferably a visible light transmittance of 88% or more, and a solar reflectance of 21% or more.

Furthermore, if you consider a heat ray shielding stack for a windshield or building window of a car In the case of a layer transparent substrate, the infrared reflecting film of the present invention is preferably capable of penetrating electromagnetic waves in a wavelength range used by a mobile phone, an ETC or the like. Therefore, compared with a film having a metal film which is electrically conductive and does not penetrate the electromagnetic wave, it is preferably a film having a resin multilayer film which can penetrate electromagnetic waves, or a reflection of infrared rays by using a cholesteric liquid crystal. The characteristics of the film.

[4 Conclusion

As described in detail above, the plasticizer dispersion liquid of the composite tungsten oxide of the present invention, or the composite tungsten oxide dispersion of the present invention, and the selective wavelength absorbing material, the polyvinyl acetal resin, and the plasticizer are kneaded and utilized. The heat ray shielding film of the present invention can be produced by forming a film into a known method.

Then, by sandwiching the heat ray shielding film of the present invention between a plurality of transparent substrates, it is possible to produce a high penetration which maintains the visible light region and exhibits a low daily wear. The present invention provides a heat ray shielding laminate transparent substrate of the present invention.

Then, by using the composite tungsten oxide fine particles and having a transmittance of 90% or more and a transmittance of 90% or more at a wavelength of 460 nm, the transmittance of the wavelength 420 nm is 40% or less. The selective wavelength absorbing material can be used in combination with a predetermined ratio, and can exhibit higher heat ray shielding characteristics than when the composite tungsten oxide fine particles are used alone.

[Examples]

Hereinafter, the present invention will be more specifically described with reference to examples. However, the invention is not limited to the following embodiments.

Moreover, the transmittance of the selective wavelength absorbing material of each embodiment having a wavelength of 420 nm, a wavelength of 460 nm, and a wavelength of 550 nm is such that the selective wavelength absorbing material is dissolved at an appropriate concentration. The solution which was dissolved in an organic solvent was placed in a quartz glass tank having a light path of 1 cm, and was measured using a spectrophotometer U-4000 manufactured by Hitachi, Ltd. The baseline is indicated only by the state in which the organic solvent used for dissolution is placed in the same tank. The organic solvent in which the selective wavelength absorbing material is dissolved is selected from the group consisting of toluene, methyl isobutyl ketone, and N-methyl-2-pyrrolidone, and the solvent solubility of the selective wavelength absorbing material is further selected and used.

The visible light transmittance and the solar transmittance of the heat ray shielding laminated transparent substrate were also measured using a spectrophotometer U-4000. Further, the solar transmittance is an index indicating the heat ray shielding performance of the heat ray shielding laminated transparent substrate. The YI of the heat ray shielding laminated transparent substrate was calculated from the transmittance of light at a wavelength of 380 to 780 nm measured using a spectrophotometer U-4000 according to JIS Z 8701 and JIS K 7373.

[Example 1]

Weighing amount: 20% by mass of composite tungsten oxide fine particles Cs _0.33 WO ₃ (hereinafter referred to as "fine particles a"), and an acrylic dispersing agent having an amine group-containing functional group (amine value: 48 mgKOH/g, decomposition temperature: 250 ° C) (below) 10% by mass of "dispersant a") and 70% by mass of triethylene glycol di-2-ethylhexanoate (hereinafter referred to as "plasticizer a"). Load these into the loaded 0.3mm In a ZrO ₂ bead paint shaker, pulverization and dispersion treatment were carried out for 10 hours to obtain a plasticizer dispersion liquid (hereinafter referred to as "fine particle dispersion A") of the fine particles a.

Here, the dispersed average particle diameter of the tungsten oxide fine particles in the fine particle dispersion A was measured by a Japanese-made Microtrac particle size distribution analyzer and found to be 24 nm.

In a mixture of 38% by weight of a plasticizer mixed with a polyvinyl butyral resin, a predetermined amount of the fine particle dispersion A, and a BONASORB UA made by Orient Chemical Industries, which is a bismuth compound used as a selective wavelength absorbing material. -3911 [CAS No. 142676-93-5. An anthracene compound represented by (Chemical Formula 1) and having an R-methyl group. When the wavelength is 550nm When the transmittance of light is 99% and the transmittance of light having a wavelength of 460 nm is 90%, the transmittance at 420 nm is 0%. Hereinafter, the "ruthenium compound A" is used, and the weight ratio of the composite tungsten oxide fine particles to the selective wavelength absorbing material [composite tungsten oxide fine particles/selective wavelength absorbing material] is 100/20, and is transparent as a laminate. When the visible light transmittance at the time of the substrate is 70% or more, a composition for producing a heat ray shielding film is prepared.

The composition for producing the heat ray shielding film was kneaded at 200 ° C by a twin-screw extruder, and then extruded by a T-die, and a sheet of 0.7 mm thick was formed by an extrude calender roll method. The heat ray shielding film of Example 1 was obtained.

The heat ray shielding film of Example 1 obtained was sandwiched between two opposing inorganic glasses, and the heat ray shielding laminated transparent substrate of Example 1 was obtained by laminating and integrating by a known method.

The optical characteristics of the heat ray-shielding laminated transparent substrate of Example 1 were 31.3% of the solar light transmittance at a visible light transmittance of 70.4%, and YI-2.6. The results are shown in Table 1.

[Examples 2 to 9]

In addition to the type of the selective wavelength absorbing material described in Example 1, and the weight ratio of the above-mentioned composite tungsten oxide fine particles to the above selective wavelength absorbing material in the composition for producing a heat ray shielding film [composite tungsten oxide fine particles / The selective wavelength absorbing material was changed to the heat ray-shielding laminated transparent substrate of Examples 2 to 9 in the same manner as in Example 1 except that the results are changed as shown in Table 1. Then, the optical characteristics of the heat ray shielding laminated transparent substrates of Examples 2 to 9 were measured in the same manner as in Example 1. The optical property measurement results of the heat ray shielding laminated transparent substrates of Examples 2 to 9 are shown in Table 1.

Further, as the selective wavelength absorbing material, the above ruthenium compound A was used in Examples 2 to 4, and the BONASORB UA-3701 (CAS No. 55567- by Orient Chemical Industry Co., Ltd. belonging to the imine compound) was used in Examples 5 to 6. 59-4. As shown in (Chemical Formula 2), when the transmittance of light having a wavelength of 550 nm is 98% and the transmittance of light having a wavelength of 460 nm is 90%, the transmittance at 420 nm is 0%. "Methylenimine Compound B"). Example 7 was made using TINUVIN 109 manufactured by BASF which is a benzotriazole compound [CAS No. 83044-89-7. As shown in (Chemical Formula 3), when the transmittance of light having a wavelength of 550 nm is 99% and the transmittance of light having a wavelength of 460 nm is 90%, the transmittance at 420 nm is 0%. Hereinafter, it is called "benzotriazole compound C"]. Example 8 is based on the use of hydroxyphenyl three The compound of BASF is manufactured by TINUVIN 479 (CAS No. 204848-45-3, as shown in (Chemical Formula 4), and when the transmittance of light having a wavelength of 550 nm is 99% and the transmittance of light having a wavelength of 460 nm is 90%) The transmittance at 420 nm is 15%. Hereinafter, it is called "hydroxyphenyl three. Compound D"). Example 9 is represented by DANOSORB P-6 (CAS No. 131-55-4, which is a chemical conversion method of a wavelength of 550 nm, and a wavelength of 550 nm, a wavelength of 550 nm, and a wavelength of 550 nm. When the transmittance at 460 nm light is 92%, the transmittance at 420 nm is 25%. Hereinafter, "diphenyl ketone compound E").

[Chemical 2]

[Comparative Example 1]

The heat ray-shielding laminated transparent substrate of Comparative Example 1 was obtained in the same manner as in Example 1 except that the selective wavelength absorbing material was not added. Then, the same measurement as in Example 1 was carried out for the optical characteristics of the heat ray shielding laminated transparent substrate of Comparative Example 1. The optical property measurement results of the heat ray shielding laminated transparent substrate of Comparative Example 1 are shown in Table 1.

[Comparative Example 2~4]

In addition to the type of the selective wavelength absorbing material described in Example 1, and the weight ratio of the above-mentioned composite tungsten oxide fine particles to the above selective wavelength absorbing material in the composition for producing a heat ray shielding film [composite tungsten oxide fine particles / The selective wavelength absorbing material] was changed to the heat ray shielding laminated transparent substrate of Comparative Examples 2 to 4 in the same manner as in Example 1 except that the results are changed as shown in Table 1. Then, the optical characteristics of the heat ray shielding laminated transparent substrate of Comparative Examples 2 to 4 were measured in the same manner as in Example 1. The results are shown in Table 1.

Further, in the selective wavelength absorbing material, the above ruthenium compound A was used in Comparative Examples 2 and 3, and C.I. Solvent Yellow 33 (CAS No. 8003-22-3 belonging to the quinophthalone compound) was used in Comparative Example 4. (Chemical 6), and when the transmittance of light having a wavelength of 550 nm is 99% and the transmittance of light having a wavelength of 460 nm is 90%, the transmittance at 420 nm is 55%. Hereinafter, it is called "quinoline yellow compound H").

[Chemical 6]

[Embodiment 10]

Weighing amount: composite tungsten oxide fine particles Rb _0.33 WO ₃ (hereinafter referred to as "fine particles b"): 20% by mass, dispersant a: 10% by mass, and plasticizer a: 70% by mass. Load these into the loaded 0.3mm In a ZrO ₂ bead paint shaker, pulverization and dispersion treatment were carried out for 10 hours to obtain a plasticizer dispersion liquid (hereinafter referred to as "fine particle dispersion B") of the fine particles b.

Here, the dispersed average particle diameter of the tungsten oxide fine particles in the fine particle dispersion B was measured by a Microtrac particle size distribution apparatus equipped with a Japanese machine, and it was 27 nm.

The heat ray-shielding laminated transparent substrate of Example 10 was obtained in the same manner as in Example 1 except that the fine particle dispersion A was used instead of the fine particle dispersion B. Then, the optical characteristics of the heat ray shielding laminated transparent substrate of Example 10 were measured in the same manner as in Example 1.

The composite tungsten oxide fine particle type of the tenth embodiment, the type of the selective wavelength absorbing material, and the weight ratio of the composite tungsten oxide fine particles to the selective wavelength absorbing material in the composition for producing a heat ray shielding film [composite Tungsten oxide microparticles/selective wavelength absorbing material] are shown in Table 1. Further, the results of measurement of optical characteristics of the heat ray-shielding laminated transparent substrate of Example 10 are shown in Table 1.

[Example 11]

With respect to 100% by mass of the polyvinyl butyral resin described in Example 1, a composition of 38% by mass of the plasticizer a was added, and a predetermined amount of the fine particle dispersion A, the hydrazine compound A, and the infrared absorption were added. Japan carlit diammonium compound CIR-RL (hereinafter referred to as "diimmonium compound F") for the organic compound, and according to the weight ratio of the above composite tungsten oxide fine particles to the above selective wavelength absorbing material [composite tungsten oxide The microparticle/selective wavelength absorbing material is 100/20, and the weight ratio of the composite tungsten oxide fine particles to the infrared absorbing organic compound [composite tungsten oxide fine particles/infrared absorbing organic compound] is 100/5, and a stack is formed. When the layer transparent substrate was added in such a manner that the visible light transmittance was 70% or more, a composition for producing a heat ray shielding film was prepared.

The composition for producing a heat ray shielding film was kneaded at 200 ° C by a twin-screw extruder, and then extruded by a T-die, and a sheet having a thickness of 0.7 mm was formed by a rolling roll method to obtain an example. 11 heat ray shielding film. The obtained heat ray shielding film was sandwiched between two opposing inorganic glasses, and laminated by lamination in accordance with a known method to obtain a heat ray shielding laminated transparent substrate of Example 11. Then, the optical characteristics of the heat ray shielding laminated transparent substrate of Example 11 were measured in the same manner as in Example 1. The composite tungsten oxide fine particle type, the selective wavelength absorbing material type, and the weight ratio of the above selective wavelength absorbing material in the composition for producing a heat ray shielding film of the eleventh embodiment [composite tungsten oxide oxidation) The weight ratio of the composite tungsten oxide fine particles to the infrared absorbing organic compound in the composition for producing the infrared absorbing organic compound and the heat ray shielding film (composite tungsten oxide fine particles) /Infrared absorption organic compound], as shown in Table 1. Further, the optical property measurement results of the heat ray-shielding laminated transparent substrate of Example 11 are as shown in Table 1. Show.

[Embodiment 12]

The heat ray-shielding laminated transparent substrate of Example 12 was obtained in the same manner as in Example 11 except that the infrared absorbing organic compound was used as the indigo compound. Then, the optical characteristics of the heat ray shielding laminated transparent substrate of Example 12 were measured in the same manner as in Example 1. The composite tungsten oxide fine particle type of the embodiment 12, the type of the selective wavelength absorbing material, and the weight ratio of the above-mentioned selective tungsten oxide fine particles to the selective wavelength absorbing material in the composition for producing a heat ray shielding film [composite tungsten oxide The weight ratio of the composite tungsten oxide fine particles to the infrared absorbing organic compound in the composition for producing the infrared absorbing organic compound and the heat ray shielding film (composite tungsten oxide fine particles) /Infrared absorption organic compound], as shown in Table 1. Further, the results of measurement of optical characteristics of the heat ray-shielding laminated transparent substrate of Example 12 are shown in Table 1.

[Example 13]

An infrared ray shielding film (Scotchtint Nano90S manufactured by Sumitomo 3M Co., Ltd.: visible light transmittance: 89%, solar radiation reflectance: 22%, hereinafter referred to as "infrared reflective film Z"), and a heat ray shielding film and a transparent PVB interlayer film obtained in Example 1 were used. The heat ray shielding laminated transparent substrate of Example 13 was obtained by sandwiching and sandwiching two sheets of opposing inorganic glass and performing lamination and integration in accordance with a known method.

Then, the optical characteristics of the heat ray shielding laminated transparent substrate of Example 13 were measured in the same manner as in Example 1. At the time of this measurement, optical characteristics were measured from the glass surface which the transparent PVB interlayer film contacted.

The composite tungsten oxide fine particle type, the selective wavelength absorbing material type, and the weight ratio of the above selective wavelength absorbing material in the composition for producing a heat ray shielding film of the thirteenth embodiment [composite tungsten oxide oxidation) The fine particles/selective wavelength absorbing material] and the infrared reflecting film used are shown in Table 1. Further, the results of measurement of optical characteristics of the heat ray-shielding laminated transparent substrate of Example 13 are shown in Table 1.

[Embodiment 14]

In the composition of the plasticizer a 38% by mass based on 100% by mass of the polyvinyl butyral resin described in Example 1, a predetermined amount of the fine particle dispersion A, the bismuth compound A, and the ultraviolet ray were added. The benzotriazole compound C for the absorbent is 100/20 in the composition according to the weight ratio of the above composite tungsten oxide fine particles to the above selective wavelength absorbing material [composite tungsten oxide fine particles/selective wavelength absorbing material]. When the content of the ultraviolet ray absorbing agent is 1.0% by weight and the visible light transmittance when the laminated transparent substrate is formed is 70% or more, a composition for producing a heat ray shielding film can be prepared.

The composition for producing a heat ray shielding film was kneaded at 200 ° C by a twin-screw extruder, and then extruded by a T-die, and a sheet having a thickness of 0.7 mm was formed by a rolling roll method to obtain an example. 14 heat ray shielding film. The obtained heat ray shielding film was sandwiched between two opposing inorganic glasses, and laminated by lamination in accordance with a known method to obtain a heat ray shielding laminated transparent substrate of Example 14. Then, the optical characteristics of the heat ray shielding laminated transparent substrate of Example 14 were measured in the same manner as in Example 1. The composite tungsten oxide fine particle type, the selective wavelength absorbing material type, and the weight ratio of the above-mentioned selective wavelength absorbing material in the composition for producing a heat ray shielding film of the fourteenth embodiment [composite tungsten oxide oxidation) Ultraviolet rays in the composition for the production of fine particles/selective wavelength absorbing materials], ultraviolet absorbing agents, and heat ray shielding films The absorbent content is as shown in Table 1. Further, the results of measurement of optical characteristics of the heat ray-shielding laminated transparent substrate of Example 14 are shown in Table 1.

[Examples 15 to 17]

The heat of Examples 15 to 17 was obtained in the same manner as in Example 14 except that the ultraviolet absorber type described in Example 14 and the ultraviolet absorber content in the heat ray shielding film were changed to those shown in Table 1. The ray shields the laminated transparent substrate. Then, the optical characteristics of the heat ray shielding laminated transparent substrates of Examples 15 to 17 were measured in the same manner as in Example 1. The results are shown in Table 1.

Further, the above-mentioned benzotriazole compound C of Example 15 was used as the ultraviolet absorber, and the TINUVIN 326 (CAS No. 3896-11-5 by BASF) represented by the benzotriazole compound (Chemical Formula 7) was used in Example 16. (hereinafter referred to as "benzotriazole compound I"), and in Example 17, the above diphenylketone compound E was used.

Transmittance*1: 420nm transmittance blend ratio at 550nm and 460nm penetration of more than 90% *2: [composite tungsten oxide microparticles] / [selective wavelength absorbing material] content rate *3: heat Content ratio blending ratio in the ray shielding film *4: [composite tungsten oxide fine particles] / [infrared absorbing organic compound]

[Evaluation of Examples 1 to 10, Examples 14 to 17, and Comparative Examples 1 to 4]

In Examples 1 to 10 and Examples 14 to 17, the selective wavelength absorbing material and the composite tungsten oxide fine particles were used in an appropriate ratio, as compared with Comparative Example 1 in which the selective wavelength absorbing material was not used in combination. Get lower sun penetration. Moreover, the YI of the laminated transparent substrate does not exceed 10, and the change in color tone due to the combination of the selective wavelength absorbing materials is also small. On the other hand, in Comparative Example 2, since the amount of the selective wavelength absorbing material added was small, sufficient absorption could not be obtained, and only the solar transmittance of the same degree as in Comparative Example 1 in which the selective wavelength absorbing material was not used in combination was obtained. In Comparative Example 3, since the addition amount of the selective wavelength absorbing material was too large, the yellowness YI was raised to 10 or more, and the color tone of the laminated transparent substrate was largely changed. In Comparative Example 4, since the selective wavelength absorbing material used a transmittance of light having a wavelength of 550 nm and a wavelength of 460 nm, the weaker quinophthalone compound H was absorbed at 420 nm, thereby causing the YI to rise to 10 or more, resulting in a laminated transparent substrate. The color tone has changed a lot.

[Evaluation of Examples 11 to 13]

In Examples 11 to 13, in addition to the selective wavelength absorbing material and the composite tungsten oxide fine particles, a wavelength of about 800 to 1100 nm which would not be sufficiently absorbed by the composite tungsten oxide fine particles or the selective wavelength absorbing material was further used in combination. An infrared absorbing organic compound or an infrared reflecting film that absorbs or reflects, so that very low sunlight penetration can be obtained. rate.

Claims (23)

A heat ray shielding film is a heat ray shielding film containing composite tungsten oxide fine particles, a selective wavelength absorbing material, a polyvinyl acetal resin, and a plasticizer, and the composite tungsten oxide fine particles are generally M _y WO _z ( Among them, M is one or more elements selected from Cs, Rb, K, Tl, In, Ba, Li, Ca, Sr, Fe, Sn, Al, and Cu, and 0.1 ≦ y ≦ 0.5, 2.2 ≦ z ≦3.0), and having a hexagonal crystal structure; wherein the selective wavelength absorbing material has a transmittance of 90% or more for a light having a wavelength of 550 nm and a transmittance of 90 for a wavelength of 460 nm. Above 100%, the transmittance of light having a wavelength of 420 nm is less than 40%; the weight ratio of the above composite tungsten oxide fine particles to the above selective wavelength absorbing material is (composite tungsten oxide fine particles/selective wavelength Absorbing material) = 100/2~100/800 range. The heat ray shielding film according to the first aspect of the invention, wherein the composite tungsten oxide fine particles are at least one selected from the group consisting of Cs _0.33 WO ₃ and Rb _0.33 WO ₃ . The heat ray shielding film according to claim 1 or 2, wherein the composite tungsten oxide fine particles are fine particles having a particle diameter of 40 nm or less. The heat ray shielding film according to any one of claims 1 to 3, wherein the selective wavelength absorbing material is a benzotriazole compound, a diphenyl ketone compound, or a hydroxyphenyl group. At least one selected from the group consisting of a compound, an anthraquinone compound, a methylimine compound, a benzotriazole-based compound, and a benzamidine-based compound. The heat ray shielding film according to any one of claims 1 to 3, wherein the selective wavelength absorbing material is a ruthenium compound. The heat ray shielding film according to any one of claims 1 to 3, wherein the selective wavelength absorbing material is an oxime compound represented by the formula (Chemical Formula 1), wherein the R is an alkane having 1 to 10 carbon atoms. a base or an aralkyl group having 7 to 10 carbon atoms; The heat ray shielding film according to any one of claims 1 to 3, wherein the selective wavelength absorbing material is a compound in which R in the formula of the formula (Chemical Formula 1) is a methyl group; The heat ray shielding film according to any one of claims 1 to 7, wherein the heat ray shielding film further contains an ultraviolet absorbing agent. A heat ray shielding film according to item 8 of the patent application, wherein the ultraviolet absorbing agent It is at least one selected from the group consisting of a benzotriazole compound and a diphenylketone compound. The heat ray shielding film according to claim 8 or 9, wherein the ultraviolet ray shielding agent content in the heat ray shielding film is 0.1% by weight or more and 5.0% by weight or less. The heat ray shielding film according to any one of claims 1 to 10, wherein the selective wavelength absorbing material has a transmittance of light having a transmittance of 90% or more and a wavelength of 460 nm when light having a wavelength of 550 nm is obtained. When the transmittance is 90% or more, the transmittance of light having a wavelength of 420 nm is a penetration distribution pattern of 15% or less. The heat ray shielding film according to any one of claims 1 to 11, wherein the heat ray shielding film further contains an infrared absorbing organic compound. The heat ray shielding film according to claim 12, wherein the infrared absorbing organic compound is from an indigo compound, a naphthalocyanine compound, an iminium compound, a diimonium compound, a polymethine compound, or a diphenylmethane. At least one selected from the group consisting of a compound, a triphenylmethane compound, an anthraquinone compound, an azo compound, a pentadiene compound, a methylimine compound, a squarylium compound, an organometallic complex, and a cyanine compound. The heat ray shielding film according to claim 12, wherein the infrared absorbing organic compound is at least one selected from the group consisting of a phthalocyanine compound and a diimmonium compound. The heat ray shielding film according to any one of claims 12 to 14, wherein the weight ratio of the infrared absorbing organic compound to the composite tungsten oxide fine particles is (composite tungsten oxide fine particles/infrared absorbing organic compound) Compound) = 100/5~100/100 range. A heat ray shielding laminated transparent substrate is provided between a plurality of transparent substrates, and the heat ray shielding film according to any one of claims 1 to 15. The heat ray-shielding laminated transparent substrate according to claim 16 of the invention, wherein the yellowness (YI) calculated according to JIS K 7373 is -20.0 or more and 10.0 or less. The heat ray-shielding laminated transparent substrate of the sixteenth aspect of the invention is characterized in that the yellowness (YI) calculated according to JIS K 7373 is -20.0 or more and 5.0 or less. The heat ray-shielding laminated transparent substrate according to any one of claims 16 to 18, wherein a visible light transmittance of 88% or more and a solar reflectance 21 are further present between the plurality of transparent substrates. More than % of infrared reflective film. The heat ray-shielding laminated transparent substrate according to any one of claims 16 to 19, wherein at least one of the transparent substrates is a glass. The heat ray-shielding laminated transparent substrate according to any one of claims 16 to 20, wherein the visible light transmittance calculated according to JIS R 3106 is 70% or more, and the visible light transmittance is 70%. The sunshine penetration rate at % is 32.5% or less. An automobile, which is a heat ray-shielding laminated transparent substrate according to any one of claims 16 to 21, which is assembled as a window material. A construction material for use as a window material in a heat ray-shielding laminated transparent substrate according to any one of claims 16 to 21.