JP2005231974A - Solar radiation screening material, solar radiation screening composite material, and dispersing liquid used for preparing solar radiation screening material or solar radiation screening composite material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new standard required for a solar radiation screening material to which rhenium trioxide is applied, a solar radiation screening material and a solar radiation screening composite material satisfying the standard, and a dispersing liquid used for preparing the solar radiation screening material or the solar radiation screening composite material. <P>SOLUTION: The solar radiation screening material containing rhenium trioxide (ReO<SB>3</SB>microparticles) has such a transmittance that the maximum value exists in a wavelength range of 380-650 nm and the minimum value exists in a wavelength range of >650 nm and ≤1,700 nm, and has a solar radiation screening characteristic satisfying the equation (1) at 35%≤VLT≤80%:P/B+0.0525×VLT≥5.3 (wherein the maximum value of the transmittance is P; the minimum value is B; and a visible light transmittance is VLT). <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention is a solar shading material such as a single plate glass, laminated glass, and plastics used in window materials for vehicles, buildings, offices, ordinary houses, telephone boxes, show windows, lighting lamps, transparent cases, etc. In particular, the present invention relates to a solar shading body and a solar shading composite having predetermined solar shading characteristics requirements and a dispersion applied to the production of these solar shading bodies or solar shading composites. .

  As a method for removing and reducing a heat component from an external light source such as sunlight or a light bulb, a heat ray reflective glass has been conventionally formed by forming a film made of a material that reflects infrared rays on the glass surface. As the material, metal oxides such as FeOx, CoOx, CrOx, and TiOx, and metal materials such as Ag, Au, Cu, Ni, and Al have been selected.

  By the way, since these materials have the property of reflecting or absorbing visible light at the same time in addition to infrared rays that greatly contribute to the thermal effect, there has been a problem that the visible light transmittance is lowered. In particular, base materials used for building materials, vehicles, telephone boxes, etc. require high transmittance in the visible light region, so that the film thickness is very thin when using materials such as the above metal oxides. Had to do. For this reason, a method of forming a thin film of 10 nm level using a physical film forming method such as spray baking, CVD method, sputtering method or vacuum vapor deposition method is employed.

  However, these film forming methods require a large-scale apparatus and vacuum equipment, and are disadvantageous in productivity and increase in area, and have a drawback that the manufacturing cost of the film becomes high. In addition, if it is attempted to increase the solar shading characteristics with these materials, the reflectance in the visible light region tends to increase at the same time, and there is also a drawback that the appearance is deteriorated by giving a glaring appearance like a mirror. . Furthermore, a film formed of these materials has a relatively low resistance and a high reflection of radio waves. For example, the radio waves of a mobile phone, a TV, a radio, etc. are reflected and cannot be received. There were also drawbacks such as causing radio interference in the area.

In order to improve such a defect, as the physical properties of the film, the reflectance of light in the visible light region is low, the reflectance in the infrared region is high, and the surface resistance of the film is approximately 10 ⁶ Ω / □. The film must be controllable as described above.

  In addition, antimony tin oxide (hereinafter abbreviated as ATO) and indium tin oxide (hereinafter abbreviated as ITO) are known as materials having high visible light transmittance and excellent solar radiation shielding function. Yes.

  And since these materials have a relatively low visible light reflectance, they do not give a glaring appearance. However, since the plasma frequency is in the near infrared region, the reflection / absorption effect is still not sufficient in the near infrared region closer to visible light. Furthermore, since these materials have a low solar radiation shielding power per unit weight, there is a problem that the amount used is increased and the cost is expensive in order to obtain a high shielding function.

Under such a technical background, the present applicant has found rhenium trioxide as a component mainly exhibiting heat ray reflection characteristics, a method for producing the rhenium trioxide fine particles, and a solar radiation shield to which the rhenium trioxide fine particles are applied. The invention regarding a heat ray reflective film | membrane etc. has already been proposed (refer patent document 1 and patent document 2).
Japanese Patent Laid-Open No. 9-142846 JP-A-9-157554

  The present invention is a further improvement of the above-described invention in which rhenium trioxide fine particles mainly exhibiting heat ray reflection / absorption characteristics are applied, and the solar radiation shielding body is in the range of 35% to 80%, which is an interesting range of visible light transmittance. Applied to the manufacture of solar shields and solar shield composites and these solar shields or solar shield composites that provide the new standards required for and that meet this standard (ie, the requirements for solar shield properties) It is to provide a dispersion.

That is, the invention according to claim 1
Assuming a solar shield containing ReO ₃ fine particles,
The transmittance has a maximum value in the wavelength range of 380 nm to 650 nm and has a minimum value in the range of more than 650 nm to 1700 nm, and the maximum value of the transmittance is P, the minimum value is B, and the visible light transmittance When VLT is VLT, it has a solar radiation shielding characteristic satisfying the following formula (1) in 35% ≦ VLT ≦ 80%.

P / B + 0.0525 × VLT ≧ 5.3 (1)
The invention according to claim 2
On the premise of the solar radiation shield according to the invention of claim 1,
It is composed of a transparent substrate made of glass or plastic and a solar shading film containing ReO ₃ fine particles formed thereon,
The invention according to claim 3
On the premise of the solar radiation shield according to the invention of claim 1,
It is characterized by being constituted by a solar shading molded body obtained by molding a molding resin base material in which ReO ₃ fine particles are dispersed into a flat or three-dimensional shape,
The invention according to claim 4
On the premise of the solar radiation shield according to any one of claims 1 to 3,
It has a cubic crystal structure with a crystallite diameter of 150 nm or less and a lattice constant of 3.6911 to 3.7511, a powder color L ^* in the L ^* a ^* b ^* color system of 30 to 50, and a ^* is The above-mentioned ReO ₃ fine particles are composed of rhenium trioxide having −5 to 15 and b ^* of −10 to 5.

Next, the invention according to claim 5 is:
Assuming a solar shading complex,
The solar radiation shielding film according to claim 2 and the glass or plastic transparent base material sandwiching the solar radiation shielding film and another base material, or the solar radiation shielding molded body according to claim 3 and a pair of base materials sandwiching the solar radiation shielding molded body. It is composed of
The invention according to claim 6
Based on the solar radiation shielding complex according to the invention of claim 5,
It has a cubic crystal structure with a crystallite diameter of 150 nm or less and a lattice constant of 3.6911 to 3.7511, a powder color L ^* in the L ^* a ^* b ^* color system of 30 to 50, and a ^* is The above-mentioned ReO ₃ fine particles are composed of rhenium trioxide having −5 to 15 and b ^* of −10 to 5.

The invention according to claim 7
It contains a solvent and rhenium trioxide fine particles dispersed in the solvent, and presupposes a dispersion applied to the production of the solar radiation shielding body according to claim 4 or the solar radiation shielding composite according to claim 6,
The dispersion particle diameter of the rhenium trioxide fine particles dispersed in the solvent is 150 nm or less,
The invention according to claim 8 provides:
Based on the dispersion according to the invention of claim 7,
Indium tin oxide fine particles and / or antimony tin oxide fine particles are added,
The invention according to claim 9 is:
Based on the dispersion according to the invention of claim 7 or 8,
An inorganic binder or a resin binder is included.

According to the solar radiation shielding body or the solar radiation shielding complex according to claim 1,
The transmittance has a maximum value in the wavelength range of 380 nm to 650 nm and has a minimum value in the range of more than 650 nm to 1700 nm, and the maximum value of the transmittance is P, the minimum value is B, and the visible light transmittance When VLT is VLT, it has solar radiation shielding characteristics satisfying the following formula (1) in 35% ≦ VLT ≦ 80%, so that it effectively transmits visible light and effectively reflects and absorbs other heat rays. Has an effect.

P / B + 0.0525 × VLT ≧ 5.3 (1)
Moreover, according to the dispersion liquid of Claims 7-9,
It has a cubic crystal structure with a crystallite diameter of 150 nm or less and a lattice constant of 3.6911 to 3.7511, a powder color L ^* in the L ^* a ^* b ^* color system of 30 to 50, and a ^* is Since the ReO ₃ fine particles are composed of rhenium trioxide having −5 to 15 and b ^* of −10 to 5, and the dispersed particle diameter of the rhenium trioxide fine particles dispersed in the solvent is 150 nm or less, the above It has the effect that a solar radiation shielding body or a solar radiation shielding complex can be manufactured easily and reliably.

  Hereinafter, the present invention will be described in detail.

  First, as described above, the solar radiation shielding body or solar radiation shielding composite according to the present invention has a maximum value in the wavelength range of 380 nm to 650 nm and a minimum value in the range of more than 650 nm to 1700 nm. In addition, when the maximum value of transmittance is P, the minimum value is B, and the visible light transmittance is VLT, it has solar radiation shielding characteristics satisfying the following formula (1) when 35% ≦ VLT ≦ 80%. It is what.

P / B + 0.0525 × VLT ≧ 5.3 (1)
Here, the visible light transmittance VLT is calculated based on the visible light transmittance calculation method (JIS A 5759), and specifically, each wavelength at intervals of 10 nm between wavelengths 380 nm to 780 nm using a spectrophotometer. The spectral transmittance τ (λ) is measured and calculated by the following formula (2).

ここで、τｖは可視光透過率ＶＬＴ、ＤλはＣＩＥ昼光色Ｄ₆₅における分光分布の値（ＪＩＳ Ａ ５７５９の添付表参照）、ＶλはＣＩＥ明順応標準比視感度、τ（λ）は分光透過率である。尚、ＣＩＥは国際照明委員会の略称である。

Here, τv is a visible light transmittance VLT, Dλ is a spectral distribution value in the CIE daylight color D ₆₅ (see the attached table of JIS A 5759), Vλ is a CIE light adaptation standard relative luminous efficiency, and τ (λ) is a spectral transmittance. It is. CIE is an abbreviation for the International Lighting Commission.

Moreover, the said Numerical formula (1) is obtained according to the following measurement procedures. That is, a reference dispersion (ReO ₃ fine particles, a resin binder or an inorganic binder, and a dispersion according to the present invention mainly composed of an organic solvent) is applied, for example, a transparent glass having a thickness of 3 mm or a transparent PET having a thickness of 50 μm. The above-mentioned solar radiation measured by a spectrophotometer comprising a transparent base material such as a film and a solar radiation shielding film having a film thickness of 10 μm or less formed of the above dispersion liquid and having a solar radiation shielding characteristic indicating an acceptance criterion. The maximum value P of the transmittance and the minimum value B of the transmittance are obtained from the transmission profile of the shield, the ratio of (maximum value P / minimum value B) is obtained, and this value (P / B) is obtained as the visible light transmittance. Plot against (VLT). In the same procedure, the film thickness of the solar radiation shielding film is changed (that is, the VLT varies with the film thickness change), and a plurality of solar radiation shielding bodies whose solar radiation shielding characteristics show acceptance criteria are repeatedly created and transmitted through each of them. While measuring the profile, the ratio (maximum value P / minimum value B) obtained by the same procedure was plotted against the visible light transmittance (VLT), and these plots were obtained from straight lines obtained by linear approximation. Can be obtained.

  In addition, as a binder of the said film with a film thickness of 10 micrometers or less, although UV curable resin and a silicate type | system | group binder can be used, if it is transparent in a visible light area | region, it will not specifically limit.

And as for the ratio (P / B) of the maximum value and the minimum value of the film transmittance in the solar radiation shielding body, the solar radiation shielding characteristics are more excellent as this value is larger. This is because the transmission profile of the ReO ₃ fine particles has a maximum value in the wavelength range of 380 nm to 650 nm and a minimum value in the range of more than 650 nm to 1700 nm, and the visible light wavelength range is 380 nm to 780 nm. It is clear considering that the visibility is a bell-shaped peak having a peak near 550 nm. That is, it is understood from this transmission characteristic that visible light is effectively transmitted and other heat rays are effectively reflected and absorbed.

For example, it has a cubic crystal structure with a crystallite diameter of 80 nm and a lattice constant of 3.747778, and the powder color L ^* in the L ^* a ^* b ^* color system is 37.8562, and a ^* is 13.7497. A reference dispersion mainly composed of ReO ₃ fine particles having a b ^* of 3.0684 and a dispersed particle diameter of 100 nm, a UV curable resin, and a mixed liquid of cyclopentanone and toluene, and visible light A plurality of the above-mentioned solar shields having different transmittances (VLT) and the solar shading characteristics exhibit acceptance criteria are created, and the value of (P / B) is obtained from each created solar shield, and the horizontal axis is VLT. According to the experimental results plotted with the vertical axis as (P / B), the ratio between the maximum value and the minimum value (P / B) of the transmittance in each solar shielding body whose solar radiation shielding characteristics indicate acceptance criteria is shown in FIG. Visible light transmittance (VLT) ) Tends to change in a parabolic manner. However, in the range of 35% ≦ VLT ≦ 80%, which is a range of interest as a solar radiation shield, a straight line (Equation 1) approximation can be performed with sufficient accuracy.

  Then, the ratio (P / B) between the maximum value and the minimum value of the transmittance in the solar radiation shielding body in which the solar radiation shielding characteristics confirmed in the above-described experiment indicates an acceptance criterion is represented by the equal sign of the above formula (1). Since it exists on a straight line, the ratio (P / B) between the maximum value and the minimum value of the transmittance in the solar radiation shield is the same as or equal to the value on the straight line represented by the equal sign of Equation (1) Is larger than that, the solar shading body has sufficient solar shading characteristics. That is, in order for the solar radiation shielding body and the solar radiation shielding composite including this solar radiation shielding body to have good solar radiation shielding characteristics, it is necessary to satisfy the formula (1).

Next, the ReO ₃ fine particles applied in the present invention have a cubic crystal structure with a crystallite diameter of 150 nm or less and a lattice constant of 3.691 to 3.7511, and an L ^* a ^* b ^* color system. Powder color L ^* is 30-50, a ^* is -5-15, and b ^* is -10-5.

Here, the crystallite diameter is a value obtained by the Sherrer method. The ReO ₃ fine particles can be produced, for example, by an alcohol reduction method. However, it is not limited to this manufacturing method as long as it has the above powder characteristics. Hereinafter, a method for producing ReO ₃ fine particles by the alcohol reduction method will be described.

First, an alcohol as a reducing agent is added to a rhenium compound (for example, perrhenic acid), these are heated to the boiling point or higher of the alcohol, and all the added alcohol is removed, and further, at a temperature lower than the temperature at which ReO ₃ decomposes. ReO ₃ fine particles having a crystallite diameter of 150 nm or less can be obtained by heat treatment.

Next, the ReO ₃ fine particles have a powder color L ^* of 30-60 in the L ^* a ^* b ^* color system (JIS Z8729) recommended by the International Commission on Illumination (CIE), and a ^* of -5. 15, those with b ^* in the range of -10 to 5 are applied. The applied ReO ₃ fine particles have a higher solar shielding effect as the crystal perfection is higher. However, even if the crystallinity is low and an extremely broad diffraction peak is generated by X-ray diffraction, it has a cubic crystal structure with a crystallite diameter of 150 nm or less and a lattice constant of 3.6911 to 3.7511. If the powder color L ^* in the L ^* a ^* b ^* color system is 30 to 50, a ^* is -5 to 15, and b ^* is -10 to 5, the desired solar radiation shielding effect is obtained. It is possible to express.

In order to improve moisture resistance, it is preferable to coat ReO ₃ fine particles in advance with a surface treatment agent containing Si, Ti, Al, Zr or the like. The Si-containing silane surface treating agent at this time is not particularly limited as long as it exhibits hydrophobicity, and examples thereof include alkoxysilane, silazane, chlorosilane and the like.

Next, the solar radiation shielding body according to the present invention includes a transparent base material such as glass or plastic, and a solar radiation shielding film formed by applying a dispersion liquid in which the ReO ₃ fine particles are dispersed in a solvent on the transparent base material. in or configured, or, ReO ₃ particles molding resin matrix dispersed (ReO ₃ particles dispersed polycarbonate resin, acrylic resin, fluorine resin, polyester resin, polyvinyl acetal resins, polyvinyl butyral resins, ethylene - acetate Solar shielding molding in which a resin base material such as a vinyl copolymer resin, or a resin base material in which the above-mentioned dispersion material in which ReO ₃ fine particles are dispersed is mixed is formed into a flat or three-dimensional shape. Consists of the body. Further, the solar radiation shielding composite according to the present invention is composed of the solar radiation shielding film and the transparent base material such as glass or plastic sandwiching the solar radiation shielding film and another base material, or the solar radiation shielding molded body and the same. It is comprised with a pair of base material pinched | interposed.

Then, by applying a dispersion liquid in which the dispersion particle diameter of the ReO ₃ fine particles dispersed in the solvent is sufficiently fine and uniformly dispersed to 150 nm or less, a solar radiation shielding body or solar radiation that satisfies the requirements of the above formula (1) A shielding complex can be obtained.

Here, the dispersed particle size means the aggregated particle size of ReO ₃ fine particles in a solvent, and can be measured by various commercially available particle size distribution analyzers. For example, sampling is performed ReO ₃ fine particles from the dispersion liquid dispersed in a solvent in the presence also aggregates of ReO ₃ particulates, Otsuka Electronics Co., Ltd. ELS-800 were the principle of dynamic light scattering method Can be measured. The dispersed particle diameter of the ReO ₃ fine particles is desirably 150 nm or less. When the particle diameter is larger than 150 nm, it becomes difficult to satisfy the requirement of the above formula (1), and it becomes a gray solar shading film or a solar shading molded body (plate, sheet, etc.) having a monotonously reduced transmittance. This is because there are cases in which In addition, when a large amount of aggregated coarse particles is contained, clouding (haze) increases when a sunscreen film or a sunscreen molded body (plate, sheet, etc.) is formed as a light scattering source, and the visible light transmittance decreases. May be the cause.

The method of dispersing the ReO ₃ fine particles in the solvent is not limited as long as it is a method of uniformly dispersing in the dispersion, and examples thereof include a bead mill, a ball mill, a sand mill, a paint shaker, and an ultrasonic homogenizer. Thereby such distributed processing conditions using equipment, even micronized proceeds by collision of simultaneously ReO ₃ grains dispersed and to ReO ₃ fine particles in the solvent, it can be dispersed by finer particles the ReO ₃ particles (That is, pulverized and dispersed).

Next, the dispersion liquid is obtained by dispersing ReO ₃ fine particles in a solvent as described above. However, the solvent is not particularly limited, and is blended according to coating conditions, coating environment, and if necessary. What is necessary is just to select suitably according to the kind of binder etc. which are made. For example, water, alcohols such as ethanol, propanol, butanol, isopropyl alcohol, isobutyl alcohol, diacetone alcohol, ethers such as methyl ether, ethyl ether, propyl ether, esters, acetone, methyl ethyl ketone, diethyl ketone, cyclohexanone, Various organic solvents such as ketones such as isobutyl ketone can be used. If necessary, the pH may be adjusted by adding an acid or alkali. Furthermore, in order to further improve the dispersion stability of the fine particles in the dispersion, various surfactants, coupling agents and the like can of course be added.

  Moreover, when mix | blending an inorganic binder and a resin binder with a dispersion liquid, the kind of binder is not specifically limited. Examples of the inorganic binder include metal alkoxides of silicon, zirconium, titanium, or aluminum, partially hydrolyzed polycondensation products thereof, or organosilazanes. The resin binder may be a thermoplastic resin such as an acrylic resin, epoxy. Examples thereof include thermosetting resins such as resins.

Moreover, since the conductivity of the film when a solar radiation shielding film is formed on a transparent substrate such as glass or plastic using the above dispersion liquid is obtained along a conductive path via the contact location of the ReO ₃ fine particles, For example, by partially cutting the conductive path by adjusting the amount of the surfactant or coupling agent, it is easy to reduce the conductivity to a surface resistance value of 10 ⁶ Ω / □ or more. . Further, the conductivity can be controlled by adjusting the content of the inorganic binder or the resin binder.

Next, when the solar radiation shielding body according to the present invention is composed of a transparent base material such as glass or plastic and a solar radiation shielding film formed thereon, the resin binder or inorganic binder contained in the dispersion is applied. After curing, there is an effect of improving the adhesion of the ReO ₃ fine particles to the substrate and further improving the hardness of the film.

  Further, a film made of a metal alkoxide of silicon, zirconium, titanium, or aluminum, or a partially hydrolyzed polycondensation product thereof is applied as a second layer on the solar radiation shielding film thus obtained. By forming an oxide film of zirconium, titanium, or aluminum, it is possible to further improve the binding force of the solar radiation shielding film to the base material, the hardness of the film, and the weather resistance.

Further, the solar radiation shielding film formed from the dispersion containing no resin binder or inorganic binder has a film structure in which only the ReO ₃ fine particles are deposited on a transparent substrate such as glass or plastic. And although it shows the solar radiation shielding effect as it is, the coating containing an inorganic binder or a resin binder composed of a metal alkoxide of silicon, zirconium, titanium, or aluminum or a partially hydrolyzed polycondensate of these on the film. A liquid is preferably applied to form a multilayer film structure. By doing so, the coating liquid component fills the gap between the ReO ₃ fine particles in the first layer, so that the haze of the film is reduced and the visible light transmittance is improved, and the fine particles are bonded to the transparent substrate. Wearability is improved.

  In addition, the method of applying the dispersion onto a transparent substrate such as glass or plastic is arbitrary, such as spin coating, bar coating, spray coating, dip coating, screen printing, roll coating, flow coating, etc. Any method can be used as long as the dispersion can be applied flatly, thinly and uniformly.

  Further, the heating temperature of the transparent substrate after application of a dispersion containing an inorganic binder composed of a metal alkoxide of silicon, zirconium, titanium, or aluminum or a partially hydrolyzed condensation polymer thereof is preferably 100 ° C. or higher. More preferably, the heating is performed at a temperature equal to or higher than the boiling point of the solvent in the dispersion. When the temperature is lower than 100 ° C., the polymerization reaction of the alkoxide contained in the coating film or its hydrolyzed polymer often remains incomplete, and the visible light transmittance of the film after heating with water or an organic solvent remaining in the film. It is because it becomes a cause of reduction of this.

  Moreover, what is necessary is just to harden according to the hardening method of each resin, when a resin binder is used. For example, if it is an ultraviolet curable resin, it may be irradiated with ultraviolet rays as appropriate, and if it is a room temperature curable resin, it may be left as it is after application. For this reason, the application | coating in the field to the existing window glass etc. is possible.

The solar radiation-shielding body according to the present invention, for example, if composed of a transparent substrate and a solar radiation shielding film formed on this, such as glass or plastic, moderately ReO ₃ particles in the solar radiation shielding film Since it is dispersed, reflection in the visible light region is less than that of an oxide thin film formed by a physical film-forming method having a mirror-like surface in which crystals are densely filled, and an adverse effect of a glaring appearance can be avoided. On the other hand, since there is a plasma frequency from the visible region to the near infrared region, the plasma reflection associated therewith increases in the near infrared region. If it is desired to further suppress the reflection in the visible light region, a low refractive index film such as SiO ₂ or MgF ₂ is easily formed on the solar radiation shielding film in which the ReO ₃ fine particles are dispersed. A multilayer film having a reflectance of 1% or less can be obtained.

  Next, the case where the solar radiation shielding body according to the present invention is constituted by a solar radiation shielding molded body obtained by molding the molding resin base material into a flat or three-dimensional shape will be described.

First, the molding resin base material in which ReO ₃ fine particles are dispersed is a resin material such as a polycarbonate resin, an acrylic resin, a fluororesin, a polyester resin, a polyvinyl acetal resin, a polyvinyl butyral resin, or an ethylene-vinyl acetate copolymer resin. The ReO ₃ fine particles are uniformly dispersed, and the ReO ₃ fine particles and the resin material are mixed with a general ribbon blender, tumbler, nauter mixer, Henschel mixer, etc., and a Banbury mixer, a kneader, It can be obtained by a method of uniformly melting and mixing with a kneader such as a roll, a single screw extruder, a twin screw extruder or the like. Note that the dispersion according to the present invention can be directly kneaded into the resin material.

The molding resin base material thus obtained is molded into a planar shape or a curved surface shape (that is, a planar shape or a three-dimensional shape) by a known molding method such as injection molding, extrusion molding, or compression molding. A solar shading compact can be produced. Further, the mixture in which the ReO ₃ fine particles are uniformly dispersed in the resin material is once pelletized by a granulating apparatus, and the pellet is added and mixed in the resin, and a solar shading molded article is manufactured by a molding method similar to the above method. You can also. In addition, the thickness of a solar radiation shielding molded object can be adjusted to arbitrary thickness from a plate shape to a thin film shape as needed.

  Next, as an example of the solar radiation shielding composite according to the present invention, the solar radiation shielding molded body and a pair of base materials sandwiching the solar radiation shielding molded body will be described as an example. Can be produced by sandwiching the film between two glass plates and crimping with an autoclave.

Further, in order to impart an ultraviolet shielding function to the solar radiation shielding body or the solar radiation shielding complex according to the present invention, particles of inorganic titanium oxide, zinc oxide, cerium oxide, etc., one kind of organic benzophenone, benzotriazole, or the like Two or more kinds may be added. In order to improve the transmittance, particles such as ATO, ITO, and aluminum-added zinc oxide (hereinafter abbreviated as AZO) may be further mixed. When these transparent particles are added, the transmittance near 750 nm increases, the near-infrared rays are shielded, the visible light transmittance is high, and the solar radiation shielding body or solar radiation shielding composite having higher solar radiation shielding characteristics. Is obtained. If the dispersion liquid according to the present invention is added to a dispersion liquid in which particles such as ATO, ITO, and AZO are dispersed, the film color of ReO ₃ is blue, so that the formed film is colored and at the same time assists the solar radiation shielding effect. You can also In this case, the solar radiation shielding effect can be assisted with only a small addition amount with respect to ATO or ITO as a main component, the required amount of ATO or ITO can be greatly reduced, and the dispersion cost can be reduced.

  Further, the dispersion according to the present invention does not form the desired solar shading body by utilizing the decomposition or chemical reaction of the liquid component due to the heat at the time of firing, and therefore forms the solar shading body with stable characteristics. Can do.

In addition, since the ReO ₃ fine particles exhibiting a solar radiation shielding effect are inorganic materials, they are superior in weather resistance compared to organic materials. For example, even if they are used in a part exposed to sunlight (ultraviolet rays), colors and functions Almost no deterioration occurs.

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

  The powder color (standard light source D65, 10 ° field of view) of the fine particles a to 1 applied in each example and comparative example 1, and a solar radiation shield obtained using a dispersion liquid in which each fine particle is dispersed ( The optical characteristics of the solar radiation shielding composites A to L were measured using a spectrophotometer U-4000 manufactured by Hitachi, Ltd.

  Further, regarding the solar radiation shielding characteristics, the maximum value P, the minimum value B, and the visible light transmittance VLT of the transmittance are obtained from the transmission profile of each solar radiation shielding body (solar radiation shielding complex), and the above-described numerical values are described above. It is calculated as the value on the left side of Equation (1) “P / B + 0.0525 × VLT ≧ 5.3”.

  The visible light transmittance VLT of each example is controlled by the film thickness of the solar radiation shielding film and the solar radiation shielding molded body, or the solar radiation shielding molded body is an intermediate film constituting a part of the solar radiation shielding composite. In some cases, the amount of filler dispersed in the intermediate film is controlled.

39.9 g of a perrhenic acid aqueous solution (containing 60% in terms of ReO ₃ ) and 58.5 g of methanol were mixed in a 500 ml separable flask, and heated at 110 ° C. in a nitrogen atmosphere while stirring. During the heating, 175.5 g of methanol was added in three portions, and then the solvent was evaporated. Thereafter, the mixture was further heated at 250 ° C. for 2 hours to completely evaporate the solvent, thereby obtaining ReO ₃ fine particles. The fine particles had a powder color of L ^* of 34.6700, a ^* of 4.9827, b ^* of −1.7658, a lattice constant of 3.74904, and a crystallite diameter of 50.5 nm.

Next, 5% by weight of the ReO ₃ fine particles, 5% by weight of a polymeric dispersant, and 90% by weight of methyl isobutyl ketone were pulverized and dispersed for 8 hours in a paint shaker containing 0.3 mm diameter ZrO ₂ beads. A dispersion (Resolution A) of ReO ₃ was prepared. Here, the dispersion particle diameter of the ReO ₃ particles in the dispersion liquid (liquid A) was 71 nm as shown in Table 1 by pulverization / dispersion treatment.

Next, 0.5 g of the obtained ReO ₃ dispersion (liquid A) and 0.8 g of UV curable resin (resin solid content 50%, residual toluene) were mixed and stirred well to obtain a dispersion (liquid B). Was prepared.

  Next, this dispersion (liquid B) was applied onto a 50 μm thick PET (polyethylene terephthalate) film using a bar coater of No. 4 bar, and then irradiated with a high pressure mercury lamp at 70 ° C. for 1 minute. A solar shading body A according to Example 1 was obtained.

  The transmission profile of the obtained solar shield A is shown in FIG.

  The maximum value P and minimum value B of the transmittance are obtained from the obtained transmission profile, and the value of the visible light transmittance VLT is obtained by the above-described method for calculating the visible light transmittance (JIS A 5759). Was substituted into the above formula (1) to determine the solar radiation shielding characteristics, and as shown in Table 1 below, it was 5.3%.

  That is, the solar radiation shielding body A according to Example 1 satisfied the requirement of Formula (1) “P / B + 0.0525 × VLT ≧ 5.3”, and had good solar radiation shielding characteristics.

  A solar radiation shield B according to Example 2 was obtained in the same manner as in Example 1 except that coating was performed using a bar coater of bar No. 8.

  And after calculating | requiring the value of the maximum value P of the transmittance | permeability, the value B of the visible light transmittance | permeability VLT like Example 1, and substituting into the said Numerical formula (1), the solar radiation shielding characteristic was calculated | required, As shown in Table 1, it was 5.5%.

  That is, the solar shading body B according to Example 2 also satisfied the requirement of the formula (1) “P / B + 0.0525 × VLT ≧ 5.3” and had good solar shading characteristics.

  A solar shading body C according to Example 3 was obtained in the same manner as in Example 1 except that coating was performed using a bar coater of bar No. 24.

  And after calculating | requiring the value of the maximum value P of the transmittance | permeability, the value B of the visible light transmittance | permeability VLT like Example 1, and substituting into the said Numerical formula (1), the solar radiation shielding characteristic was calculated | required, As shown in Table 1, it was 7.4%.

  That is, the solar radiation shielding body C according to Example 3 also satisfied the requirement of the formula (1) “P / B + 0.0525 × VLT ≧ 5.3” and had good solar radiation shielding characteristics.

A solar shading body D according to Example 4 was obtained in the same manner as in Example 1 except that the heat treatment was performed at 250 ° C. for 2 hours at the time of obtaining ReO ₃ fine particles, except that 150 ° C. was set for 2 hours.

  And after calculating | requiring the value of the maximum value P of the transmittance | permeability, the value B of the visible light transmittance | permeability VLT like Example 1, and substituting into the said Numerical formula (1), the solar radiation shielding characteristic was calculated | required, As shown in Table 1, it was 5.3%.

  That is, the solar shading body D according to Example 4 also satisfied the requirement of the formula (1) “P / B + 0.0525 × VLT ≧ 5.3” and had good solar shading characteristics.

A solar radiation shield E according to Example 5 was obtained in the same manner as in Example 1 except that the heat treatment was performed at 250 ° C. for 2 hours at the time of obtaining the ReO ₃ fine particles, and that the temperature was 310 ° C. for 2 hours.

  And after calculating | requiring the value of the maximum value P of the transmittance | permeability, the value B of the visible light transmittance | permeability VLT like Example 1, and substituting into the said Numerical formula (1), the solar radiation shielding characteristic was calculated | required, As shown in Table 1, it was 5.4%.

  That is, the solar radiation shielding body E according to Example 5 also satisfied the requirement of the formula (1) “P / B + 0.0525 × VLT ≧ 5.3” and had good solar radiation shielding characteristics.

ReO ₃ fine particles were obtained in the same manner as in Example 1 except that the heat treatment was performed at 250 ° C. for 2 hours instead of the heat treatment at 250 ° C. for obtaining ReO ₃ fine particles. The solar radiation shielding body F which concerns on Example 6 was obtained like Example 1 except having apply | coated using the bar coater.

  And after calculating | requiring the value of the maximum value P of the transmittance | permeability, the value B of the visible light transmittance | permeability VLT like Example 1, and substituting into the said Numerical formula (1), the solar radiation shielding characteristic was calculated | required, As shown in Table 1, it was 5.5%.

  That is, the solar shading body F according to Example 6 also satisfied the requirement of the formula (1) “P / B + 0.0525 × VLT ≧ 5.3” and had good solar shading characteristics.

ReO ₃ fine particles were obtained in the same manner as in Example 1 except that the heat treatment was performed at 250 ° C. for 2 hours instead of 250 ° C. for obtaining ReO ₃ fine particles, and bar No. 24 was obtained in the same manner as in Example 3. The solar radiation shielding body G which concerns on Example 7 was obtained like Example 1 except having apply | coated using the bar coater.

  And after calculating | requiring the value of the maximum value P of the transmittance | permeability, the value B of the visible light transmittance | permeability VLT like Example 1, and substituting into the said Numerical formula (1), the solar radiation shielding characteristic was calculated | required, As shown in Table 1, it was 8.8%.

  That is, the solar radiation shielding body G according to Example 7 also satisfied the requirement of the mathematical formula (1) “P / B + 0.0525 × VLT ≧ 5.3” and had good solar radiation shielding characteristics.

Dispersion of ReO ₃ in Example 1 (A solution) was added to a polyvinyl butyral as a resin material, and triethylene glycol as a plasticizer - di-2-ethyl butyrate was added, ReO ₃ particle concentration is 0. An intermediate film composition was obtained by preparing such that 0164% by weight and the polyvinyl butyral concentration was 71.1% by weight.

Next, the composition was kneaded with a roll and formed into a sheet having a thickness of 0.76 mm to produce an intermediate film, and then the above-mentioned between two green glass substrates having a thickness of about 2 mm and a size of 100 mm × 100 mm. The intermediate film was sandwiched, heated to 80 ° C. and temporarily bonded, and further subjected to main bonding by an autoclave at 140 ° C. and 14 Kg / cm ² to prepare a solar radiation shielding composite H according to Example 8, that is, laminated glass H.

  And after calculating | requiring the value of the maximum value P of the transmittance | permeability, the value B of the visible light transmittance | permeability VLT like Example 1, and substituting into the said Numerical formula (1), the solar radiation shielding characteristic was calculated | required, As shown in Table 1, it was 6.1%.

  That is, the solar radiation shielding composite H according to Example 8 also satisfied the requirement of the mathematical formula (1) “P / B + 0.0525 × VLT ≧ 5.3” and had good solar radiation shielding characteristics.

After mixing 30% by weight of indium tin oxide (ITO) fine particles having a specific surface area of 77.6 m ² / g, 56% by weight of isobutyl alcohol, and 14% by weight of a dispersant, and filling the container with glass beads having a diameter of 0.15 mm, An ITO dispersion liquid (C liquid) was prepared by performing a bead mill dispersion treatment for 1 hour.

Then, the ReO ₃ dispersion (liquid A) in Example 1 and this liquid C were mixed well, methyl isobutyl ketone was added as a diluent, and the ReO ₃ concentration was 0.0106 wt% and the ITO concentration was 0.14 wt%. An intermediate film composition and an intermediate film were produced in the same manner as in Example 8 except that the dispersion liquid of No. 1 was prepared, and a solar radiation shielding composite I, that is, a laminated glass I according to Example 9 was obtained.

  And after calculating | requiring the value of the maximum value P of the transmittance | permeability, the value B of the visible light transmittance | permeability VLT like Example 1, and substituting into the said Numerical formula (1), the solar radiation shielding characteristic was calculated | required, As shown in Table 1, it was 6.1%.

  That is, the solar radiation shielding complex I according to Example 9 also satisfied the requirement of the formula (1) “P / B + 0.0525 × VLT ≧ 5.3” and had good solar radiation shielding characteristics.

After mixing 30% by weight of antimony tin oxide (ATO) fine particles having a specific surface area of 43.7 m ² / g, 55% by weight of isobutyl alcohol, and 15% by weight of a dispersant, the mixture was filled into a container together with glass beads having a diameter of 0.15 mm. A bead mill dispersion treatment was performed for 5 hours to prepare an ATO dispersion liquid (liquid D).

Then, the ReO ₃ dispersion (liquid A) in Example 1 and this liquid D were mixed well, methyl isobutyl ketone was added as a diluent, the ReO ₃ concentration was 0.0168 wt%, and the ATO fine particle concentration was 0.14 wt. An intermediate film composition and an interlayer film were produced in the same manner as in Example 8 except that a% dispersion liquid was prepared, and a solar radiation shielding composite J, that is, a laminated glass J according to Example 10, was obtained.

  And after calculating | requiring the value of the maximum value P of the transmittance | permeability, the value B of the visible light transmittance | permeability VLT like Example 1, and substituting into the said Numerical formula (1), the solar radiation shielding characteristic was calculated | required, As shown in Table 1, it was 6.4%.

  That is, the solar radiation shielding composite J according to Example 10 also satisfied the requirement of the formula (1) “P / B + 0.0525 × VLT ≧ 5.3” and had good solar radiation shielding characteristics.

When obtaining ReO ₃ fine particles, except that Re and Re ₂ O ₇ were applied instead of perrhenic acid, and Re and Re ₂ O ₇ were mixed at 1: 1, followed by heat treatment at 250 ° C. for 3 hours. It is to give the ReO ₃ fine particles in the same manner as in example 1 to obtain a solar radiation-shielding body K according to example 11 in the same manner as in example 1 using the ReO ₃ particles. When obtaining the ReO ₃ fine particles, the pulverizing / dispersing time in the paint shaker was 4 hours.

  And after calculating | requiring the value of the maximum value P of the transmittance | permeability, the value B of the visible light transmittance | permeability VLT like Example 1, and substituting into the said Numerical formula (1), the solar radiation shielding characteristic was calculated | required, As shown in Table 1, it was 5.5%.

That is, the solar shading body K according to Example 11 also satisfied the requirement of the formula (1) “P / B + 0.0525 × VLT ≧ 5.3” and had good solar shading characteristics.
[Comparative Example 1]
In Example 1, the solar shading body L according to Comparative Example 1 was obtained in the same manner as in Example 1 except that the dispersion was performed for 4 minutes with a paint shaker and the dispersion particle diameter of the ReO ₃ fine particles was changed to 177 nm.

  And after calculating | requiring the value of the maximum value P of the transmittance | permeability, the value B of the visible light transmittance | permeability VLT like Example 1, and substituting into the said Numerical formula (1), the solar radiation shielding characteristic was calculated | required, As shown in Table 1, it was 4.7%.

  That is, the solar shading body L according to the comparative example 1 does not satisfy the requirement of the mathematical formula (1) “P / B + 0.0525 × VLT ≧ 5.3”, and the solar shading characteristics are inferior compared with the respective examples. It was confirmed that

In addition, the reason that the solar shading property of the solar shading body L according to Comparative Example 1 is inferior is that the dispersed particle diameter of the ReO ₃ particles in the dispersion (liquid A) exceeds 150 nm.

  As described above, the solar radiation shielding body and the solar radiation shielding composite according to the present invention are excellent in the solar radiation shielding characteristics. Therefore, the window material of a vehicle, a building, an office, a general house, a telephone box, a show window, and an illumination lamp. It is suitable for use in visible light transmitting materials that require solar radiation shielding properties such as single plate glass, laminated glass, and plastics used in transparent cases.

The graph which shows the relationship between VLT and P / B of the solar radiation shield produced using the dispersion liquid used as a reference | standard. The graph which shows the permeation | transmission profile of the solar radiation shield which concerns on Example 1. FIG.

Claims (9)

In the solar shield containing ReO ₃ fine particles,
The transmittance has a maximum value in the wavelength range of 380 nm to 650 nm and has a minimum value in the range of more than 650 nm to 1700 nm, and the maximum value of the transmittance is P, the minimum value is B, and the visible light transmittance The solar shading body is characterized by having solar shading characteristics satisfying the following formula (1) when 35% ≦ VLT ≦ 80%.
P / B + 0.0525 × VLT ≧ 5.3 (1) The solar shading body according to claim 1, comprising a transparent base material made of glass or plastic and a solar shading film containing ReO ₃ fine particles formed thereon. The solar radiation shielding body according to claim 1, wherein the solar radiation shielding body is constituted by a solar radiation shielding molded body obtained by molding a molding resin base material in which ReO ₃ fine particles are dispersed into a flat or three-dimensional shape. It has a cubic crystal structure with a crystallite diameter of 150 nm or less and a lattice constant of 3.6911 to 3.7511, a powder color L ^* in the L ^* a ^* b ^* color system of 30 to 50, and a ^* is The solar radiation shield according to any one of claims 1 to 3, wherein the ReO ₃ fine particles are composed of rhenium trioxide having -5 to 15 and b ^* of -10 to 5.   The solar radiation shielding film according to claim 2 and the glass or plastic transparent base material sandwiching the solar radiation shielding film and another base material, or the solar radiation shielding molded body according to claim 3 and a pair of base materials sandwiching the solar radiation shielding molded body. A solar radiation shielding complex characterized by comprising: It has a cubic crystal structure with a crystallite diameter of 150 nm or less and a lattice constant of 3.6911 to 3.7511, a powder color L ^* in the L ^* a ^* b ^* color system of 30 to 50, and a ^* is 6. The solar radiation shielding composite according to claim 5, wherein the ReO ₃ fine particles are composed of rhenium trioxide having −5 to 15 and b ^* of −10 to 5. A dispersion liquid containing a solvent and rhenium trioxide fine particles dispersed in the solvent, and applied to the production of the solar radiation shielding body according to claim 4 or the solar radiation shielding composite according to claim 6,
A dispersion liquid, wherein the dispersion particle diameter of rhenium trioxide fine particles dispersed in a solvent is 150 nm or less.   8. The dispersion liquid according to claim 7, wherein indium tin oxide fine particles and / or antimony tin oxide fine particles are added. The dispersion liquid according to claim 7 or 8, wherein an inorganic binder or a resin binder is contained.

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