JP2014088494A - Heat ray-shielding resin sheet material and automobile - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a heat ray-shielding resin sheet material exhibiting excellent heat shielding properties while using a polycarbonate resin frequently used as a window material, and an automobile mounted with the heat ray-shielding resin sheet material as a window material.SOLUTION: Provided is a heat ray-shielding resin sheet material comprising: a compound having a heat ray-shielding function; and a polycarbonate resin including a selective wavelength absorption material, and in which the selective wavelength absorption material has a transmission profile that the transmission factor of light with a wavelength of 550 nm is 90% or higher, and also, the transmission factor of light with a wavelength of 450 nm is 40% or lower. Also provided is an automobile mounted with the heat ray-shielding resin sheet material as a window material.

Description

  INDUSTRIAL APPLICABILITY The present invention is used for vehicle windows or openings such as roofs and walls of buildings, arcades, ceiling domes, etc., has good visible light permeability and excellent heat ray shielding properties, and is also resistant to shock and water. The present invention also relates to an excellent heat ray shielding resin sheet material and an automobile.

Conventionally, so-called openings such as windows of various buildings and vehicles are made of a transparent glass plate or resin plate for taking in sunlight. However, the sun rays include ultraviolet rays and infrared rays in addition to visible rays, and in particular, near infrared rays having a wavelength of 800 to 2500 nm among infrared rays are called heat rays, and cause the temperature of the room or the like to rise by entering from the opening. It becomes.
Therefore, in recent years, heat ray shielding materials have been investigated as window materials for various buildings and vehicles, which shield heat rays while sufficiently incorporating visible light, and maintain the brightness while simultaneously suppressing temperature rise in the room. Various means for this purpose have been proposed.

  For example, Patent Document 1 proposes 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.

  In addition to the method of applying a heat ray reflective film or a heat ray shielding resin sheet material on the transparent substrate as a means for heat ray shielding, for example, Patent Literature 2 and Patent Literature 3 include transparent resins such as acrylic resin and polycarbonate resin. Furthermore, a heat ray shielding plate formed by kneading mica coated with titanium oxide as heat ray reflective particles has been proposed.

On the other hand, the present applicant, in Patent Document 4, pays attention to the hexaboride fine particles having a large amount of free electrons as a component having a heat ray shielding effect, and the hexaboride fine particles are dispersed in the polycarbonate resin or the acrylic resin. Alternatively, a heat ray shielding resin sheet material in which hexaboride fine particles and ITO fine particles and / or ATO fine particles are dispersed has already been proposed.
The optical properties of the heat-shielding resin sheet material to which hexaboride fine particles alone or hexaboride fine particles and ITO fine particles and / or ATO fine particles are applied have a maximum visible light transmittance in the visible light region and a near infrared region. Therefore, the visible light transmittance was 70% or more and the solar transmittance was reduced to the 50% level.

In addition, the present inventors have disclosed, as Patent Document 5, a heat ray shielding resin sheet material in which composite tungsten oxide fine particles are contained in a transparent resin base material.
As described in Patent Document 5, the heat-ray shielding resin sheet material has a solar radiation transmittance when the visible light transmittance is 70% or more, compared with the conventional heat-ray shielding resin sheet materials described in Patent Documents 1 to 4. It was improved until it was around 35%.

JP-A 61-277437 JP-A-5-78544 JP-A-2-173060 JP 2003-327717 A Japanese Patent Laid-Open No. 2006-219661

However, as a result of further studies by the present inventors, the following problems have been found.
That is, the heat ray shielding resin sheet material described in Patent Document 1 has a drawback that not only the heat reflection film itself is very expensive, but also a complicated process such as an adhesion process is required, which results in a very high cost. It was. Moreover, since the adhesiveness of a transparent base material and a heat ray reflective film is not good, there existed a problem that a heat ray reflective film peeled with a time-dependent change.

  A number of heat ray shielding plates have been proposed in which a metal or metal oxide is directly deposited on the surface of a transparent substrate and a heat ray shielding resin sheet material is applied. However, a vapor deposition apparatus that requires high vacuum and high-precision atmosphere control is proposed. Since it had to be used, there was a problem that the mass productivity was poor, the versatility was poor, and the heat ray shielding plate was very expensive.

  In the heat ray shielding plates described in Patent Documents 2 and 3, it is necessary to add a large amount of heat ray reflective particles in order to enhance the heat ray shielding performance, but when the addition amount of the heat ray reflective particles is increased, the visible light transmittance is lowered. There was a problem of doing. On the contrary, if the addition amount of the heat ray reflective particles is decreased, the visible light transmittance is increased, but the heat ray shielding property is lowered. Therefore, it is difficult to satisfy the heat ray shielding property and the visible light transmittance at the same time. Further, when a large amount of heat ray reflective particles are blended, there is also a drawback in strength that the physical properties, in particular, impact resistance and toughness of the transparent resin as the base material are lowered.

  Furthermore, none of the heat ray shielding resin sheet materials according to the conventional techniques described in Patent Documents 1 to 3 have a sufficient heat ray shielding function when high visible light transmittance is required.

  On the other hand, in the market, there is a high demand for further enhancement of the heat shielding function from the viewpoint of improving the comfort in the automobile or improving the fuel efficiency by reducing the load on the air conditioner. From this viewpoint, the heat ray shielding resin sheet materials described in Patent Documents 4 and 5 still have room for improvement.

  The present invention has been made paying attention to the above problems. The problem to be solved is a heat ray shielding resin sheet material that exhibits excellent heat shielding properties while using a polycarbonate resin frequently used as a window material, and the heat ray shielding resin sheet material is mounted as a window material. To provide a car.

In order to solve the above-mentioned problems, the present inventors have conducted intensive research on a method for improving heat ray shielding characteristics while maintaining high visible light transmittance.
The present inventors paid attention to the wavelength distribution of the weight coefficient used in the visible light transmittance calculation described in JIS R 3106. Specifically, the wavelength distribution of the weight coefficient used for calculating the visible light transmittance and the solar radiation energy in the short wavelength region were studied in detail. And the knowledge that it was possible to reduce only the solar radiation transmittance | permeability was maintained, keeping visible light transmittance | permeability high by shielding the short wavelength area | region of visible light suitably.

Specifically, in the prior art, in order to prevent any decrease in visible light transmittance and to prevent the heat ray shielding sheet material from being colored yellow, an ultraviolet shielding agent that does not cut the visible light region as much as possible is used. Was common sense.
On the other hand, the present invention strongly absorbs light in the vicinity of a wavelength of 450 nm, but does not absorb in the vicinity of a wavelength of 550 nm, which is a region that greatly contributes to the calculation of the visible light transmittance, in spite of the common sense of the prior art. (In the present invention, it may be described as “selective wavelength absorbing material”.) Is conceived in a configuration in which it coexists with a compound having a heat ray shielding function, and the present invention has been completed.

That is, the first invention is
Including a polycarbonate resin containing a compound having a heat ray shielding function and a selective wavelength absorbing material,
The selective wavelength absorbing material has a transmission profile in which the transmittance of light having a wavelength of 550 nm is 90% or more and the transmittance of light having a wavelength of 450 nm is 40% or less, and the selective wavelength absorbing material and the heat ray shielding The heat ray shielding resin sheet material is characterized in that the weight ratio with the compound having a function is in the range of [compound having a heat ray shielding function / selected wavelength absorbing material] = 99/1 to 70/30.
The second invention is
The compound having the heat ray shielding function is selected from the general formula M _y WO _Z (where the element M is selected from Cs, Rb, K, Tl, In, Ba, Li, Ca, Sr, Fe, Sn, Al, Cu) 1 or more elements, 0.1 ≦ y ≦ 0.5, 2.2 ≦ z ≦ 3.0), and a composite tungsten oxide fine particle having a hexagonal crystal structure, The heat ray shielding resin sheet material according to the first invention.
The third invention is
The composite tungsten oxide fine particles are fine particles having a dispersed particle size of 40 nm or less. The heat ray shielding resin sheet material according to the second aspect of the invention.
The fourth invention is:
The selective wavelength absorbing material is at least one selected from quinophthalone compounds, nickel azo compounds, isoindoline compounds, quinoxaline compounds, condensed diazo compounds, isoindolinone compounds, and bismuth vanadate compounds. It is a heat ray shielding resin sheet material described in the invention.
The fifth invention is:
The heat ray shielding resin sheet material according to the first aspect, wherein the selective wavelength absorbing material is at least one selected from a quinophthalone pigment and a nickel azo pigment.
The sixth invention is:
The selective wavelength absorbing material has a transmission profile in which the transmittance of light having a wavelength of 550 nm is 90% or more and the transmittance of light having a wavelength of 450 nm is 15% or less. It is a heat ray shielding resin sheet material in any one of invention.
The seventh invention
The heat ray shielding resin sheet material according to any one of the first to sixth inventions, wherein the heat ray shielding resin sheet material further contains an infrared absorbing organic compound.
The eighth invention
The infrared absorbing organic compound is a diimonium compound, phthalocyanine compound, naphthalocyanine compound, imonium compound, polymethine compound, diphenylmethane compound, triphenylmethane compound, quinone compound, azo compound, pentadiene compound, azomethine compound, squarylium compound, organometallic complex The heat ray shielding resin sheet material according to the seventh aspect of the invention, wherein the heat ray shielding resin sheet material is at least one selected from cyanine compounds.
The ninth invention
The infrared ray absorbing organic compound is at least one selected from a phthalocyanine compound and a diimonium compound, and is the heat ray shielding resin sheet material according to the seventh invention.
The tenth invention is
A weight ratio of the infrared absorbing organic compound and the composite tungsten oxide fine particles is in the range of [composite tungsten oxide fine particles / infrared absorbing organic compound] = 95/5 to 50/50. It is a heat ray shielding resin sheet material in any one of 9th invention.
The eleventh invention is
The heat ray according to any one of the first to tenth inventions, wherein the visible light transmittance calculated by JIS R 3106 is 70% or more and the solar radiation transmittance is 32.5% or less. It is a shielding resin sheet material.
The twelfth invention
A heat ray shielding resin sheet material according to any one of the first to eleventh inventions is mounted as a window material.

  According to the present invention, a polycarbonate resin containing a compound having a heat ray shielding function and a selective wavelength absorbing material in a polycarbonate resin, and using the polycarbonate resin containing the compound having the heat ray shielding function and the selective wavelength absorbing material is used. A shielding resin sheet material was obtained. The heat ray shielding resin sheet material exhibited excellent optical properties and high weather resistance. Furthermore, by mounting the heat ray shielding resin sheet material on a vehicle as a window material, it has become possible to suppress a rise in the interior temperature in the summer.

It is a graph which shows the relationship between the visible light transmittance | permeability and the solar radiation transmittance | permeability in the heat ray shielding resin sheet material which concerns on Examples 1-4 and Comparative Examples 1 and 3. FIG. It is a graph which shows the relationship between the visible light transmittance | permeability in the heat ray shielding resin sheet material which concerns on Examples 5-7, and the comparative example 1, and solar radiation transmittance | permeability. It is a graph which shows the relationship between the visible light transmittance | permeability in the heat ray shielding resin sheet material which concerns on Examples 19-20 and the comparative example 1, and solar radiation transmittance.

Hereinafter, embodiments of the present invention will be described in detail.
The heat ray shielding resin sheet material according to the present invention includes a polycarbonate resin containing fine particles of a compound having a heat ray shielding function, a dispersant, a selective wavelength absorbing material, an infrared absorbing organic compound as required, and optionally other additives. It is out.
In order to produce the heat ray shielding resin sheet material according to the present invention, first, after obtaining a dispersion in which fine particles of a compound having a heat ray shielding function and a dispersant are dispersed in an appropriate organic solvent, the organic solvent is removed. Thus, a fine particle dispersion of a compound having a heat ray shielding function in a state where fine particles of a compound having a heat ray shielding function are dispersed in a solid dispersant is obtained. The kneaded product is produced by kneading the obtained dispersion, the selective wavelength absorbing material, and the polycarbonate resin, and then molding the kneaded material into a sheet shape by a known method such as an extrusion molding method or an injection molding method. I can do it.
The heat ray shielding resin sheet material according to the present invention can be used as it is as a heat ray shielding transparent base material, but can also be used in combination with a transparent base material such as glass.

Hereinafter, the component of the heat ray shielding resin sheet material and the heat ray shielding resin sheet material according to the present invention will be described in detail.
As the fine particles of the compound having a heat ray shielding function according to the present invention, composite tungsten oxide fine particles, ITO fine particles, ATO fine particles and the like can be used, but use of composite tungsten oxide fine particles is preferable. Therefore, in the following description, a case where composite tungsten oxide fine particles are used as fine particles of a compound having a heat ray shielding function will be described. However, when the fine particles of the compound having a heat ray shielding function are ITO fine particles, ATO fine particles or the like, or when the composite tungsten oxide fine particles are combined with the ITO fine particles, the ATO fine particles, etc., the composite tungsten oxide fine particles are used. A heat ray shielding resin sheet material can be manufactured by performing the same operation as in the case of using.

[1] Constituent Component of Heat Ray Shielding Resin Sheet Material Regarding the heat ray shielding resin sheet material according to the present invention, first, fine particles having a heat ray shielding function as a constituent component thereof, a production method thereof, a dispersing agent, a selective wavelength absorbing material, infrared absorption The organic organic compound, polycarbonate resin, and other additives will be described.

(1) Fine particles having a heat ray shielding function A preferred example of the fine particles having a heat ray shielding function according to the present invention is composite tungsten oxide fine particles. Since the composite tungsten oxide fine particles absorb a large amount of light in the near infrared region, particularly a wavelength of 1000 nm or more, the transmitted color tone often has a blue color tone.
The composite tungsten oxide fine particles are represented by the general formula M _y WO _Z (where M is one type selected from Cs, Rb, K, Tl, In, Ba, Li, Ca, Sr, Fe, Sn, Al, Cu) The above elements, 0.1 ≦ y ≦ 0.5, 2.2 ≦ z ≦ 3.0), and preferably have a hexagonal crystal structure.

In the composite tungsten oxide fine particles described above, examples of preferable composite tungsten oxide fine particles include Cs _0.33 WO ₃ , Rb _0.33 WO ₃ , K _0.33 WO ₃ , Ba _0.33 WO _{3 and the} like. I can list them. However, if the values of y and z are within the above ranges, 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, and more preferably around 0.33. This is because the value 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 the above-mentioned WO _x works, even in z ≦ 3.0, above This is because free electrons are supplied by the addition of the element M. However, from the viewpoint of optical characteristics, 2.45 ≦ z ≦ 3.00 is more preferable.

  The particle diameter of the composite tungsten oxide fine particles can be appropriately selected depending on the purpose of use of the heat ray shielding resin sheet material. For example, when the heat ray shielding resin sheet material is used for applications requiring transparency, the composite tungsten oxide fine particles preferably have a dispersed particle diameter of 40 nm or less. If the composite tungsten oxide fine particles have a dispersed particle size smaller than 40 nm, light is not completely blocked by scattering, and visibility in the visible light region is maintained, and at the same time, transparency is efficiently maintained. Because you can.

When the heat ray shielding resin sheet material according to the present invention is applied to an application in which the transparency in the visible light region is particularly important, such as an automobile windshield, further reduction of scattering by the composite tungsten oxide fine particles should be considered. Is preferred. In consideration of the further reduction in scattering, the dispersed particle diameter of the composite tungsten oxide fine particles is 30 nm or less, preferably 25 nm or less.
This is because if the composite tungsten oxide fine particles have a small dispersed particle diameter, light scattering in the visible light region having a wavelength of 400 nm to 780 nm due to geometric scattering or Mie scattering is reduced. By reducing the scattering of light of the wavelength, it is possible to avoid a situation in which the heat ray shielding resin sheet material has an appearance like a frosted glass when strong light is irradiated and the clear transparency is lost.
This is because when the composite tungsten oxide fine particles have a dispersed particle diameter of 40 nm or less, the above-described geometrical scattering or Mie scattering is reduced and a Rayleigh scattering region is obtained. In the Rayleigh scattering region, the scattered light is reduced in inverse proportion to the sixth power of the particle diameter, so that the scattering is reduced and the transparency is improved as the dispersed particle diameter is reduced. Furthermore, it is preferable that the dispersed tungsten oxide fine particles have a dispersed particle diameter of 25 nm or less because the scattered light is extremely reduced.

As described above, from the viewpoint of avoiding light scattering, it is preferable that the dispersed tungsten oxide fine particles have a small dispersed particle diameter. On the other hand, if the dispersed particle diameter of the composite tungsten oxide fine particles is 1 nm or more, industrial production is easy.
The amount of the composite tungsten oxide fine particles contained in the heat ray shielding resin sheet material, per unit area 0.2g ^{/ m 2} ~2.5g ^/ m 2 is desirable.

(2) Manufacturing method of fine particles having a heat ray shielding function The composite tungsten oxide fine particles represented by the general formula M _y WO _Z are obtained by heat-treating a tungsten compound starting material in an inert gas atmosphere or a reducing gas atmosphere. Can be obtained.

First, the tungsten compound starting material will be described.
Tungsten compound starting materials include tungsten trioxide powder, tungsten dioxide powder, tungsten oxide hydrate powder, tungsten hexachloride powder, ammonium tungstate powder, or tungsten hexachloride powder dissolved in alcohol and then dried. Tungsten oxide hydrate powder obtained by dissolving tungsten hexachloride in alcohol and then adding water to precipitate and drying it, or Preferred examples are those containing at least one selected from tungsten compound powder obtained by drying an aqueous solution of ammonium tungstate and metallic tungsten powder, and further containing element M in the form of a single element or compound. Can be cited.

  Here, in order to produce a starting material in which each component is uniformly mixed at the molecular level, it is preferable to mix each material in the form of a solution. Therefore, it is preferable that the tungsten compound starting material containing the element M is soluble in a solvent such as water or an organic solvent. Examples include element M, tungstate, tungsten chloride, tungsten nitrate, tungsten sulfate, tungsten oxalate, tungsten oxide, tungsten carbonate, tungsten hydroxide, etc. Although it is mentioned, it is not limited to these, It is preferable if it becomes a solution form.

Next, heat treatment will be described.
First, when the heat treatment is performed in an inert gas atmosphere, the temperature condition is preferably 400 ° C. or higher and 1200 ° C. or lower. The starting material heat-treated at 400 ° C. or more and 1200 ° C. or less has a sufficient near-infrared absorbing power and is efficient as heat ray shielding fine particles. As the inert gas, an inert gas such as Ar or N ₂ is preferably used.

When heat treatment is performed in a reducing gas atmosphere, the starting material is first heat treated at 100 ° C. or higher and 400 ° C. or lower in a reducing gas atmosphere, and then 400 ° C. or higher and 1200 ° C. or lower in an inert gas atmosphere. Heat treatment at a temperature is good. The reducing gas at this time is not particularly limited, but H ₂ is preferable. And what if _{H 2} is used as the reducing gas, the composition of the reducing atmosphere, for example, Ar, mixing less than 100% greater than 0.1% by volume of _{H 2} in an inert gas such as _{N 2} It is preferable to use H ₂ gas itself, and more preferably, 0.2% or more and less than 100% is mixed with an inert gas such as Ar or N ₂ . H ₂ can be advanced efficiently reduced if more than 0.1% by volume.

  It is preferable from the viewpoint of improving the weather resistance that the composite tungsten oxide fine particles according to the present invention are surface-treated and coated with a compound containing at least one selected from Si, Ti, Zr, and Al, preferably with an oxide. . In order to perform the surface treatment, a known surface treatment may be performed using an organic compound containing one or more selected from Si, Ti, Zr, and Al. For example, the composite tungsten oxide fine particles according to the present invention and an organosilicon compound may be mixed and subjected to a hydrolysis treatment.

(3) Dispersant The dispersant according to the present invention is used to uniformly disperse the above-described composite tungsten oxide fine particles according to the present invention or a selective wavelength absorbing material described later in a polycarbonate resin described later.
The dispersant according to the present invention has a thermal decomposition temperature of 250 ° C. or higher measured with a differential thermothermal gravimetric simultaneous measurement apparatus (hereinafter sometimes referred to as “TG-DTA”), and is urethane, acrylic, styrene. A dispersant having a main chain is preferred. Here, the thermal decomposition temperature is a temperature at which weight loss due to thermal decomposition of the dispersant begins in the TG-DTA measurement.
This is because when the thermal decomposition temperature is 250 ° C. or higher, the dispersant is hardly decomposed during kneading with the polycarbonate resin. As a result, it is possible to avoid the browning of the heat ray shielding resin sheet material due to the decomposition of the dispersant, the reduction in visible light transmittance, and the inability to obtain the original optical characteristics.

In addition, the dispersant is preferably a dispersant having 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 composite tungsten oxide fine particles or the selective wavelength absorbing material to prevent the aggregation of the particles, and have an effect of uniformly dispersing the fine particles or the selective wavelength absorbing material even in the heat ray shielding resin sheet material. . Specific examples include acrylic-styrene copolymer dispersants having a carboxyl group as a functional group, and acrylic dispersants having an amine-containing group as a functional group. The dispersant having a functional group containing an amine is preferably one having a molecular weight Mw of 2,000 to 200,000 and an amine value of 5 to 100 mgKOH / g. Moreover, in the dispersing agent which has a carboxyl group, the thing of molecular weight Mw2000-200000 and an acid value of 1-50 mgKOH / g is preferable.
The addition amount of the dispersant is desirably in the range of 10 parts by weight to 1000 parts by weight, more preferably in the range of 30 parts by weight to 400 parts by weight with respect to 100 parts by weight of the composite tungsten oxide fine particles or the selective wavelength absorbing material. It is. If the added amount of the dispersant is within the above range, the composite tungsten oxide fine particles or the selective wavelength absorbing material is uniformly dispersed in the polycarbonate resin, and the physical properties of the obtained heat ray shielding resin sheet material are not adversely affected. Because.

(4) Selected Wavelength Absorbing Material The selected wavelength absorbing material according to the present invention is a material that selectively and strongly absorbs only light in a certain wavelength region.
As described above, the present inventors considered the wavelength distribution of the weight coefficient used in the visible light transmittance calculation described in JIS R 3106, and sufficiently shielded with the above-described composite tungsten oxide fine particles alone. A structure in which a selective wavelength absorbing material that strongly absorbs light in the vicinity of a wavelength of 450 nm and does not absorb in the vicinity of a wavelength of 550 nm, which is a wavelength region that greatly contributes to calculation of visible light transmittance, is used in combination with the composite tungsten oxide fine particles. I came up with it. Then, the composite tungsten oxide fine particles are used alone by using a configuration in which the selective wavelength absorbing material that strongly absorbs light in the vicinity of the wavelength of 450 nm and does not absorb near the wavelength of 550 nm is used in combination with the composite tungsten oxide fine particles. Compared to the case, a lower solar radiation transmittance could be obtained.

In addition, for example, when a heat ray shielding resin sheet material is used as a member that requires high visibility, such as an automobile windshield, strong light such as direct sunlight or a headlamp is irradiated on the heat ray shielding resin sheet material. In some cases, fine particles such as composite tungsten oxide fine particles contained are strongly scattered in the short wavelength region of visible light, and the heat ray-shielding resin sheet material becomes cloudy white.
Here, the inventors of the present invention can generate the above-described cloudiness by absorbing the scattered light in the short-wavelength region of visible light generated by the above-described selective wavelength absorption material being scattered by fine particles such as composite tungsten oxide fine particles. It was also conceived that the effect of increasing the transparency of the heat ray shielding resin sheet material according to the present invention is also exhibited.

As the optical characteristics of the selective wavelength absorbing material according to the present invention, the transmittance of light having a wavelength of 550 nm of the selective wavelength absorbing material itself excluding the absorption of the medium or the substrate is 90% or more, and the light having a wavelength of 450 nm is transmitted. The rate is preferably 40% or less. More preferably, the transmittance of light having a wavelength of 550 nm is 90% or more, and the transmittance of light having a wavelength of 450 nm is 15% or less.
If the light transmittance of the selected wavelength absorbing material is 90% or more with respect to light having a wavelength of 550 nm and 40% or less with respect to light having a wavelength of 450 nm, the selected wavelength absorbing material and composite tungsten are used. This is because when the oxide fine particles are used in combination, the visible light transmittance does not decrease, and further, absorption of light in the vicinity of a wavelength of 450 nm can be sufficiently obtained. As a result, compared with the case where the composite tungsten oxide fine particles are used alone, the solar radiation transmittance is lowered and the heat shielding characteristics are improved.

  Specific examples of the selective wavelength absorbing material used in the present invention include quinophthalone compounds, nickel azo compounds, isoindoline compounds, quinoxaline compounds, condensed diazo compounds, isoindolinone compounds, and bismuth vanadate compounds. In particular, in order to reduce the transmittance of light having a wavelength of 450 nm to 15% or less, at least one selected from a quinophthalone compound and a nickel azo compound can be given as a preferred example.

The mixing ratio of the selective wavelength absorbing material and the composite tungsten oxide fine particles is preferably in the range of [composite tungsten oxide fine particles / selected wavelength absorbing material] = 99/1 to 70/30 as a weight ratio. More preferably, it is in the range of 95/5 to 80/20, and more preferably in the range of 90/10 to 80/20.
If the mixing ratio of the addition amount of the selective wavelength absorbing material is less than 70/30 in the weight ratio described above, the visible wavelength region is not strongly absorbed by the selective wavelength absorbing material, and the visible light transmittance is maintained. As a result, the solar radiation transmittance is maintained as compared with the case where the composite tungsten oxide fine particles are used alone, and the heat shielding characteristics are maintained.
Moreover, if the addition amount of the selective wavelength absorbing material is larger than 99/1 in the above-mentioned weight ratio, sufficient absorption of light in the vicinity of a wavelength of 450 nm can be obtained and the effect of addition can be exhibited.

As a method of adding the selective wavelength absorbing material to the heat ray shielding resin sheet material, the selective wavelength absorbing material is added to the composition of the polycarbonate resin and the plasticizer as it is, as in the composite tungsten oxide fine particle dispersion described later. I can do it.
However, in consideration of the transparency of the obtained heat ray shielding resin sheet material, a dispersion liquid in which the selected wavelength absorbing material is dispersed in a plasticizer or a state in which the selected wavelength absorbing material is dispersed in a solid dispersant. It is also a preferable configuration that the dispersion is added to the heat ray shielding resin sheet material.
In any case, the selected wavelength absorbing material only needs to be uniformly dispersed or dissolved in the heat ray shielding resin sheet material, and any method that does not impair the transparency of the obtained heat ray shielding resin sheet material is suitable. Can be used.

(5) Infrared absorbing organic compound In the present invention, if desired, an infrared absorbing organic compound having strong absorption in the near infrared region may be further added to the heat ray shielding resin sheet material.
Examples of the infrared absorbing organic compound used for the purpose include diimonium compounds, phthalocyanine compounds, naphthalocyanine compounds, imonium compounds, polymethine compounds, diphenylmethane compounds, triphenylmethane compounds, quinone compounds, azo compounds, pentadiene compounds, One or more selected from azomethine compounds, squarylium compounds, organometallic complexes, cyanine compounds and the like can be used.

The infrared-absorbing organic compound is more preferably a material that strongly absorbs light in the range from the visible long wavelength region to the near infrared region having a wavelength of 650 nm to 1000 nm. This is because there is a large synergistic effect when the infrared absorbing organic compound having the optical characteristics and the composite tungsten oxide fine particles having strong absorption in the wavelength region of 800 nm or more are used in combination. This is because a higher heat shielding performance can be obtained as compared with the case of using in the above.
From this point of view, the infrared absorbing organic compound used in the present invention is particularly preferably a diimonium compound or a phthalocyanine 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] = 95/5 to 50/50.
When the mixing ratio of the addition amount of the infrared absorbing organic compound is more than 95/5 by the above-mentioned weight ratio, the infrared absorbing organic compound strongly increases the light in the visible light long wavelength region from the wavelength range of 650 nm to 1000 nm to the near infrared region. The absorption effect is exhibited and the effect of addition is obtained, which is preferable. Moreover, if the mixing ratio of the addition amount of the infrared absorbing organic compound is less than 50/50 in the above-mentioned weight ratio, the light near the wavelength of 550 nm, which is a wavelength region that greatly contributes to the calculation of the visible light transmittance by the infrared absorbing organic compound. As a result, the visible light transmittance is maintained. Therefore, it is preferable because the heat shielding property does not deteriorate even when the visible light transmittance is combined.

(6) Polycarbonate resin The polycarbonate resin used in the heat ray shielding resin sheet material according to the present invention is obtained by reacting a dihydric phenol with a carbonate precursor by a solution method or a melting method. As the dihydric phenol, 2,2-bis (4-hydroxyphenyl) propane [bisphenol A], 1,1-bis (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) cyclohexane, , 2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, 2,2-bis (4-hydroxy-3-methyl) Representative examples include phenyl) propane, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfone, and the like.
Moreover, as a preferable dihydric phenol, there is a bis (4-hydroxyphenyl) alkane type, and a bisphenol A as a main component is particularly preferable.

(7) Other additives It is also possible to mix | blend a general additive with the heat ray shielding resin sheet material which concerns on this invention if desired. For example, azo dyes, cyanine dyes, quinoline dyes, perylene dyes, carbon black, etc., which are generally used for coloring thermoplastic resins to give an arbitrary color tone as desired. It may be added. Particularly in the present invention, since the light on the short wavelength side of visible light is absorbed, the transmitted light color is yellowish. Therefore, it is preferable to adjust the color tone of the heat ray shielding resin sheet material by adding compounds such as dyes and pigments.
As other additives, an ultraviolet absorber, a coupling agent, a surfactant, an antistatic agent, and the like can be added.

[2] Heat ray shielding resin sheet material (1) Production of heat ray shielding resin sheet material As described above, in order to produce the heat ray shielding resin sheet material according to the present invention, first, fine particles and dispersion of a compound having a heat ray shielding function are used. A compound having a heat ray shielding function in a state in which fine particles of a compound having a heat ray shielding function are dispersed in a solid dispersant by obtaining a dispersion in which an agent is dispersed in an appropriate organic solvent and then removing the organic solvent To obtain a fine particle dispersion. After kneading the obtained dispersion, the selective wavelength absorbing material, and the polycarbonate resin, the kneaded product is obtained by a known method such as an extrusion molding method or an injection molding method, for example, a planar or curved sheet. A heat ray shielding resin sheet material can be produced by molding the material.
Furthermore, if desired, if an infrared absorbing organic compound is added to the heat ray shielding resin sheet material, higher heat ray shielding properties can be obtained.
In addition, a mixture in which a composite tungsten oxide fine particle dispersion and a selective wavelength absorbing material are uniformly dispersed in a polycarbonate resin is once pelletized by a granulating apparatus, and then the pellets are publicly known such as an extrusion molding method and an injection molding method. By performing this method, a heat ray shielding resin sheet material can also be produced.

In addition, the thickness of the heat ray shielding resin sheet material can be adjusted to an arbitrary thickness as necessary from a thick plate shape to a thin film shape.
When the heat ray shielding resin sheet material has a predetermined thickness, the heat ray shielding resin sheet material itself can be used as it is. On the other hand, when the heat ray shielding resin sheet material is in the form of a film or plate, it can be used together with a transparent substrate such as glass.

  A hard coat layer having scratch resistance may be formed on the surface of at least one of the heat ray shielding resin sheet materials. For example, a silicate-based or acrylic-based scratch-resistant hard coat layer can be formed on the heat ray shielding resin sheet material. By forming this scratch-resistant hard coat layer, the scratch resistance of the heat ray shielding resin sheet material can be improved. The heat ray shielding resin sheet material with improved scratch resistance can be applied to vehicles, automobile windows, and the like.

(2) Heat-shielding property of heat-ray shielding resin sheet material The heat-shielding property of the heat-ray shielding resin sheet material according to the present invention is indicated by the solar radiation transmittance with respect to the visible light transmittance. The lower the solar transmittance relative to the visible light transmittance, the more the heat ray shielding resin sheet material has better heat shielding properties. Specifically, when the visible light transmittance of the heat ray shielding resin sheet material is 70%, the solar radiation transmittance is preferably 32.5% or less, more preferably 31% or less, and 30% or less. More preferably.

This is because, when the heat ray shielding resin sheet material according to the present invention is used for a window material such as a windshield of an automobile, high heat ray shielding ability is required while satisfying the transmittance of 70% or more stipulated by the Road Transport Vehicle Law. It is because it is said.
On the other hand, if the solar radiation transmittance of the heat ray shielding resin sheet material is 32.5% or less, the power consumption of the air conditioner when the outside air temperature is 30 ° C. or higher is compared with the case where the ordinary laminated glass is mounted. Reduced by 5% or more. As a result, especially in a vehicle using a battery such as a hybrid car or an electric vehicle, the consumption of the battery can be suppressed, so that a significant effect is exhibited in extending the cruising distance. Therefore, it can be expected to contribute to improving the fuel efficiency of automobiles and reducing greenhouse gas emissions, and in the future, it is expected to become an essential member in the design of automobiles.

[3] Summary As described above in detail, the composite tungsten oxide fine particle dispersion according to the present invention, the selective wavelength absorbing material, and the polycarbonate resin are kneaded, and the kneaded product is further obtained by a known method. The heat ray shielding resin sheet material according to the present invention can be produced by molding into a plate shape or a sheet shape.
And the heat ray shielding resin sheet material according to the present invention maintains a high transmittance in the visible light region and has a low solar transmittance.
And, by using the composite tungsten oxide fine particles together with a selected wavelength absorbing material having a transmission profile with a wavelength 550 nm transmittance of 90% or more and a wavelength 450 nm transmittance of 40% or less in a predetermined ratio, Compared with the case where the composite tungsten oxide fine particles are used alone, higher heat ray shielding characteristics can be exhibited.

Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples.
In addition, the light transmittance at a wavelength of 450 nm, the light transmittance at a wavelength of 550 nm, the visible light transmittance of the heat-shielded inorganic glass, and the solar transmittance of the selected wavelength absorbing material plasticizer dispersion liquid in each example are Hitachi Measurement was performed using a spectrophotometer U-4000 manufactured by Seisakusho. In addition, the said solar transmittance is an parameter | index which shows the heat ray shielding performance of a heat ray shielding resin sheet material.
Moreover, the haze value was measured based on JISK7105 using HR-200 made by Murakami Color Research Laboratory Co., Ltd. In addition, the said haze value is a parameter | index which shows the transparency of a heat ray shielding resin sheet material.

[Example 1]
50 g of H ₂ WO ₄ and 18.7 g of Cs (OH) ₂ (corresponding to Cs / W (molar ratio) = 0.33) were sufficiently mixed in an agate mortar to obtain a mixed powder. The mixed powder was heated under supply of 5% H ₂ gas using N ₂ gas as a carrier, subjected to reduction treatment at a temperature of 600 ° C. for 1 hour, and then fired at 800 ° C. for 30 minutes in an N ₂ gas atmosphere. Thus, composite tungsten oxide fine particles (hereinafter abbreviated as “fine particles a”) were obtained.
The composition formula of the fine particles a was Cs _0.33 WO ₃ .

20% by mass of fine particles a, 10% by mass of an acrylic dispersant having an amine-containing group (amine value 48 mgKOH / g, decomposition temperature 250 ° C., hereinafter abbreviated as “dispersant a”), 70% by mass of toluene. Weighed. These were loaded into a paint shaker containing 0.3 mmφZrO ₂ beads and pulverized and dispersed for 10 hours to obtain a plasticizer dispersion of composite tungsten oxide fine particles (hereinafter abbreviated as “fine particle dispersion A”).

Here, the dispersion average particle size of the composite tungsten oxide fine particles in the fine particle dispersion A was measured with a Nikkiso Microtrac particle size distribution meter and found to be 24 nm.
An acrylic dispersant having an epoxy group as a functional group (epoxy value 34 mgKOH / g decomposition temperature 280 ° C., hereinafter abbreviated as “dispersant b”) is further added to the dispersion A, and the dispersant b and composite tungsten are added. The oxide fine particles were prepared so that the weight ratio of [dispersant b / composite tungsten oxide fine particles] = 3. Next, toluene was removed from the composite tungsten oxide fine particle dispersion using a spray drier to obtain a composite tungsten oxide fine particle dispersed powder (hereinafter abbreviated as dispersion powder A).

On the other hand, 20% by mass of a quinophthalone compound manufactured by BASF Corporation, 10% by mass of a dispersant, and 70% by mass of toluene were weighed as selective wavelength absorbing materials. These are loaded into a paint shaker containing 0.3 mmφZrO ₂ beads and pulverized and dispersed for 1 hour to obtain a selected wavelength absorbing material plasticizer dispersion (hereinafter, abbreviated as a selected wavelength absorbing material dispersion α). It was.
The selected wavelength absorbing material dispersion α was diluted with toluene to a predetermined concentration, and placed in a glass cell. The optical characteristics were measured. The transmittance of light having a wavelength of 450 nm was 5.3%, and the light having a wavelength of 550 nm was transmitted. The rate was 92.8%. Prior to the measurement, only the toluene was added to the glass cell to measure the baseline.

Dispersant b was further added to the selective wavelength absorbing material dispersion liquid α so that the weight ratio of the dispersant b to the quinophthalone compound was [dispersant b / quinophthalone compound] = 3. Next, toluene was removed from the selected wavelength-absorbing material dispersion using a spray dryer to obtain a quinophthalone compound dispersion powder (hereinafter abbreviated as dispersion powder α).
A predetermined amount of dispersion powder A and dispersion powder α are added to the polycarbonate resin, the concentration of fine particles a in the mixture is 0.050 mass%, the concentration of the selective wavelength absorbing material is 0.00263 mass%, and heat ray shielding A composition A-1 for producing a resin sheet material was obtained. Similarly, the concentration of fine particles a was 0.0667% by mass, and the concentration of the selective wavelength absorbing material was 0.00350% by mass to obtain a composition A-2 for producing a heat ray shielding resin sheet material. Similarly, the concentration of fine particles a was 0.0833 mass%, the concentration of the selective wavelength absorbing material was 0.00440 mass%, and a composition A-3 for producing a heat ray shielding resin sheet material was obtained. Similarly, the concentration of fine particles a was 0.1000% by mass, and the concentration of the selective wavelength absorbing material was 0.00527% by mass to obtain a composition A-4 for producing a heat ray shielding resin sheet material. As a result, the weight ratio of the selected wavelength absorbing material and the composite tungsten oxide fine particles in the compositions A-1 to A-4 for producing the heat ray shielding resin sheet material is [composite tungsten oxide fine particles / selected wavelength absorbing material]. = 95/5.

The compositions A-1 to A-4 for producing the heat ray shielding film were kneaded at 200 ° C. using a twin screw extruder, extruded from a T die, and used as a sheet material having a thickness of 2.0 mm. Shielding resin sheet materials A-1 to A-4 were obtained.
As shown in Table 1, when the visible light transmittance is 77.5%, the optical characteristics of the heat ray shielding resin sheet material according to Example 1 are 41.1%, and the haze value is 0.5%. there were. When the visible light transmittance was 74.2%, the solar radiation transmittance was 35.4%, and the haze value was 0.6%. When the visible light transmittance was 70.2%, the solar radiation transmittance was 31.2%, and the haze value was 0.6%. When the visible light transmittance was 66.4%, the solar radiation transmittance was 28.5%, and the haze value was 0.6%. From here, the relationship between visible light transmittance and solar radiation transmittance is plotted in FIG. From the reading of FIG. 1, the solar radiation transmittance was calculated to be 31.0% when the visible light transmittance was 70%. The results are shown in Table 1.

[Examples 2 to 12]
Example 2 was carried out in the same manner as in Example 1 except that the concentration of the fine particles a in the composition A for producing a heat ray shielding film, the type of the selective wavelength absorbing material, and the concentration described in Example 1 were changed. The heat ray shielding resin sheet material which concerns on -12 was obtained. And the optical characteristic of the heat ray shielding resin sheet material which concerns on the said Examples 2-12 was measured similarly to Example 1. FIG.
Tables 1 and 2 show the concentrations of the fine particles a, the types of the selective wavelength absorbing materials, and the concentrations in Examples 2 to 12. Furthermore, the optical characteristic measurement result of the heat ray shielding resin sheet material which concerns on Examples 2-12 was shown to Tables 1-2. For Examples 2 to 7, the relationship between the visible light transmittance and the solar light transmittance is plotted in FIGS. 1-2, and the solar light transmittance when the visible light transmittance is 70% calculated in the same manner as in Example 1 is shown in Table 1. It was shown to.

  As the selective wavelength absorbing material, the above-described quinophthalone compound is used in Examples 2 to 4, the nickel azo compound is used in Examples 5 to 7, and the isoindoline compound is used in Example 8. In Example 9, a quinoxaline compound was used, in Example 10, a condensed diazo compound was used, in Example 11, an isoindolinone compound was used, and in Example 12, a bismuth vanadate compound was used.

[Comparative Example 1]
According to Comparative Example 1 as in Example 1, except that the concentration of the fine particles a in the composition A for manufacturing a heat ray shielding film described in Example 1 was changed and the selective wavelength absorbing material was not added. A heat ray shielding resin sheet material was obtained. And the optical characteristic of the heat ray shielding resin sheet material which concerns on the said comparative example 1 was measured similarly to Example 1. FIG.
The concentration of the fine particles a in Comparative Example 1 is shown in Table 2. Furthermore, the optical characteristic measurement result of the heat ray shielding resin sheet material according to Comparative Example 1 is shown in Table 2. Table 2 shows the solar radiation transmittance calculated in the same manner as in Example 1 when the visible light transmittance is 70%.

[Comparative Examples 2-3]
Comparative Examples 2 to 3 were carried out in the same manner as in Example 1 except that the concentration of fine particles a in the composition A for manufacturing a heat ray shielding film described in Example 1 and the type and concentration of the selective wavelength absorbing material were changed. The heat ray shielding resin sheet material was obtained. The results are shown in Table 2. And the optical characteristic of the heat ray shielding resin sheet material which concerns on the said Comparative Examples 2-3 was measured similarly to Example 1. FIG.
Table 2 shows the concentration of the fine particles a, the type and concentration of the selected wavelength absorbing material in Comparative Examples 2 to 3. Furthermore, the optical characteristic measurement result of the heat ray shielding resin sheet material which concerns on Comparative Examples 2-3 was shown in Table 2. As for Comparative Example 3, the solar radiation transmittance when the visible light transmittance is 70% calculated in the same manner as in Example 1 is shown in Table 2.

  As the selective wavelength absorbing material, a benzimidazolone compound was used in Comparative Example 2, and the quinophthalone compound described above was used in Comparative Example 3.

[Example 13]
8.8 g of RbNO ₃ was dissolved in 13.5 g of water, added to 45.3 g of H ₂ WO ₄ (corresponding to Rb / W (molar ratio) = 0.33), sufficiently stirred, and dried. The dried product was heated while supplying 2% H ₂ gas with N ₂ gas as a carrier, baked at a temperature of 800 ° C. for 30 minutes, and then baked at 800 ° C. for 90 minutes in an N ₂ gas atmosphere at the same temperature. Thus, Rb-added composite tungsten oxide fine particles (hereinafter abbreviated as fine particles b) were obtained.
The composition formula of the fine particles b was Rb _0.33 WO ₃ .

20% by mass of fine particles b, 10% by mass of dispersant a, and 70% by mass of plasticizer a were weighed. These were loaded into a paint shaker containing 0.3 mmφZrO ₂ beads and pulverized and dispersed for 10 hours to obtain a plasticizer dispersion of Rb-added composite tungsten oxide fine particles (hereinafter abbreviated as fine particle dispersion B). It was. Here, the dispersion average particle diameter of the Rb-added tungsten oxide fine particles in the fine particle dispersion B was 28 nm as measured with a Nikkiso Microtrac particle size distribution meter.

  Dispersant b was further added to the fine particle dispersion B so that the weight ratio of the dispersant to the composite tungsten oxide fine particles was [dispersant b / composite tungsten oxide fine particles] = 3. Next, toluene was removed from the composite tungsten oxide fine particle dispersion using a spray dryer to obtain composite tungsten oxide fine particle dispersion powder (hereinafter, abbreviated as dispersion powder B).

  A predetermined amount of dispersion powder B and dispersion powder α are added to the polycarbonate resin, the concentration of fine particles b in the mixture is 0.050 mass%, the concentration of the selective wavelength absorbing material is 0.00263 mass%, and heat ray shielding is performed. A composition B for producing a resin sheet material was obtained. As a result, the weight ratio of the selected wavelength absorbing material to the composite tungsten oxide fine particles in the composition A for manufacturing a heat ray shielding film is [composite tungsten oxide fine particles / selected wavelength absorbing material] = 0.15 / 0.0079. = 95/5.

The composition B for producing the heat ray shielding film was kneaded at 200 ° C. using a twin screw extruder, extruded from a T die, and a 2.0 mm thick sheet material was obtained as a heat ray shielding resin sheet material according to Example 13. It was.
As shown in Table 2, the optical characteristics of the heat ray shielding resin sheet material according to Example 13 are as follows. The solar radiation transmittance was 28.9% when the visible light transmittance was 70.7%, and the haze value was 0.6%. Met.

[Examples 14 to 18]
Heat ray shielding resin sheets according to Examples 14 to 18 in the same manner as in Example 13 except that the type and concentration of the selective wavelength absorbing material in the composition B for producing a heat ray shielding film described in Example 13 were changed. The material was obtained. And the optical characteristic of the heat ray shielding resin sheet material which concerns on the said Examples 14-18 was measured similarly to Example 13. FIG.
Table 2 shows the concentration of the fine particles b, the type and concentration of the selected wavelength absorbing material in Examples 14 to 18. Furthermore, the optical characteristic measurement result of the heat ray shielding resin sheet material which concerns on Examples 14-18 was shown in Table 2.

  As the selective wavelength absorbing material, a nickel azo compound is used in Example 14, an isoindoline compound is used in Example 15, a quinoxaline compound is used in Example 16, and a condensed diazo compound is used in Example 17. In Example 18, an isoindolinone compound was used.

[Comparative Example 4]
A heat ray shielding resin sheet material according to Comparative Example 4 was obtained in the same manner as Example 13 except that the selective wavelength absorbing material was not added. The results are shown in Table 2. And the optical characteristic of the heat ray shielding resin sheet material which concerns on the said comparative example 4 was measured similarly to Example 13. FIG.
The concentration of the fine particles b in Comparative Example 4 is shown in Table 2. Furthermore, the optical characteristic measurement result of the heat ray shielding resin sheet material according to Comparative Example 4 is shown in Table 2.

[Example 19]
To the polycarbonate resin, the dispersion powder A and dispersion powder α described in Example 1 and a diimonium compound CIR-RL manufactured by Nippon Carlit Co., Ltd. as an infrared absorbing organic compound are added, and the concentration of the fine particles a in the mixture is adjusted. 0.0417 mass%, the density | concentration of the selection wavelength absorption material was 0.00463 mass%, and the infrared absorptive organic compound was 0.00463 mass%, and the composition C-1 for manufacture of a heat ray shielding resin sheet material was obtained. Similarly, the concentration C of the fine particles a is 0.0557% by mass, the concentration of the selective wavelength absorbing material is 0.00617% by mass, the infrared absorbing organic compound is 0.00617% by mass, and the composition C for manufacturing the heat ray shielding resin sheet material is used. -2 was obtained. Similarly, the concentration C of the fine particles a is 0.0693% by mass, the concentration of the selective wavelength absorbing material is 0.00770% by mass, the infrared absorbing organic compound is 0.00772% by mass, and the composition C for manufacturing the heat ray shielding resin sheet material is used. -3 was obtained. Similarly, the concentration C of the fine particles a is 0.0833 mass%, the concentration of the selective wavelength absorbing material is 0.00927 mass%, the infrared absorbing organic compound is 0.00926 mass%, and the composition C for manufacturing the heat ray shielding resin sheet material is used. -4 was obtained. As a result, the weight ratio of the selected wavelength absorbing material to the composite tungsten oxide fine particles in the compositions C-1 to C-4 for producing the heat ray shielding resin sheet material is [composite tungsten oxide fine particles / selected wavelength absorbing material]]. = 90/10, and the weight ratio of the infrared absorbing organic compound to the composite tungsten oxide fine particles was [composite tungsten oxide fine particles / infrared absorbing organic compound)] = 90/10.

The composition C-1 to C-4 for production of this heat ray shielding resin sheet material was kneaded at 200 ° C. using a twin screw extruder, extruded from a T die, and used as a sheet material having a thickness of 2.0 mm by a calender roll method. Heat ray shielding resin sheet materials C-1 to C-4 according to No. 19 were obtained.
As shown in Table 2, the optical characteristics of the heat ray shielding resin sheet material were as follows. When the visible light transmittance was 77.4%, the solar radiation transmittance was 37.7%, and the haze value was 0.6%. When the visible light transmittance was 74.0%, the solar radiation transmittance was 31.2%, and the haze value was 0.6%. When the visible light transmittance was 70.2%, the solar radiation transmittance was 27.4%, and the haze value was 0.5%. When the visible light transmittance was 66.0%, the solar radiation transmittance was 24.6%, and the haze value was 0.6%. From here, the relationship between visible light transmittance and solar radiation transmittance is plotted in FIG. From the reading of FIG. 3, the solar radiation transmittance was calculated to be 27.2% when the visible light transmittance was 70%.

[Examples 20 to 24]
Except for changing the type and concentration of the selective wavelength absorbing material in the composition for producing a heat ray shielding resin sheet material described in Example 19 and the type and concentration of the infrared absorbing organic compound, the same procedure as in Example 19 was performed. The heat ray shielding resin sheet material which concerns on Examples 20-24 was obtained. And the optical characteristic of the heat ray shielding resin sheet material which concerns on the said Examples 20-24 was measured similarly to Example 19. FIG.
Table 2 shows the concentration of the fine particles a, the type and concentration of the selective wavelength absorbing material, and the type and concentration of the infrared absorbing organic compound in Examples 20 to 24. Furthermore, the optical characteristic measurement result of the heat ray shielding resin sheet material which concerns on Examples 20-24 was shown in Table 2. For Example 20, the relationship between visible light transmittance and solar light transmittance was plotted in FIG. 3, and the solar light transmittance when the visible light transmittance was 70% calculated in the same manner as in Example 19 is shown in Table 2.

As the selective wavelength absorbing material, the above-described quinophthalone compound was used in Examples 21, 23, and 24, and the nickel azo compound was used in Example 22.
On the other hand, as examples of the infrared absorbing organic compound, the diimonium compounds described above were used in Examples 23 to 24, and the phthalocyanine compounds were used in Examples 21 to 22.

[Evaluation of Examples 1 to 24 and Comparative Examples 1 to 4]
In the heat ray shielding resin sheet materials according to Examples 1 to 7, the composite tungsten compound and the selective wavelength absorbing material were appropriately used in combination. As a result, the solar radiation transmittance was improved to 32.5% or less when the visible light transmittance was 70%.
On the other hand, in the heat ray shielding resin sheet material according to Comparative Example 1 using only the composite tungsten compound, the solar radiation transmittance was 32.8% when the visible light transmittance was 70%.

  In the heat ray shielding resin sheet materials according to Examples 8 to 18, the composite tungsten compound and the selective wavelength absorbing material were appropriately used in combination. As a result, a heat ray shielding resin sheet having a visible light transmittance of 70% or more and a solar radiation transmittance of 32.5% or less could be produced.

  In the heat ray shielding resin sheet materials according to Examples 19 to 24, an infrared absorbing organic compound was appropriately used in addition to the composite tungsten compound and the selective wavelength absorbing material. As a result, the solar radiation transmittance when the visible light transmittance is 70% is 32.5% or less, or the visible light transmittance is 70% or more and the solar radiation transmittance is 32.5% or less. Was able to be produced.

  In the heat ray shielding resin sheet material according to Comparative Example 1, only the composite tungsten compound was used without using the selective wavelength absorbing material and the infrared absorbing organic compound as described above. As a result, the solar radiation transmittance was 32.5% when the visible light transmittance was 70%, and the heat ray shielding ability was inferior.

  In the heat ray shielding resin sheet material according to Comparative Example 2, the light transmittance at a wavelength of 550 nm of the selected wavelength absorbing material itself excluding the absorption of the medium and the base material is 90% or more, and the light transmittance at a wavelength of 450 nm is A benzimidazolone compound that does not satisfy the condition of “40% or less” was used as the selective wavelength absorbing material. As a result, the visible light transmittance of the heat ray shielding resin sheet was lowered, and the solar light transmittance exceeded 32.5% despite the visible light transmittance being less than 70%, and the heat ray shielding ability was inferior.

  In the heat ray shielding resin sheet material according to Comparative Example 3, the addition amount of the selective wavelength absorbing material was too large. As a result, the visible light transmittance of the heat ray shielding resin sheet was lowered, and the solar radiation transmittance was 32.5% when the visible light transmittance was 70%, which was inferior in the heat ray shielding ability.

  In the heat ray shielding resin sheet material according to Comparative Example 4, as in Comparative Example 1, only the composite tungsten compound was used without using the selective wavelength absorbing material and the infrared absorbing organic compound. As a result, although the visible light transmittance was less than 70%, the solar radiation transmittance exceeded 32.5%, and the heat ray shielding characteristics were inferior.

Claims (12)

Including a polycarbonate resin containing a compound having a heat ray shielding function and a selective wavelength absorbing material,
The selective wavelength absorbing material has a transmission profile in which the transmittance of light having a wavelength of 550 nm is 90% or more and the transmittance of light having a wavelength of 450 nm is 40% or less, and the selective wavelength absorbing material and the heat ray shielding The heat ray shielding resin sheet material, wherein the weight ratio of the compound having a function is in the range of [compound having a heat ray shielding function / selected wavelength absorbing material] = 99/1 to 70/30. The compound having the heat ray shielding function is selected from the general formula M _y WO _Z (where the element M is selected from Cs, Rb, K, Tl, In, Ba, Li, Ca, Sr, Fe, Sn, Al, Cu) 1 or more elements, 0.1 ≦ y ≦ 0.5, 2.2 ≦ z ≦ 3.0), and a composite tungsten oxide fine particle having a hexagonal crystal structure, The heat ray shielding resin sheet material according to claim 1.   The heat ray shielding resin sheet material according to claim 2, wherein the composite tungsten oxide fine particles are fine particles having a dispersed particle diameter of 40 nm or less.   2. The selective wavelength absorbing material is at least one selected from quinophthalone compounds, nickel azo compounds, isoindoline compounds, quinoxaline compounds, condensed diazo compounds, isoindolinone compounds, and bismuth vanadate compounds. The heat ray shielding resin sheet material described in 1.   2. The heat ray shielding resin sheet material according to claim 1, wherein the selective wavelength absorbing material is at least one selected from a quinophthalone pigment and a nickel azo pigment.   6. The selective wavelength absorbing material according to claim 1, wherein the transmittance of light having a wavelength of 550 nm is 90% or more and the transmittance of light having a wavelength of 450 nm is 15% or less. The heat ray shielding resin sheet material according to any one of the above.   The heat ray shielding resin sheet material according to any one of claims 1 to 6, wherein the heat ray shielding resin sheet material further contains an infrared absorbing organic compound.   The infrared absorbing organic compound is a diimonium compound, phthalocyanine compound, naphthalocyanine compound, imonium compound, polymethine compound, diphenylmethane compound, triphenylmethane compound, quinone compound, azo compound, pentadiene compound, azomethine compound, squarylium compound, organometallic complex The heat ray shielding resin sheet material according to claim 7, wherein the heat ray shielding resin sheet material is at least one selected from cyanine compounds.   The heat ray shielding resin sheet material according to claim 7, wherein the infrared absorbing organic compound is at least one selected from a phthalocyanine compound and a diimonium compound.   The weight ratio between the infrared absorbing organic compound and the composite tungsten oxide fine particles is in the range of [composite tungsten oxide fine particles / infrared absorbing organic compound] = 95/5 to 50/50. To 9 in the heat ray shielding resin sheet material.   The heat ray shielding resin according to any one of claims 1 to 10, wherein the visible light transmittance calculated by JIS R 3106 is 70% or more and the solar radiation transmittance is 32.5% or less. Sheet material. An automobile, wherein the heat ray shielding resin sheet material according to any one of claims 1 to 11 is mounted as a window material.

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