CN117043299A - Infrared absorbing particles, infrared absorbing particle dispersion, infrared absorbing interlayer transparent substrate, and infrared absorbing transparent substrate - Google Patents
Infrared absorbing particles, infrared absorbing particle dispersion, infrared absorbing interlayer transparent substrate, and infrared absorbing transparent substrate Download PDFInfo
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- CN117043299A CN117043299A CN202280022950.7A CN202280022950A CN117043299A CN 117043299 A CN117043299 A CN 117043299A CN 202280022950 A CN202280022950 A CN 202280022950A CN 117043299 A CN117043299 A CN 117043299A
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- infrared absorbing
- particle dispersion
- particles
- resin
- transparent substrate
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Abstract
An infrared absorbing particle is provided, which is an infrared absorbing particle containing a composite tungsten oxide particle having a hexagonal crystal structure and represented by the general formula M x W y O z (wherein M is 1 or more element selected from Cs, rb, K, tl, ba, ca, sr, fe, W is tungsten, O is oxygen, and 0.25.ltoreq.x/y.ltoreq. 0.39,2.70.ltoreq.z/y.ltoreq.2.90).
Description
Technical Field
The present invention relates to infrared absorbing particles, an infrared absorbing particle dispersion, an infrared absorbing interlayer transparent substrate, and an infrared absorbing transparent substrate.
Background
As a method for removing and reducing the heat component from an external light source such as sunlight or a bulb, a film formed of a material reflecting infrared rays to the surface of glass has been conventionally formed to produce a heat ray reflective glass. Moreover, the material uses FeO x 、CoO x 、CrO x 、TiO x Metal oxide, ag, au, cu, ni, al, and the like.
However, these metal oxides and metal materials have properties that visible light is reflected or absorbed simultaneously, in addition to infrared rays that greatly contribute to the thermal effect, and therefore there is a problem that the visible light transmittance of the heat ray reflective glass is lowered. In particular, since a substrate used for building materials, vehicles, telephone boxes, and the like needs to have high transmittance in the visible light range, when the above-mentioned material such as metal oxide is used, the film thickness thereof needs to be extremely thin. Therefore, a method of forming a film using a thin film having a thickness of 10nm level by using a physical film forming method such as a spray sintering method, a CVD method, a sputtering method, or a vacuum deposition method is employed.
However, these film forming methods require a large-scale apparatus and vacuum equipment, and have difficulty in productivity and large area, and have a disadvantage in that the film manufacturing cost increases. Further, if these materials are used to improve the solar shading characteristics, the reflectance of light in the visible light range tends to be high at the same time, and there is a disadvantage that the appearance of a mirror is given to be dazzling, and the appearance is impaired.
In order to solve such a problem, it is considered that a film having low reflectance of light in the visible light region and high reflectance in the infrared region, which are physical properties of the film, is required.
As materials having high visible light transmittance and excellent solar shielding function, antimony tin oxide (hereinafter, abbreviated as ATO) and indium tin oxide (hereinafter, abbreviated as ITO) are known. These materials do not give a sparkling appearance because of their relatively low visible light reflectance. However, since the plasma frequency is in the near infrared region, the reflection and absorption effects are still insufficient for light in the near infrared region, which is closer to the visible region. Further, these materials have a problem that the amount of the materials used is increased to obtain a high shielding function because the sunlight shielding force per unit weight is low.
Further, as an infrared shielding film material having a solar shielding function, a film in which tungsten oxide, molybdenum oxide, and vanadium oxide are slightly reduced is exemplified. These films are materials used as so-called electrochromic materials, but are transparent in a state of being sufficiently oxidized, and if reduced electrochemically, absorption occurs from the visible light region of long wavelength to the near infrared region.
Patent document 1 proposes a heat ray-shielding glass characterized in that a 1 st dielectric film as a 1 st layer is provided on a transparent glass substrate on the substrate side, a composite tungsten oxide film containing at least 1 metal element selected from the group consisting of group IIIa, group IVa, group Vb, group VIb and group VIIb of the periodic table is provided as a 2 nd layer on the 1 st layer, and a 2 nd dielectric film as a 3 rd layer is provided on the 2 nd layer.
Patent document 2 proposes an ultraviolet ray heat ray blocking glass, characterized in that a 1 st transparent dielectric film as a 1 st layer is provided on a transparent glass substrate, the 1 st transparent dielectric film containing an oxide having ultraviolet ray blocking performance containing at least 1 kind of a group consisting of zinc, cerium, titanium and cadmium as a component, a composite oxide of these oxides or a composite oxide of these oxides to which a trace amount of a metal element is added, a 2 nd transparent dielectric film as a 2 nd layer is provided on the 1 st layer, a composite tungsten oxide film containing at least 1 kind of a metal element selected from the group consisting of group IIIa, group IVa, group Vb, group VIb and group VIIb of the periodic table as a 3 rd layer is provided on the 2 nd layer, and a 3 rd transparent dielectric film as a 4 rd layer is provided on the 3 rd layer.
Patent document 3 proposes a heat ray-shielding glass characterized in that a composite tungsten oxide film containing at least 1 metal element selected from the group consisting of group IIIa, group IVa, group Vb, group VIb and group VIIb of the periodic table is provided as a 1 st layer on the substrate side on a transparent substrate, and a transparent dielectric film is provided as a 2 nd layer on the 1 st layer.
Patent document 4 proposes a method for forming a tungsten oxide film on a substrate, which is characterized in that sputtering is performed in an atmosphere containing carbon dioxide using a target formed of tungsten. According to such a film formation method, a tungsten oxide film having high heat shielding properties and uniform in-plane optical characteristics is disclosed.
For example, as described in patent documents 1 to 4, a sputtering method has been conventionally used as a method for producing an infrared shielding layer containing a tungsten compound. However, such a physical film forming method requires a large-scale apparatus and vacuum equipment, and has a problem in terms of productivity, and there is a problem that the manufacturing cost of the film becomes high even if the film is technically possible to be made large-area.
The applicant has disclosed in patent document 5 that light in the visible region is transmitted and light in the infrared region is absorbed by the general formula W y O x Expressed by the general formula M x W y O z An infrared shielding material fine particle dispersion in which the expressed composite tungsten oxide fine particles are dispersed in a medium, an infrared shielding body, a method for producing the infrared shielding material fine particles, and the infrared shielding material fine particles.
Further, the present inventors have disclosed in patent document 6 that light in the visible light region is transmitted and light in the infrared region is transmittedAbsorbed by general formula W y O x Expressed by the general formula M x W y O z The method for producing the tungsten oxide fine particles for forming solar radiation shielding body of the expressed composite tungsten oxide fine particles, and the tungsten oxide fine particles for forming solar radiation shielding body.
As disclosed in patent documents 5 and 6, the solar shielding body containing tungsten oxide fine particles and the like does not require a large-scale apparatus or vacuum equipment such as a physical film forming method, and is high in productivity and can be produced at low cost. Further, from the viewpoint of the characteristics as a solar radiation shield, the solar radiation shield including tungsten oxide fine particles or the like can further improve light transmittance in the visible light region without reducing the infrared radiation shielding performance.
Prior art literature
Patent literature
Patent document 1 Japanese patent laid-open No. 8-12378
Patent document 2 Japanese patent laid-open No. 8-59301
Patent document 3 Japanese patent laid-open No. 8-283044
Patent document 4 Japanese patent laid-open No. 10-183334
Patent document 5 Japanese patent No. 4096205
Patent document 6 Japanese patent No. 4626284
Disclosure of Invention
Problems to be solved by the invention
However, it contains a conventionally used compound of the general formula W y O x Expressed by the general formula M x W y O z The optical member (film, resin sheet, etc.) of the expressed composite tungsten oxide fine particles exhibits blue color peculiar to tungsten oxide. Therefore, lighter colors are required depending on the application.
In addition, when the infrared absorbing material is used, it is sometimes placed under a high-temperature and high-humidity environment due to heat caused by solar rays and the like and due to moisture in the atmosphere. Therefore, even when the infrared absorbing material is placed in a high-temperature and high-humidity environment, it is required to suppress the decrease in the infrared absorbing property (solar radiation shielding property), that is, to have excellent weather resistance.
In view of the above problems of the prior art, an object of one aspect of the present invention is to provide infrared absorbing particles which are light blue and have excellent weather resistance and infrared absorbing properties.
Means for solving the problems
In one aspect of the present invention, there is provided an infrared absorbing particle comprising composite tungsten oxide particles,
the composite tungsten oxide particles have a hexagonal crystal structure and are represented by the general formula M x W y O z (wherein M is 1 or more element selected from Cs, rb, K, tl, ba, ca, sr, fe, W is tungsten, O is oxygen, and 0.25.ltoreq.x/y.ltoreq. 0.39,2.70.ltoreq.z/y.ltoreq.2.90).
ADVANTAGEOUS EFFECTS OF INVENTION
In one aspect of the present invention, infrared absorbing particles having light blue color and excellent weather resistance and infrared absorbing properties can be provided.
Drawings
Fig. 1 is a schematic view of an infrared absorbing particle dispersion.
Fig. 2 is a schematic illustration of an infrared absorbing particle dispersion.
FIG. 3 is a schematic cross-sectional view of an infrared absorbing interlayer transparent substrate.
FIG. 4 is a schematic cross-sectional view of an infrared absorbing transparent substrate.
Fig. 5 is an XRD pattern of the infrared absorbing particles obtained from example 3.
Fig. 6 shows XRD patterns of the infrared absorbing particles obtained in comparative examples 1 and 2.
Detailed Description
Specific examples of the infrared absorbing particles, the infrared absorbing particle dispersion, the infrared absorbing interlayer transparent substrate, and the infrared absorbing transparent substrate according to an embodiment of the present disclosure (hereinafter referred to as "the present embodiment") will be described below. The present invention is not limited to these examples, and all changes that come within the meaning and range of equivalency of the claims are intended to be embraced therein.
Hereinafter, the present embodiment will be described in the order of 1. IR-absorbing particles, 2. Process for producing IR-absorbing particles, 3. IR-absorbing particle dispersion, 4. IR-absorbing particle dispersion, 5. IR-absorbing interlayer transparent substrate, 6. IR-absorbing transparent substrate, and 7. Physical properties.
1. Infrared absorbing particles
The infrared absorbing particles according to the present embodiment may contain composite tungsten oxide particles. In addition, the infrared absorbing particles of the present embodiment may be composed of only composite tungsten oxide particles, but even in this case, inclusion of unavoidable impurities is not excluded.
The composite tungsten oxide particles can be represented by the general formula M x W y O z Particles of the composite tungsten oxide are described.
The element M in the above general formula may be 1 or more elements selected from Cs, rb, K, tl, ba, ca, sr, fe, W is tungsten, and O is oxygen. x, y and z can satisfy x/y is more than or equal to 0.25 and less than or equal to 0.39,2.70 and z/y is more than or equal to 2.90.
The composite tungsten oxide particles can have a hexagonal crystal structure.
(composition, crystallization, lattice constant of composite tungsten oxide particles)
In the above general formula of the composite tungsten oxide particles, the value of x/y representing the addition amount of the element M is preferably 0.25 to 0.39, more preferably 0.25 to 0.32. This is because if the value of x is 0.25 to 0.39, hexagonal crystal composite tungsten oxide particles are easily obtained, and the infrared absorption effect is sufficiently exhibited. The infrared absorbing particles may contain tetragonal crystals or M in addition to particles of hexagonal composite tungsten oxide 0.36 WO 3.18 (Cs 4 W 11 O 35 Etc.) of orthorhombic crystals shown, which do not affect the infrared absorption effect. It is considered that the composite tungsten oxide particles theoretically have an x/y value of 0.33, and that the added M element is disposed inAll of the hexagonal voids.
In addition, the value of z/y in the above formula is preferably 2.70.ltoreq.z/y.ltoreq.2.90. By setting the value of z/y to 2.70 or more, it is possible to produce infrared absorbing particles which are bluish in color and excellent in weather resistance and infrared absorbing properties. Further, by setting the value of z/y to 2.70 or more, the light transmittance at a wavelength of 850nm, for example, can be improved. With the increase in the functionality of automobiles, in-vehicle devices and sensors that perform control using infrared communication waves are widely used. In order to improve the accuracy of control and detection accuracy of the sensor of various kinds of in-vehicle devices, it is also required to design the light transmittance at a wavelength of 850nm to be high. As described above, the infrared absorbing particles of the present embodiment have excellent light transmittance at a wavelength of 850nm, and therefore, in an automobile or the like in which an infrared absorbing particle dispersion or the like using the infrared absorbing particles is disposed in an opening such as a window, accuracy in control of in-vehicle equipment and detection by a sensor is improved.
By setting the value of z/y to 2.90 or less, the absorption/reflection characteristics in the infrared region are improved, and therefore, a particularly sufficient amount of free electrons can be generated, and infrared absorbing particles can be efficiently formed.
In the composite tungsten oxide particles, it is not relevant that a part of oxygen is replaced with another element. Examples of the other element include nitrogen, sulfur, and halogen.
The composite tungsten oxide particles preferably have a hexagonal crystal structure. This is because, in the case where the composite tungsten oxide particles have a hexagonal crystal structure, the transmittance of light in the visible light region and the absorption of light in the near infrared region of the composite tungsten oxide particles, the infrared absorbing particles containing the composite tungsten oxide particles are particularly improved.
In addition, if 1 or more kinds of elements selected from Cs, rb, K, tl, ba, ca, sr, fe are used as the M element, hexagonal crystals are easily formed. Therefore, the M element preferably contains 1 or more elements selected from Cs, rb, K, tl, ba, ca, sr, fe.
The lattice constant of the composite tungsten oxide particles is not particularly limited,for example, the a-axis is preferablyAbove mentionedThe c-axis is->Above->The following is given. As described later, the infrared absorbing particles containing the composite tungsten oxide particles may be pulverized to form a desired particle diameter, and the lattice constants of the composite tungsten oxide particles before and after pulverization preferably satisfy the above range.
(regarding particle diameter)
The particle size of the infrared absorbing particles of the present embodiment can be selected according to the purpose of use of the infrared absorbing particles, the infrared absorbing particle dispersion, the infrared absorbing interlayer transparent substrate, the infrared absorbing transparent substrate, and the like, and is not particularly limited.
The average dispersion particle diameter of the infrared absorbing particles is, for example, preferably 1nm to 800nm, more preferably 1nm to 400 nm. This is because the infrared absorbing particles can exert strong infrared absorbing energy if the average dispersion particle diameter is 800nm or less, and the industrial production is easy if the average dispersion particle diameter is 1nm or more.
In particular, when the average dispersion particle diameter is 400nm or less, the infrared absorbing film and the molded article (plate or sheet) can be prevented from being gray-colored, which monotonically decreases in transmittance. Further, by setting the average dispersion particle diameter to 400nm or less, when using the infrared absorbing particle dispersion liquid, it is possible to suppress fogging and improve the visible light transmittance, in particular, in the case of producing an infrared absorbing particle dispersion or the like.
In the case of using the infrared absorbing particle dispersion or the like for an application requiring transparency to light in the visible light range, the infrared absorbing particles preferably have an average dispersion particle diameter of 40nm or less. The average particle diameter was 50% by volume of the cumulative particle size measured using DLS-8000, manufactured by Katsukamu electronics Co., ltd. Using the dynamic light scattering method as a principle. This is because if the infrared absorbing particles have an average dispersion particle diameter of less than 40nm, scattering of light due to mie scattering and rayleigh scattering of the infrared absorbing particles can be sufficiently suppressed, the visibility of light in the visible light region can be maintained high, and the transparency can be maintained efficiently. In the case of use in an automobile, such as windbreak, where transparency is particularly required, the average dispersion particle diameter of the infrared absorbing particles is more preferably 30nm or less, and still more preferably 25nm or less, in order to further suppress scattering.
The particle size of the composite tungsten oxide particles related to the infrared absorbing particles described above can be appropriately selected depending on the purpose of use of the composite tungsten oxide particles, the infrared absorbing film produced using the dispersion, the infrared absorbing particle dispersion, the infrared absorbing transparent substrate, and the infrared absorbing interlayer transparent substrate, and is not particularly limited. The particle diameter of such composite tungsten oxide particles is preferably 1nm to 800 nm. In addition, when transparency is important, the particle diameter of the composite tungsten oxide particles is preferably 200nm or less, more preferably 100nm or less. This is because if the particle size is large, light in the visible light range of 380nm to 780nm is scattered by geometric scattering or Mie scattering, and it is difficult to obtain clear transparency as if the appearance of the infrared absorbing material is blurred glass. If the particle diameter is 200nm or less, the scattering is reduced, and a Rayleigh scattering region is formed. In the rayleigh scattering region, scattered light decreases in proportion to the 6 th power of the particle diameter, and therefore scattering decreases and transparency increases with the decrease in the particle diameter. Further, if the particle diameter is 100nm or less, scattered light becomes extremely small, which is preferable. As described above, if the particle diameter is 800nm or less, the composite tungsten oxide particles according to the present embodiment can exhibit excellent infrared absorption characteristics, and if the particle diameter is 1nm or more, industrial production is easy.
The particle size here can be calculated by measuring the particle sizes of a plurality of particles using a Transmission Electron Microscope (TEM) or the like in a state where the composite tungsten oxide particles are dispersed, for example. Further, since the composite tungsten oxide particles are generally amorphous, the diameter of the smallest circle circumscribing the particles can be set to the particle diameter of the particles. For example, in the case where the particle diameter of a plurality of particles is measured for each particle using a transmission electron microscope as described above, the particle diameters of all the particles preferably satisfy the above range. The number of particles to be measured is not particularly limited, and is preferably 10 or more and 50 or less, for example.
(regarding color)
The color tone of the infrared absorbing particles according to the present embodiment when light absorption by the infrared absorbing particles alone is calculated is preferably L ＊ a ＊ b ＊ The color system satisfies b ＊ ＞0。
This is because the color tone at the time of light absorption by the infrared absorbing particles alone is calculated to pass through the color filter L ＊ a ＊ b ＊ The color system satisfies b ＊ > 0, and can be bluish.
The calculation of light absorption by only the infrared absorbing particles means that the blank measurement is performed even when the evaluation is performed, and the influence of reflection of light by a cell or the like used in the measurement is removed by subtracting the blank evaluation result from the evaluation result of the infrared absorbing particles.
(coating)
The infrared absorbing particles may be subjected to surface treatment for the purpose of surface protection, improvement in durability, oxidation prevention, improvement in water resistance, and the like. The specific content of the surface treatment is not particularly limited, and for example, the infrared absorbing particles of the present embodiment can coat the surface of the infrared absorbing particles with a compound containing 1 or more atoms selected from Si, ti, zr, al. That is, the infrared absorbing particles can have a coating using the above-described compound. In this case, the compound containing 1 or more atoms selected from Si, ti, zr, al includes 1 or more atoms selected from oxides, nitrides, carbides, and the like.
2. Method for producing infrared absorbing particles
According to the method for producing infrared absorbing particles of the present embodiment, the infrared absorbing particles already described can be produced. Therefore, the description is omitted for the already described matters.
The present inventors have studied a method for producing infrared absorbing particles having light blue color and excellent weather resistance and infrared absorbing properties.
The weather resistance here means that, for example, the deterioration of the solar radiation shielding property can be suppressed when the infrared absorbing particle dispersion is used and the dispersion is placed in an environment of high temperature and high humidity.
As a result, it has been found that the following 1 st heat treatment step and 2 nd heat treatment step are performed on a predetermined raw material to obtain infrared absorbing particles capable of solving the above-mentioned problems, and the present invention has been completed.
The 1 st heat treatment step (oxidizing gas heat treatment step) is a step of performing heat treatment in an atmosphere of 1 st gas containing at least an oxygen source.
The 2 nd heat treatment step (non-oxidizing gas heat treatment step) is a step of performing heat treatment in an atmosphere containing 1 or more kinds of 2 nd gas selected from the group consisting of a reducing gas and an inert gas.
The order of performing the 1 st heat treatment step and the 2 nd heat treatment step is not particularly limited, and for example, the 2 nd heat treatment step may be performed after the 1 st heat treatment step, or the 1 st heat treatment step may be performed after the 2 nd heat treatment step.
The raw material powder to be supplied to the heat treatment will be described herein, and the heat treatment conditions will be described in detail.
(1) Raw material powder
Here, the raw material powder is a powder selected from tungstic acid (H 2 WO 4 ) Or a mixed powder of a tungstic acid mixture and a compound containing M element, and tungstic acid (H 2 WO 4 ) Or 1 or more of the dry powders of a mixed solution of a tungstic acid mixture and a solution containing M element.
The tungstic acid mixture is tungstic acid (H) 2 WO 4 ) And tungsten oxide.
The above mixed powder and dry powder will be described.
(Mixed powder)
As the raw material powder, as described above, a mixed powder can be used. As the mixed powder, for example, mixed powder of tungstic acid and a compound containing M element, mixed powder of tungstic acid mixture and a compound containing M element can be used.
Here, tungstic acid (H) used in the raw material powder 2 WO 4 ) The raw material powder to be an oxide by firing is not particularly limited. In addition, tungsten oxide used in the tungstic acid mixture may be W 2 O 3 、WO 2 、WO 3 Any of the above).
Further, the compound containing M element for adding M element is preferably 1 or more selected from the group consisting of oxides, hydroxides and carbonates, mixed with tungstic acid or a tungstic acid mixture. Therefore, the compound containing the M element is preferably 1 or more selected from the group consisting of an oxide of the M element, a hydroxide of the M element, and a carbonate of the M element.
The M element is preferably 1 or more elements selected from Cs, rb, K, tl, ba, ca, sr, fe.
Tungstic acid (H) 2 WO 4 ) Or mixing of the tungstic acid mixture with the M element-containing compound may be carried out by using a commercially available kneader, ball mill, sand mill, paint shaker or the like (mixing step).
(Dry powder)
Further, as the raw material powder, tungstic acid (H 2 WO 4 ) Or a mixed solution of a tungstic acid mixture and a solution containing an element M.
The description of the tungstic acid and the tungstic acid mixture is given by using the mixed powder, and the description is omitted here.
The solution containing the M element is preferably 1 or more selected from the group consisting of an aqueous solution of a metal salt of the M element, a colloidal solution of a metal oxide of the M element, and an alkoxy solution of the M element.
The type of metal salt used in the aqueous solution of the metal salt of M element is not particularly limited, and examples thereof include nitrate, sulfate, chloride, carbonate, and the like.
The drying temperature and time in preparing the dry powder are not particularly limited.
The raw material powder preferably contains tungsten and M element in a proportion corresponding to the target composition. For example, the raw material powder preferably contains M element (M) and tungsten (W) in a molar ratio of 0.25 to 0.39.
(2) Heat treatment process
As described above, the method for producing the infrared absorbing particles according to the present embodiment may include the 1 st heat treatment step and the 2 nd heat treatment step of heat treating the raw material powder.
(2-1) the 1 st Heat treatment step
The 1 st heat treatment step (oxidizing gas heat treatment step) is a step of performing heat treatment in an atmosphere of 1 st gas containing at least an oxygen source.
The oxygen source gas is not particularly limited, but is preferably 1 or more selected from the group consisting of oxygen gas, air gas, and water vapor.
The gas other than the oxygen source of the 1 st gas is not particularly limited, and may contain an inert gas, for example. The inert gas is not particularly limited, and 1 or more kinds of gases selected from nitrogen, argon, helium, and the like can be used.
The concentration of the oxygen source in the 1 st gas is not particularly limited as long as it is appropriately selected depending on the heat treatment temperature and the amount of the heat-treated material, and if it is excessively oxidized, the infrared absorption function may be lowered, so that it is preferable to oxidize only the surface of the particles.
The temperature at the time of the heat treatment is not particularly limited as long as it is appropriately selected according to the amount of the heat-treated raw material powder or the like. For example, it is preferably 400℃to 850 ℃.
By performing the oxidation treatment in the 1 st heat treatment step, the surface of the composite tungsten oxide particles can be oxidized, for example, and no polaron is absorbed. By performing the 1 st heat treatment step, the transmittance of the wavelength of the infrared communication wave is increased, and the infrared absorbing particles having light blue color and high weather resistance (heat resistance, moist heat resistance) are obtained.
The 1 st heat treatment step may be performed in 1 step, and a plurality of steps in which the atmosphere and the temperature are changed during the heat treatment may be employed. For example, the heat treatment may be performed at 400 ℃ to 850 ℃ in the mixed gas atmosphere of the inert gas and the oxygen source gas in step 1, and the heat treatment may be performed at 400 ℃ to 850 ℃ in the inert gas atmosphere in step 2. By performing the heat treatment step 1 in a plurality of steps in this way, infrared absorbing particles having particularly excellent infrared absorbing function can be obtained.
(2-2) the 2 nd Heat treatment step
The 2 nd heat treatment step (non-oxidizing gas heat treatment step) is a step of performing heat treatment in an atmosphere containing 1 or more kinds of 2 nd gas selected from the group consisting of a reducing gas and an inert gas.
By performing the 2 nd heat treatment step, oxygen pores can be formed in the infrared absorbing particles.
The atmosphere at the time of heat treatment in the 2 nd heat treatment step may be an inert gas alone, a reducing gas alone, or a mixture of an inert gas and a reducing gas as described above.
The inert gas is not particularly limited, and 1 or more kinds of gases selected from nitrogen, argon, helium, and the like can be used.
The reducing gas is not particularly limited, and for example, 1 or more kinds of gases selected from hydrogen, alcohols, and the like can be used.
When a mixed gas of an inert gas and a reducing gas is used as the 2 nd gas, the concentration of the reducing gas in the inert gas is not particularly limited as long as it is appropriately selected according to the heat treatment temperature, the amount of the heat-treated raw material powder, and the like. The concentration of the reducing gas in the 2 nd gas is, for example, preferably 20% by volume or less, more preferably 10% by volume or less, and still more preferably 7% by volume or less.
This is because by making the 2 nd gasThe concentration of the reducing gas in (2) is 20 vol% or less, thereby avoiding WO having no infrared shielding function due to rapid reduction 2 And W, etc.
When a mixed gas is used as the 2 nd gas, the concentration of the reducing gas in the 2 nd gas, that is, the lower limit value of the content ratio is not particularly limited, and the content ratio of the reducing gas in the 2 nd gas is preferably more than 1% by volume. This is because, when the content of the reducing gas in the 2 nd gas exceeds 1% by volume, oxygen voids can be more reliably formed.
The temperature at the time of heat treatment in the 2 nd heat treatment step is not particularly limited as long as it is appropriately selected depending on the atmosphere, the amount of the heat-treated raw material powder, and the like. In the case where the atmosphere is a single inert gas, the temperature is preferably 400 to 1200 ℃, more preferably 500 to 1000 ℃, still more preferably 500 to 900 ℃ from the viewpoints of crystallinity and coloring power. Even when the 2 nd gas contains a reducing gas, the 2 nd heat treatment temperature is not particularly limited, and the temperature range described above can be set to a suitable range, for example, in the same manner as when the 2 nd gas is an inactive gas alone.
The 2 nd heat treatment step may be performed in 1 step, and a plurality of steps in which the atmosphere and the temperature are changed during the heat treatment may be employed. For example, in the step 1, the heat treatment may be performed at 400 ℃ to 850 ℃ under a mixed gas atmosphere of an inert gas and a reducing gas, and in the step 2, the heat treatment may be performed at 800 ℃ to 1000 ℃ under an inert gas atmosphere. By performing the heat treatment step 2 in a plurality of steps in this way, infrared absorbing particles having particularly excellent infrared absorbing function can be obtained.
The heat treatment time in the 2 nd heat treatment step is not particularly limited, and may be appropriately selected depending on the heat treatment temperature, atmosphere, and amount of the heat-treated raw material powder, and may be, for example, 5 minutes to 7 hours.
The above heat treatment steps are performed, whereby the infrared absorbing particles described above can be obtained. The method for producing infrared absorbing particles according to the present embodiment may also include a pulverizing step of pulverizing the infrared absorbing particles, a sieving step, and the like, as necessary, in order to form a desired particle diameter.
(3) Modification step
As already described, the infrared absorbing particles may be modified on the surface thereof with a compound containing 1 or more atoms selected from Si, ti, zr, al. Accordingly, the method for producing the infrared absorbing particles may further include a modification step of modifying the infrared absorbing particles with a compound containing 1 or more atoms selected from Si, ti, zr, al, for example.
In the modification step, specific conditions for modifying the infrared absorbing particles are not particularly limited. For example, the method may include a modification step of adding an alkoxide containing 1 or more metals selected from the group of metals to the modified infrared absorbing particles to form a coating film on the surface of the infrared absorbing particles.
3. Infrared absorbing particle dispersion
The infrared absorbing particle dispersion of the present embodiment may contain a liquid medium and the infrared absorbing particles described above. Specifically, for example, as schematically shown in fig. 1, the infrared-absorbing particle dispersion 10 can have a liquid medium 12 and the infrared-absorbing particles 11 that have been described. The infrared absorbing particles 11, which have been described, are preferably disposed in the liquid medium 12, and dispersed in the liquid medium 12. Fig. 1 is a schematic view, and the infrared absorbing particle dispersion liquid according to the present embodiment is not limited to this form. For example, in fig. 1, the infrared absorbing particles 11 are described as spherical particles, and the shape of the infrared absorbing particles 11 is not limited to such a shape, and may have any shape. As already described, the infrared absorbing particles 11 can also have a coating or the like on the surface, for example. The infrared absorbing particle dispersion 10 may contain other additives as needed in addition to the infrared absorbing particles 11 and the liquid medium 12.
(1) Regarding the contained components
As described above, the infrared absorbing particle dispersion liquid of the present embodiment may contain a liquid medium and the infrared absorbing particles described above. The infrared absorbing particles will be described, and therefore, description thereof will be omitted. Hereinafter, the liquid medium and the infrared absorbing particle dispersion may contain a dispersant or the like as necessary.
(1-1) liquid Medium
The liquid medium is not particularly limited, and various liquid mediums can be used, and for example, 1 kind selected from the group of liquid medium materials consisting of water, an organic solvent, grease, a liquid resin, and a liquid plasticizer for plastics, or a mixture of 2 or more kinds selected from the group of liquid medium materials can be used.
The organic solvent may be any of various organic solvents such as alcohols, ketones, esters, amides, hydrocarbons, and glycols. Specifically, examples thereof include alcohol solvents such as methanol, ethanol, 1-propanol, isopropanol (isopropyl alcohol), butanol, amyl alcohol, benzyl alcohol, diacetone alcohol, and 1-methoxy-2-propanol; ketone solvents such as dimethyl ketone, acetone, methyl ethyl ketone, methyl propyl ketone, methyl isobutyl ketone, cyclohexanone, and isophorone; ester solvents such as 3-methyl-methoxy-propionate and butyl acetate; glycol inducers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol isopropyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol methyl ether acetate, and propylene glycol ethyl ether acetate; amides such as formamide, N-methylformamide, dimethylformamide, dimethylacetamide and N-methyl-2-pyrrolidone; aromatic hydrocarbons such as toluene and xylene; halogenated hydrocarbons such as ethylene chloride and chlorobenzene. Among these, organic solvents having low polarity are preferable, and isopropyl alcohol, ethanol, 1-methoxy-2-propanol, dimethyl ketone, methyl ethyl ketone, methyl isobutyl ketone, toluene, propylene glycol monomethyl ether acetate, n-butyl acetate, and the like are more preferable. These solvents can be used in 1 kind or in combination of 2 or more kinds. In addition, an acid or a base may be added as necessary to adjust the pH.
Examples of the oils and fats include 1 or more kinds of petroleum solvents selected from drying oils such as linseed oil, sunflower oil, tung oil, etc., semi-drying oils such as sesame oil, cottonseed oil, rapeseed oil, soybean oil, rice bran oil, etc., non-drying oils such as olive oil, coconut oil, palm oil, dehydrated castor oil, etc., fatty acid monoesters obtained by directly reacting fatty acids of vegetable oils with monohydric alcohols, ethers, ISOPER (registered trademark) E, EXXSOL (registered trademark) Hexane, heptane, E, D, D40, D60, D80, D95, D110, D130 (above, manufactured by EXXON MOBIL), etc.
As the liquid resin, a liquid resin in which a monomer, oligomer, thermoplastic resin, or the like cured by polymerization or the like of methyl methacrylate, styrene, or the like is dissolved in a liquid medium can be used.
Examples of the liquid plasticizer for plastics include plasticizers which are compounds of monohydric alcohols and organic acid esters, ester plasticizers which are compounds of polyhydric alcohols and organic acid esters, and phosphoric plasticizers which are organic phosphoric plasticizers. Among them, triethylene glycol di-2-ethylhexanoate, triethylene glycol di-2-ethylbutyrate and tetraethylene glycol di-2-ethylhexanoate are more preferable because of low hydrolyzability.
(1-2) dispersants, coupling agents, surfactants
The infrared absorbing particle dispersion of the present embodiment may contain 1 or more kinds selected from a dispersant, a coupling agent, and a surfactant, as necessary.
The dispersant, the coupling agent, and the surfactant may be selected according to the purpose, and a material having an amine-containing group, a hydroxyl group, a carboxyl group, or an epoxy group as a functional group can be suitably used.
The functional group has an effect of dispersing the infrared absorbing particles particularly uniformly in the infrared absorbing film even when the functional group is adsorbed on the surface of the infrared absorbing particles to prevent aggregation of the infrared absorbing particles, for example, when the infrared absorbing film is formed.
The infrared absorbing particle dispersion of the present embodiment may contain a dispersing agent. Such dispersants also include coupling agents and surfactants that function as dispersants. Examples of the dispersant that can be suitably used include 1 or more selected from the group consisting of phosphate compounds, polymer dispersants, silane coupling agents, titanate coupling agents, aluminum coupling agents, and the like, but are not limited thereto.
The polymer-based dispersant may be at least 1 selected from an acrylic polymer-based dispersant, a urethane polymer-based dispersant, an acrylic-block copolymer polymer-based dispersant, a polyether-based dispersant, a polyester polymer-based dispersant, and the like.
The amount of the dispersant to be added is preferably in the range of 10 to 1000 parts by mass, more preferably in the range of 20 to 200 parts by mass, based on 100 parts by mass of the infrared absorbing particles. If the amount of the dispersant is within the above range, the infrared absorbing particles do not cause aggregation in the liquid medium, and in particular, dispersion stability can be maintained.
(2) Method for adding infrared absorbing particles to liquid medium
The method of adding the infrared absorbing particles to the liquid medium is not particularly limited, and a method capable of uniformly dispersing the infrared absorbing particles in the liquid medium is preferable.
For example, the ultrasonic wave homogenizer may be 1 or more selected from a bead mill, a ball mill, a sand mill, a paint shaker, an ultrasonic wave homogenizer, and the like.
By the dispersion treatment using these dispersing means, the infrared absorbing particles are dispersed in the liquid medium, and at the same time, the infrared absorbing particles are micronized by collision or the like between the infrared absorbing particles, so that the infrared absorbing particles can be further micronized and dispersed. That is, when the dispersion treatment is performed, the pulverization and the dispersion treatment can be performed.
The content of the infrared absorbing particles in the infrared absorbing particle dispersion is not particularly limited, and the infrared absorbing particle dispersion of the present embodiment preferably contains 0.001 mass% to 80.0 mass% of the infrared particles. If the content is 0.001 mass% or more, the composition can be suitably used for the production of 1 kind of coating layer, plastic molded body, etc. as an infrared absorbing particle dispersion containing infrared absorbing particles, and if the content is 80.0 mass% or less, the industrial production is easy. The content of the infrared absorbing particles in the infrared absorbing particle dispersion is more preferably 0.01 mass% to 80.0 mass%, and still more preferably 1 mass% to 35 mass%.
Further, when the visible light transmittance of the infrared absorbing particle dispersion is set to 80%, the concentration of the infrared absorbing particles in the infrared absorbing particle dispersion is preferably 0.05 mass% or more and 0.20 mass% or less.
When the concentration of the infrared absorbing particles in the infrared absorbing particle dispersion is set to 0.05 mass% or more and 0.20 mass% or less when the visible light transmittance of the infrared absorbing particle dispersion is set to 80%, the infrared absorbing particle dispersion can have sufficient near infrared absorbing properties.
The color tone at the time of light absorption by the infrared absorbing particles alone is preferably calculated to be L based on the transmittance of light of the liquid medium in the infrared absorbing particle dispersion of the present embodiment ＊ a ＊ b ＊ B in the color system ＊ > 0. By satisfying the above range, light blue infrared absorbing particles are meant.
The light transmittance of the infrared absorbing particle dispersion of the present embodiment can be measured as a function of wavelength using a spectroluminance meter by placing the infrared absorbing particle dispersion in an appropriate transparent container.
(3) Regarding the average dispersed particle diameter
The characteristic of the infrared absorbing particle dispersion of the present embodiment can be confirmed by measuring the dispersion state of the infrared absorbing particles when the infrared absorbing particles are dispersed in a liquid medium. For example, the infrared absorbing particle dispersion of the sample embodiment can be measured by a commercially available particle size distribution meter to confirm the state of the infrared absorbing particles in the dispersion. As a particle size distribution meter, for example, DLS-8000 manufactured by Katsukamu electronics Co., ltd.) based on the dynamic light scattering method can be used.
The particle size of the infrared absorbing particles in the infrared absorbing particle dispersion of the present embodiment can be selected according to the purpose of use of the infrared absorbing dispersion or the like, and is not particularly limited.
In the infrared absorbing particle dispersion of the present embodiment, the average dispersion particle diameter of the infrared absorbing particles is preferably, for example, 1nm to 800nm, more preferably 1nm to 400 nm. This is because the infrared absorbing particles can exert strong infrared absorbing energy if the average dispersion particle diameter is 800nm or less, and the industrial production is easy if the average dispersion particle diameter is 1nm or more.
Particularly, when the average dispersion particle diameter is 400nm or less, it is possible to avoid the infrared shielding film and the molded article (plate or sheet) from being gray-colored, which monotonically decreases in transmittance. Further, by setting the average dispersion particle diameter to 400nm or less, when using the infrared absorbing particle dispersion liquid, it is possible to suppress fogging and improve the visible light transmittance, in particular, in the case of producing an infrared absorbing particle dispersion or the like.
When the infrared absorbing particle dispersion is used for applications requiring transparency of light in the visible light range, the infrared absorbing particles in the infrared absorbing particle dispersion preferably have an average dispersion particle diameter of 40nm or less. Here, the average dispersed particle size was 50% by volume cumulative particle size measured using DLS-8000, manufactured by Katsukamu electronics Co., ltd. Using the dynamic light scattering method as a principle. This is because if the infrared absorbing particles have an average dispersion particle diameter of less than 40nm, scattering of light due to mie scattering and rayleigh scattering of the infrared absorbing particles can be sufficiently suppressed, the visibility of light in the visible light region can be maintained high, and the transparency can be maintained efficiently. In the case of use in windbreak applications for automobiles, particularly applications requiring transparency, the average dispersion particle diameter of the infrared absorbing particles is more preferably 30nm or less, and still more preferably 25nm or less, in order to further suppress scattering.
4. Infrared absorbing particle dispersion
Next, the infrared absorbing particle dispersion according to the present embodiment will be described.
The infrared absorbing particle dispersion of the present embodiment can include a solid medium and the already described infrared absorbing particles disposed in the solid medium. Specifically, for example, as schematically shown in fig. 2, the infrared absorbing particle dispersion 20 can have a solid medium 22 and the infrared absorbing particles 21 that have been described, and the infrared absorbing particles 21 can be disposed in the solid medium 22. The infrared absorbing particles 21 are preferably dispersed in a solid medium 22. Fig. 2 is a schematic view, and the infrared absorbing particle dispersion according to the present embodiment is not limited to this form. For example, in fig. 2, the infrared absorbing particles 21 are described as spherical particles, but the shape of the infrared absorbing particles 21 is not limited to such a form, and may have any shape. The infrared absorbing particles 21 may have a coating or the like on the surface thereof, for example. The infrared absorbing particle dispersion 20 may contain other additives as required in addition to the infrared absorbing particles 21 and the solid medium 22.
(1) Regarding the contained components
As described above, the infrared absorbing particle dispersion of the present embodiment can contain a solid medium and the infrared absorbing particles already described. As for the infrared absorbing particles, description has been made, and explanation is omitted. Hereinafter, the components that can be contained in the solid medium and the infrared absorbing particle dispersion as needed will be described.
(1-1) solid Medium
First, a solid medium that is a solid medium will be described.
The solid medium is not particularly limited as long as it can be cured in a state in which the infrared absorbing particles are dispersed. Examples thereof include inorganic binders obtained by hydrolyzing metal alkoxides and organic binders such as resins.
In particular, the solid medium preferably contains a thermoplastic resin or a UV curable resin (ultraviolet curable resin). In addition, in the infrared absorbing particle dispersion of the present embodiment, if the manufacturing process is solid even if it is liquid, it may be a solid medium.
In the case where the solid medium includes a thermoplastic resin, the thermoplastic resin is not particularly limited, and may be arbitrarily selected according to the required transmittance, strength, and the like. As the thermoplastic resin, for example, any one selected from 1 resin of a resin group consisting of polyethylene terephthalate resin, polycarbonate resin, acrylic resin, styrene resin, polyamide resin, polyethylene resin, vinyl chloride resin, olefin resin, epoxy resin, polyimide resin, fluorine resin, ethylene-vinyl acetate copolymer, and polyvinyl acetal resin, a mixture of 2 or more resins selected from the above resin group, or a copolymer of 2 or more resins selected from the above resin group can be preferably used.
On the other hand, when the solid medium contains a UV curable resin, the UV curable resin is not particularly limited, and for example, an acrylic UV curable resin can be suitably used.
(1-2) concerning other ingredients
In the method for producing the infrared absorbing particle dispersion, the infrared absorbing particle dispersion may contain a dispersant, a plasticizer, and the like, as will be described later.
(2) Regarding the content of infrared absorbing particles
The content of the infrared absorbing particles contained in the infrared absorbing particle dispersion is not particularly limited, and may be arbitrarily selected according to the application and the like. The content of the infrared absorbing particles in the infrared absorbing particle dispersion is, for example, preferably 0.001 mass% to 80.0 mass%, more preferably 0.01 mass% to 70.0 mass%.
If the content of the infrared absorbing particles in the infrared absorbing particle dispersion is 0.001 mass% or more, the thickness of the infrared absorbing particle dispersion can be suppressed so as to obtain a necessary infrared absorbing effect. This is because the number of usable applications increases and transportation is easy.
Further, this is because the content of the infrared absorbing particles is 80.0 mass% or less, whereby the content of the solid medium in the infrared absorbing particle dispersion can be ensured, and the strength can be increased.
Each unit dose contained in the infrared absorbing particle dispersionThe content of the infrared absorbing particles in the shadow area is preferably 0.04g/m 2 10.0g/m above 2 The following is given. The term "content per unit projected area" means the content per unit area (m 2 ) The weight (g) of the infrared absorbing particles contained in the thickness direction thereof.
By setting the content per unit projected area of the infrared absorbing particle dispersion to the above range, the infrared absorbing effect can be maintained high while maintaining the strength of the infrared absorbing particle dispersion.
In the infrared absorbing particle dispersion of the present embodiment, it is preferable that the color tone at the time of light absorption by the infrared absorbing particles alone is calculated to be L ＊ a ＊ b ＊ B in the color system ＊ > 0. By satisfying the above range, it means light blue infrared absorbing particles. The same applies to an infrared absorbing interlayer transparent substrate described later.
(3) Shape of infrared absorbing particle dispersion
The infrared absorbing particle dispersion can be molded into any shape according to the application, and the shape thereof is not particularly limited.
The infrared absorbing particle dispersion can have, for example, a sheet shape, a plate shape, or a film shape, and can be used for various applications.
(4) Method for producing infrared absorbing particle dispersion
Here, a method for producing the infrared absorbing particle dispersion according to the present embodiment will be described.
The infrared absorbing particle dispersion can be produced, for example, by mixing the above-described solid medium with the infrared absorbing particles, molding the mixture into a desired shape, and then curing the mixture.
Further, the infrared absorbing particle dispersion can also be produced using, for example, the already described infrared absorbing dispersion liquid. In this case, the infrared absorbing particle dispersion described below can be produced by first producing an infrared absorbing particle dispersion powder, a plasticizer dispersion liquid, a master batch, and then using the infrared absorbing particle dispersion powder or the like. The following is a specific description.
First, a mixing process of mixing the infrared absorbing particle dispersion liquid, which has been described, with a thermoplastic resin or a plasticizer can be performed. Next, a drying step of removing the solvent component (liquid medium component) derived from the infrared absorbing particle dispersion can be performed.
By removing the solvent component, it is possible to obtain infrared absorbing particle dispersion powder (hereinafter, simply referred to as "dispersion powder") which is a dispersion in which infrared absorbing particles are dispersed at a high concentration in 1 or more materials selected from the group consisting of thermoplastic resins and dispersing agents derived from infrared absorbing particle dispersions, and a dispersion in which infrared absorbing particles are dispersed at a high concentration in a plasticizer (hereinafter, simply referred to as "plasticizer dispersion").
The method for removing the solvent component from the mixture of the infrared absorbing particle dispersion and the thermoplastic resin or the like is not particularly limited, and for example, a method of drying the mixture of the infrared absorbing particle dispersion and the thermoplastic resin or the like under reduced pressure is preferably used. Specifically, a mixture of the infrared absorbing particle dispersion and the thermoplastic resin or the like is dried under reduced pressure while stirring, and is separated into a dispersion powder or plasticizer dispersion and a solvent component. The apparatus used for the reduced pressure drying is not particularly limited as long as it is a vacuum agitation type dryer having the above-mentioned functions. The pressure value at the time of decompression in the drying step is not particularly limited, and may be arbitrarily selected.
When the solvent component is removed, the efficiency of removing the solvent from the mixture of the infrared absorbing particle dispersion and the thermoplastic resin can be improved by using a reduced pressure drying method. In addition, in the case of using the reduced pressure drying method, since the infrared absorbing particle dispersion powder and the plasticizer dispersion liquid are not exposed to high temperature for a long period of time, aggregation of the infrared absorbing particles dispersed in the dispersion powder and the plasticizer dispersion liquid does not occur, which is preferable. Further, the productivity of the infrared absorbing particle dispersion powder and the plasticizer dispersion is also improved, and the solvent to be evaporated is easily recovered, which is preferable from the viewpoint of environment.
In addition, as described above, a master batch can be used also in the production of the infrared absorbing particle dispersion.
For example, the master batch can be produced by dispersing an infrared absorbing particle dispersion liquid and an infrared absorbing particle dispersion powder in a resin, and granulating the resin.
As another method for producing the master batch, first, an infrared absorbing particle dispersion liquid, an infrared absorbing particle dispersion powder, and a powder or granule of a thermoplastic resin, and other additives as needed, are uniformly mixed. The mixture is kneaded by a vented uniaxial or biaxial extruder, and then processed into pellets by a method of cutting a general melt-extruded strand, whereby the pellets can be produced. In this case, examples of the shape include a columnar master batch and a prismatic master batch. In addition, a so-called thermal cutting method in which the molten extrudate is directly cut can also be employed. In this case, a shape close to a sphere is generally adopted.
By the above steps, an infrared absorbing particle dispersion powder, a plasticizer dispersion liquid, and a master batch can be produced.
The infrared absorbing particle dispersion according to the present embodiment can be produced by uniformly mixing an infrared absorbing particle dispersion powder, a plasticizer dispersion liquid, or a master batch in a solid medium, and molding the mixture into a desired shape. At this time, as the solid medium, as already described, an inorganic binder, an organic binder such as a resin, or the like can be used. As the binder, a thermoplastic resin or a UV curable resin can be particularly preferably used. As for the thermoplastic resin and the UV curable resin which can be particularly suitably used, description has been made, and the explanation is omitted here.
In the case of using a thermoplastic resin as a solid medium, an infrared absorbing particle dispersion powder, a plasticizer dispersion liquid or master batch, a thermoplastic resin, and other additives according to a desired plasticizer can be first kneaded. The kneaded material can be produced into, for example, an infrared absorbing particle dispersion shaped into a planar or curved sheet by various molding methods such as extrusion molding, injection molding, calender roll molding, extrusion, casting, and inflation.
In addition, as the solid medium, for example, in the case where the infrared absorbing particle dispersion using the thermoplastic resin is used as an intermediate layer disposed between, for example, transparent substrates, or the like, if the thermoplastic resin contained in the infrared absorbing particle dispersion does not have sufficient flexibility and adhesion to the transparent substrate or the like, a plasticizer may be added at the time of producing the infrared absorbing particle dispersion. Specifically, for example, when the thermoplastic resin is a polyvinyl acetal resin, it is preferable to further add a plasticizer.
The plasticizer to be added is not particularly limited, and any plasticizer can be used as long as it is a substance that acts as a plasticizer for the thermoplastic resin to be used. For example, in the case of using a polyvinyl acetal resin as the thermoplastic resin, a plasticizer which is a compound of a monohydric alcohol and an organic acid ester, an ester plasticizer such as a polyhydric alcohol organic acid ester compound, a phosphoric acid plasticizer such as an organic phosphoric acid plasticizer, and the like can be preferably used as the plasticizer.
The plasticizer is preferably liquid at room temperature, and is therefore preferably an ester compound synthesized from a polyol and a fatty acid.
Further, as has been described, the infrared absorbing particle dispersion of the present embodiment can have an arbitrary shape, for example, can have a sheet shape, a plate shape, or a film shape.
5. Transparent substrate with infrared absorption interlayer
Next, a configuration example of the infrared absorbing interlayer transparent substrate according to the present embodiment will be described.
The infrared absorbing interlayer transparent substrate of the present embodiment may have a plurality of transparent substrates and the infrared absorbing particle dispersion of the present embodiment. The infrared absorbing particle dispersion may have a laminated structure in which a plurality of transparent substrates are arranged therebetween.
Specifically, as shown in fig. 3, which is a schematic cross-sectional view along the lamination direction of the transparent substrate and the infrared absorbing particle dispersion, the infrared absorbing interlayer transparent substrate 30 may have a plurality of transparent substrates 311 and 312 and the infrared absorbing particle dispersion 32. The infrared absorbing particle dispersion 32 can be disposed between a plurality of transparent substrates 311 and 312. Fig. 3 shows an example having 2 transparent substrates 311 and 312, but is not limited to this configuration.
The infrared absorbing interlayer transparent substrate of the present embodiment may have a structure in which an infrared absorbing particle dispersion as an intermediate layer is sandwiched between both sides thereof using a transparent substrate (transparent substrate).
The transparent substrate is not particularly limited, and may be arbitrarily selected in consideration of visible light transmittance and the like. For example, as the transparent substrate, 1 or more kinds selected from plate glass, plate-like plastic, film-like plastic, and the like can be used. In addition, the transparent substrate is preferably transparent in the visible light region.
In the case of using a transparent base material made of plastic, the material of the plastic is not particularly limited, and may be selected according to the application, and a polycarbonate resin, an acrylic resin, a polyethylene terephthalate resin, a polyamide resin, a vinyl chloride resin, an olefin resin, an epoxy resin, a polyimide resin, a fluorine resin, or the like may be used.
In addition, the infrared absorbing interlayer transparent substrate of the present embodiment can use 2 or more transparent substrates, and when using 2 or more transparent substrates, for example, transparent substrates formed of different materials may be used in combination as the transparent substrate. The thicknesses of the transparent substrates are not necessarily the same, and transparent substrates having different thicknesses may be used in combination.
The infrared absorbing interlayer transparent substrate of the present embodiment can use the infrared absorbing particle dispersion that has been described as an intermediate layer. As for the infrared absorbing particle dispersion, description has been made, and the explanation is omitted here.
The infrared absorbing particle dispersion used for the infrared absorbing interlayer transparent substrate of the present embodiment is not particularly limited, and a material molded into a sheet shape, a plate shape, or a film shape can be preferably used.
The infrared absorbing interlayer transparent substrate of the present embodiment can be manufactured by bonding and integrating a plurality of transparent substrates which are opposed to each other and exist in a state of being sandwiched by infrared absorbing particle dispersions formed into a sheet shape or the like.
In the case of an infrared absorbing interlayer transparent substrate having 3 or more transparent substrates, the transparent substrates are positioned at 2 or more positions therebetween, and it is not necessary to dispose an infrared absorbing particle dispersion between all the transparent substrates, and it is only necessary to dispose an infrared absorbing particle dispersion at least at 1 position.
6. Infrared absorbing transparent substrate
The infrared absorbing transparent substrate of the present embodiment may have a transparent substrate and an infrared absorbing layer disposed on at least one surface of the transparent substrate. Moreover, the infrared absorbing layer can be made of the infrared absorbing particle dispersion already described. Specifically, as shown in fig. 4, which is a schematic cross-sectional view along the lamination direction of the transparent substrate and the infrared absorbing layer, the infrared absorbing transparent substrate 40 may have a transparent substrate 41 and an infrared absorbing layer 42. The infrared absorbing layer 42 can be disposed on at least one surface 41A of the transparent substrate 41.
The method for producing the infrared absorbing transparent substrate is not particularly limited. For example, the above-mentioned infrared absorbing particle dispersion liquid can be used to form a coating layer as an infrared absorbing layer containing infrared absorbing particles on a transparent substrate (transparent substrate) selected from film substrates and glass substrates. By such an operation, an infrared absorbing film or an infrared absorbing glass as an infrared absorbing transparent substrate can be produced.
The coating layer can be produced using a coating liquid in which, for example, the infrared absorbing particle dispersion liquid and the plastic or monomer which have been described are mixed.
For example, the infrared absorbing film can be produced as follows.
A medium resin which becomes a solid medium after curing is added to the infrared absorbing particle dispersion liquid to obtain a coating liquid. After the coating liquid is applied to the surface of the film substrate, a liquid medium containing the coating liquid is evaporated. Further, by curing the medium resin by a method corresponding to the medium resin used, a coating layer (coating film) in which the infrared absorbing particles are dispersed in a solid medium can be formed, and an infrared absorbing film can be produced.
In addition, by using the transparent substrate as a glass substrate, an infrared absorbing glass can be produced in the same manner.
The dielectric resin of the coating layer may be selected from, for example, UV curable resins, thermosetting resins, electron beam curable resins, room temperature curable resins, thermoplastic resins, and the like, depending on the purpose. Specific examples of the medium resin include polyethylene resin, polyvinyl chloride resin, polyvinylidene chloride 1, 1-resin, polyvinyl alcohol resin, polystyrene resin, polypropylene resin, ethylene vinyl acetate copolymer, polyester resin, polyethylene terephthalate resin, fluorine resin, polycarbonate resin, acrylic resin, polyvinyl butyral resin, and the like.
These medium resins may be used alone or in combination. Among the dielectric resins for the coating layer, the use of a UV curable resin binder is most particularly preferable from the viewpoints of productivity, equipment cost, and the like.
In addition, an adhesive using a metal alkoxide can be used. As the metal alkoxide, an alkoxide such as Si, ti, al, zr is typical. The binder using these metal alkoxides is hydrolyzed and polycondensed by heating or the like, so that the solid medium can form a coating layer formed of an oxide film.
As the material of the film base material, for example, a polyester resin, an acrylic resin, a urethane resin, a polycarbonate resin, a polyethylene resin, an ethylene vinyl acetate copolymer, a vinyl chloride resin, a fluorine resin, or the like can be used according to various purposes. The film base material of the infrared absorbing film is preferably a polyester film, and most preferably a polyethylene terephthalate (PET) film. The film base material is a plastic base material as a synthetic resin, and the thickness and shape thereof are not limited.
In addition, in order to achieve easiness of adhesion of the coating layer to the film substrate, the surface of the film substrate is preferably surface-treated. In order to improve the adhesion between the glass substrate or the film substrate and the coating layer, it is also preferable to form an intermediate layer on the glass substrate or the film substrate and form the coating layer on the intermediate layer. The intermediate layer may be formed by, for example, a polymer film, a metal layer, an inorganic layer (for example, an inorganic oxide layer of silica, titania, zirconia, or the like), an organic/inorganic composite layer, or the like.
The method of applying the coating liquid containing the infrared absorbing particle dispersion liquid or the like to the film substrate or the glass substrate is not particularly limited as long as the coating liquid containing the infrared absorbing particle dispersion liquid or the like can be uniformly applied to the surface of the substrate. Examples thereof include bar coating, gravure coating, spray coating, dip coating, and the like.
For example, in the case of bar coating using UV curable resin, an infrared absorbing transparent substrate can be produced as follows.
The concentration of the liquid can be adjusted so as to have proper leveling property, and a coating film can be formed on a film substrate or a glass substrate by using a coating liquid to which an additive is properly added, and by using a wire rod having a rod number selected according to the thickness of the coating layer, the content of infrared absorbing particles, and the like. Further, the liquid medium contained in the coating liquid is dried and removed, and then irradiated with ultraviolet light to cure the solid medium, whereby a coating layer can be formed on the film substrate or the glass substrate. In this case, the drying conditions of the coating film vary depending on the respective components, the type of the liquid medium, and the use ratio, and are usually about 60 ℃ to 140 ℃ for 20 seconds to 10 minutes. The irradiation of ultraviolet rays is not particularly limited, and a UV exposure machine such as an ultra-high pressure mercury lamp can be suitably used.
In addition, in the pre-step or post-step of forming the coating layer, the adhesion between the transparent substrate and the coating layer, the smoothness of the coating film at the time of coating, the drying property of the organic solvent, and the like can be adjusted. The pre-step includes, for example, a surface treatment step of a transparent substrate, a pre-baking (pre-heating of the substrate), and the like, and the post-step includes a post-baking (post-heating of the substrate) step and the like, and can be appropriately selected. The heating temperature in the pre-baking step and the post-baking step is preferably 80 to 200 ℃, and the heating time is preferably 30 to 240 seconds.
The thickness of the coating layer on the film substrate or the glass substrate is not particularly limited, but is preferably 10 μm or less, more preferably 6 μm or less in practical use. This is because if the thickness of the coating layer is 10 μm or less, sufficient pencil hardness is exhibited to provide abrasion resistance, and further, occurrence of warpage of the film base material and the like can be prevented when the liquid medium in the coating layer volatilizes and the solid medium is cured.
The content of the infrared absorbing particles of the coating layer is not particularly limited, and the content per unit projected area of the coating layer is preferably 0.1g/m 2 10.0g/m above 2 The following is given. This is because if the content per unit projected area is 0.1g/m 2 As described above, the infrared absorbing particles can exhibit particularly high infrared absorbing characteristics.
Furthermore, this is because if the content per unit projected area is 10.0g/m 2 Hereinafter, the visible light transmittance of the infrared absorbing transparent substrate can be sufficiently maintained.
In order to further impart an ultraviolet absorbing function to the infrared absorbing film and the infrared absorbing glass which are the infrared absorbing transparent substrate of the present embodiment, at least 1 or more of particles of inorganic titanium oxide, zinc oxide, cerium oxide, etc., organic benzophenone, benzotriazole, etc. may be added to the coating layer, etc.
7. Physical properties
The infrared absorbing particle dispersion, the infrared absorbing interlayer transparent substrate, and the infrared absorbing transparent substrate (hereinafter referred to as "infrared absorbing particle dispersion or the like") are described, and the optical characteristics of the infrared absorbing particle dispersion or the like can be selected according to the application or the like, and are not particularly limited.
The transmittance of light having a wavelength of 850nm, such as an infrared absorbing particle dispersion, is preferably 30% or more, more preferably 35% or more. This is because the transmittance of the signals of the mobile phone and various sensors can be improved by setting the light transmittance at 850nm to 30% or more.
The visible light transmittance of the infrared absorbing particle dispersion liquid or the like is preferably 70% or more. This is because the visible light transmittance is 70% or more, and thus it is shown that the transparency to visible light is excellent, and even when used for a window glass of a passenger car, the visibility can be sufficiently improved.
The solar transmittance of the infrared absorbing particle dispersion or the like is preferably 65% or less, more preferably 60% or less. This is because the solar transmittance is 65% or less, so that the invasion of infrared rays into a room or the like can be sufficiently suppressed.
Further, the infrared absorbing particle dispersion or the like preferably has a light transmittance of 25% or less at a wavelength of 1550nm from the viewpoint of effectively suppressing a hot and spicy feeling.
The haze value of the infrared absorbing particle dispersion or the like is preferably 2% or less, more preferably 1% or less. By setting the haze value to 2% or less, blurring is suppressed, and visibility for use in window glass and the like can be improved.
The infrared absorbing particles, the infrared absorbing particle dispersion, the infrared absorbing interlayer transparent substrate, and the infrared absorbing transparent substrate according to the present embodiment can be used for various applications, and the application is not particularly limited. For example, the present invention can be used in a wide range of fields where a single-plate glass, laminated glass, plastic, fiber, and other infrared absorbing functions are required, such as those used for windows of vehicles, buildings, offices, general houses, etc., telephone boxes, display windows, illumination lamps, transparent housings, and the like.
Examples
Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to the following examples.
First, the method for evaluating the samples in the following examples and comparative examples will be described.
(1) Chemical analysis
The chemical analysis of the composite tungsten oxide particles contained in the obtained infrared absorbing particles was performed by atomic Absorption Analysis (AAS) for Cs and ICP emission spectrometry (ICP-OES) for W. Oxygen was analyzed by melting a sample in He gas by a light element analyzer (type manufactured by LECO Co., ltd.: ON-836) and quantifying CO gas generated by a reaction with carbon in an analysis crucible by an IR absorption spectroscopy method.
(2) Crystal structure, lattice constant
The crystal structure and lattice constant of the composite tungsten oxide particles contained in the infrared absorbing particles obtained in the examples and comparative examples below were measured and calculated.
First, the X-ray diffraction pattern of the infrared absorbing particles was measured by a powder X-ray diffraction method (θ—2θ method) using a powder X-ray diffraction apparatus (X' Pert-PRO/MPD manufactured by spectros corporation, PANalytical). The crystal structure of the composite tungsten oxide particles contained in the particles is specified from the obtained X-ray diffraction pattern, and the lattice constant is further calculated by Rietveld analysis. In addition, rietveld analysis uses an external standard method. The Rietveld analysis of the X-ray diffraction pattern of the Si standard powder (NIST 640 c) measured at the same time was first performed, and the zero offset value and the half-value width parameter obtained at this time were set as device parameters, and the Rietveld analysis of the target composite tungsten oxide particles was refined.
(3) Spectral transmittance and color system of infrared absorbing particle dispersion
In the following examples and comparative examples, the transmittance of the infrared absorbing particle dispersion was measured by holding the dispersion in a spectro-luminance meter unit (model: S10-SQ-1, manufactured by GL Sciences Co., ltd., material: synthetic quartz, optical path length: 1 mm) and using a spectro-luminance meter U-4100 manufactured by Hitachi Corp.
In this measurement, the transmittance of a liquid medium (methyl isobutyl ketone or the like, hereinafter abbreviated as mibk) of the dispersion was measured in a state of being filled with the above units, and a baseline for the transmittance measurement was obtained. As a result, the spectral transmittance and the visible light transmittance described below are calculated by excluding contributions due to light reflection from the surface of the spectroluminance meter unit and light absorption by the liquid medium, and light absorption by only the infrared absorbing particles is calculated.
The visible light transmittance and solar light transmittance are measured at 5nm intervals in the range of 200nm to 2600nm, and calculated in the range of 300nm to 2100nm based on JIS A5759 (2016).
Furthermore, L based on JIS Z8701 (1999) is used as the color system ＊ a ＊ b ＊ Color system (D65 light source/10 degree field of view), measurement of L ＊ 、a ＊ 、b ＊ Is a value of (2).
(4) Infrared absorbing transparent substrate and infrared absorbing interlayer transparent substrate, and spectral transmittance and color system thereof
The transmittance of the infrared absorbing transparent substrate and the transmittance of the infrared absorbing sandwich transparent substrate were also measured using a spectro-luminance meter U-4100 manufactured by Hitachi Co., ltd. The solar transmittance and the visible light transmittance were measured and calculated under the same conditions as those in the case of the evaluation before and after the heat resistance test and the like. For the infrared absorption interlayer transparent substrate, the light transmittance at a wavelength of 850nm was measured.
Furthermore, L based on JIS Z8701 (1999) is used as the color system ＊ a ＊ b ＊ Color system (D65 light source/10 degree field of view), measurement of L ＊ 、a ＊ 、b ＊ Is a value of (2).
Further, the infrared absorption transparent substrates before and after the heat resistance test and the wet heat resistance test described later were measured for transmission spectra at 5nm intervals in the range of 200nm to 2600nm, and the visible light transmittance and solar light transmittance were calculated in the range of 300nm to 2100nm based on JIS a 5759 (2016). Heat resistance test and wet heat resistance test for each test, test pieces cut out from the infrared absorbing transparent substrates produced in each example and comparative example were provided.
In addition, the heat resistance test and the wet heat resistance test were performed on the infrared absorbing interlayer transparent substrate in the same manner, and solar transmittance before and after the heat resistance test and the wet heat resistance test was calculated. For the infrared absorbing interlayer transparent substrates, samples subjected to the spectral transmittance, the heat resistance test, and the wet heat resistance test were prepared in each of examples and comparative examples, and each evaluation was performed.
(5) Evaluation of Heat resistance
The infrared absorbing transparent substrate was kept in the atmosphere at 120 ℃ for 125 hours, and the change in visible light transmittance and solar light transmittance before and after the exposure to the atmosphere was evaluated. The heat resistance was judged to be good when the amount of change in solar transmittance before and after exposure was 1.0% or less, and the heat resistance was judged to be insufficient when the amount of change exceeded 1.0%.
The heat resistance of the infrared absorbing interlayer transparent substrate was evaluated under the same conditions.
(6) Evaluation of moist Heat resistance
The infrared absorbing transparent substrate was kept at 85 ℃ for 94 hours in an atmosphere having a humidity of 95%, and the change in visible light transmittance and solar light transmittance before and after exposure to the atmosphere was evaluated. The case where the amount of change in solar transmittance before and after exposure in the infrared absorbing transparent substrate was less than 2.0% was judged to be good in wet heat resistance, and the case where the amount of change was 2.0% or more was judged to be insufficient in wet heat resistance.
The infrared absorbing sandwich transparent substrate was evaluated for wet heat resistance under the same conditions.
The following describes the conditions for producing samples of examples and comparative examples.
Example 1
(1) Manufacture of infrared absorbing particles
Tungstic acid (H) 2 WO 4 ) And cesium carbonate (Cs) 2 CO 3 ) The powders of (a) were weighed in a ratio of Cs/W (molar ratio) =0.29/1.00, and then thoroughly mixed by a kneader to prepare a mixed powder (mixing step).
The mixed powder is prepared by mixing N 2 The gas was 3% by volume H of the carrier gas 2 The reduction treatment was performed at 570℃for 1 hour under the supply of gas (heat treatment step 2).
Next, after N is set 2 Firing at 820 ℃ with 1% by volume compressed air supply with gas as carrier gas5 hours (heat treatment step 1, step 1), further, in N 2 Firing at 820℃for 0.5 hours under a gas atmosphere (heat treatment step 1, step 2).
By the above operation, cesium tungsten alloy (bronze) having hexagonal crystals, i.e., infrared absorbing particles formed of particles of cesium tungsten oxide (hereinafter simply referred to as "powder A1") was obtained.
As a result of the chemical analysis of powder A1, cs/W (molar ratio) =0.29/1. The composition ratios of the other components are shown in the columns of the chemical analysis composition ratios in Table 1. The crystal structure and lattice constant of cesium tungsten oxide particles as composite tungsten oxide particles are shown in table 1.
(2) Infrared absorbing particle dispersion
23.0 mass% of powder A1, 18.4 mass% of an acrylic polymer dispersant having an amine-containing group as a functional group (an acrylic dispersant having an amine value of 48mgKOH/g and a decomposition temperature of 250 ℃ C.) and 58.6 mass% of MIBK as a liquid medium were weighed. They were packed with ZrO 0.3mm 2 The beads were subjected to pulverization and dispersion treatment for 4 hours in a paint shaker to obtain an infrared absorbing particle dispersion (hereinafter referred to simply as "dispersion B1").
The obtained dispersion B1 was diluted with MIBK so that the visible light transmittance became 80%, and was put into a unit for a spectroluminance meter, and the spectral light transmittance was measured. The concentration of the infrared absorbing particles at this time is shown in table 2 as the concentration of the infrared absorbing particles. The color system was measured from a transmission spectrum obtained by measuring the dilution ratio adjusted so that the visible light transmittance became 80%. Table 2 shows the solar transmittance and the evaluation results of the above-mentioned color system.
(3) Infrared absorbing transparent substrate
An infrared absorbing glass and an infrared absorbing film were produced and evaluated by the following steps. The infrared absorbing glass and the infrared absorbing film are examples of an infrared absorbing transparent substrate, and the coating layer as the infrared absorbing layer (infrared absorbing particle layer) is an infrared absorbing particle dispersion.
(3-1) production of Infrared absorbing glass
100% by mass of the obtained dispersion B1 was mixed with 50% by mass of Aronix UV-3701 (hereinafter referred to as UV-3701) which was an ultraviolet curable resin for hard coat layer, and an infrared absorbing particle coating liquid (hereinafter referred to as "coating liquid C1") was prepared. The coating liquid C1 was applied on a blue glass plate (HPE-50, manufactured by Di) having a thickness of 3mm using a bar coater (No. 16) to form a coating film. In other examples and comparative examples, the same glass was used for the production of the infrared absorbing glass.
The glass provided with the coating film was dried at 70 ℃ for 60 seconds, and the solvent as a liquid medium was evaporated and then cured by a high-pressure mercury lamp. Thus, an infrared absorbing glass having a coating layer containing infrared absorbing particles on one surface of a glass substrate was produced.
(3-2) production of Infrared absorbing film
Further, the coating liquid C1 was applied on a PET film substrate having a thickness of 50. Mu.m, using a bar coater (No. 8), to form a coating film. In other examples and comparative examples, the same PET film was used for the production of the infrared absorbing film.
The PET film provided with the coating film was dried at 70 ℃ for 60 seconds, and the solvent as a liquid medium was evaporated and then cured by a high-pressure mercury lamp. Thus, an infrared absorbing film having a coating layer containing infrared absorbing particles was formed on one surface of the PET film base material.
The obtained infrared absorbing transparent substrate was evaluated for optical characteristics. The evaluation results are shown in table 3. In table 3, the evaluation results of the infrared absorbing glass were obtained when the type of the substrate was glass, and the evaluation results of the infrared absorbing film were obtained when the type of the substrate was PET.
(3-3) evaluation of Heat resistance and moist Heat resistance
The heat resistance of the infrared absorbing glass and the moist heat resistance of the infrared absorbing film according to example 1 were evaluated.
(3-3-1) evaluation of Heat resistance
The visible light transmittance and solar light transmittance before and after exposure in the infrared absorbing glass according to example 1 were evaluated.
The evaluation results are shown in table 4.
(3-3-2) evaluation of moist Heat resistance
The infrared absorbing film of example 1 was evaluated for visible light transmittance and solar transmittance before and after exposure.
The evaluation results are shown in table 5.
(4) Transparent substrate with infrared absorption interlayer
Further, to the dispersion B1 which is the infrared absorbing particle dispersion liquid according to example 1, a dispersant a was further added, and the mass ratio of the dispersant a to the infrared absorbing particles was adjusted so that [ dispersant a/infrared absorbing particles ] =3. Next, methyl isobutyl ketone was removed from the adjusted dispersion using a spray dryer, and an infrared absorbing particle dispersion powder (hereinafter sometimes referred to as "dispersion powder") was obtained.
A predetermined amount of the dispersion powder was added to a polycarbonate resin as a thermoplastic resin so that the visible light transmittance of the produced infrared absorbing sheet (1.0 mm thickness) became 80%, to prepare a composition for producing an infrared absorbing sheet.
The composition for producing an infrared absorbing sheet was kneaded at 280℃using a twin-screw extruder, extruded from a T die, and a sheet having a thickness of 1.0mm was produced by a calender roll method, whereby an infrared absorbing sheet according to example 1 was obtained. The infrared absorbing sheet is an example of an infrared absorbing particle dispersion.
The obtained infrared absorbing sheet was sandwiched between 2 sheets of green glass substrate having a thickness of 100mm X about 2mm, heated to 80℃for temporary bonding, and then heated to 140℃at 14kg/cm 2 Under the conditions of (1) the above-mentioned steps were carried out in an autoclave to prepare an infrared absorbing sandwich transparent substrate.
The obtained infrared absorbing interlayer transparent substrate was evaluated for optical characteristics, heat resistance, and wet heat resistance. The evaluation results are shown in tables 6, 7 and 8.
Example 2
When preparing the infrared absorbing particle dispersion, the pulverizing and dispersing time was set to 10 hours. Except for the above, the same operation as in example 1 was performed to obtain powder A2, dispersion B2, infrared absorbing glass, and infrared absorbing interlayer transparent substrate according to example 2. The evaluation results are shown in tables 1 to 3 and 6.
Example 3
Tungstic acid (H) 2 WO 4 ) And cesium carbonate (Cs) 2 CO 3 ) The powders of (a) were weighed and mixed in a ratio equal to Cs/W (molar ratio) =0.27/1.00 (mixing step).
The mixed powder is prepared by mixing N 2 The gas was 5% by volume H of the carrier gas 2 The mixture was heated under the supply of gas, and the reduction treatment was performed at 570℃for 1 hour (heat treatment step 2).
Next, after N is set 2 The gas was heated under the supply of compressed air of 1% by volume of carrier gas, and burned at 820℃for 0.5 hours (heat treatment step 1, step 1).
Further, at N 2 Firing at 820℃for 0.5 hours under a gas atmosphere (heat treatment step 1, step 2). The pulverizing and dispersing time was set to 8 hours.
The same operations as in example 1 were performed except that the above-described conditions were changed, specifically, the conditions of the mixing step and the heat treatment step in the production of the infrared absorbing particles and the conditions of the pulverization and dispersion time in the preparation of the infrared absorbing particle dispersion, and the powder A3, the dispersion B3, the infrared absorbing glass, the infrared absorbing film, and the infrared absorbing interlayer transparent substrate according to example 3 were produced and evaluated. The evaluation results are shown in tables 1 to 8.
In examples 4 to 15 and comparative examples 1 to 6 described below, some or all of the conditions of the mixing step and the heat treatment step in producing the infrared absorbing particles and the conditions of the pulverization and the dispersion time in preparing the infrared absorbing particle dispersion are changed to those described below.
The X-ray diffraction pattern of the obtained powder A3 was displayedFig. 5. As shown in FIG. 5, powder A3 was identified as hexagonal Cs 0.3 (WO 3 ) (ICDD 01-081-1244) single-phase is an infrared absorbing particle formed of particles of hexagonal cesium tungsten oxide.
Example 4
When preparing infrared absorbing particles, mixing the powder with N 2 The gas was heated under the supply of compressed air at a concentration of 1% by volume of the carrier gas, and burned at a temperature of 820℃for 0.5 hour (heat treatment step 1). Next, after N is set 2 The gas was 5% by volume H of the carrier gas 2 The mixture was heated under the supply of gas and burned at 570℃for 1 hour (heat treatment step 2, step 1). Further, at N 2 Firing at 820℃for 0.5 hours under a gas atmosphere (heat treatment step 2, step 2).
In addition, when preparing the infrared absorbing particle dispersion, the pulverizing and dispersing time was set to 8 hours.
Except for the above, the same procedure as in example 1 was carried out to produce the powder A4, the dispersion B4, the infrared absorbing glass and the infrared absorbing interlayer transparent substrate according to example 4, and evaluation was carried out.
As shown in table 1, the powder A4 is an infrared absorbing particle formed of particles of a composite tungsten oxide having a hexagonal crystal structure.
The evaluation results are shown in tables 1 to 3 and 6.
Example 5
Tungstic acid (H) 2 WO 4 ) And cesium carbonate (Cs) 2 CO 3 ) The powders of (a) were weighed and mixed in a ratio of Cs/W (molar ratio) =0.33/1.00 (mixing step).
The mixed powder is prepared by mixing N 2 The gas was 5% by volume H of the carrier gas 2 The mixture was heated under the supply of gas, and the reduction treatment was performed at 570℃for 1 hour (heat treatment step 2).
Next, after N is set 2 Heating under the supply of compressed air with gas as carrier gas at 820 deg.C for 0.5 hr (heat treatment step 1, step 1), and further heating under N 2 Firing at 820℃for 0.5 hours under a gas atmosphere (heat treatment step 1, step 2).
When preparing the infrared absorbing particle dispersion, the pulverizing and dispersing time was set to 5 hours.
Except for the above, the same procedure as in example 1 was carried out to produce the powder A5, the dispersion B5 and the infrared absorbing interlayer transparent substrate according to example 5, and evaluation was carried out.
As shown in table 1, the powder A5 is an infrared absorbing particle formed of particles of a composite tungsten oxide having a hexagonal crystal structure.
The evaluation results are shown in tables 1, 2 and 6.
Example 6
Tungstic acid (H) 2 WO 4 ) And cesium carbonate (Cs) 2 CO 3 ) The powders of (a) were weighed and mixed in a ratio of Cs/W (molar ratio) =0.32/1.00 (mixing step).
The mixed powder is prepared by mixing N 2 The gas was 5% by volume H of the carrier gas 2 The mixture was heated under the supply of gas, and the reduction treatment was performed at 570℃for 1 hour (heat treatment step 2).
Next, after N is set 2 Heating under the supply of compressed air with gas as carrier gas at 820 deg.C for 0.5 hr (heat treatment step 1, step 1), and further heating under N 2 The firing was performed at a temperature of 820℃for 0.5 hours in a gas atmosphere (heat treatment step 1, step 2).
When preparing the infrared absorbing particle dispersion, the pulverizing and dispersing time was set to 5 hours.
Except for the above, the same procedure as in example 1 was carried out to produce the powder A6, the dispersion B6 and the infrared absorbing interlayer transparent substrate according to example 6, and evaluation was carried out.
As shown in table 1, the powder A6 is an infrared absorbing particle formed of particles of a composite tungsten oxide having a hexagonal crystal structure.
The evaluation results are shown in tables 1, 2 and 6.
Example 7
Tungstic acid (H) 2 WO 4 ) And cesium carbonate (Cs) 2 CO 3 ) The powders of (a) were weighed and mixed in a ratio of Cs/W (molar ratio) =0.31/1.00 (mixing step).
The mixed powder is prepared by mixing N 2 The gas was 5% by volume H of the carrier gas 2 The mixture was heated under the supply of gas, and the reduction treatment was performed at 570℃for 1 hour (heat treatment step 2).
Next, after N is set 2 Heating under the supply of compressed air with gas as carrier gas at 820 deg.C for 0.5 hr (heat treatment step 1, step 1), and further heating under N 2 Firing at 820℃for 0.5 hours under a gas atmosphere (heat treatment step 1, step 2).
When preparing the infrared absorbing particle dispersion, the pulverizing and dispersing time was set to 5 hours.
Except for the above, the same procedure as in example 1 was carried out to produce the powder A7, the dispersion B7 and the infrared absorbing interlayer transparent substrate according to example 7, and evaluation was carried out.
As shown in table 1, the powder A7 is an infrared absorbing particle formed of particles of a composite tungsten oxide having a hexagonal crystal structure.
The evaluation results are shown in tables 1, 2 and 6.
Example 8
Tungstic acid (H) 2 WO 4 ) And cesium carbonate (Cs) 2 CO 3 ) The powders of (a) were weighed and mixed in a ratio of Cs/W (molar ratio) =0.30/1.00 (mixing step).
The mixed powder is prepared by mixing N 2 The gas was 5% by volume H of the carrier gas 2 The mixture was heated under the supply of gas, and the reduction treatment was performed at 570℃for 1 hour (heat treatment step 2).
Next, after N is set 2 Heating under the supply of compressed air with gas as carrier gas at 820 deg.C for 0.5 hr (heat treatment step 1, step 1), and further heating under N 2 Under the gas atmosphere, at 820 DEG CIs fired for 0.5 hour (heat treatment step 1, step 2).
When preparing the infrared absorbing particle dispersion, the pulverizing and dispersing time was set to 5 hours.
Except for the above, the same procedure as in example 1 was carried out to produce the powder A8, the dispersion B8 and the infrared absorbing interlayer transparent substrate according to example 8, and evaluation was carried out.
As shown in table 1, the powder A8 is an infrared absorbing particle formed of particles of a composite tungsten oxide having a hexagonal crystal structure.
The evaluation results are shown in tables 1, 2 and 6.
Example 9
Tungstic acid (H) 2 WO 4 ) And cesium carbonate (Cs) 2 CO 3 ) The powders of (a) were weighed and mixed in a ratio of Cs/W (molar ratio) =0.29/1.00 (mixing step).
The mixed powder is prepared by mixing N 2 The gas was 5% by volume H of the carrier gas 2 The mixture was heated under the supply of gas, and the reduction treatment was performed at 570℃for 1 hour (heat treatment step 2).
Next, after N is set 2 Heating under the supply of compressed air with gas as carrier gas at 820 deg.C for 0.5 hr (heat treatment step 1, step 1), and further heating under N 2 The firing was performed at a temperature of 820℃for 0.5 hours in a gas atmosphere (heat treatment step 1, step 2).
When preparing the infrared absorbing particle dispersion, the pulverizing and dispersing time was set to 5 hours.
Except for the above, the same procedure as in example 1 was carried out to produce powder A9, dispersion B9 and infrared absorbing sandwich transparent substrate according to example 9, and evaluation was carried out. The mixing step was performed under the same conditions as in example 1, and was described for the purpose of confirmation.
As shown in table 1, the powder A9 is an infrared absorbing particle formed of particles of a composite tungsten oxide having a hexagonal crystal structure.
The evaluation results are shown in tables 1, 2 and 6.
Example 10
Tungstic acid (H) 2 WO 4 ) And cesium carbonate (Cs) 2 CO 3 ) The powders of (a) were weighed and mixed in a ratio of Cs/W (molar ratio) =0.28/1.00 (mixing step).
The mixed powder is prepared by mixing N 2 The gas was 5% by volume H of the carrier gas 2 The mixture was heated under the supply of gas, and the reduction treatment was performed at 570℃for 1 hour (heat treatment step 2).
Next, after N is set 2 Heating under the supply of compressed air with gas as carrier gas at 820 deg.C for 0.5 hr (heat treatment step 1, step 1), and further heating under N 2 Firing at 820℃for 0.5 hours under a gas atmosphere (heat treatment step 1, step 2).
When preparing the infrared absorbing particle dispersion, the pulverizing and dispersing time was set to 5 hours.
Except for the above, the same procedure as in example 1 was carried out to produce the powder a10, the dispersion B10 and the infrared absorbing interlayer transparent substrate according to example 10, and evaluation was carried out.
As shown in table 1, the powder a10 is an infrared absorbing particle formed of particles of a composite tungsten oxide having a hexagonal crystal structure.
The evaluation results are shown in tables 1, 2 and 6.
Example 11
Tungstic acid (H) 2 WO 4 ) And cesium carbonate (Cs) 2 CO 3 ) The powders of (a) were weighed and mixed in a ratio of Cs/W (molar ratio) =0.26/1.00 (mixing step).
The mixed powder is prepared by mixing N 2 The gas was 5% by volume H of the carrier gas 2 The mixture was heated under the supply of gas, and the reduction treatment was performed at 570℃for 1 hour (heat treatment step 2).
Next, after N is set 2 The gas was heated under the supply of compressed air of 1% by volume of carrier gas, and the mixture was burned at 820℃for 0.5 hour (heat treatment step 1, Step 1), further, in N 2 Firing at 820℃for 0.5 hours under a gas atmosphere (heat treatment step 1, step 2).
When preparing the infrared absorbing particle dispersion, the pulverizing and dispersing time was set to 5 hours.
Except for the above, the same procedure as in example 1 was carried out to produce the powder a11, the dispersion B11 and the infrared absorbing interlayer transparent substrate according to example 11, and evaluation was carried out.
As shown in table 1, the powder a11 is an infrared absorbing particle formed of particles of a composite tungsten oxide having a hexagonal crystal structure.
The evaluation results are shown in tables 1, 2 and 6.
Example 12
Tungstic acid (H) 2 WO 4 ) And cesium carbonate (Cs) 2 CO 3 ) The powders of (a) were weighed and mixed in a ratio of Cs/W (molar ratio) =0.27/1 (mixing step).
The mixed powder is prepared by mixing N 2 The gas was 5% by volume H of the carrier gas 2 The mixture was heated under the supply of gas, and the reduction treatment was performed at 570℃for 1 hour (heat treatment step 2).
Next, after N is set 2 The gas was heated under the supply of compressed air of 1% by volume of carrier gas, and burned at 820℃for 1 hour (heat treatment step 1, step 1).
Further, at N 2 Firing at 820℃for 0.5 hours under a gas atmosphere (heat treatment step 1, step 2).
When preparing the infrared absorbing particle dispersion, the pulverizing and dispersing time was set to 8 hours.
Except for the above, the same operations as in example 1 were performed to produce the powder a12 and the dispersion B12 according to example 12, and evaluation was performed.
As shown in table 1, the powder a12 is an infrared absorbing particle formed of particles of a composite tungsten oxide having a hexagonal crystal structure.
The evaluation results are shown in tables 1 and 2.
Example 13
Tungstic acid (H) 2 WO 4 ) And cesium carbonate (Cs) 2 CO 3 ) The powders of (a) were weighed and mixed in a ratio of Cs/W (molar ratio) =0.27/1 (mixing step).
The mixed powder is prepared by mixing N 2 The gas was 5% by volume H of the carrier gas 2 The mixture was heated under the supply of gas, and the reduction treatment was performed at 570℃for 1 hour (heat treatment step 2).
Next, after N is set 2 The gas was heated under the supply of compressed air at a concentration of 1% by volume of the carrier gas, and burned at a temperature of 820℃for 1.5 hours (heat treatment step 1, step 1).
Further, at N 2 Firing at 820℃for 0.5 hours under a gas atmosphere (heat treatment step 1, step 2).
When preparing the infrared absorbing particle dispersion, the pulverizing and dispersing time was set to 8 hours.
Except for the above, the same operations as in example 1 were performed to produce the powder a13 and the dispersion B13 according to example 13, and evaluation was performed.
As shown in table 1, the powder a13 is an infrared absorbing particle formed of particles of a composite tungsten oxide having a hexagonal crystal structure.
The evaluation results are shown in tables 1 and 2.
Example 14
Tungstic acid (H) 2 WO 4 ) And cesium carbonate (Cs) 2 CO 3 ) The powders of (a) were weighed and mixed in a ratio of Cs/W (molar ratio) =0.27/1 (mixing step).
The mixed powder is prepared by mixing N 2 The gas was 5% by volume H of the carrier gas 2 The mixture was heated under the supply of gas, and the reduction treatment was performed at 570℃for 1 hour (heat treatment step 2).
Next, after N is set 2 The gas was heated under the supply of compressed air of 1% by volume of carrier gas, and burned at 820℃for 45 minutes (heat treatment step 1, step 1).
Further, at N 2 Firing at 820℃for 15 minutes in a gas atmosphere (heat treatment step 1, step 2).
When preparing the infrared absorbing particle dispersion, the pulverizing and dispersing time was set to 8 hours.
Except for the above, the same operations as in example 1 were performed to produce the powder a14 and the dispersion B14 according to example 14, and evaluation was performed.
As shown in table 1, the powder a14 is an infrared absorbing particle formed of particles of a composite tungsten oxide having a hexagonal crystal structure.
The evaluation results are shown in tables 1 and 2.
Example 15
Tungstic acid (H) 2 WO 4 ) And cesium carbonate (Cs) 2 CO 3 ) The powders of (a) were weighed and mixed in a ratio of Cs/W (molar ratio) =0.27/1 (mixing step).
The mixed powder is prepared by mixing N 2 The gas was 5% by volume H of the carrier gas 2 The mixture was heated under the supply of gas, and the reduction treatment was performed at 570℃for 1 hour (heat treatment step 2).
Next, after N is set 2 The gas was heated under the supply of compressed air of 1% by volume of carrier gas, and burned at 820℃for 2 hours (heat treatment step 1, step 1).
When preparing the infrared absorbing particle dispersion, the pulverizing and dispersing time was set to 8 hours.
Except for the above, the same operations as in example 1 were performed to produce the powder a15 and the dispersion B15 according to example 15, and evaluation was performed.
As shown in table 1, the powder a15 is an infrared absorbing particle formed of particles of a composite tungsten oxide having a hexagonal crystal structure.
The evaluation results are shown in tables 1 and 2.
Example 16
Using the dispersion B3 of example 3, a composition was prepared which was composed of 0.15 mass% of cesium tungsten oxide particles as infrared absorbing particles, 73.0 mass% of polyvinyl butyral resin (PVB), and 26.85 mass% of triethylene glycol di-2-ethylhexanoate (3 GO) as a plasticizer. Further, the composition was kneaded by a twin-screw extruder, extruded through a T-die, and a sheet having a thickness of 0.16mm was produced by a calender roll method, whereby an infrared absorbing sheet according to example 16 was obtained.
An infrared absorbing interlayer transparent substrate according to example 16 was obtained in the same manner as in example 1, except that the obtained infrared absorbing sheet was sandwiched between 2 sheets of glass substrates having a thickness of 100mm×100mm×3 mm.
The evaluation results of the obtained infrared absorbing interlayer transparent substrate are shown in table 9.
Comparative example 1
Tungstic acid (H) 2 WO 4 ) And cesium carbonate (Cs) 2 CO 3 ) The powders of (a) were weighed and mixed in a ratio of Cs/W (molar ratio) =0.33/1.00 (mixing step).
The mixed powder obtained in the mixing step is mixed in a state of N 2 The gas was 5% by volume H of the carrier gas 2 The mixture was heated under the supply of gas, and the reduction treatment was performed at 570℃for 1 hour.
Next, at N 2 Firing at 820℃for 1 hour under a gas atmosphere. In addition, the step 1 corresponding to the 1 st heat treatment step in example 1 was not performed.
When preparing the infrared absorbing particle dispersion, the pulverizing and dispersing time was set to 10 hours.
Except for the above, the same operation as in example 1 was performed to obtain powder a21, dispersion B21, infrared absorbing glass, infrared absorbing film, and infrared absorbing interlayer transparent substrate according to comparative example 1. Further, XRD pattern measurement was performed on the obtained powder a 21. The evaluation results are shown in fig. 6, tables 1 to 8.
Comparative example 2
When the infrared absorbing particles are prepared, N is added to the mixed powder 2 The gas was heated with a compressed air supply of 1% by volume of carrier gas and burned at a temperature of 820 c for 0.5 hours. In addition, no implementation is madeThe 2 nd heat treatment step in example 1 corresponds to the 2 nd step of the 1 st heat treatment step.
When preparing the infrared absorbing particle dispersion, the pulverizing and dispersing time was set to 8 hours.
The same procedure as in example 1 was carried out except for the above, to obtain powder a22, dispersion B22 and infrared absorbing glass according to comparative example 2. Further, XRD pattern measurement was performed on the obtained powder a 22. The evaluation results are shown in fig. 6, tables 1 to 3.
Comparative example 3
Tungstic acid (H) 2 WO 4 ) And cesium carbonate (Cs) 2 CO 3 ) The powders of (a) were weighed and mixed in a ratio of Cs/W (molar ratio) =0.27/1.00. The same procedure as in comparative example 1 was performed except for the above, and powder a23 and dispersion B23 according to comparative example 3 were obtained. The evaluation results are shown in tables 1 and 2.
Comparative example 4
Tungstic acid (H) 2 WO 4 ) And cesium carbonate (Cs) 2 CO 3 ) The powders of (a) were weighed and mixed in a ratio of Cs/W (molar ratio) =0.26/1.00. The same procedure as in comparative example 1 was performed except for the above, and powder a24 and dispersion B24 according to comparative example 4 were obtained. The evaluation results are shown in tables 1 and 2.
Comparative example 5
Tungstic acid (H) 2 WO 4 ) And cesium carbonate (Cs) 2 CO 3 ) The powders of (a) were weighed and mixed in a ratio of Cs/W (molar ratio) =0.25/1.00. The same procedure as in comparative example 1 was performed except for the above, and powder a25 and dispersion B25 according to comparative example 5 were obtained. The evaluation results are shown in tables 1 and 2.
Comparative example 6
Tungstic acid (H) 2 WO 4 ) And cesium carbonate (Cs) 2 CO 3 ) The powders of (a) were weighed and mixed in a ratio corresponding to Cs/W (molar ratio) =0.20/1.00. The same procedure as in comparative example 1 was performed except for the above, and powder a26 and dispersion B26 according to comparative example 6 were obtained.The evaluation results are shown in tables 1 and 2.
Comparative example 7
An infrared absorbing interlayer transparent substrate according to comparative example 7 was obtained in the same manner as in example 16, except that the dispersion B21 according to comparative example 1 was used.
The evaluation results of the obtained infrared absorbing interlayer transparent substrate are shown in table 9.
Reference example 1
Instead of the powder A1, a tin-doped indium oxide powder manufactured by NYACOL was used to prepare a powder a30.
A dispersion B30 according to reference example 1 was obtained in the same manner as in example 1 except that the powder a30 was used. The evaluation results are shown in tables 1 and 2.
TABLE 1
TABLE 2
TABLE 3
TABLE 4
TABLE 5
TABLE 6
TABLE 7
TABLE 8
TABLE 9
Induction
From the evaluation results, it was confirmed that the infrared absorbing particles according to examples 1 to 15 had a hexagonal crystal structure and were particles of a composite tungsten oxide having a predetermined composition.
The concentration of the infrared absorbing particles is 0.05 to 0.20 mass% based on 80% of the visible light transmittance in the infrared absorbing particle dispersion. Further, the infrared absorbing particle dispersions b of examples 1 to 15 ＊ Since the infrared absorbing particles are larger than 0, it can be confirmed that the infrared absorbing particles contained in the infrared absorbing particle dispersion liquid are bluish. Further, it was confirmed that the infrared absorbing interlayer transparent substrates of examples 1 to 3 and 16 had a light transmittance of at least 30% at 850nm, which was higher than that of comparative examples 1 and 7. That is, it can be confirmed that the transmittance of signals of the mobile phone and the various sensors is high, and the detection accuracy of the various sensors is improved.
For the infrared absorbing transparent substrate subjected to the evaluation of the color system, it was confirmed that L ＊ a ＊ b ＊ B in the color system ＊ > 0. Further, it was confirmed that the heat resistance of the infrared absorbing transparent substrates of example 1 and example 3, whose weather resistance was evaluated, was not more than Δ days The transmittance of sunlight was 1.0% or less, the heat and humidity resistance was less than 2.0% and the weather resistance was superior to that of the infrared transparent substrate of comparative example 1.
The same trend was also exhibited for the weather resistance evaluation for the infrared absorbing transparent substrates of other examples which did not show the evaluation results.
That is, in examples 1 to 15, it was confirmed that light blue infrared absorbing particles excellent in weather resistance and infrared absorbing properties were obtained.
On the other hand, the infrared absorbing particles according to comparative examples 1, 3 to 6 had a hexagonal crystal structure, but it was calculated that the color tone at the time of light absorption by only the infrared absorbing particles in the infrared absorbing particle dispersion was L ＊ a ＊ b ＊ B in the color system ＊ And < 0. The infrared absorbing particles of comparative example 2 were a mixture of materials having a crystal structure other than hexagonal, and as apparent from the evaluation results of the infrared absorbing particle dispersion shown in table 2, it can be said that the solar transmittance was high and the infrared absorbing property was poor.
The present application claims that the entire contents of Japanese patent application Nos. 2021-060997 and 2021-140530 are incorporated into this international application based on the priorities of Japanese patent application Nos. 2021-060997 of 31-day Japanese patent application of 2021 and of Japanese patent application No. 2021-140530 of 8-day Japanese patent application of 2021.
Description of symbols
10. Infrared absorbing particle dispersion
11. 21 infrared absorbing particles
12. Liquid medium
20. 32 infrared absorbing particle dispersion
22. Solid medium
30. Transparent substrate with infrared absorption interlayer
311. 312, 41 transparent substrate
40. Infrared absorbing transparent substrate
41A side
42. Infrared absorbing layer
Claims (18)
1. An infrared absorbing particle comprising composite tungsten oxide particles,
the composite tungsten oxide particles have a hexagonal crystal structure and are represented by the general formula M x W y O z The particles of the composite tungsten oxide are described, wherein M is 1 or more element selected from Cs, rb, K, tl, ba, ca, sr, fe, W is tungsten, O is oxygen, and 0.25.ltoreq.x/y.ltoreq. 0.39,2.70.ltoreq.z/y.ltoreq.2.90.
2. The infrared absorbing particle according to claim 1, wherein the surface is coated with a compound containing 1 or more atoms selected from Si, ti, zr, al.
3. An infrared absorbing particle dispersion comprising:
a liquid medium, and
the infrared absorbing particles according to claim 1 or 2 disposed in the liquid medium.
4. The infrared absorbing particle dispersion according to claim 3,
The infrared absorbing particles have an average dispersion particle diameter of 1nm to 800 nm.
5. The infrared absorbing particle dispersion according to claim 3 or 4,
the liquid medium is 1 selected from the group of liquid medium materials consisting of water, organic solvents, oils and fats, liquid resins and liquid plasticizers for plastics, or a mixture of 2 or more selected from the group of liquid medium materials.
6. The infrared absorbing particle dispersion according to any one of claim 3 to 5,
the infrared absorbing particle dispersion contains a dispersant.
7. The infrared absorbing particle dispersion according to any one of claims 3 to 6,
comprising 0.001 to 80.0 mass% of the infrared absorbing particles.
8. The infrared absorbing particle dispersion according to any one of claims 3 to 7,
calculating the color tone at the time of light absorption by the infrared absorbing particles alone to be L ＊ a ＊ b ＊ B in the color system ＊ ＞0。
9. The infrared absorbing particle dispersion according to any one of claim 3 to 8,
when the visible light transmittance is made 80%,
the concentration of the infrared absorbing particles is 0.05 to 0.20 mass%.
10. An infrared absorbing particle dispersion having:
A solid medium, and
the infrared absorbing particles according to claim 1 or 2 disposed in the solid medium.
11. The infrared absorbing particle dispersion of claim 10,
calculating the color tone at the time of light absorption by the infrared absorbing particles alone to be L ＊ a ＊ b ＊ B in the color system ＊ ＞0。
12. The infrared absorbing particle dispersion according to claim 10 or 11,
the solid medium comprises a thermoplastic resin or a UV curable resin.
13. The infrared absorbing particle dispersion of claim 12,
the thermoplastic resin is 1 resin selected from the group consisting of polyethylene terephthalate resin, polycarbonate resin, acrylic resin, styrene resin, polyamide resin, polyethylene resin, vinyl chloride resin, olefin resin, epoxy resin, polyimide resin, fluorine resin, ethylene-vinyl acetate copolymer, and polyvinyl acetal resin, a mixture of 2 or more resins selected from the group, or a copolymer of 2 or more resins selected from the group.
14. The infrared absorbing particle dispersion according to any one of claims 10 to 13,
which has a sheet shape, a plate shape or a film shape.
15. An infrared absorbing interlayer transparent substrate having:
a plurality of transparent substrates, and
the infrared absorbing particle dispersion of any one of claim 10 to 14,
the infrared absorbing particle dispersion has a laminated structure disposed between a plurality of transparent substrates.
16. The infrared absorbing interlayer transparent substrate of claim 15,
the transmittance of light with the wavelength of 850nm is more than 30%.
17. An infrared absorbing transparent substrate comprising:
a transparent substrate, and
an infrared absorbing layer disposed on at least one surface of the transparent substrate,
the infrared absorbing layer is the infrared absorbing particle dispersion according to any one of claims 10 to 14.
18. The infrared absorbing transparent substrate of claim 17,
the transmittance of light with the wavelength of 850nm is more than 30%.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2021-060997 | 2021-03-31 | ||
| JP2021140530 | 2021-08-30 | ||
| JP2021-140530 | 2021-08-30 | ||
| PCT/JP2022/010625 WO2022209712A1 (en) | 2021-03-31 | 2022-03-10 | Infrared absorbing particles, infrared-absorbing particle dispersion liquid, infrared-absorbing particle dispersion material, infrared-absorbing laminate transparent substrate, and infrared-absorbing transparent substrate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117043299A true CN117043299A (en) | 2023-11-10 |
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ID=88634126
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202280022950.7A Pending CN117043299A (en) | 2021-03-31 | 2022-03-10 | Infrared absorbing particles, infrared absorbing particle dispersion, infrared absorbing interlayer transparent substrate, and infrared absorbing transparent substrate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117043299A (en) |
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2022
- 2022-03-10 CN CN202280022950.7A patent/CN117043299A/en active Pending
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