JP2003277644A - Composition particle for screening infrared light, infrared light-screening material and infrared light- screening member - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an infrared light-screening member wherein prescribed functional coating layers are formed on the surfaces of ZnO particles and which can thereby prevent the clouding with the ZnO particles due to chemical agents and can screen ultraviolet light, and the like. <P>SOLUTION: The composite particles which can be dispersed and held in a transparent matrix, exhibit an infrared light-screening ability, and are used for screening the infrared light, are characterized by comprising the ZnO particles 1 and the functional coating layers 2 having the prescribed functions and coated on the surfaces of the ZnO particles 1. The functional coating layers 2 have, for example, a function capable of preventing the clouding with the ZnO particles 1 due to the chemical agents, a function capable of screening ultraviolet light, and a function capable of preventing the decomposition of organic materials due to the ZnO particles. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an infrared-shielding composite particle, an infrared-shielding material, and an infrared-shielding member. The infrared blocking composite particles and the like according to the present invention can be applied to window glasses, coating films, etc. of vehicles and buildings.

[0002]

2. Description of the Related Art Zinc oxide (ZnO), indium tin oxide (ITO) and the like have been conventionally known as substances having an infrared ray blocking ability.

For example, Japanese Patent Laid-Open No. 9-176527 discloses an ultraviolet ray and / or an ultraviolet ray which contains ZnO particles and / or ITO particles and which can be applied to window glass for vehicles and buildings to block ultraviolet rays and / or infrared rays. Alternatively, an infrared blocking film is disclosed.

This ultraviolet and / or infrared ray blocking film comprises a blocking layer as a first layer formed on a transparent substrate and the first blocking layer.
It has a two-layer structure including a silica protective layer as a second layer formed on the layer. The blocking layer as the first layer is composed of ZnO particles as ultraviolet blocking particles and / or ITO particles as infrared blocking particles, and silica as a matrix portion that binds these blocking particles.

This barrier film is formed by forming a particle layer composed of ZnO particles and / or ITO particles as barrier particles on a transparent substrate, coating silica sol on the transparent substrate to impregnate the particle layer, and then heating and drying. It is formed by That is, the silica sol permeates between the barrier particles and functions as a binder, and after heating, a barrier layer formed by binding the barrier particles with silica is formed, and the silica sol accumulated on the particle layer causes the barrier layer to adhere to the barrier layer. A silica protective layer composed of only silica is formed.

In Japanese Patent Laid-Open No. 2000-24591, ZnO particles are used as ultraviolet blocking particles and ITO particles are used as infrared blocking particles, and these particles are dispersed and held in a transparent matrix portion made of an organic material. A barrier film is disclosed.

In the techniques disclosed in Japanese Patent Laid-Open No. 9-176527 and Japanese Patent Laid-Open No. 2000-24591, Zn is used as the ultraviolet blocking particles having the ultraviolet blocking ability.
In addition to using O particles, ITO particles are used as infrared blocking particles having an infrared blocking ability, and one or both of ZnO particles and ITO particles are used as ultraviolet rays and / or infrared blocking particles depending on the application. That is, when only the UV blocking ability is required for the blocking film, only ZnO particles are used. Conversely, when only the infrared blocking ability is required for the blocking film, only ITO particles are used. When both blocking ability is required, both ZnO particles and ITO particles are used.

[0008]

Among the substances having the infrared ray blocking ability, ITO is higher in cost than ZnO and is disadvantageous in using in large quantities. Therefore, in terms of cost, it is desirable to use only ZnO as the substance having an infrared ray blocking ability without using ITO.

However, since ZnO has low chemical resistance,
If an acidic solution, an alkaline solution, or chemicals such as salt water or fruit juice adheres, it becomes cloudy (cloudy or white)
There is a drawback that. For this reason, in a barrier film in which ZnO powder is directly dispersed and held in the matrix portion, the orange turbidity is caused only by the attachment of mandarin orange juice or the like.

The barrier film disclosed in the above-mentioned Japanese Patent Laid-Open No. 9-176527 has a two-layer structure in which a silica protective layer is further formed on a barrier layer formed by bonding barrier particles with silica. However, since the ZnO particles as the blocking particles are protected by silica, it seems that the chemical resistance is also good.

However, even a two-layered barrier film having ZnO particles coated on a glass surface, silica sol impregnated in the particle layer, and a silica protective layer formed on the silica sol is used, the chemical resistance is also high. It has been confirmed by the present inventor that is not always sufficient. This is the Zn protruding on the outermost surface.
It is considered that the presence of O particles and the entry of chemicals through the pores of the silica protective layer.

It is possible to improve the chemical resistance by increasing the density and thickness of the silica protective layer. However, for that purpose, in addition to adjusting the concentration and viscosity of the silica sol solution used, it is necessary to control the temperature and humidity during heating and drying. For example, when forming a barrier film on vehicle glass, When mass-producing large-scale parts, large-scale temperature / humidity control equipment is required, which is not easy.

Further, in the barrier films disclosed in both of the above publications, both ZnO particles and ITO particles are used when the barrier films are required to have the ability to block both ultraviolet rays and infrared rays. As described above, under the concept of using blocking particles having respective functions in combination so that both blocking ability of ultraviolet rays and infrared rays can be imparted to the blocking film, there are the following problems. That is, if there is a portion where one of the blocking particles is unevenly distributed in the blocking film, the function of the other blocking particle is deteriorated at the unevenly distributed portion. Therefore, in order to homogenize the respective functions in the entire blocking film, both blocking particles must be mixed and dispersed sufficiently or uniformly in the entire blocking film, or the film thickness of the blocking film must be made sufficiently thick. There is a problem that it must be. Further, since the reflectance of the unevenly distributed portion is different from that of the other portions, there is a problem that reflected light or interference light is generated.

On the other hand, when the ZnO particles and the like are dispersed and held in a transparent matrix portion made of an organic material like the barrier film disclosed in the above-mentioned Japanese Patent Application Laid-Open No. 2000-24591, the following problems occur. . That is, the ZnO particles cause a photocatalytic reaction when irradiated with light. For this reason,
When the ZnO particles are irradiated with light, the photocatalytic reaction causes decomposition and deterioration of the organic material forming the matrix portion, and there is a problem that durability of the barrier film is reduced.

The present invention has been made in view of the above circumstances, and uses the ZnO particles as the infrared shielding particles and forms the predetermined functional coat layer on the surface of each ZnO particle to solve the above-mentioned problems. It is a technical problem to be solved to provide an infrared blocking member or the like that can be solved.

[0016]

The infrared-blocking composite particles according to claim 1 for solving the above-mentioned problems are infrared-blocking composite particles dispersed and held in a transparent matrix portion and exhibiting an infrared-blocking ability. , ZnO particles, and a functional coating layer having a predetermined function and coated on the surface of the ZnO particles.

In the infrared blocking composite particle according to claim 1, it is preferable that the functional coating layer has a function of preventing clouding of the ZnO particles due to a chemical.

In the infrared shielding composite particle according to claim 1 or 2, it is preferable that the functional coating layer has a function of blocking ultraviolet rays.

In the infrared-shielding composite particle according to claim 1, 2 or 3, it is preferable that the functional coat layer has a function of preventing decomposition of the organic material by the ZnO particles.

In order to solve the above-mentioned problems, the infrared ray blocking material according to claim 5 is a composite particle comprising ZnO particles and a functional coating layer having a predetermined function and coated on the surface of the ZnO particles, and the composite particle is dispersed. And a transparent matrix portion for holding.

In the infrared shielding material according to claim 5, it is preferable that the functional coating layer has a function of preventing clouding of the ZnO particles due to a chemical.

In the infrared ray blocking material according to claim 5 or 6, it is preferable that the functional coat layer has a function of blocking ultraviolet rays.

In the infrared ray blocking material according to claim 5, 6 or 7, the matrix portion is made of an organic material, and the functional coat layer has a function of preventing decomposition of the organic material by the ZnO particles. Is preferred.

An infrared shielding member according to claim 9 for solving the above-mentioned problems is an infrared shielding member comprising a base material and an infrared shielding film formed on the surface of the base material, wherein the infrared shielding film is The present invention is characterized by comprising composite particles composed of ZnO particles and a functional coat layer coated on the surface of the ZnO particles and having a predetermined function, and a transparent matrix portion for dispersing and holding the composite particles.

In the infrared ray blocking member according to claim 9,
The functional coat layer preferably has a function of preventing clouding of the ZnO particles due to a chemical.

In the infrared ray blocking member according to claim 9 or 10, it is preferable that the base material is a transparent base material, and the functional coat layer has a function of blocking ultraviolet rays.

In the infrared ray blocking member according to claim 9, 10 or 11, the matrix portion is made of an organic material, and the functional coat layer has a function of preventing decomposition of the organic material by the ZnO particles. Is preferred.

Here, the term "clouding of ZnO particles with a chemical agent" means that ZnO particles become a carbonate and become cloudy or white due to an acidic substance such as an acidic aqueous solution or an alkaline substance such as an alkaline aqueous solution.

[0029]

BEST MODE FOR CARRYING OUT THE INVENTION The composite particles for blocking infrared rays according to the present invention have an infrared blocking ability and are used by being dispersed and held in a transparent matrix portion. The infrared blocking composite particles, together with the matrix portion, form an infrared blocking material according to the present invention described below or an infrared blocking film in an infrared blocking member according to the present invention described below.

Here, the material forming the transparent matrix portion may be either an organic material or an inorganic material as long as it can transmit visible light.

When the transparent matrix portion is made of an organic material, any of thermosetting, ultraviolet curable or electron beam curable resins may be used in addition to the thermoplastic resin.
Examples of the organic material that constitutes the transparent matrix portion include acrylic resin, silicone resin, acrylic / silicone resin, urethane resin, epoxy resin, melamine resin, polyester, polycarbonate, polyimide and polyvinyl chloride.

On the other hand, in the case of an inorganic material, for example, a binder in the form of a sol or emulsion (emulsion liquid) obtained by dissolving an organic compound such as a metal alkoxide or a carboxylate in a suitable solvent (organic solvent or water). A transparent matrix part can be formed by a metal oxide (silica, zirconia, alumina, etc.) formed by hydrolyzing or thermally decomposing a solution.

The above infrared-shielding composite particles are composed of ZnO particles and a functional coating layer having a predetermined function and coated on the surfaces of the ZnO particles.

In the present invention, ZnO particles are used as infrared ray blocking particles having an infrared ray blocking ability.
The particles also exhibit an ultraviolet blocking ability.

The upper limit of the average particle size of the ZnO particles is 20.
nm is preferable, and 15 nm is more preferable. An infrared shielding material or an infrared shielding film in which ZnO particles having an average particle diameter of more than 20 nm are dispersed and held in a transparent matrix portion is transparent because the ZnO particles having a large particle diameter reduce the transmittance of visible light. May deteriorate. On the other hand, the lower limit of the average particle diameter of ZnO particles is preferably 5 nm, more preferably 8 nm. ZnO having an average particle size smaller than 5 nm
The infrared ray blocking material or infrared ray blocking film in which the particles are dispersed and held in the transparent matrix portion has a reduced infrared ray blocking area in each ZnO particle, so that the infrared ray blocking ability is lowered.

The ZnO particles can be manufactured by a known method. For example, a method of hydrolyzing an alkoxide of zinc, a method of thermally decomposing after adding sodium carbonate to an acidic zinc salt, and a method of dissolving or dispersing metallic zinc, zinc oxide and a monocarboxylic acid in a solvent containing at least an alcohol. It can be produced by a method of keeping the mixture at a temperature of 100 ° C. or higher.

The above-mentioned functional coat layer has a desired function which is desired according to the characteristics required of the blocking film and blocking material for blocking infrared rays, the material of the matrix portion and the like. By thus providing the functional coat layer with a desired function, it is possible to provide an infrared ray blocking member or an infrared ray blocking member capable of solving the above-mentioned problems.

The function of the functional coat layer is, for example, a function of preventing clouding of the ZnO particles by a chemical, a function of blocking ultraviolet rays, and a function of preventing decomposition of the organic material by the ZnO particles. Can be mentioned. The functional coat layer preferably has both of these functions.

The above-mentioned Zn by chemicals is added to the above-mentioned functional coat layer.
When the O particles have a function of preventing clouding, a functional coat or the like can be formed of a material having such a function. In this way, when the functional coat layer has a function of preventing clouding of the ZnO particles due to chemicals, each of the ZnO particles dispersed and held in the matrix portion has a function coat layer having such a function. Since it is coated, it becomes possible to reliably prevent the clouding of ZnO particles due to chemicals. Further, since a functional coat layer is formed around ZnO particles,
By using the sputtering method, the sol-gel method, or the like, the functional coat layer can be easily and reliably formed on the surface of the ZnO particles.

Materials having the function of preventing the clouding of ZnO particles due to chemicals include ITO, SiO ₂ , and Al _2.
O ₃ , TiO ₂ , SrTiO ₃ , ZrO _{2 and the} like can be mentioned. Note that these materials have high chemical resistance and can effectively prevent clouding of ZnO particles due to chemicals.

When the functional coat layer has a function of blocking ultraviolet rays, the functional coat layer can be composed of a material having such a function. When the functional coating layer has a function of blocking ultraviolet rays as described above, both the infrared blocking ability of the ZnO particles and the ultraviolet blocking ability of the functional coating layer can be exhibited. Since the surface of the ZnO particles exhibiting the infrared shielding ability is coated with the functional coating layer exhibiting the ultraviolet shielding ability, the whole infrared shielding material described later according to the present invention or the infrared shielding material described later according to the present invention This is advantageous in homogenizing the functions of infrared ray blocking and ultraviolet ray blocking in the entire infrared ray blocking film of the member. That is, regarding the individual composite particles, the infrared shielding ability is exhibited in the area range corresponding to the outer diameter of the ZnO particles, and
The O-particle surface exhibits the UV-blocking ability in the area range corresponding to the outer diameter of the composite particle formed by coating the functional coating layer having the UV-blocking ability. Therefore, by uniformly dispersing the composite particles in the matrix portion, it becomes possible to homogenize the functions of the infrared blocking and the ultraviolet blocking in the entire infrared blocking material and the like. Further, if the functional coat layer has an ultraviolet blocking ability, the amount of the ultraviolet blocking material used is markedly reduced as compared with the case where ultraviolet blocking particles are separately added and mixed, which also contributes to cost reduction. Therefore, the ultraviolet blocking ability can be effectively exhibited while suppressing the addition amount (use amount) of the ultraviolet blocking material.

Examples of the material having a function of blocking ultraviolet rays include TiO ₂ , SnO ₂ , SrTiO ₃ and KTaO ₃ . The reason why these materials exhibit the function of blocking ultraviolet rays is that, as is generally considered, energy is consumed when electrons are excited by ultraviolet rays. Further, in the infrared ray blocking member according to the present invention, which will be described later, when a transparent substrate is used as the substrate, it is preferable that the functional coat layer also have a function of blocking ultraviolet rays.

When the functional coat layer has a function of preventing decomposition of the organic material by the ZnO particles,
The functional coat layer can be composed of a material having such a function. Since ZnO particles cause a photocatalytic reaction by light irradiation, when the ZnO particles are irradiated with light, the organic material forming the matrix portion is decomposed and deteriorated by the photocatalytic reaction. In this respect, when the functional coat layer is provided with the function of preventing the decomposition of the organic material by the ZnO particles, the decomposition of the organic material forming the matrix portion can be prevented, and therefore the durability of the matrix portion can be improved. It is possible to improve.

Materials having a function of preventing the decomposition of the organic material by the ZnO particles include ITO, SiO ₂ and Al.
₂ O ₃ , SrTiO ₃ , ZrO _{2 and the} like can be mentioned. The reason why these materials exhibit the function of preventing the decomposition of the organic material by ZnO particles is that these materials are stable materials having no photocatalytic action. Further, when the matrix portion for dispersing and holding the above composite particles is an organic material, it is preferable that the functional coat layer also have a function of preventing decomposition of the organic material by ZnO particles.

Here, the clouding of ZnO particles by chemicals
ITO and Si exemplified as materials having preventable functions
O₂, Al₂O₃, TiO₂, SrTiO₃And ZrO
₂Out of TiO₂And SrTiO₃Also has UV blocking ability
Also, ITO, SiO ₂, Al₂O₃, SrTi
O₃And ZrO₂Is the decomposition of organic materials by ZnO particles
It also has a preventable function, and ITO blocks infrared rays.
Also has Noh.

Further, among the above-mentioned materials having a function of preventing clouding of ZnO particles due to chemicals, materials having a function of blocking ultraviolet rays, and materials having a function of preventing decomposition of an organic material by ZnO particles. From, namely ITO,
SiO ₂ , Al ₂ O ₃ , TiO ₂ , SrTiO ₃ , Zr
It is preferable that the functional coat layer is composed of two or more kinds of materials selected and combined from O ₂ , SnO ₂ and KTaO ₃ . When the functional coat layer is composed of two or more kinds of materials, a preferable combination is ITO.
And SiO ₂ and ITO and TiO ₂ .

The upper limit of the thickness of the functional coat layer is 5 nm.
Is preferable, and 4 nm is more preferable. If the thickness of the functional coat layer is thicker than 5 nm, the cost becomes high. On the other hand, the lower limit of the thickness of the functional coat layer is preferably 0.5, and more preferably 1 nm. A functional coat layer thinner than 0.5 nm cannot fulfill its function sufficiently.

From the viewpoint of more effectively exerting the function of preventing the clouding of ZnO particles due to chemicals, the higher the density of the coating layer, the more preferable. From this point of view, the lower limit of the density of the coat layer is preferably 98% (generally, the relative density at which the communicating holes disappear), and more preferably 100%.

The method of coating the surface of the ZnO particles with the coating layer is not particularly limited. For example, a vapor phase method such as a sputtering method, a vacuum deposition method or a CVD method, or a sol-gel method can be used. By these methods,
A coat layer having a predetermined thickness and a predetermined density can be easily and reliably formed on the entire surface of the ZnO particles.

The infrared shielding material according to the present invention is the above ZnO.
The composite particles are composed of the particles and the functional coat layer coated on the surface of the ZnO particles and having a predetermined function, and the transparent matrix part for dispersing and holding the composite particles. That is, as the composite particles forming the infrared blocking material, the infrared blocking composite particles according to the present invention described above can be used as they are, and as the matrix portion forming the infrared blocking material, the matrix portion described above can be used as they are. be able to. Therefore, this infrared blocking material exerts its respective function and effect in accordance with the various functions of the functional coating layer.

The shape of the matrix portion constituting the infrared ray blocking material, that is, the shape of the infrared ray blocking material itself is not particularly limited, and the usage form of the infrared ray blocking material is also not particularly limited. For example, an infrared ray blocking film that can be used as an infrared ray blocking film (painting film) formed on the surface of an outer plate of a vehicle or a building, an outer wall or a glass plate, or an intermediate film of a laminated glass for a vehicle or a building. Alternatively, it may be an infrared ray blocking glass (inorganic glass or so-called resin glass) used for vehicles, buildings, etc. formed into a plate shape.

For example, when the infrared ray blocking material according to the present invention is applied to an infrared ray blocking film formed on the surface of a glass plate or the like, as a material forming the matrix portion, an inorganic resin such as silica or an acrylic resin is used. Organic materials such as silicone resin or silicone / acrylic resin can be adopted.

When the infrared ray blocking material according to the present invention is applied to an infrared ray blocking film which can be used as an intermediate film of laminated glass, polyvinyl butyral (PVB) or polyethylene terephthalate (PET) is used as a material constituting the matrix portion. ) Etc. can be adopted.

When the infrared ray shielding material according to the present invention is applied to so-called resin glass, polycarbonate (PC), polymethylmethacrylate (PMA) or the like can be adopted as the material forming the matrix portion.

When the infrared ray blocking material according to the present invention is applied to inorganic glass, silica, zirconia, alumina or the like can be adopted as the material forming the matrix portion.

In addition to the composite particles, it is of course possible to add a predetermined additive to the matrix portion, if necessary. For example, TiO ₂ particles, SnO ₂ particles, Sr as UV blocking particles having UV blocking ability.
At least one of TiO ₃ particles and KTaO ₃ particles
It is also possible to add seeds or coloring components such as transition metal alkoxides.

The compounding amount of the composite particles dispersed and retained in the matrix part can be appropriately selected. When the matrix part is 100 parts by weight, the composite particles are about 10 to 40 parts by weight. can do.

The infrared ray blocking member according to the present invention comprises a base material,
An infrared ray blocking film formed on the surface of the base material.

The type of the base material is not particularly limited,
Various transparent and opaque substrates can be adopted.
Examples of transparent substrates include transparent inorganic glass and transparent resin glass (polycarbonate (PC), polymethylmethacrylate (PMA), etc.), as well as transparent resin (polyvinyl butyral (PVB) and polyethylene terephthalate (P).
ET) and the like) films and the like. In addition, examples of the opaque base material include a metal material and a resin material that form an outer plate or outer wall of a vehicle or a building.

The infrared ray blocking film constituting the infrared ray blocking member is composed of ZnO particles and composite particles which are coated on the surface of the ZnO particles and have a function of improving the chemical resistance of the ZnO particles, and the composite particles. And a matrix part for dispersing and holding the particles. That is, as the infrared blocking film forming the infrared blocking member according to the present invention, the infrared blocking material according to the present invention can be used as it is.

The method of forming the infrared blocking film on the surface of the substrate is not particularly limited. For example, a coating solution (solution) for forming an infrared shielding film containing a binder solution prepared by dissolving a binder to be a matrix part in a solvent, and the composite particles dispersed in the binder solution is prepared by a spray method. By brushing method, dip method or mist method,
An infrared ray blocking film can be formed on the base material by applying this coating material on the surface of the base material and then drying or curing (heat curing, ultraviolet curing, etc.). Further, a preformed film-shaped (or plate-shaped) infrared ray blocking film may be adhered to the surface of the base material with an adhesive or the like.

As described above, the infrared-shielding composite particles, the infrared-shielding film, and the infrared-shielding member according to the present invention are applied to window glass of vehicles and buildings, glass for greenhouses, outer walls of vehicles and buildings, and the like. In addition to coating films, interlayer films of laminated glass used for vehicles and buildings, etc., cathode ray tubes (C
It can be applied to various display devices such as an RT tube), a liquid crystal display (LCD) panel and a plasma display panel (PDP).

[0063]

EXAMPLES Specific examples of the present invention will be described below.

(Example 1) A material having a function of preventing clouding of ZnO particles 1 by chemicals and a function of blocking infrared rays on the surface of ZnO particles 1 having an average particle diameter of 10 nm by using a sputtering method. And the functional coat layer 2 made of ITO was formed to a thickness of 3 nm. The functional coat layer 2 has a density of 99%.

That is, using ITO as a sputtering target, Zn was placed in a container dish capable of vibration in the sputtering chamber.
O particles 1 were added. And 90% argon / 10 oxygen
% Of the target was irradiated, and the surface of the ZnO particle 1 was coated with ITO while vibrating the ZnO particle 1.

In this way, infrared shielding composite particles 3 comprising the ZnO particles 1 and the functional coating layer 2 having a predetermined function coated on the surface of the ZnO particles 1 were obtained.

Further, TiO ₂ particles having an average particle diameter of 10 nm were prepared as UV blocking particles having a UV blocking ability, and a transition metal alkoxide was prepared as a coloring component.

On the other hand, a silica sol solution containing silica sol as a main component and ethanol as an organic solvent added was prepared. Specifically, tetraethoxysilane as a metal alkoxide: 0.02 mol, deionized water: 0.04 m
and 1 mol of ethanol as an organic solvent were mixed to prepare a silica sol solution.

Then, to the silica sol solution, 3:20 wt% of the composite particles, 10 wt% of TiO ₂ particles as the UV blocking particles, and 0.05 wt% of the transition metal alkoxide were added and uniformly added. By dispersing, a barrier film forming solution was obtained.

In the solution for forming the barrier film,
The addition amount of the composite particles 3 is preferably 10 to 40 wt% (20 wt% in this embodiment), and the addition amount of the ultraviolet blocking particles is 5 to 30 wt% (10 w in this embodiment).
t%) is preferable.

The obtained barrier film forming solution was applied to the surface of the transparent substrate 4 made of an inorganic glass plate by a spray method to a predetermined thickness. Then, a hard infrared ray blocking film 6 (thickness: 200 nm) was formed on the surface of the transparent substrate 4 by heat treatment at 400 ° C. to cause a dehydration condensation reaction.

Thus, the transparent substrate 4 and this transparent substrate 4
Infrared ray blocking member formed on the surface of the composite particle 3 and an infrared ray blocking film 6 as an infrared ray blocking material comprising a matrix portion 5 (where the matrix portion is made of silica) for uniformly dispersing and holding the ultraviolet ray blocking particles. Got 7.

In the infrared blocking member 7, the functional coat layer 2 of the composite particle 3 is made of ITO. The ITO has a function of preventing clouding of ZnO particles due to chemicals. Therefore, the infrared blocking member 7 has improved chemical resistance.

Comparative Example 1 ZnO used in Example 1 above
Particles: 20 wt%, n-butoxy titanate titanate monomer as an organic titanium compound: 20 wt%, and a solution obtained by mixing ethanol as an organic solvent were applied to the surface of the inorganic glass plate used in Example 1. Then, the solvent was evaporated by leaving it to form a ZnO particle layer on the surface of the inorganic glass plate. Then, after applying the silica sol solution used in the above-mentioned Example 1 on this ZnO particle layer, 30
Heat treatment was performed at 0 ° C. As a result, a barrier layer formed by bonding ZnO particles with silica was formed, and a silica protective layer made of only silica was formed on the barrier layer by the silica sol accumulated on the ZnO particle layer.

Thus, a transparent substrate made of an inorganic glass plate, a blocking layer as a first layer formed on the transparent substrate, and a silica protective layer as a second layer formed on the first layer. An infrared shielding member having a two-layer structure was obtained.

(Evaluation of Chemical Resistance) The infrared ray blocking members obtained in Example 1 and Comparative Example 1 were evaluated for chemical resistance. This is the surface of each sample placed on a flat surface under the conditions of a temperature of 23 ° C. and a humidity of 60% (the surface of the infrared blocking film 6 for the infrared blocking member 7 of the present Example 1, the infrared blocking member of Comparative Example 1). For the surface of the silica protective layer)
1 cc of each of the chemicals was dripped on, and after 12 hours, the degree of whitening was visually examined to compare the carbonation prevention performance of ZnO. The results are shown in Table 1. In addition,
In Table 1, ∘ indicates that whitening did not occur, Δ indicates that slight clouding was observed, and x indicates that whitening was complete.

[0077]

[Table 1]

As is clear from Table 1, the infrared ray blocking member 7 of the present Example 1 can be used for any chemicals such as acidic solution (sulfuric acid), alkaline solution (sodium hydroxide), salt water and fruit juice (mandarin orange). It did not turn cloudy and showed good chemical resistance. This is because in the infrared ray blocking member 7 of Example 1, the individual ZnO particles 1 were reliably covered by the functional coating layer 2 made of ITO having a function of preventing clouding of the ZnO particles 1 due to chemicals. Because there is
It is considered that it was possible to reliably prevent the chemical from reaching the nO particles 1.

On the other hand, the infrared shielding member of Comparative Example 1 was clouded or whitened when each of the chemicals adhered. This is considered to be because the infrared blocking member of Comparative Example 1 had ZnO particles protruding on the outermost surface and that chemicals entered through the pores of the silica protective layer.

(Example 2) As the composite particles 3, the surface of ZnO particles 1 having an average particle diameter of 15 nm was subjected to the sol-gel method.
The functional coating layer 2 made of SiO ₂ as a material having a function of preventing the clouding of ZnO particles due to a chemical is formed in a thickness of 4 n.
The procedure is the same as in Example 1 above, except that a film having a thickness of m is used.

That is, silica gel (ethyl silicate): 3 wt% and isopropyl alcohol: 20 wt% were mixed in deionized water, and Zn was added thereto while stirring.
3% by weight of O particles 1 was added. Then, diluted hydrochloric acid was added to adjust the pH to 2-3. As a result, due to the relationship of the zeta potential, the Si gel core particles were aggregated on the surface of the ZnO particles 1. After that, by heat treatment 300 ° C. to dehydration condensation reaction, thereby forming a functional coating layer 2 made of SiO ₂ on the surface of the ZnO grains 1.

In this way, infrared shielding composite particles 3 comprising ZnO particles 1 and the functional coating layer 2 having a predetermined function coated on the surface of the ZnO particles 1 were obtained.

After that, the infrared ray blocking member 7 was obtained in the same manner as in Example 1 above.

In this infrared ray blocking member 7, the functional coat layer 2 of the composite particles 3 is made of SiO ₂ . And
This SiO ₂ has a function of preventing clouding of ZnO particles due to chemicals. Therefore, this infrared blocking member 7
Has improved chemical resistance.

(Example 3) An infrared blocking member 7 was obtained in the same manner as in Example 1 except that ultraviolet blocking particles having an ultraviolet blocking ability were not added.

(Evaluation of Infrared Blocking Performance and Ultraviolet Blocking Performance) With respect to the infrared blocking member 7 of Examples 1 to 3 above, a light transmission spectrum was measured using a spectrophotometer to obtain a transmittance spectral curve. For comparison, a transmittance spectral curve was similarly obtained for the inorganic glass plate constituting the transparent substrate 4. The results are shown in FIG. In addition, in FIG.
The thick line indicates the result of Example 1, the thin line indicates the result of Example 2, the dotted line indicates the result of Example 3, and the alternate long and short dash line indicates the result of the inorganic glass plate.

As is apparent from FIG. 3, the present Examples 1 to 3 were used.
The infrared ray blocking members 7 of Nos. 6 and 7 showed good infrared ray blocking performance and ultraviolet ray blocking performance. The infrared blocking member 7 of Example 1 having the functional coat layer 2 made of ITO exhibited particularly good infrared blocking performance and ultraviolet blocking performance.

In addition, the infrared ray blocking ability of the first embodiment is the same as that of the second embodiment.
The reason why it is slightly better than that is that the ITO constituting the functional coat layer 2 has an infrared ray blocking ability.

The ultraviolet blocking performance of Examples 1 and 2 is superior to that of Example 3 because the ultraviolet blocking particles are added to the infrared blocking film 6 separately. In addition, the reason why the infrared blocking member 7 of Example 3 to which ultraviolet blocking particles are not separately added exhibits the ultraviolet blocking performance is that the ZnO particles 1 have the ultraviolet blocking ability.

(Example 4) As the composite particles 3, a functional coat layer 2 made of TiO ₂ as a material having a function of blocking ultraviolet rays was formed on the surface of ZnO particles 1 having an average particle diameter of 15 nm to a thickness of 4 nm. Using the one formed in
Further, an infrared blocking member 7 was obtained in the same manner as in Example 1 except that the ultraviolet blocking particles having the ultraviolet blocking ability were not added. The functional coat layer 2 was formed by using a sol-gel method using n-butoxy titanate monomer as a raw material and isopropyl alcohol and ion-exchanged water.

With respect to the infrared blocking member 7 thus obtained, a light transmission spectrum was measured using a spectrophotometer in the same manner as described above to obtain a transmittance spectral curve. As a result, the infrared blocking member 7 of the present Example 4 showed good infrared blocking performance and ultraviolet blocking performance comparable to those of the above Example 2.

(Example 5) As composite particles 3, on the surface of ZnO particles 1 having an average particle diameter of 15 nm, ITO as a material having a function of blocking infrared rays and TiO as a material having a function of blocking ultraviolet rays are used. the use of the functional coating layer 2 made of ₂ that was formed to a thickness of 4 nm, and except that no addition of UV blocking particles having ultraviolet screening ability, in the same manner as in example 1, an infrared blocking member 7 Got The functional coat layer 2 made of two or more kinds of materials was formed by adding isopropyl alcohol, ion-exchanged water and ITO particles to a titanate n-butoxy monomer and using a sol-gel method.

With respect to the obtained infrared shielding member 7, the light transmission spectrum was measured using a spectrophotometer in the same manner as described above, and the transmittance spectral curve was obtained. As a result, the infrared ray blocking member 7 of Example 5 exhibited the same good infrared ray blocking performance and ultraviolet ray blocking performance as those of Example 1 above.

Example 6 As composite particles 3, ZnO particles with a chemical agent were formed on the surface of ZnO particles 1 having an average particle diameter of 15 nm.
A functional coat layer 2 made of SiO _{2 having} a function of preventing clouding of particles and a function of preventing decomposition of an organic material by ZnO particles was formed to a thickness of 4 nm. The functional coat layer 2 was formed by the sol-gel method.

On the other hand, acrylic resin (methyl acrylate) as a coating resin used for coating a vehicle outer panel: 80 wt% and toluene as a solvent: 20 wt.
% Of 30% by weight of the composite particles 3 and uniformly dispersed,
A coating material for coating the outer panel was prepared by mixing. The amount of the composite particles 3 added to the coating material for coating the outer panel was 10%.
It is preferably about 40 to 40 wt% (30 wt% in this embodiment).

The obtained coating material for coating the outer panel is applied to the surface of an opaque base material made of a vehicle outer panel ( steel material) with a predetermined thickness by a spray method, and an infrared ray blocking film is formed on the surface of the opaque base material. Was formed as a coating film (thickness: 100 μm).

Thus formed on the surface of the opaque substrate,
An infrared blocking film as an infrared blocking material comprising a matrix part (where the matrix part is made of acrylic resin) for uniformly dispersing and holding the composite particles 3 was obtained.

Since the infrared ray can be blocked by this infrared ray blocking film, it is possible to suppress the temperature rise in the passenger compartment in the summer.

In the infrared ray blocking film as the infrared ray blocking material, the functional coating layer 2 of the composite particles 3 is made of Si.
It consists of O ₂ . And this SiO ₂ is Z
It has both the function of preventing white turbidity of nO particles and the function of preventing decomposition of an organic material by ZnO particles. Therefore, the infrared blocking film as the infrared blocking material has improved chemical resistance. Further, since the acrylic resin forming the matrix portion can be prevented from being decomposed, the durability of the infrared ray blocking film as the infrared ray blocking material can be improved.

(Example 7) As composite particles 3, ZnO particles with an average particle diameter of 15 nm were formed on the surface of ZnO particles 1 by a chemical agent.
A functional coat layer 2 made of SiO _{2 having} a function of preventing clouding of particles and a function of preventing decomposition of an organic material by ZnO particles was formed to a thickness of 4 nm. The functional coat layer 2 was formed by the sol-gel method.

On the other hand, 30 wt% of the above composite particles 3 was added to PVB (polyvinyl butyral) and uniformly dispersed and mixed to prepare a molten resin. The amount of the composite particles 3 added to the molten resin is preferably about 10 to 40 wt% (30 wt% in this embodiment).

The obtained molten resin was injection-molded into a plate shape and then rolled into a film to form a transparent resin film (thickness: 300 μm).

Thus, the composite particles 3 are uniformly dispersed,
A transparent resin film as an infrared shielding material comprising a matrix portion to be held (the matrix portion is made of PVB) was obtained.

Then, this transparent resin film was attached as an intermediate film to a predetermined inorganic glass plate as a transparent substrate. Thus, as an infrared ray blocking film (infrared ray blocking material) comprising a transparent base material and a matrix part (the matrix part is made of PVB) formed on the surface of the transparent base material and uniformly dispersing and holding the composite particles 3 therein. A laminated glass for a vehicle front windshield was prepared as an infrared ray blocking member composed of the transparent resin film.

In this laminated glass, since the infrared ray can be blocked by the infrared ray blocking film, it is possible to suppress the temperature rise in the passenger compartment in the summer.

In this infrared ray blocking member, the functional coat layer 2 of the composite particles 3 is made of SiO ₂ . This SiO ₂ is the PVB that constitutes the matrix part.
Since it exhibits the function of preventing the decomposition of the infrared shielding film, the durability of the infrared shielding film as the infrared shielding material is improved.

(Example 8) As composite particles 3, ZnO particles with an average particle diameter of 15 nm were formed on the surface of ZnO particles 1 by chemicals.
A functional coat layer 2 made of SiO _{2 having} a function of preventing clouding of particles and a function of preventing decomposition of an organic material by ZnO particles was formed to a thickness of 4 nm. The functional coat layer 2 was formed by the sol-gel method.

On the other hand, 30 wt% of the composite particles 3 is added to PC.
A molten resin that was added, uniformly dispersed, and mixed was prepared. In addition, the addition amount of the composite particles 3 in the molten resin is 10 to 40.
It is preferable to set it to about wt% (30 wt% in this embodiment).

The obtained molten resin was formed into a plate shape by injection molding to form a transparent resin glass (thickness: 5 mm) for vehicles.

Thus, the composite particles 3 are uniformly dispersed,
A transparent resin glass as an infrared ray blocking material comprising a matrix portion (the matrix portion is made of PET) to be held was obtained.

If this transparent resin glass is used for a window glass for a vehicle or the like, it is possible to block infrared rays, so that it is possible to suppress the temperature rise in the vehicle interior in the summer.

Further, in this infrared ray blocking material,
The functional coat layer 2 of the particles 3 is SiO ₂Consists of. That
And this SiO₂Is the cloudiness of ZnO particles caused by chemicals.
Preventable function and decomposition of organic materials by ZnO particles
It also has preventable functions. Therefore, this infrared block
The transparent resin glass as a material has improved chemical resistance.
Also, it prevents the disassembly of the PC that constitutes the matrix section.
Since it is possible to use transparent resin glass as an infrared shielding material
The durability of the fabric is also improved.

[0113]

INDUSTRIAL APPLICABILITY As described in detail above, according to the present invention, the composite particles for infrared ray shielding, which are obtained by forming a desired functional coating layer on the surface of ZnO particles, are used as an infrared ray shielding film or an infrared ray shielding member. It is to be dispersed and held in the matrix portion constituting the barrier material. Therefore, according to the present invention, by providing the functional coat layer with a desired function, it is possible to provide an infrared ray blocking member or an infrared ray blocking member capable of solving the problems in the prior art.

That is, an infrared ray blocking member or an infrared ray blocking member capable of preventing clouding due to the attachment of chemicals such as fruit juice, blocking ultraviolet rays, and preventing decomposition and deterioration of the matrix portion made of an organic material. It becomes possible to provide.

[Brief description of drawings]

FIG. 1 is a cross-sectional view of infrared-shielding composite particles according to this example.

FIG. 2 is a sectional view of an infrared ray blocking member according to the present embodiment.

FIG. 3 is a transmittance spectral curve for evaluating the infrared blocking performance and the ultraviolet blocking performance of the infrared blocking member according to the present embodiment.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1 ... ZnO particle 2 ... Functional coat layer 3 ... Composite particle 4 ... Transparent base material 5 ... Matrix part 6 ... Infrared ray blocking film (infrared ray blocking material) 7 ... Infrared ray blocking member

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Masayuki Ichiyanagi             1 Toyota Town, Toyota City, Aichi Prefecture Toyota Auto             Car Co., Ltd. F term (reference) 4J037 AA11 CA09 CA12 CA24 EE03                       EE23 FF13                 4J038 HA212 HA441 MA03 NA19                       PB05 PB07 PC03

Claims (12)

[Claims] 1. A composite particle for infrared ray shielding, which is dispersed and held in a transparent matrix portion and exhibits an infrared ray shielding ability, wherein the ZnO particle and the surface of the ZnO particle have a predetermined function. A composite particle for blocking infrared rays, which comprises a transparent coat layer. 2. The infrared-shielding composite particles according to claim 1, wherein the functional coat layer has a function of preventing clouding of the ZnO particles due to a chemical. 3. The infrared-shielding composite particle according to claim 1, wherein the functional coat layer has a function of blocking ultraviolet rays. 4. The infrared shielding composite particle according to claim 1, wherein the functional coat layer has a function of preventing decomposition of an organic material by the ZnO particles. 5. A composite particle comprising ZnO particles and a functional coating layer having a predetermined function coated on the surface of the ZnO particle, and a transparent matrix part for dispersing and holding the composite particle. Infrared blocking material. 6. The infrared blocking material according to claim 5, wherein the functional coating layer has a function of preventing clouding of the ZnO particles due to a chemical. 7. The infrared ray blocking material according to claim 5, wherein the functional coating layer has a function of blocking ultraviolet rays. 8. The matrix portion is made of an organic material, and the functional coating layer has a function of preventing decomposition of the organic material by the ZnO particles. Infrared blocking material. 9. An infrared blocking member comprising a base material and an infrared blocking film formed on the surface of the base material, wherein the infrared blocking film is ZnO particles and a predetermined coating coated on the surface of the ZnO particles. An infrared ray blocking member comprising: a composite particle comprising a functional coat layer having the above function; and a transparent matrix part for dispersing and holding the composite particle. 10. The infrared ray blocking member according to claim 9, wherein the functional coating layer has a function of preventing clouding of the ZnO particles due to a chemical. 11. The infrared ray blocking member according to claim 9, wherein the base material is a transparent base material, and the functional coating layer has a function of blocking ultraviolet rays. 12. The matrix portion is made of an organic material, and the functional coat layer has a function of preventing decomposition of the organic material by the ZnO particles. Infrared blocking member.