JP2013119511A - Coated member - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a coated member in which, though a coating layer containing a silicon compound is disposed on a substrate containing an alkali component, attack of the coating layer by the alkali component in the substrate can be suppressed over a long period of time.SOLUTION: The coated member 1 comprises a substrate 2 containing an alkali component, a coating layer 3 containing a silicon compound, and an intermediate layer 4 interposed between the substrate 2 and the coating layer 3. The intermediate layer 4 contains at least one selected from calcium oxide, aluminum oxide, boron oxide, zirconium oxide, titanium oxide, hafnium oxide, and cerium oxide.

Description

  The present invention relates to a covering member provided with a covering layer containing a silicon compound.

  A coating layer containing a silicon compound has been widely applied to impart various functions to various members.

  For example, a coating layer (antireflection layer) made of a silica film formed by a sol-gel method or the like and further containing hollow silica particles is applied for antireflection in an optical member. Further, a coating layer (photocatalyst layer) composed of a silica film formed by a sol-gel method or the like and further containing a photocatalyst such as titanium oxide is applied for improving the antifouling property of the member. The antireflection layer is used for improving visibility and improving transmittance by reducing surface reflectance in advertising display devices such as digital signage for outdoor use and solar cells that have been attracting attention in recent years. Moreover, a photocatalyst layer is utilized in order to provide antifouling properties to the surfaces of glass for building members, exterior materials, and the like.

  Such a coating layer containing a silicon compound has a problem that it is weak against an alkali component. For example, base materials such as tempered glass, optical glass, and outer wall materials often contain alkali components such as sodium and lithium, and a coating layer is formed on such a base material. When moisture enters the interface between the coating layer and the coating layer, the alkali component moves from the base material to the coating layer through this moisture, and this causes the alkali component to react with the coating layer, resulting in deterioration of the coating layer. May end up. If it does so, malfunction will arise, such as a deterioration of the appearance of a coating layer, the fall of intensity | strength, and the fall of the function of a coating layer.

  As a method for coping with the problem due to the alkali component, for example, in Patent Document 1, a chemically strengthened glass substrate is formed by chemically strengthening a glass substrate, and a transparent conductive film is formed on the chemically strengthened glass substrate. In a chemically strengthened glass substrate with a conductive film, an alkali intermediate layer such as silicon oxide may be provided between the glass substrate and the transparent conductive film in order to prevent alkali migration from the glass substrate to the transparent conductive film such as a tin oxide film. Are disclosed.

JP 2004-131314 A (paragraph 0034)

  However, even if an alkali intermediate layer is formed from silicon oxide as in Patent Document 1, the alkali intermediate layer is attacked by an alkali component. That is, in Patent Document 1, by sacrificing the alkali intermediate layer, the time required for the alkali component to reach the transparent conductive film from the glass substrate is merely prolonged.

  For this reason, even if it uses the technique of patent document 1 in order to protect a coating layer from an alkaline component, sufficient effect cannot be expected.

  The present invention has been made in view of the above-mentioned reasons. The object of the present invention is to provide a coating layer containing a silicon compound on a base material containing an alkali component, although the coating layer is based on this coating layer. An object of the present invention is to provide a covering member that can be inhibited from being attacked by an alkali component in a material for a long period of time.

The covering member according to the present invention comprises a base material containing an alkali component, a covering layer containing a silicon compound, and an intermediate layer interposed between the base material and the covering layer,
The intermediate layer includes at least one of calcium oxide, aluminum oxide, boron oxide, zirconium oxide, titanium oxide, hafnium oxide, and cerium oxide.

  In the present invention, the intermediate layer may be composed of oxide particles composed of at least one of calcium oxide, aluminum oxide, boron oxide, zirconium oxide, titanium oxide, hafnium oxide, and cerium oxide, and an inorganic matrix. Good.

  In the present invention, the intermediate layer may be made of a metal oxide selected from calcium oxide, aluminum oxide, boron oxide, zirconium oxide, titanium oxide, hafnium oxide, and cerium oxide.

  In this invention, it is preferable that the ratio of the said oxide particle in the said intermediate | middle layer is the range of 5-90 mass%.

  According to the present invention, although the coating layer containing the silicon compound is provided on the base material containing the alkali component, the intermediate layer prevents the coating layer from being attacked by the alkali component in the base material for a long time. It can be suppressed over the range.

It is sectional drawing of the coating | coated member which shows one Embodiment of this invention.

  In the present embodiment, the covering member 1 includes a base material 2 containing an alkali component, a covering layer 3 containing a silicon compound, and an intermediate layer 4 interposed between the base material 2 and the covering layer 3. . That is, the covering member 1 includes a base material 2, an intermediate layer 4, and a covering layer 3, and has a structure in which the base material 2, the intermediate layer 4, and the covering layer 3 are laminated in this order.

  If the base material 2 contains an alkali component, it will not be restrict | limited especially, For example, the board | plate material formed from the glass containing an alkali component, the inorganic type base material 2, the metal type base material 2, etc. are mentioned. Examples of the glass containing an alkali component include soda lime glass.

  The intermediate layer 4 includes at least one of calcium oxide, aluminum oxide, boron oxide, zirconium oxide, titanium oxide, hafnium oxide, and cerium oxide. These oxides have a relatively stable bond, and therefore hardly react with alkali components such as sodium and lithium. For this reason, the alkali resistance of the intermediate layer 4 containing these oxides is high. For this reason, even if an alkali component enters the intermediate layer 4 from the base material 2 through moisture that has entered the base material 2 or the like from the air, the intermediate layer 4 is hardly deteriorated or decomposed. Since the component remains, the movement of the alkaline component from the intermediate layer 4 to the coating layer 3 is suppressed over a long period of time.

  In the intermediate layer 4, the refractive index of the intermediate layer 4 varies according to the ratio of the oxide in the intermediate layer 4. For this reason, it is also possible to control the optical characteristics of the covering member 1 by adjusting the kind and ratio of the oxide in the intermediate layer 4. In particular, when the coating layer 3 is an antireflection layer having a low refractive index, the refractive index of the intermediate layer 4 is made higher than that of the antireflection layer by appropriately setting the type and ratio of the oxide particles in the intermediate layer 4. At the same time, by appropriately controlling the value of the refractive index, the light reflectance of the covering member 1 can be greatly reduced, and thereby the function of the covering member 1 can be enhanced.

  In the first aspect of the present embodiment, the intermediate layer 4 is composed of an inorganic matrix and oxide particles dispersed in the inorganic matrix. The inorganic matrix is composed of, for example, siloxane (silicone). The intermediate layer 4 is preferably formed by a wet film forming method. In this case, the intermediate layer 4 is formed from a coating composition containing, for example, a matrix forming material and oxide particles.

  Examples of the matrix forming material include hydrolyzable silicon compounds such as methyl silicate and tetraethyl orthosilicate (TEOS).

  The oxide particles are made of at least one of calcium oxide, aluminum oxide, boron oxide, zirconium oxide, titanium oxide, hafnium oxide, and cerium oxide. The oxide particles may include only one kind or two or more kinds of the oxide particles. The average particle size of the oxide particles is not particularly limited, but from the viewpoint of improving the strength of the intermediate layer 4 and ensuring good transparency of the intermediate layer 4, the average particle size may be 100 nm or less. The range is preferably 5 to 80 nm, more preferably 10 to 60 nm. The average particle diameter is a volume average diameter measured by a dynamic light scattering method, and is measured using, for example, a dynamic light scattering photometer (model number DLS-6500) manufactured by Otsuka Electronics Co., Ltd.

  When the coating composition is prepared, oxide particles having an appropriate form are used. For example, a powder of oxide particles is used, or a sol containing oxide particles is used. When a sol containing oxide particles, that is, an oxide colloid is used, for example, a water-dispersible oxide colloid is used, or a hydrophilic organic solvent-dispersible oxide colloid such as alcohol is used. In general, such an oxide colloid contains 5 to 50% by mass of oxide fine particles as a solid content, and the blending amount of the oxide particles can be determined from this value.

  In this embodiment, the ratio of the oxide particles in the intermediate layer 4 is not particularly limited, but is preferably in the range of 5 to 90% by mass, and more preferably in the range of 30 to 70% by mass. That is, when the intermediate layer 4 is formed from the coating composition, the content of the oxide particles in the coating composition is in the range of 5 to 90% by mass with respect to the total solid content in the coating composition. It is more preferable that it is in the range of 30 to 70% by mass. If this ratio is 5 mass% or more, preferably 30 mass% or more, the alkali resistance of the intermediate layer 4 is sufficiently improved by the oxide particles. Further, when this ratio is 90% by mass or less, preferably 70% by mass or less, good adhesion between the intermediate layer 4 and the substrate 2 and between the intermediate layer 4 and the coating layer 3 is obtained. Therefore, the performance of the coating layer 3 such as adhesion and wear resistance is maintained high.

  The intermediate layer 4 can be formed on the substrate 2 by applying such a coating composition on the substrate 2 and further drying and curing the coating composition.

  The method for applying the coating composition onto the substrate 2 is not particularly limited. For example, brush coating, spray coating, dipping (dipping, dip coating), roll coating, flow coating, curtain coating, knife coating, spin coating. Selected from various conventional coating film forming methods such as table coat, sheet coat, sheet coat, die coat, bar coat, meniscus coater, flexographic printing, screen printing, and bead coater.

  The coating composition applied to the substrate 2 is preferably further heat-treated after being dried. By this heat treatment, the mechanical strength of the intermediate layer 4 is further improved. Conditions for the heat treatment may be appropriately set so that the effect of the heat treatment can be sufficiently obtained. For example, the heating temperature is set to a relatively low temperature, for example, a range of 100 to 300 ° C., and the processing time is set to a range of 5 to 30 minutes. It is preferable that In addition, when the coating composition contains a hydrolyzable silicon compound and the coating composition is cured by the hydrolysis reaction of the hydrolyzable silicon compound, the heat treatment temperature is low even if the heat treatment temperature is as low as about 100 ° C. Since the mechanical strength equivalent to that at a high temperature can be given to the intermediate layer 4, the manufacturing cost can be reduced. In particular, when the base material 2 is made of glass, since the thermal conductivity of the base material 2 is low, it takes time to raise the temperature and cool down. Therefore, the higher the heat treatment temperature, the longer the time required for the treatment. On the contrary, when the processing temperature is low, the time required for the processing is shortened, so that the manufacturing efficiency is improved.

  When the coating composition is applied and formed in this manner, the matrix forming material is hydrolyzed in a state where the matrix forming material and the oxide particles are mixed in the coating composition, thereby forming an inorganic matrix. The oxide fine particles are fixed in a dispersed state in the inorganic matrix. Thereby, the intermediate | middle layer 4 comprised from an inorganic matrix and the oxide particle disperse | distributed in this inorganic matrix is formed.

  When the intermediate layer 4 is configured in this way, oxide particles that are stable with respect to the alkali component are dispersed in the intermediate layer 4, thereby reducing the proportion of the inorganic matrix in the intermediate layer 4. For this reason, even when the inorganic matrix is composed of siloxane (silicone) that easily reacts with the alkali component, Si—O bonds that easily react with the alkali component are reduced in the intermediate layer 4, and as a result, the intermediate layer The number of sites that react by being attacked by the alkali component in 4 is reduced. For this reason, a sufficiently high alkali resistance is imparted to the intermediate layer 4, and thus the movement of the alkali component from the intermediate layer 4 to the coating layer 3 is suppressed over a long period of time.

  In the second aspect of the present embodiment, the intermediate layer 4 is made of a metal oxide selected from calcium oxide, aluminum oxide, boron oxide, zirconium oxide, titanium oxide, hafnium oxide, and cerium oxide.

  The intermediate layer 4 is preferably formed by a wet film forming method. For example, in this embodiment, the intermediate layer 4 includes a calcium hydrolyzable compound, an aluminum hydrolyzable compound, a boron hydrolyzable compound, a zirconium hydrolyzable compound, a titanium hydrolyzable compound, and a hafnium hydrolyzable compound. It is formed from a coating composition containing at least one of a compound and a hydrolyzable compound of cerium. Examples of such hydrolyzable compounds include calcium alkoxide, aluminum alkoxide, boron alkoxide, zirconium alkoxide, titanium alkoxide, hafnium alkoxide, cerium alkoxide and the like. The coating composition may contain appropriate additives other than these hydrolyzable compounds.

  Using such a coating composition, the coating composition is applied onto the substrate 2 in the same manner as in the first embodiment, and further, this coating composition is dried and formed into a film so that an intermediate is formed on the substrate 2. Layer 4 can be formed.

  In the second embodiment, the intermediate layer 4 made of a metal oxide selected from calcium oxide, aluminum oxide, boron oxide, zirconium oxide, titanium oxide, hafnium oxide, and cerium oxide is formed by a dry process such as vapor deposition or sputtering. You may form by the film-forming method.

  The intermediate layer 4 may be composed of only one layer containing the oxide as described above, but may be composed of two or more layers containing the oxide. Moreover, the intermediate | middle layer 4 may be comprised from the layer in which multiple types of oxides were mixed.

  Although the thickness of the intermediate layer 4 is appropriately set, the thickness is preferably 5 nm or more so that the alkali component of the coating layer 3 is sufficiently suppressed from being attacked by the alkali component. The thickness of the intermediate layer 4 is further preferably in the range of 5 to 1000 nm, and more preferably in the range of 10 to 300 nm.

  As long as the coating layer 3 contains a silicon compound, the details thereof are not particularly limited, and the coating layer 3 having an appropriate configuration is formed according to the intended use and purpose of the coating member 1. Specific examples of the coating layer 3 include the following antireflection layer and photocatalyst layer.

  The antireflection layer is a low refractive index layer including an inorganic matrix made of, for example, siloxane (silicone). The refractive index of the antireflection layer is, for example, in the range of 1.30 to 1.45. The antireflection layer is formed, for example, from a composition containing a binder material made of a silicon compound and particles for adjusting the refractive index used as necessary. When the binder material and the particles for adjusting the refractive index are used in combination, the refractive index of the antireflection layer is appropriately adjusted depending on the combination, blending ratio, and the like.

For example, a hydrolyzable silicon compound is used as the binder material. As the hydrolyzable silicon compound, silicon alkoxide represented by R _m Si (OR ′) _n (R and R ′ are alkyl groups having 1 to 10 carbon atoms, m + n = 4, m and n are integers). Examples include oligomers and polymers that are partially hydrolyzed condensates. Specific examples of the silicon alkoxide include tetramethoxysilane, tetraethoxysilane, tetra-iso-propoxysilane, tetra-n-propoxysilane, tetra-n-butoxysilane, tetra-sec-butoxysilane, and tetra-tert-butoxy. Silane, tetrapentaethoxysilane, tetrapenta-iso-propoxysilane, tetrapenta-n-propoxysilane, tetrapenta-n-butoxysilane, tetrapenta-sec-butoxysilane, tetrapenta-tert-butoxysilane, methyltrimethoxysilane, methyltriethoxy Silane, methyltripropoxysilane, methyltributoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethylethoxysilane, dimethylmethoxysilane, di Chill propoxysilane, dimethyl-butoxy silane, methyl dimethoxy silane, methyl diethoxy silane, hexyl trimethoxy silane, and the like.

  As the binder material, a reactive organosilicon compound having a plurality of groups (polymerizable double bond groups and the like) that undergo reactive crosslinking by heat or ionizing radiation may be used. The molecular weight of the organosilicon compound is preferably 5000 or less. Such reactive organosilicon compounds are obtained by reacting one terminal vinyl functional polysilane, both terminal vinyl functional polysilane, one terminal vinyl functional polysiloxane, both terminal vinyl functional polysiloxane, and these compounds. Examples include vinyl functional polysilanes and vinyl functional polysiloxanes. In addition to these, examples of the reactive organosilicon compound include (meth) acryloxysilane compounds such as 3- (meth) acryloxypropyltrimethoxysilane and 3- (meth) acryloxypropylmethyldimethoxysilane.

  As the particles for adjusting the refractive index, it is preferable to use particles having a relatively low refractive index. Examples of the material for adjusting the refractive index include silica, magnesium fluoride, lithium fluoride, aluminum fluoride, calcium fluoride, sodium fluoride, and the like. It is preferable that the refractive index adjusting particles include hollow particles. A hollow particle is a particle having a cavity surrounded by an outer shell. The refractive index of the hollow particles is preferably 1.20 to 1.45. As particles for adjusting the refractive index, it is particularly preferable to use hollow particles (hollow silica) made of silica.

  The particles for adjusting the refractive index are preferably subjected to a surface treatment for improving the wettability with the binder material, if necessary.

  The particle diameter of the refractive index adjusting particles is preferably sufficiently small, that is, the refractive index adjusting particles are preferably so-called ultrafine particles, and in this case, the light transmittance of the antireflection layer is sufficiently maintained. Become. The particle diameter of the particles for adjusting the refractive index is particularly preferably in the range of 0.5 nm to 200 nm. The particle diameter of the particles for adjusting the refractive index is the diameter of a circle (area equivalent circle) having the same area as the projected area calculated from the electron micrograph image of the particles.

  The content of the particles for adjusting the refractive index in the antireflection layer is appropriately adjusted so that the refractive index value of the antireflection layer becomes an appropriate value. In particular, the particles for adjusting the refractive index in the antireflection layer. It is preferable to adjust so that the ratio may become 20-99 volume%.

  The composition may further contain a water and oil repellent material. In this case, antifouling properties can be imparted to the antireflection layer. As the water and oil repellent material, a general wax-based material or the like can be used. In particular, when a fluorine-containing compound is used, the removability of the antireflection layer such as dirt and fingerprints is particularly improved, and the frictional resistance of the surface of the antireflection layer is reduced to improve the wear resistance of the antireflection layer.

  The antireflection layer is preferably formed from a composition containing tetramethoxysilane partial hydrolysis condensate as a binder material and hollow silica particles as refractive index adjusting particles. In this case, it is particularly easy to reduce the refractive index of the antireflection layer.

  In the antireflection layer, the composition as described above is applied on the intermediate layer 4, and this composition is further subjected to treatment such as heating, humidification, ultraviolet irradiation, and electron beam irradiation according to the properties of the binder material. It can be formed by curing.

  The thickness of the antireflection layer is appropriately set according to the performance required for the antireflection layer, and is, for example, in the range of 50 to 400 nm.

  A photocatalyst layer is a layer provided with the inorganic matrix comprised, for example from siloxane (silicone), and the photocatalyst currently disperse | distributed in this inorganic matrix. The photocatalyst layer is formed, for example, by coating a coating composition containing a photocatalyst on the surface of the intermediate layer 4.

  The coating composition contains, for example, a partial hydrolysis condensate of silicon alkoxide. The coating composition is prepared, for example, by adding a condensation reaction catalyst such as polyorganosiloxane or an alkyl titanate to a silica-dispersed oligomer solution of organosilane, or further adding silica.

  Photocatalysts include titanium oxide, zinc oxide, tin oxide, iron oxide, zirconium oxide, tungsten oxide, chromium oxide, molybdenum oxide, ruthenium oxide, germanium oxide, lead oxide, cadmium oxide, copper oxide, vanadium oxide, niobium oxide, oxide In addition to metal oxides such as tantalum, manganese oxide, cobalt oxide, rhodium oxide, nickel oxide, and rhenium oxide, strontium titanate and the like can be given. Among these metal oxides, titanium oxide is particularly preferable in terms of its photocatalytic performance, safety, availability, and cost. In addition, when using titanium oxide as a photocatalyst, it is stronger to use a crystal type of anatase type (anatase type), and the photocatalytic performance and curing accelerating performance are strong. Is preferable in that it develops in a shorter time. Only one photocatalyst may be used, or two or more photocatalysts may be combined.

  The content of the photocatalyst in the photocatalyst layer is not particularly limited, but is preferably in the range of, for example, 20 to 80% by mass with respect to the photocatalyst layer, that is, 20% of the total solid content in the inorganic paint containing the photocatalyst. It is preferable to be in the range of ˜80 mass%.

  Such an inorganic paint is applied by, for example, electrostatic coating or spray coating, and then baked and dried at 60 to 120 ° C. to form a photocatalyst layer. The thickness of the photocatalyst layer is not particularly limited, but is formed in the range of 0.2 to 10 μm, for example.

  The covering member 1 configured as described above deteriorates due to the alkali component of the covering layer 3 even when used in an environment that is particularly susceptible to the effects of ultraviolet rays, rain, humidity, etc., such as outdoors, and requires high durability. Is suppressed over a long period of time. For this reason, the performance of the coating layer 3 comes to be exhibited stably over a long period of time.

  The use of the covering member 1 is not particularly limited. For example, a member constituting the outermost surface portion of an outdoor display (glass with a functional film); automotive side mirror, front glass, side glass, rear glass, and other vehicle glass ( Glass with functional film for automobiles); building material glass (glass with functional film for building materials) and exterior materials; members constituting the light path such as glass with functional film in optical devices such as solar cells, etc. Can be mentioned. The covering member 1 is particularly preferably used for outdoor applications that require high weather resistance.

  In addition to these applications, high durability is required, and any application that suppresses the deterioration of the coating layer 3 due to the alkali component in the substrate 2 can be widely applied.

  Hereinafter, the present invention will be described with reference to examples. The present invention is not limited to these examples.

[Example 1]
In this example, an antireflection layer composed of hollow silica particles and a silicon-based inorganic matrix was first selected as the coating layer, and the difference in performance deterioration of the antireflection layer due to the presence or absence of an intermediate layer was verified.

(Example 1-1)
A coating composition for forming an antireflection layer was prepared as follows. First, 72.23 parts by mass of propylene glycol monomethyl ether and 3.78 parts by mass of an aqueous nitric acid solution (0.1N) were added to 3.92 parts by mass of methyl silicate MS51 manufactured by Mitsubishi Chemical Corporation. Was mixed well using a disper to obtain a mixed solution. 15.0 parts by mass of an isopropyl alcohol dispersion of hollow silica particles (manufactured by JGC Catalysts & Chemicals, solid content 20% by mass, average particle size 40 nm) is added to this mixed solution, and these are mixed well at room temperature. The mixture was stirred and mixed for 1 hour in a constant temperature atmosphere at 25 ° C. Thereby, the coating composition whose ratio of the hollow silica particle with respect to solid content whole quantity is 60 mass% was obtained.

  Moreover, the coating composition for forming an intermediate | middle layer was prepared as shown next. First, 78.37 parts by mass of propylene glycol monomethyl ether was added to 7.84 parts by mass of methyl silicate MS51 manufactured by Mitsubishi Chemical Corporation, and 8.78 parts by mass of an aqueous nitric acid solution (0.1N) was added. Was mixed well using a disper to obtain a mixed solution. To this mixture, 5.00 parts by mass of propylene glycol monomethyl ether dispersion of zirconia particles (manufactured by CIK Nanotech, solid content 20% by mass, average particle size 40 nm) is added, and these are mixed well at room temperature. The mixture was stirred and mixed for 1 hour in a constant temperature atmosphere. Thereby, the coating composition whose ratio of a zirconia particle with respect to solid content whole quantity is 20 mass% was obtained.

  These two types of coating compositions were allowed to stand for more than 1 hour after preparation.

  A tempered glass plate was prepared as a substrate, dirt was removed from the surface of the tempered glass, and then a coating composition for forming an intermediate layer on the surface of the tempered glass was applied by a spin coater. Subsequently, the coating composition was heat-treated at 200 ° C. for 10 minutes. Thereby, an intermediate layer having a thickness of 100 nm was formed.

  Subsequently, a coating composition for forming an antireflection layer was applied on the intermediate layer by a spin coater. Subsequently, the coating composition was heat-treated at 200 ° C. for 10 minutes. Thereby, an antireflection layer having a thickness of 130 nm was formed.

  This obtained the coating | coated member provided with a base material, an intermediate | middle layer, and a coating layer (antireflection layer).

(Example 1-2)
A coating composition for forming an antireflection layer was prepared in the same manner as in Example 1-1.

  Moreover, the coating composition for forming an intermediate | middle layer was prepared as shown next. First, 73.82 parts by mass of propylene glycol monomethyl ether was added to 4.90 parts by mass of methyl silicate MS51 manufactured by Mitsubishi Chemical Corporation, and 8.78 parts by mass of an aqueous nitric acid solution (0.1N) was added. Was mixed well using a disper to obtain a mixed solution. To this mixed liquid, 12.50 parts by mass of propylene glycol monomethyl ether dispersion of zirconia particles (manufactured by CIK Nanotech Co., Ltd., solid content 20% by mass, average particle size 40 nm) is added, and these are mixed well at room temperature. The mixture was stirred and mixed for 1 hour in a constant temperature atmosphere at 25 ° C. Thereby, the coating composition whose ratio of a zirconia particle with respect to solid content whole quantity is 50 mass% was obtained.

  These two types of coating compositions were allowed to stand for 1 hour or longer after preparation, and subsequently, an intermediate layer having a thickness of 100 nm and a thickness of 130 nm were formed on the tempered glass plate by the same method as in Example 1-1. Were sequentially formed.

  This obtained the coating | coated member provided with a base material, an intermediate | middle layer, and a coating layer (antireflection layer).

(Example 1-3)
A coating composition for forming an antireflection layer was prepared in the same manner as in Example 1-1.

  Moreover, the coating composition for forming an intermediate | middle layer was prepared as shown next. First, 69.26 parts by mass of propylene glycol monomethyl ether is added to 1.96 parts by mass of methyl silicate MS51 manufactured by Mitsubishi Chemical Corporation, and 8.78 parts by mass of an aqueous nitric acid solution (0.1N) is added. Was mixed well using a disper to obtain a mixed solution. 20.00 parts by mass of propylene glycol monomethyl ether dispersion of zirconia particles (manufactured by CIK Nanotech Co., Ltd., solid content 20% by mass, average particle size 40 nm) is added to this mixed solution, and these are mixed well at room temperature. The mixture was stirred and mixed for 1 hour in a constant temperature atmosphere at 25 ° C. Thereby, the coating composition whose ratio of a zirconia particle with respect to solid content whole quantity is 80 mass% was obtained.

  These two types of coating compositions were allowed to stand for 1 hour or longer after preparation, and subsequently, an intermediate layer having a thickness of 100 nm and a thickness of 130 nm were formed on the tempered glass plate by the same method as in Example 1-1. Were sequentially formed.

  This obtained the coating | coated member provided with a base material, an intermediate | middle layer, and a coating layer (antireflection layer).

(Example 1-4)
A coating composition for forming an antireflection layer was prepared in the same manner as in Example 1-1.

  Moreover, the coating composition for forming an intermediate | middle layer was prepared as shown next. First, 89.26 parts by mass of propylene glycol monomethyl ether was added to 1.96 parts by mass of zirconium alkoxide (manufactured by Matsumoto Fine Chemical, 1-propanol solvent, solid 75% by mass), and 8.78 parts by mass of nitric acid aqueous solution ( 0.1N) was added, and these were mixed well using a disper to obtain a mixed solution. 20.00 parts by mass of propylene glycol monomethyl ether dispersion of zirconia particles (manufactured by CIK Nanotech Co., Ltd., solid content 20% by mass, average particle size 40 nm) is added to this mixed solution, and these are mixed well at room temperature. The mixture was stirred and mixed for 1 hour in a constant temperature atmosphere at 25 ° C. Thereby, the coating composition whose ratio of a zirconia particle with respect to solid content whole quantity is 80 mass% was obtained.

  These two types of coating compositions were allowed to stand for 1 hour or longer after preparation, and subsequently, an intermediate layer having a thickness of 100 nm and a thickness of 130 nm were formed on the tempered glass plate by the same method as in Example 1-1. Were sequentially formed.

  This obtained the coating | coated member provided with a base material, an intermediate | middle layer, and a coating layer (antireflection layer).

(Comparative Example 1-1)
A coating composition for forming an antireflection layer was prepared in the same manner as in Example 1-1. This coating composition was allowed to stand for more than 1 hour after preparation.

  A tempered glass plate was prepared as a substrate, dirt was removed from the surface of the tempered glass, and then a coating composition for forming an antireflection layer on the surface of the tempered glass was applied by a spin coater. Subsequently, the coating composition was heat-treated at 200 ° C. for 10 minutes. Thereby, an antireflection layer having a thickness of 130 nm was formed.

  This obtained the coating | coated member provided with a base material and a coating layer (antireflection layer).

(Comparative Example 1-2)
A coating composition for forming an antireflection layer was prepared in the same manner as in Example 1-1. This coating composition was allowed to stand for more than 1 hour after preparation.

  A tempered glass plate was prepared as a substrate, and dirt was removed from the surface of the tempered glass. Subsequently, a 100 nm thick layer made of silicon dioxide was formed on the surface of the tempered glass using silane gas by a CVD method. On this layer, a coating composition for forming an antireflection layer was applied by a spin coater. Subsequently, the coating composition was heat-treated at 200 ° C. for 10 minutes. Thereby, an antireflection layer having a thickness of 130 nm was formed.

  This obtained the coating | coated member provided with the base material, the layer which consists of silicon dioxide, and the coating layer (antireflection layer).

(Evaluation of initial transmittance)
The spectral transmittance in the wavelength range of 300 to 1500 nm of the covering member obtained in each example and comparative example was measured using a spectrophotometer (manufactured by Hitachi, Ltd., model number U-4100), and the result Based on the above, the average of the transmittance in the range of 400 to 1100 nm was calculated. In addition, the result in the case of only a tempered glass plate is 91.0%.

(Durability evaluation)
Using a small environmental testing apparatus (Espec, model number SH-241), the covering members obtained in each Example and Comparative Example were exposed to a high temperature and high humidity atmosphere at a temperature of 85 ° C. and a humidity of 80% for 1000 hours. . Then, the average of the transmittance | permeability in the range of 400-1100 nm of the coating | coated member was computed by the same method as the case of the said initial stage transmittance | permeability evaluation. Furthermore, the change rate from the initial transmittance of the transmittance value thus obtained was calculated.

(Abrasion resistance evaluation)
Using a wear tester (manufactured by Shinbun Kagaku Co., model number HEIDON-14DR), the surface of the coating member of each example and comparative example on which the antireflection layer is formed is steel wool # 0000 with a load of 500 g. Then, the surface of the covering member was visually observed. As a result, the case where scratches are not recognized on the surface of the covering member or the number of scratches is less than 10 is indicated as ◯, the case where scratches are recognized between 10 and less than 50 are indicated as Δ, and the case where scratches are recognized as 50 or more as ×. evaluated.

(Pencil hardness)
The pencil hardness of the surface on which the antireflection layer was formed in the covering members of each Example and Comparative Example was evaluated according to JIS K5600.

  The above results are shown in Table 1 below.

  As shown in Table 1, in each of the examples and comparative examples, the transmittance of the covering member is 2% or more higher than that of the case of using only the tempered glass. Therefore, the initial optical performance of these covering members is good. It was. In particular, the transmittance was particularly high in Examples 1-2, 1-3, and 1-4. This is presumably because the antireflection performance of the antireflection layer was particularly improved by appropriately adjusting the refractive index of the intermediate layer with zirconia, which is a high refractive index material.

  Regarding the evaluation of durability, in Comparative Example 1, the transmittance decreased by 1.2%. This is presumably because the antireflection layer was rapidly attacked by the alkali component in the tempered glass plate because the covering member did not include the intermediate layer.

  Further, in Comparative Example 2, a decrease in transmittance was suppressed as compared with Comparative Example 1. This is considered to be because the movement of the alkali component from the tempered glass plate to the antireflection layer was suppressed to some extent by the layer made of silicon dioxide. However, even in Comparative Example 2, the durability of the antireflection layer is not sufficient.

  On the other hand, in each Example, the transmittance | permeability was restrained within 0.5%. This is considered to be because the movement of the alkali component from the tempered glass plate to the antireflection layer was sufficiently suppressed by the intermediate layer containing zirconia having high alkali resistance. According to the results of Examples 1-1, 1-2, and 1-3, this effect can also be confirmed from the fact that the decrease in transmittance is improved as the proportion of zirconia particles in the intermediate layer is increased. . Further, when an intermediate layer made of zirconia was formed as in Example 4, the durability of the antireflection layer was the highest.

[Example 2]
In this example, a photocatalyst layer composed of titanium oxide particles and a silicon-based inorganic matrix was selected as the coating layer, and the difference in performance degradation of the photocatalyst layer due to the presence or absence of an intermediate layer was verified.

(Example 2-1)
A coating composition for forming a photocatalyst layer was prepared as follows. First, 79.99 parts by mass of methanol was added to 4.90 parts by mass of methyl silicate MS51 manufactured by Mitsubishi Chemical Corporation, and then 8.78 parts by mass of an aqueous nitric acid solution (0.1 N) was added. The mixture was obtained by mixing well. To this mixed solution was added 8.33 parts by mass of an aqueous dispersion of anatase type titanium oxide particles (manufactured by Ishihara Sangyo Co., Ltd., product number STS-01, solid content 30% by mass), and these were mixed well at room temperature. The mixture was stirred and mixed for 1 hour in a constant temperature atmosphere at 25 ° C. Thereby, the coating composition whose ratio of the hollow silica particle with respect to solid content whole quantity is 50 mass% was obtained.

  Moreover, the coating composition for forming an intermediate | middle layer was prepared as shown next. First, 432.04 parts of methanol was added to 31.46 parts by mass of methyl silicate MS51 manufactured by Mitsubishi Chemical Corporation, and further calcium methoxide (GELEID, Ltd., product number AKC-165) and aqueous nitric acid solution (0. 1N) was mixed at a mass ratio of 1.5: 48.5, and 50.0 parts of the mixed solution was added, and these were mixed well using a disper to obtain a mixed solution. This mixed solution was allowed to stand for 24 hours in a constant temperature atmosphere at 25 ° C. Subsequently, the mixture was diluted with isopropanol. This obtained the coating composition.

  These two types of coating compositions were allowed to stand for more than 1 hour after preparation.

  A soda lime glass plate (refractive index 1.54) was prepared as a base material, and the surface of this soda lime glass plate was polished and washed with fine cerium oxide particles. Subsequently, a coating composition for forming an intermediate layer on the surface of the soda lime glass plate was applied by a spin coater. Subsequently, the coating composition was heat-treated at 200 ° C. for 10 minutes. Thereby, an intermediate layer having a thickness of 100 nm was formed.

  Then, the coating composition for forming a photocatalyst layer was apply | coated with the spin coater on the intermediate | middle layer. Subsequently, the coating composition was heat-treated at 200 ° C. for 15 minutes. Thereby, a photocatalyst layer having a thickness of 300 nm was formed.

  This obtained the coating | coated member provided with a base material, an intermediate | middle layer, and a coating layer (photocatalyst layer).

(Example 2-2)
A coating composition for forming a photocatalyst layer was prepared in the same manner as in Example 2-1.

  Moreover, the coating composition for forming an intermediate | middle layer was prepared as shown next. First, 74.47 parts by mass of propylene glycol monomethyl ether and 2.78 parts by mass of an aqueous nitric acid solution (0.1 N) were added to 2.75 parts by mass of methyl silicate MS51 manufactured by Mitsubishi Chemical Corporation. Was mixed well using a disper to obtain a mixed solution. To this mixed liquid was added 14.00 parts by mass of a methyl isobutyl ketone solvent dispersion of alumina particles (manufactured by CIK Nanotech Co., Ltd., solid content 15% by mass, average particle size 40 nm), and these were mixed well at room temperature. Further, the mixture was stirred and mixed in a constant temperature atmosphere at 25 ° C. for 1 hour. This obtained the coating composition whose ratio of the alumina particle with respect to solid content whole quantity is 60 mass%.

  These two types of coating compositions were allowed to stand for 1 hour or longer after preparation, and then, by the same method as in Example 2-1, an intermediate layer having a thickness of 100 nm and a thickness of 300 nm were formed on the tempered glass plate. Were sequentially formed.

  This obtained the coating | coated member provided with a base material, an intermediate | middle layer, and a coating layer (photocatalyst layer).

(Example 2-3)
A coating composition for forming a photocatalyst layer was prepared in the same manner as in Example 2-1.

  Moreover, the coating composition for forming an intermediate | middle layer was prepared as shown next. First, 74.47 parts by mass of isopropyl alcohol was added to 2.75 parts by mass of methyl silicate MS51 manufactured by Mitsubishi Chemical Corporation, and 8.78 parts by mass of an aqueous nitric acid solution (0.1 N) was added. Was mixed well to obtain a mixed solution. 14.00 parts by mass of an isopropyl solvent dispersion of rutile titanium oxide particles (manufactured by CIK Nanotech Co., Ltd., solid content: 15% by mass, average particle size: 40 nm) is added to this mixed solution, and these are mixed well at room temperature. Further, the mixture was stirred and mixed for 1 hour in a constant temperature atmosphere at 25 ° C. This obtained the coating composition whose ratio of the titanium oxide particle with respect to solid content whole quantity is 60 mass%.

  These two types of coating compositions were allowed to stand for 1 hour or longer after preparation, and then, by the same method as in Example 2-1, an intermediate layer having a thickness of 100 nm and a thickness of 300 nm were formed on the tempered glass plate. Were sequentially formed.

  This obtained the coating | coated member provided with a base material, an intermediate | middle layer, and a coating layer (photocatalyst layer).

(Comparative Example 2-1)
A coating composition for forming a photocatalyst layer was prepared in the same manner as in Example 2-1. This coating composition was allowed to stand for more than 1 hour after preparation.

  A soda lime glass plate (refractive index 1.54) was prepared as a base material, and the surface of this soda lime glass plate was polished and washed with fine cerium oxide particles. Then, the coating composition for forming a photocatalyst layer was apply | coated to the surface of the soda-lime glass plate with the spin coater. Subsequently, the coating composition was heat-treated at 200 ° C. for 15 minutes. As a result, a light reflecting layer having a thickness of 300 nm was formed.

  This obtained the coating | coated member provided with a base material and a coating layer (photocatalyst layer).

(Initial photocatalyst performance evaluation)
Oleic acid was applied on the photocatalyst layer in the covering member obtained in each Example and Comparative Example, and subsequently, the photocatalyst layer was irradiated with ultraviolet rays from a black light at an intensity of 1 mW / cm ² for 24 hours. Subsequently, the contact angle of water on the photocatalyst layer was measured. In this case, it is determined that the smaller the contact angle of water, the more the photocatalytic performance of the photocatalytic layer functions and the decomposition of oleic acid on the photocatalytic layer is promoted.

(Durability evaluation)
Using a small environmental testing apparatus (Espec, model number SH-241), the covering members obtained in each Example and Comparative Example were exposed to a high temperature and high humidity atmosphere at a temperature of 85 ° C. and a humidity of 80% for 1000 hours. . Subsequently, the contact angle of water in the photocatalyst layer was measured by the same method as in the case of the initial photocatalyst performance evaluation.

  The above results are shown in Table 2 below.

  According to the results shown in Table 2, the evaluation result of the initial photocatalytic activity in each example and comparative example is a water contact angle of 30 ° or less, whereby the initial photocatalytic activity in any of the examples and comparative examples is It was confirmed to be high.

  However, after the high temperature and high humidity test, the contact angle of water greatly exceeded 30 ° in Comparative Example 2-1. This is considered to be because, in Comparative Example 2-1, the alkali component moved from the soda lime glass plate to the photocatalyst layer, the photocatalyst layer was greatly deteriorated, and the photocatalytic performance was greatly reduced.

  On the other hand, in Examples 2-1, 2-2, and 2-3, the contact angle of water was maintained at 30 ° or less even after the high temperature and high humidity test. This is considered to be because the movement of the alkali component from the soda lime glass plate to the photocatalyst layer was sufficiently suppressed by the intermediate layer containing an oxide having high alkali resistance.

DESCRIPTION OF SYMBOLS 1 Coating member 2 Base material 3 Coating layer 4 Intermediate layer

Claims (4)

A base material containing an alkali component, a coating layer containing a silicon compound, and an intermediate layer interposed between the base material and the coating layer,
A covering member in which the intermediate layer contains at least one of calcium oxide, aluminum oxide, boron oxide, zirconium oxide, titanium oxide, hafnium oxide, and cerium oxide. The intermediate layer includes an inorganic matrix and oxide particles made of at least one of calcium oxide, aluminum oxide, boron oxide, zirconium oxide, titanium oxide, hafnium oxide, and cerium oxide dispersed in the inorganic matrix. The covering member according to claim 1 constituted. The covering member according to claim 1, wherein the intermediate layer is made of a metal oxide selected from calcium oxide, aluminum oxide, boron oxide, zirconium oxide, titanium oxide, hafnium oxide, and cerium oxide. The covering member according to claim 2, wherein a ratio of the oxide particles in the intermediate layer is in a range of 5 to 90 mass%.

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