JP6106796B1 - Transparent glass coating material that shields ultraviolet rays and infrared rays and has photocatalytic action, method for producing the same, and method for producing a coating film using the same - Google Patents

Abstract

The present invention provides a transparent medium coating that transmits visible light, shields infrared rays and ultraviolet rays, has photocatalytic activity, and has a self-cleaning action, an antifouling action, an antibacterial action, an odor prevention action, and the like. A first solvent which is an amphiphilic solvent comprising a reaction product of an acrylic polyol resin and an aliphatic polyisocyanate, fine particles of an infrared shielding inorganic compound, fine particles of anatase-type titanium oxide, and peroxotitanic acid. And a transparent glass paint that is uniformly dispersed in a mixed solvent comprising a second solvent that is the same as or different from the first solvent, and water. This transparent glass paint forms a structure that prevents active oxygen generated by the photocatalyst from invading the polymer resin of the paint by applying and drying. [Selection figure] None

Description

  The present invention relates to a coating material for transparent glass that shields ultraviolet rays and infrared rays and has a photocatalytic action. The present invention relates to a coating material for transparent glass that shields ultraviolet rays and infrared rays that can be applied to glass and has a photocatalytic action, which protects the polymer resin constituting the coating film from invading.

  The glass window introduces sunlight into the room, brightens the room and allows the outside scenery to be seen, giving a sense of openness, and the exterior of the glass building gives a modern impression. A lot of glass has come to be used for the exterior of buildings, and there are many buildings with crows on the entire outer wall. Furthermore, when there are no or few glass windows, the room must be illuminated even in the daytime, so the glass windows have an energy saving effect.

  On the other hand, the amount of energy that falls from the sun to the earth in 30 minutes is so large that it is said to be equivalent to the amount of energy consumed worldwide for one year. Solar energy light contains 45% visible light, 50% infrared light, and 5% ultraviolet light, and ordinary glass transmits not only visible light in sunlight but also infrared light and ultraviolet light.

  Infrared rays are heat rays.Excessive irradiation in summer increases the power consumption of the air conditioner by excessively raising the indoor temperature, and ultraviolet rays damage the skin and cause sunburn. Cause serious problems. The problem of excessive irradiation with sunlight is occurring not only in the window glass of buildings, but also in the window glass windows of vehicles such as automobiles and trains.

  Accordingly, it is desirable to add a property to glass that transmits only useful visible light and shields ultraviolet rays and infrared rays. On the other hand, as a method of shielding infrared rays and ultraviolet rays while transmitting visible light in sunlight, the glass itself has a function of shielding infrared rays and ultraviolet rays, or the glass has a function of shielding infrared rays and ultraviolet rays. A transparent film is attached, or a transparent paint is applied.

Here, glass having an infrared and ultraviolet shielding effect is known but expensive, and it is economically difficult to use as a general window glass.
An infrared shielding transparent film for window glass is described in Patent Document 1.
However, since windows have various shapes and large ones have a length of several meters or more, it is necessary to apply advanced technology to paste a transparent film on a completed building so as not to cause unevenness. .

An ultraviolet / near-infrared shielding water-based paint containing an inorganic infrared absorber and an organic ultraviolet absorber is known. However, glass adsorbs oil and fat on the surface and repels water, creating polka dots, and it is not easy to clean the glass so that polka dots are not formed. Is a tough job.
As described above, a transparent glass coating material that shields ultraviolet rays and infrared rays is not known to have sufficient performance.

Various infrared screening agents are known, but inorganic oxide compositions such as indium doped tin oxide, antimony doped tin oxide and gallium doped zinc oxide are known to exhibit excellent properties. (See, for example, cited document 1).
On the other hand, as an ultraviolet shielding material, many organic compounds have been disclosed in the fields of cosmetic sunscreen and dye / photosensitive material. However, considering the usage environment in which window glass is exposed to direct sunlight for several years, there is a problem with the stability of organic compounds.

  Furthermore, it is known that fine powder of anatase-type titanium oxide having a photocatalytic action absorbs ultraviolet rays and generates active oxygen. However, the conventional anatase-type titanium oxide fine powder could not be formed into a film or paint because it could not be formed unless it was fired at several hundred degrees. The fine powder of titanium oxide that is commercially available in recent years has a nano-scale primary particle size, but the secondary particle is a powder in which thousands of primary particles are associated with each other, and there is a problem with the transmittance of visible light. There are many things. Furthermore, since the active oxygen generated by the photocatalyst oxidizes and decomposes the polymer resin that is the base material of the film or paint, there is a problem that the active oxygen cannot be mixed into the paint or film.

  Patent Document 2 discloses a composition comprising anatase-type titanium oxide, an inorganic oxide containing antimony-doped tin oxide, an inorganic material containing silica and alumina, and a polymer resin resin. Anatase-type titanium oxide Describes that the inorganic material protects the active oxygen produced by absorbing ultraviolet rays from destroying the resin. However, since all the disclosed inorganic materials are powders and do not include those that form a film, the ability of these inorganic materials to protect the resin from active oxygen is not sufficient.

JP 2013-230613 A JP 2008-302351 A Japanese Patent No. 3490013 Japanese Patent No. 3490012

  The present invention has been made to solve such problems, and by applying the transparent glass paint having a photocatalytic action that shields the ultraviolet rays and infrared rays of the present invention, infrared rays and ultraviolet rays are allowed to pass through. A transparent glass coating material that has high photocatalytic activity and has self-cleaning action, antifouling action, antibacterial action, deodorization action, air cleaning action, etc. The issue is to provide.

  In addition, the present invention provides a polymer resin excellent in durability and weather resistance, which forms a structure having a high transparency and a strong coating film, and also protects the coating film of the polymer resin from active oxygen generated by the photocatalyst. It is an object to provide a paint.

  Furthermore, the present invention provides a method for easily producing a coating material for transparent glass having a photocatalytic action by shielding ultraviolet rays and infrared rays, and the coating material has high wettability with respect to glass so that the transparent coating material can be easily applied to glass. It aims at providing the manufacturing method of the coating film for transparent glass which can be apply | coated uniformly.

  In order to solve this problem, the transparent glass coating material for shielding ultraviolet rays and infrared rays according to the present invention and having a photocatalytic action is composed of 15 to 30 parts by mass of an acrylic polyol resin and aliphatic when the total mass of the coating is 100 parts by mass. 4-9 parts by mass of the reaction product of 1-6 parts by mass of polyisocyanate, fine particles of infrared shielding inorganic compound, 0.1-2 parts by mass of fine particles of anatase-type titanium oxide, and peroxotitanic acid converted to titanium oxide 0.1 to 2 parts by mass of the first solvent 35 to 55 parts by mass which is an amphiphilic solvent having a boiling point of 140 ° C. or higher and 200 ° C. or lower, and 1 to 3 parts by mass of the second solvent which is the same as or different from the first solvent And a solvent having a water content of 20 to 50% by mass when the total of the mass of the amphiphilic solvent and the mass of water is 100% by mass. And wherein the dispersed one.

  The amphiphilic solvent is selected from ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol diacetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, or diethylene glycol diethyl ether 1 or more.

The infrared shielding inorganic compound is one or more selected from antimony oxide, tin oxide, indium oxide, gallium oxide, and zinc oxide.
Moreover, it is preferable that ratio of the mass of acrylic polyol resin and the mass of aliphatic polyisocyanate is the range of 20: 1-20: 3.

The method for producing a coating material for transparent glass that shields ultraviolet rays and infrared rays and has a photocatalytic action according to the present invention is a method for producing a coating material for transparent glass, and when the total mass of the coating material is 100 parts by mass, acrylic polyol resin 15 1 to 6 parts by mass of a polyol solution and aliphatic polyisocyanate and 1 to 3 parts by mass of a second solvent in which thirty to 30 parts by mass are dissolved in 35 to 55 parts by mass of an amphiphilic solvent having a boiling point of 140 ° C. or higher and 200 ° C. or lower. A resin solution production stage for producing an acrylic urethane resin solution by reacting a dissolved aliphatic polyisocyanate solution, and a peroxotitanic acid aqueous solution having a concentration of 0.1 to 10% by mass of peroxotitanic acid converted to titanium oxide. 20 to 10 parts by weight of an anatase-type titanium oxide fine particle aqueous dispersion having a titanium oxide concentration of 0.1 to 10% by weight. 0 part by mass, and 4 to 9 parts by mass of fine particles of an infrared shielding inorganic compound are mixed to produce a functional inorganic substance liquid, and a resin solution and a functional inorganic substance are mixed with the amphiphilic solvent. And a paint manufacturing stage in which the water content of the solvent is 20 to 50% by mass when the total of the mass and the mass of water is 100% by mass, and the mixture is uniformly dispersed.
Furthermore, according to the present invention, a coating film for transparent glass having a photocatalytic action by shielding ultraviolet rays and infrared rays can be produced by applying the transparent glass coating material to the surface of a glass substrate and drying it.

  The paint for transparent glass which shields ultraviolet rays and infrared rays and has a photocatalytic action of the present invention strongly shields infrared rays and ultraviolet rays while allowing visible light to pass through, and has high photocatalytic activity, self-cleaning action, antifouling action The present invention provides a transparent glass paint having antibacterial action, deodorization action, air cleaning action and the like.

In addition, the paint according to the present invention has a high transparency and can form a strong coating film, and can spontaneously constitute a structure that protects the coating film of the polymer resin from invasion by active oxygen generated by the photocatalyst. A polymer resin paint excellent in durability and weather resistance is provided.
Furthermore, the present invention provides a coating material for transparent glass and a method for producing a coating film by using a water-containing amphiphilic solvent as a solvent so that the coating material has high wettability with respect to glass and can be easily and uniformly applied. I will provide a.

(About fine particles)
In the present invention, the term “fine particles” is used to mean “particles whose size is smaller than the wavelength of visible light (380 to 780 nm) and whose dispersion is transparent even when dispersed in transparent solutions having different refractive indices”. . In general, “fine particle powder” corresponds to “powder composed of particles having a size of 1 μm or less”.
The titanium oxide fine particles used in the present invention are, for example, anatase-type titanium oxide fine particles having a particle diameter of 8 nm described in Patent Document 4, and a transparent coating film is formed by applying and drying an aqueous dispersion. Peroxotitanic acid is an aqueous solution, and forms an amorphous transparent coating film by coating and drying. On the other hand, as the fine particle powder of the infrared shielding agent, a commercial product can be purchased.

(About the present invention)
The photocatalyst activates oxygen in the air upon irradiation with light, and the generated active oxygen oxidizes and decomposes the organic substance. Therefore, the photocatalyst cannot usually be applied on the organic base material. However, the present inventor specified a peroxotitanic acid aqueous solution (see, for example, Patent Document 3), an aqueous dispersion of anatase-type titanium oxide fine particles (see, for example, Patent Document 4), and an oil-soluble polymer resin. It was found that the invasion to the polymer resin by active oxygen is significantly protected when it is uniformly dispersed in a high-boiling amphiphilic solvent containing water at a water content of

This phenomenon is presumed that the resin component disproportionation occurred on the coating film during the process of evaporating water from the coating material, and the film structure protecting active oxygen was spontaneously formed.
By adding fine particles of an inorganic compound having an infrared shielding function to the above composition, the coating composition for transparent glass having the photocatalytic action by shielding ultraviolet rays and infrared rays of the present invention was reached.

(Polymer resin component)
The transparent glass coating material that shields ultraviolet rays and infrared rays according to the present invention and has a photocatalytic action has an acrylic polyol resin 15 to 15 when the total mass of the coating material is 100 parts by mass (hereinafter, the parts by mass are the same unless otherwise specified). Acrylic urethane resin, which is a reaction product of 30 parts by mass and aliphatic polyisocyanate 1 to 6 parts by mass, 4 to 9 parts by mass of fine particles of an infrared shielding inorganic compound, and 0.1 to 0.1 parts of fine particles of anatase-type titanium oxide 2 parts by mass, 0.1 to 2 parts by mass of peroxotitanic acid converted to titanium oxide, 35 to 55 parts by mass of an amphiphilic solvent having a boiling point of 140 ° C. or higher and 200 ° C. or lower, and the second solvent 1 The water content of the solvent is 20 to 50 when the total of the mass of the amphiphilic solvent and the mass of water is 100% by mass in addition to the solvent consisting of ˜3 parts by mass and 15 to 30 parts by mass of water. mass% Characterized in that there.

The acrylic polyol resin is a polymer all obtained by polymerizing an acrylate ester having a hydroxyl group in an ester portion, reacts with a polyisocyanate, undergoes a crosslinking reaction, and further polymerizes to become an acrylic urethane resin and solidifies.
Since acrylic urethane using an acrylic polyol resin is known, detailed description thereof is omitted.
The content of the acrylic polyol resin of the present invention is preferably in the range of 15 to 30 parts by mass, more preferably in the range of 20 to 30 parts by mass, and most preferably in the range of 20 to 25 parts by mass. It is.

Moreover, the aliphatic polyisocyanate content of the present invention is preferably 1 to 6 parts by mass, more preferably 2 to 5 parts by mass. Moreover, it is preferable that ratio of the mass of acrylic polyol resin and the mass of aliphatic polyisocyanate is the range of 20: 1-20: 3.
Since the reaction between the acrylic polyol resin and the aliphatic polyisocyanate does not enter and exit the material, the content of the acrylic urethane resin of the present invention is 16 to 36 parts by mass.
The second solvent is not particularly limited as long as it dissolves the aliphatic polyisocyanate and does not react. The amount of the second solvent can be 1 to 3 parts by mass.

(Infrared shielding inorganic compound)
The infrared shielding inorganic compound of the present invention is at least one selected from metal oxides consisting of antimony oxide, tin oxide, indium oxide, gallium oxide, and zinc oxide. Further, the present invention can be a composition of two or more inorganic oxides. Among these combinations, preferred specific examples include tin oxide (ATO) containing a small amount of antimony oxide, tin oxide (ITO) containing a small amount of indium oxide, and zinc oxide containing a small amount of gallium oxide. .
Note that the metal oxide includes metal oxides of all valences.

The infrared shielding inorganic compound used in the present invention is preferably 4 to 9 parts by mass, more preferably 5 to 8 parts by mass, when the total mass of the coating is 100 parts by mass. Also, the ratio of antimony oxide to tin oxide can range from 1: 5 to 20.
Tin oxide and zinc oxide can be purchased in fine powder. Since antimony oxide, indium oxide, and gallium oxide have a small amount of use, so long as they are invisible (for example, 10 μm or less), there is no problem even if powdered by a normal method is used. .

(Peroxotitanic acid)
The amount of peroxotitanic acid of the present invention is preferably 0.1 to 2 parts by mass in terms of titanium oxide when the total mass of the coating is 100 parts by mass. A larger amount of peroxotitanic acid is preferable, but a peroxytitanic acid aqueous solution having a high concentration has a high viscosity and is difficult to produce. Therefore, if more peroxotitanic acid is added, the amount of water in the solvent is reduced. May be too high.
(Natase type titanium oxide fine particles)
The amount of the anatase-type titanium oxide fine particles of the present invention is preferably 0.1 to 2 parts by mass. Although the amount of anatase-type titanium oxide fine particles is preferably within a larger range, the present invention uses an aqueous dispersion of anatase-type titanium oxide fine particles produced by heating an aqueous peroxotitanic acid solution at 70 to 200 ° C. As with titanic acid, adding more anatase-type titanium oxide fine particles may result in excessively high water content in the solvent.

(solvent)
The first solvent of the present invention is preferably an amphiphilic solvent having a boiling point of 140 ° C. or higher and 200 ° C. or lower.
Moreover, it is preferable that the quantity of a 1st solvent is 35-55 mass parts, and it is more preferable that it is 40-50 mass parts. When the amount of the first solvent is 35 parts by mass or less, the acrylic urethane resin may not be sufficiently dissolved. When the amount exceeds 55 parts by mass, the amount of the polymer resin component decreases, and infrared / ultraviolet ray shielding is achieved. Activity and photocatalytic activity may be reduced.

In the present invention, when the water content of the solvent is calculated with the total amount of the amphiphilic solvent and water being 100% by mass, the water content is preferably 20 to 50% by mass, and the water content is 25 to 40%. It is more preferable that
When the water content is less than 20% by mass, hydrophilic anatase-type titanium oxide, peroxotitanic acid, and an infrared shielding inorganic compound may be precipitated. When the water content exceeds 50% by mass, an oil-based paint film is formed. The constituting polymer resin may be precipitated, and the evaporation of water may be delayed to form a film structure that protects active oxygen.

  Any amphiphilic solvent may be used as long as it has a boiling point of 140 ° C. or higher and 200 ° C. or lower and can contain water up to a mass ratio of 1: 1. Preferred examples include ethylene glycol monomethyl ether acetate, ethylene glycol Mention may be made of monoethyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol diacetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate and diethylene glycol diethyl ether. However, the amphiphilic solvent of the present invention is not limited to this.

  The second solvent of the present invention is not particularly limited as long as it can dissolve the coating film curing agent, but if the amphiphilic solvent used for the first solvent can dissolve the coating film curing agent, the same amphiphile is used. It is preferable to use an ionic solvent.

Below, the manufacturing method of the photocatalyst coating material of this invention is demonstrated.
(Resin solution production stage)
A polyol solution prepared by dissolving 15 to 30 parts by mass of an acrylic polyol resin in 35 to 55 parts by mass of an amphiphilic solvent having a boiling point of 140 ° C. or more and 200 ° C. or less, 1 to 6 parts by mass of an aliphatic polyisocyanate, and 1 to 2 of a second solvent. The polyisocyanate solution dissolved in 3 parts by mass was mixed and stirred to produce an acrylic urethane resin solution.

(Functional inorganic liquid production stage)
<Peroxotitanic acid aqueous solution production stage>
To the aqueous solution containing titanium raw material, an excess amount of hydrogen peroxide than the reaction equivalent is added, and then neutralized by adding ammonia water. The resulting yellow solution is left to precipitate peroxotitanate, and the precipitate is collected by filtration. After washing, suspending in water and adding hydrogen peroxide, a yellow transparent peroxotitanic acid aqueous solution is obtained. The applied and dried peroxotitanic acid aqueous solution forms an amorphous strong coating film having a peroxo group when applied to a substrate and dried.

The concentration of the peroxotitanic acid aqueous solution is preferably 0.1 to 10% by mass when the mass of the peroxotitanic acid aqueous solution is 100% by mass and the peroxotitanic acid aqueous solution is converted to titanium oxide.
If the concentration of the aqueous solution of peroxotitanic acid is less than 0.1% by mass, an amorphous solid film having a sufficient thickness cannot be formed after drying, and an aqueous solution of peroxotitanic acid exceeding 10% by mass is produced. Have difficulty.

  Amorphous peroxotitanic acid formed by drying and solidifying a peroxotitanic acid aqueous solution has high film-forming properties, and forms a strong film by bonding to many substrates. In particular, it has a strong affinity with an anatase-type titanium oxide film produced from a peroxotitanic acid aqueous solution. It can be used for the purpose of enhancing the strength of the titanium oxide film.

<Production stage of aqueous dispersion of anatase-type titanium oxide fine particles>
The peroxotitanic acid aqueous solution is heated at 70 ° C. to 200 ° C. for 2 to 40 hours, preferably 80 to 120 ° C. for 3 to 30 hours, most preferably 90 ° C. to less than 100 ° C. for 5 to 20 hours. A dispersion of anatase-type titanium oxide fine particles can be produced. When the heating temperature is 70 ° C. or lower, the reaction takes too much time, which is not preferable. Even if it is heated to 200 ° C. or higher, the reaction becomes too fast and it becomes difficult to control, and the apparatus becomes large and there is no effect commensurate with it.

An aqueous dispersion of anatase-type titanium oxide fine particles produced by heating a peroxotitanic acid aqueous solution to 70 ° C. to 200 ° C. is a pale yellow transparent liquid. The particle size of the titanium fine particles is 8 nm.
A photocatalyst film can be formed by applying an aqueous dispersion of synthesized anatase-type titanium oxide fine particles to a substrate and drying it. The photocatalyst film synthesized here has an excellent feature of exhibiting a photocatalytic function even with visible light.

  The concentration of the aqueous dispersion of anatase-type titanium oxide fine particles used in the present invention can be 0.1 to 10% by mass when the mass of the aqueous dispersion of anatase-type titanium oxide fine particles is 100% by mass.

  When the concentration of the aqueous dispersion of anatase-type titanium oxide fine particles is less than 0.1% by mass, a sufficient amount of anatase-type titanium oxide fine particles cannot be formed after drying, and the photocatalytic activity of the resulting paint is insufficient In an aqueous dispersion of anatase-type titanium oxide fine particles exceeding 10% by mass, it is difficult to produce a peroxotitanic acid aqueous solution as a raw material.

(Paint production stage)
By adding and uniformly dispersing the functional inorganic liquid into the acrylic urethane resin solution, it is possible to produce the transparent glass paint having a photocatalytic action by shielding ultraviolet rays and infrared rays of the present invention.
The water content of the solvent is 20 to 50% by mass when the total of the mass of the amphiphilic solvent and the mass of water is 100% by mass of the acrylic urethane resin solution and the functional inorganic liquid. It is preferable to mix in proportion and uniformly disperse.
Throughout the examples and comparative examples, the mass of the aliphatic polyisocyanate was 1/10 of the mass of the acrylic polyol resin, and the mass of the second solvent was 1/2 of the mass of the aliphatic polyisocyanate. .

[Example 1]
(First step) Resin liquid production stage When the total mass of the coating is 100 parts by mass, a polyol solution in which 20 parts by mass of acrylic polyol resin is dissolved in 51 parts by mass of ethylene glycol monobutyl ether acetate and 2 parts by mass of aliphatic polyisocyanate 74 parts by mass of an acrylic urethane resin solution was prepared by mixing and stirring a polyisocyanate solution having 1 part by mass dissolved in 1 part by mass of propylene glycol monoethyl ether acetate.

(2nd process) Functional inorganic substance manufacturing stage <Manufacture of 5 mass% concentration of peroxotitanic acid aqueous solution>
Titanium hydroxide was precipitated by dropwise addition of 440 mL of 2.5% (mass / volume) ammonia water to a solution of 39.6 mL of 60% (mass / volume) aqueous solution of titanium tetrachloride in 4000 mL with distilled water. . The precipitate was collected by filtration, washed with distilled water, and then added with 80 mL of 30% (mass / volume) hydrogen peroxide solution to a titanium hydroxide suspension to 72 mL by adding distilled water and stirred. The mixture was allowed to stand at 7 ° C. for 24 hours to decompose excess hydrogen peroxide solution, and water was further added to obtain 200 g of a peroxotitanic acid aqueous solution having a concentration of 5% by mass in terms of titanium oxide.

<Production of dispersion of 5% by mass anatase-type titanium oxide fine particles>
The aqueous peroxotitanic acid solution obtained in the first step was sealed in a pressure-resistant glass container and boiled in a water bath for 12 hours (98 to 100 ° C.) to produce an aqueous dispersion of 5% by mass anatase-type titanium oxide fine particles.

<Functional inorganic liquid production stage>
When the total mass of the coating is 100 parts by mass, 10 parts by mass of a 5% by mass peroxotitanic acid aqueous solution in terms of titanium oxide, 10 parts by mass of an aqueous dispersion of 5% by mass anatase-type titanium oxide fine particles, tin oxide 26 parts by mass of a functional inorganic liquid was produced by mixing 5 parts by mass of fine particles (SN-100P, Ishihara Sangyo Co., Ltd.) and 1 part by mass of antimony trioxide.

(3rd process) Paint manufacturing stage 100 mass parts transparent glass by mixing and stirring the 74 mass parts acrylic urethane resin solution manufactured at the 1st process, and 26 mass parts functional inorganic substance liquid manufactured at the 2nd process. A paint was produced. The water content of the first solvent (ethylene glycol monobutyl ether acetate) is 27.1% by mass.

[Example 2]
As in Example 1, except that as shown in Table 1, the amount of the 5% by mass concentration of peroxotitanic acid aqueous solution and the amount of the 5% by mass concentration of anatase-type titanium oxide fine particles in aqueous dispersion were increased. The clear glass paint of Example 2 was prepared with the modification to reduce the amount of glycol monobutyl ether acetate. The water content of the first solvent (ethylene glycol monobutyl ether acetate) is 41.0% by mass.

[Comparative Examples 1 and 2]
As in Example 1, except that, as shown in Table 1, the amount of the 5 mass% concentration of peroxotitanic acid aqueous solution and the amount of the 5 mass% concentration of anatase-type titanium oxide fine particles in the aqueous dispersion were greatly increased or decreased. The coating material for transparent glass was produced by changing the amount of glycol monobutyl ether acetate. The water content of the first solvent (ethylene glycol monobutyl ether acetate) is 13.5% by mass in Comparative Example 1 and 55.1% by mass in Comparative Example 2.

[Example 3]
As in Example 1, but as shown in Table 1, a transparent glass paint was produced by increasing the amount of the polymer resin constituting the coating film. The water content of the first solvent is 32.5% by mass.

[Comparative Examples 3 and 4]
As in Examples 1 and 3, but as shown in Table 1, the amounts of the polymer resin and ethylene glycol monoethyl ether acetate constituting the coating film were further greatly changed to produce a coating material for transparent glass. The water content of the first solvent in the produced paint is 23.3% by mass in Comparative Example 3, and 40.4% by mass in Comparative Example 4. Comparative Examples 3 and 4 had poor film forming properties.

[Example 4]
The concentration and amount of peroxytitanic acid aqueous solution were increased.
(First step)
Same as Example 1.
(Second step)
<Production of 10 mass% concentration of peroxotitanic acid aqueous solution>
Titanium hydroxide was precipitated by dropwise addition of 440 mL of 2.5% (mass / volume) ammonia water to a solution of 39.6 mL of 60% (mass / volume) aqueous solution of titanium tetrachloride in 4000 mL with distilled water. The precipitate was collected by filtration, washed with distilled water, 30% (mass / volume) hydrogen peroxide water and 80 mL were added and stirred. The mixture was allowed to stand at 7 ° C. for 24 hours to decompose excess hydrogen peroxide water, and water was further added to obtain 100 g of a peroxotitanic acid aqueous solution having a concentration of 10% by mass in terms of titanium oxide in a yellow viscous liquid.
<Manufacture of aqueous dispersion of 5% by mass concentration of Natase type titanium oxide fine particles>
Thereafter, in the same manner as in Example 1, except that an aqueous dispersion of 10% by mass of anatase-type titanium oxide fine particles was used instead of an aqueous dispersion of 5% by mass of anatase-type titanium oxide fine particles. Manufactured. The water content of the first solvent is 39.7% by mass.

[Example 5]
The concentration and amount of the aqueous dispersion of anatase-type titanium oxide fine particles were increased.
(First step)
Same as Example 1.
(Second step)
<Manufacture of an aqueous dispersion of 10% by mass concentration of Natase type titanium oxide fine particles>
A 10 mass% concentration of peroxotitanic acid aqueous solution was sealed in a pressure-resistant glass container and boiled in a water bath for 12 hours (98 to 100 ° C.) to produce an aqueous dispersion of 10 mass% concentration of anatase type titanium oxide fine particles.
Thereafter, in the same manner as in Example 1, except that an aqueous dispersion of 10% by mass of anatase-type titanium oxide fine particles was used instead of an aqueous dispersion of 5% by mass of anatase-type titanium oxide fine particles. Manufactured. The water content of the first solvent is 39.7% by mass.

[Example 6]
(First step)
Same as Example 1.
(Second step)
<Production of 1.0 mass% concentration of peroxotitanic acid aqueous solution>
Titanium hydroxide was precipitated by dropwise addition of 440 mL of 2.5% (mass / volume) ammonia water to a solution of 39.6 mL of 60% (mass / volume) aqueous solution of titanium tetrachloride in 4000 mL with distilled water. The precipitate was collected by filtration, washed with distilled water, and then added with 80 mL of 30% (mass / volume) hydrogen peroxide water to a titanium hydroxide suspension to which 720 mL was added by adding distilled water and stirred. The mixture was allowed to stand at 7 ° C. for 24 hours to decompose excess hydrogen peroxide solution, and water was further added to obtain 1000 g of a 1 mass% peroxotitanic acid aqueous solution in terms of titanium oxide in a yellow viscous liquid.
<Production of 1% by mass anatase-type titanium oxide dispersion>
The peroxotitanic acid aqueous solution having a concentration of 1% by mass obtained in the first step is sealed in a pressure-resistant glass container and boiled in a water bath for 12 hours (98 to 100 ° C.), and water dispersion of anatase-type titanium oxide fine particles having a concentration of 5% by mass is carried out. A liquid was produced.
Thereafter, in the same manner as in Example 1, except that an aqueous dispersion of 1% by mass of anatase-type titanium oxide fine particles was used instead of an aqueous dispersion of 5% by mass of anatase-type titanium oxide fine particles. Manufactured. The water content of the first solvent is 28.0% by mass.

[Comparative Examples 5 to 8]
As in Example 4, except that, as shown in Table 2, the concentrations and amounts of the aqueous dispersion of anatase-type titanium oxide fine particles and the aqueous solution of peroxotitanic acid were changed to produce bright glass paints of Comparative Examples 5-8. did. The aqueous dispersion of 0.5 mass% anatase-type titanium oxide fine particles and the aqueous solution of peroxotitanic acid were diluted with 1 mass% and used.
The moisture content of the produced first solvent is 53.7% by mass in Comparative Examples 5 and 6, and 28.0% by mass in Comparative Examples 7 and 8.

[Examples 7 and 8]
As in Example 1, except that the amount of the infrared shielding inorganic compound and the amount of ethylene glycol monobutyl ether acetate were changed as shown in Table 3, a transparent glass paint was produced. The moisture content of the produced first solvent is 26.4% by mass in Example 7, and 28.4% by mass in Example 8.

[Comparative Examples 7 and 8]
As in Example 1, except that the amount of the infrared shielding inorganic compound and the amount of ethylene glycol monobutyl ether acetate were changed as shown in Table 3, a transparent glass paint was produced. The moisture content of the produced first solvent is 25.7% by mass in Comparative Example 7, and 29.7% by mass in Comparative Example 8.

[Reference Examples 1 to 4]
As in Example 1, except that as shown in Table 4, any one of the peroxotitanic acid aqueous solution, the aqueous dispersion of anatase-type titanium oxide fine particles, and the infrared shielding inorganic compound of each component of Example 11 Reference Examples 1 to 4 were prepared, which are water-based emulsion paints that contain no water or a water to toluene ratio of 1: 1 instead of the first solvent.

[Test example]
(Preparation of test specimen)
The glass piece for test was washed using an automatic washing machine until it was no longer watered even after draining and then dried with a hot air dryer (60 ° C.). The test coating composition was applied to this glass piece for test using a spray coater, and 20 g per 1 m ² , and naturally dried in a dark room temperature for 10 days to prepare a test sample piece.

(Visible light transmission)
The intensity of visible light (VIS) transmitted through the glass piece coated with the composite coating film of the present invention and the intensity of visible light (VIS ₀ ) transmitted through the glass piece not coated with the composite coating film were measured, and the formula (1) Was used to calculate the visible light shielding rate (%).
(Formula 1) Visible light shielding rate (%) = (VIS / VIS ₀ ) × 100
Visible light shielding rate of 80% or more was evaluated as ◯, 60 to less than 80% as Δ, less than 60% as ×, and Δ or more as acceptable.

(Infrared shielding test)
Using an infrared lamp and an infrared measuring instrument, the intensity of infrared rays (IR) transmitted through a glass piece coated with the composite coating film of the present invention and the intensity of infrared rays (IR ₀ ) transmitted through a glass piece coated with no composite coating film. Was measured, and the infrared shielding rate (%) was calculated using the formula (2).
(Formula 2) Infrared shielding rate (%) = {(IR ₀ −IR) / IR ₀ } × 100
Infrared shielding rate of 80% or more was evaluated as ◯, 60 to less than 80% as Δ, less than 60% as ×, and Δ or more as acceptable.

(UV shielding test)
Using a medium-pressure ultraviolet lamp (output wavelength: 200 to 600 nm) and an ultraviolet ray measuring instrument, the intensity (UV) of ultraviolet rays transmitted through the glass piece coated with the composite coating film of the present invention and the glass piece not coated with the composite coating film The intensity of the transmitted ultraviolet rays (UV ₀ ) was measured, and the infrared shielding rate (%) was calculated using Equation (3).
(Formula 3) Ultraviolet ray shielding rate (%) = {(UV ₀ −UV) / UV ₀ } × 100
Infrared shielding rate of 80% or more was evaluated as ◯, 60 to less than 80% as Δ, less than 60% as ×, and Δ or more as acceptable.

(Photocatalytic activity test)
Add 15 mL of water, 1 mL of 0.01 M aqueous ammonia and a few drops of phenolphthalein indicator to a glass petri dish with a diameter of 7 cm, cover the petri dish with the sample coating surface of the test piece facing down, and apply a 10 W UV lamp from above. After irradiation, the time until oxygen peroxide generated by the photocatalyst oxidizes ammonia and the red color of phenolphthalein disappears was measured.
Since there is a slight time lag before the photocatalyst is activated, the phenolphthalein color disappearance time of less than 20 minutes is marked as ◯, 20 minutes or more but less than 30 minutes as △, and more than 30 minutes Was evaluated as x, and Δ or higher was regarded as acceptable.

(Corrosion resistance test)
A 50 W medium pressure ultraviolet lamp (output wavelength: 200 to 600 nm) was irradiated for 20 hours from a distance of 50 cm from the test specimen, and the appearance of the specimen was compared before and after irradiation. By visual inspection, no change before and after UV irradiation was evaluated as ◯, slightly colored as △, colored or turbid as x, and Δ or higher as acceptable.

(Adhesion test)
Using a cutter knife, the coating on the surface of the test piece was scratched in a grid pattern with 1 mm length and width, and 100 1 mm square coating blocks were formed, and cellophane tape (manufactured by Nichiban) was applied to the surface and then peeled. The number of paint film blocks peeled off was counted. The peeled coating block was evaluated as 0, 0 or less as Δ, 6 or more as x, and Δ or more as acceptable.

[Test results]
The test results are shown in Table 5.

  As shown in Table 5, any of the photocatalyst paints included in the claims of the present application exhibits visible light transmittance. In addition, the paints of Examples 1 to 8 included in the scope of the claims of the present invention have excellent shielding activity against infrared rays and ultraviolet rays when applied to glass, and further have a photocatalytic activity, and a polymer. It was shown that the active ingredient is prevented from invading the resin component and has excellent corrosion resistance.

Table 1 shows the amounts of peroxotitanic acid, anatase-type titanium oxide fine powder, and acrylic polyol resin varied. Comparative Example 1 in which the water content in the first solvent is too small from the scope of the claims of the present invention And Comparative Examples 2, 5, and 6 which contain too much water, and Reference Example 4 which is a water-to-toluene 1: 1 water-based paint instead of the first solvent show deterioration of the coating film after completion of the corrosion resistance test. It was observed that the active oxygen produced by the photocatalyst invaded the polymer resin of the coating film.
Comparative Example 3 with few polymer resin components had poor film-forming properties, and Comparative Example 4 with too much polymer component had relatively low active components, and the infrared and ultraviolet shielding effects and photocatalytic activity were low.

Table 2 shows the limit of adding peroxotitanic acid and anatase-type titanium oxide fine powder, which are aqueous components.
In Comparative Examples 5 and 6 in which the amount of peroxotitanic acid or anatase-type titanium oxide fine powder added is too large, the water content of the amphiphilic solvent becomes too high to form a protective film as described above. Irradiation caused significant invasion of the coating film, indicating that the active oxygen produced by the photocatalyst invaded the polymer resin of the coating film.

  In Comparative Example 7 in which the amount of peroxotitanic acid added was too small, the photocatalyst could not be prevented from invading the polymer resin, and the corrosion resistance test was rejected. Further, Comparative Example 8 in which the addition amount of the anatase-type titanium oxide fine powder was too small failed in the ultraviolet shielding effect and photoactivity. Further, the film formability was inferior, and the adhesion was slightly weak.

Table 3 shows the limit of adding fine particles of the infrared shielding inorganic compound. Comparative Example 9 in which the addition amount of the fine particles of the infrared shielding inorganic compound was too small failed in the infrared shielding effect, and in the comparative example too much, the film forming property was inferior and the adhesion was unsatisfactory.
From the results of Tables 3 and 5, it was determined that the addition amount of the fine particles of the infrared shielding inorganic compound was 4 to 9 parts by mass.

Claims (9)

When the total mass of the transparent glass paint is 100 parts by mass,
Reaction product of acrylic polyol resin 15 to 30 parts by mass and aliphatic polyisocyanate 1 to 6 parts by mass, fine particles of infrared shielding inorganic compound 4 to 9 parts by mass, and anatase titanium oxide fine particles 0.1 to 2 parts by mass And a solid component containing 0.1 to 2 parts by mass of peroxotitanic acid converted to titanium oxide,
35 to 55 parts by mass of a first solvent which is an amphiphilic solvent having a boiling point of 140 ° C. or more and 200 ° C. or less, 1 to 3 parts by mass of a second solvent which is the same as or different from the first solvent, and 15 to 30 parts by mass of water , And is uniformly dispersed in a solvent having a water content of 20 to 50% by mass when the total of the mass of the amphiphilic solvent and the mass of water is 100% by mass. A paint for transparent glass that shields ultraviolet rays and infrared rays and has a photocatalytic action.   The amphiphilic solvent is selected from ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol diacetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, or diethylene glycol diethyl ether The transparent glass paint having a photocatalytic action by shielding ultraviolet rays and infrared rays according to claim 1.   The photocatalyst that blocks ultraviolet rays and infrared rays according to claim 1 or 2, wherein the infrared shielding inorganic compound is at least one selected from antimony oxide, tin oxide, indium oxide, gallium oxide, and zinc oxide. Transparent glass paint with action.   4. The ultraviolet ray according to claim 1, wherein the ratio of the mass of the acrylic polyol resin to the mass of the aliphatic polyisocyanate is in a range of 20: 1 to 20: 3. 5. Transparent glass paint that shields infrared rays and has photocatalytic activity. A method for producing a coating material for transparent glass, wherein the total mass of the coating material for transparent glass is 100 parts by mass,
A polyol solution prepared by dissolving 15 to 30 parts by mass of an acrylic polyol resin in 35 to 55 parts by mass of an amphiphilic solvent having a boiling point of 140 ° C. or higher and 200 ° C. or lower; 1 to 6 parts by mass of an aliphatic polyisocyanate; A resin solution production step of producing an acrylic urethane resin solution by reacting an aliphatic polyisocyanate solution dissolved in 3 parts by mass;
10 to 20 parts by mass of a peroxotitanic acid aqueous solution having a peroxotitanic acid concentration of 0.1 to 10% by mass in terms of titanium oxide, and anatase-type titanium oxide fine particles having a titanium oxide concentration of 0.1 to 10% by mass A functional inorganic material liquid production stage in which 10 to 20 parts by mass of an aqueous dispersion and 4 to 9 parts by mass of fine particles of an infrared shielding inorganic compound are mixed to produce a functional inorganic liquid.
Solvent when the resin solution and the functional inorganic liquid are 100% by mass of the total of the mass of the amphiphilic solvent contained in the resin solution and the mass of water contained in the functional inorganic liquid. A coating production stage in which the water content is mixed and uniformly dispersed so that the water content is 20 to 50% by mass;
A method for producing a coating material for transparent glass having a photocatalytic action by shielding ultraviolet rays and infrared rays.   The amphiphilic solvent is selected from ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol diacetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, or diethylene glycol diethyl ether The method for producing a coating material for transparent glass having a photocatalytic action by shielding ultraviolet rays and infrared rays according to claim 5.   6. The ultraviolet ray and infrared ray shielding and photocatalytic activity according to claim 5, wherein the infrared ray shielding inorganic compound is at least one selected from antimony oxide, tin oxide, indium oxide, gallium oxide, and zinc oxide. The manufacturing method of the coating material for transparent glass which has.   6. The transparent material having a photocatalytic action by shielding ultraviolet rays and infrared rays according to claim 5, wherein the ratio of the mass of the acrylic polyol resin to the mass of the aliphatic polyisocyanate is in the range of 20: 1 to 20: 3. A method for producing a paint for glass.   A transparent glass coating film having a photocatalytic action that blocks ultraviolet rays and infrared rays, wherein the transparent glass coating material according to any one of claims 1 to 4 is applied to a surface of a glass substrate and dried. Method.