JPH05147978A - Ultraviolet absorbent glass - Google Patents

Abstract

PURPOSE:To obtain the UV absorbent glass which is mechanically and chemically improved in surface characteristics by providing a UV absorbent film on glass and providing an oxide film as an external coating thereon. CONSTITUTION:This UV absorbent glass is provided with the UV absorbent film on glass and has the oxide film as the external coating. The UV absorbent film includes the films obtd. by physical film forming methods, such as vacuum vapor deposition, sputtering, reactive sputtering and ion plating, of metals, the oxide of which have absorbance bands, or the oxides thereof, or a method subjecting compds. consisting of such metals, as constituting elements to oxidation and decomposition reactions on glass, etc. The metal oxide film to be formed as the external coating is exemplified by films obtd. by the physical film forming methods, such as vacuum vapor deposition, sputtering, reactive sputtering and ion plating, of Si, Ti, Zr or the oxides thereof, and the films obtd. a chemical vapor deposition method, etc., using silane and oxygen-contg. gases as raw materials.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a UV absorber having a zinc oxide film formed on a glass substrate and a multilayer film structure having an outer surface coated with a silica film or the like, the surface characteristics of which are mechanically and chemically improved. Regarding glass.

[0002]

2. Description of the Related Art Generally, in order to prevent the transmission of ultraviolet rays, the glass is provided with a function of selectively reflecting or absorbing only ultraviolet rays in order to have transparency, which is an excellent characteristic of glass. There is a way to do it. Selective reflection characteristics can be obtained by alternately laminating films with different refractive indexes on the glass surface, but extremely sophisticated film forming technology is required for manufacturing, and for example, a large area such as a window glass for a house is manufactured. Is difficult to do. On the other hand, in order to give the glass an ultraviolet ray absorbing function, the glass itself should be a glass having a composition that absorbs ultraviolet rays, or an ultraviolet absorbing film should be provided on the surface or in the middle of soda lime glass produced with a normal plate glass composition. There are two possible ways of providing it.

The former glass which absorbs ultraviolet rays can be obtained by adding cerium oxide, iron oxide, titanium oxide, vanadium oxide or the like to a usual glass composition.
Manufacturing glass of such a special composition is not only time-consuming, but also expensive. Further, the mechanical strength and chemical properties of glass also fluctuate, which is not preferable in terms of design and construction before use.

As a method of installing the ultraviolet absorbing coating on the outside of the glass, (1) a method of adhering an organic polymer film containing an ultraviolet absorber of an organic or inorganic compound to the glass surface or inserting it between two pieces of glass , (2) a method of adhering an ultraviolet absorber of an organic or inorganic compound to a glass surface via a binder made of an organic or inorganic substance, and (3) a method of forming a film of a substance itself having an ultraviolet absorbing ability on the glass surface. It can be taken.

Of these, the organic polymer film or the film using an organic substance as a binder has a low surface hardness, and since the film itself is deteriorated by ultraviolet rays, it is not suitable for exposure to high-density ultraviolet rays or long-term use. Not suitable. Further, the ultraviolet absorber made of an organic compound has a drawback that it is itself unstable to ultraviolet rays.

By the way, as a method for forming a film of a substance itself having an ultraviolet absorbing ability on the glass surface, there are vacuum deposition, sputtering, reactive sputtering of a metal whose oxide has an absorption band in the ultraviolet region or its oxide, A physical film forming method such as ion plating or a method of subjecting a compound having the metal as a constituent element to oxidation and / or decomposition reaction on glass can be exemplified.

However, if these various film forming methods are considered from a practical point of view, the physical film forming method such as vacuum deposition requires a vacuum system, and therefore, the apparatus and operation, and therefore the object to be processed. Although it cannot be said that it is a very preferable method from the viewpoint of product throughput, the method utilizing oxidative decomposition is relatively economically advantageous.
No. 201 discloses that a zinc oxide film can be formed on soda lime glass by an oxidative decomposition reaction of zinc octylate. Further, Japanese Patent Application Laid-Open No. 62-297470 describes a method for producing a zinc oxide film by oxidative decomposition of zinc 2-ethylhexanoate.

Since most of the metal oxides have an absorption band in the ultraviolet region, various metals such as Cr, Mn, Fe, Co, Ni,
Although V, Pb, Ce, Ti, Zn, etc. can be enumerated, usually Ce, Ti, Zn, etc. whose oxide has little absorption in the visible region are preferred. In particular, since zinc oxide efficiently absorbs ultraviolet rays and has excellent visible light transmittance, it can be fully expected that a glass having such a zinc oxide coating will be useful as a so-called ultraviolet absorbing glass. By the way.

However, the ultraviolet absorbing glass having a zinc oxide film has a problem that the hardness of the film is low and the glass is easily scratched not only when used outdoors but also when cleaning or wiping indoors. Further, it is known that zinc oxide is easily dissolved when it comes into contact with acidic and basic solutions, and thus strict caution is required in using it as compared with ordinary glass. Therefore, practically suitable ultraviolet absorbing glass could not be obtained by simply coating with zinc oxide.

[0010]

[Means for Solving the Problems] The present inventors have used zinc oxide, which has an excellent ultraviolet absorbing ability, as an ultraviolet absorber,
Moreover, investigations were conducted to obtain a large-area ultraviolet absorbing glass having excellent surface hardness and chemical stability, and the present invention was reached.

That is, the present invention is an ultraviolet absorbing glass having an ultraviolet absorbing film provided on glass and further having an oxide coating as an outer coating. The ultraviolet absorbing film is a metal whose oxide has an absorption band in the ultraviolet region or a vacuum deposition of the oxide or its oxide, sputtering, reactive sputtering,
Examples of the film include, but are not limited to, a film obtained by a physical film forming method such as ion plating, or a method of subjecting a compound having the metal as a constituent element to oxidation and decomposition reaction on glass.

Since many metal oxides have an absorption band in the ultraviolet region, various metals such as, for example,
Although Cr, Mn, Fe, Co, Ni, V, Pb, Ce, Ti, Zn and the like can be applied, Ce, Ti, Zn and the like whose oxides have little absorption in the visible region are preferable. In particular, zinc oxide is the most preferable oxide because it efficiently absorbs ultraviolet rays and has excellent visible light transmittance.

Also for the metal oxide film to be the outer coating, a physical film forming method such as vacuum deposition of Si, Ti Zr or an oxide thereof, sputtering, reactive sputtering, ion plating, silane and an oxygen-containing gas are used. Examples of the film obtained by the chemical vapor deposition method using as a raw material, or a method by subjecting a compound having one or more of Si and Ti Zr as constituent elements to oxidation and decomposition reaction on glass are mentioned. It's not limited.

The film structure of the present invention is provided on at least one surface of the glass substrate. Further, the ultraviolet absorbing film and the outer coating do not necessarily have to be a single film or a single composition, and may be a multi-layer or a multi-composition depending on a film forming method. The oxide as used herein does not need to have a constant stoichiometric ratio. For example, in the case of zinc, zinc oxide means not only stoichiometric ZnO, but also a non-stoichiometric compound of zinc and oxygen or a compound thereof. Also includes mixtures.

The case of an ultraviolet absorbing glass having an ultraviolet absorbing film made of zinc oxide will be described below. However, when applying other metals, it may be necessary to make changes that can be easily conceived by those skilled in the art. ..

When the ultraviolet absorbing film is produced by a method of subjecting it to an oxidation and / or decomposition reaction, a salt of zinc soluble in a solvent, for example, a salt of an inorganic acid such as nitric acid or hydrochloric acid, caprylic acid or palmitic acid. , Stearic acid, oleic acid, naphthenic acid, linoleic acid, linolenic acid, 2-
Salts of C _{8 to} C ₂₀ higher fatty acids such as ethylhexanoic acid, diketone chelate compounds such as acetylacetone, benzoylacetone, benzotrifluoroacetone, dibenzoylmethane, furoylacetone, trifluoroacetylacetone, or the general formula Zn (0R ¹ ) (0R ² ) or
ZnCl (0R ¹ ) (wherein R ¹ and R ² are any of a methyl group, an ethyl group, a normal propyl group, an isopropyl group, a normal butyl group, a secondary butyl group, a methoxyethyl group, an ethoxyethyl group or a phenyl group. In particular, dimethoxyzinc, diethoxyzinc, diisopropoxyzinc, chloromethoxyzinc, chloroethoxyzinc and the like can be mentioned, and one or more selected from them can be used alone or in combination. Used.

As a method for coating the raw material of the ultraviolet absorbing film on the glass substrate, there are methods such as a flow coating method, a spraying method, a roll coating method, a spin coating method, a dipping method and a screen printing method. Which of these methods is used. Although it may be adopted, the properties of the coating solution used in each method are different. Therefore, it is common to add various additives to the coating liquid for the purpose of a diluent, a viscosity modifier, a leveling agent, an oxidation accelerator, a stabilizer, etc., depending on the form of use.

Solvents used as diluents or viscosity modifiers include alcohols such as methanol, ethanol, isopropanol, normal butanol, ethoxyethanol, ethylene glycol, benzyl alcohol, methyl acetate, ethyl acetate, isopropyl acetate, butyl acetate, acetic acid. Esters such as benzyl, ethyl acetoacetate and dibutyl phthalate, ketones such as acetone, methyl ethyl ketone, diethyl ketone, acetylacetone and isophorone, aromatic hydrocarbons such as benzene, toluene and xylene, tetrachloroethylene, trichloroethylene, trichloroethane, methylene chloride , Halogen solvent such as chloroform, carbon tetrachloride, or water is used.

As the viscosity modifier or leveling agent, modified celluloses such as hydroxypropyl cellulose, carboxymethyl cellulose and nitrocellulose, dimethyl silicone, methylphenyl silicone,
Silicone oils such as silicone reoxyethylene copolymer, silicone polyoxyalkylene copolymer and amino-modified silicone oil are used.

For the purpose of accelerating the oxidative polymerization of higher fatty acids,
It is effective to add an organic peroxide, but 3,3,3
5-trimethylcyclohexanone peroxide, te
rt-butyl peroxyenzoate, di (tert-
Butyl) peroxide, 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane and the like are used.

As the coating solution for the ultraviolet absorbing film, various compositions are used, and in any case, it is treated with zinc oxide by heating at 400 ° C. or higher in the atmosphere after coating or in the atmosphere with a high oxygen concentration. To do.

The concentration of the coating chemical solution used for forming the ultraviolet absorbing film is 0.1 to 30 as the ratio of zinc in the solution.
Weight% is preferred, but 3-20 weight% is more preferred.
When the zinc concentration is lower than 0.1% by weight, the film formed in one coating operation becomes thin and repeated coating is required, which is practically inconvenient. On the contrary, if the zinc concentration is too high, there is a disadvantage that it becomes difficult to obtain a smooth film. However, it is not always necessary that this concentration condition be satisfied, and adjustment is possible depending on the types of additives and solvents.

The thickness of the ultraviolet absorbing film obtained at this time is
0.1 to 2 μm is preferable, and 0.5 to 1.5 μm is more preferable. A film thinner than 0.1 μm does not have a sufficient ultraviolet ray absorbing effect, while a film thicker than 2 μm absorbs visible light, so that it is desirable to avoid it. The ultraviolet absorbing film can be formed by coating once or plural times.

The chemical used for forming the oxide film is Si, T
i, Zr alkoxide, chlorine-containing alkoxide or inorganic salt, but also Si alkoxide, Na, Ca, K, B,
A solution having a glass-forming composition containing an alkoxide of Zn, Ti, Zr, Al, Pb, etc., a chlorine-containing alkoxide, and an inorganic salt at the same time can be used as it is or after being partially hydrolyzed. The presence of Na, Ca, K, B, Zn and Pb is an especially preferable additive because it has the effect of facilitating glass formation.

Specifically, if silica sol is used as the Si raw material,
The general formula Si (0R¹) (0R²) (0R³) (0R ^Four), SiCl (0R¹) (0R²)
(0R³), SiCl₂(0R¹) (0R²) Or SiCl₃(0R¹), R¹Si (0
R²) (0R ³) (0R^Four), R¹R²Si (0R³) (0R^Four) (However, in the formula R¹,
R², R³, R^FourIs methyl group, ethyl group, normal propyl
Group, isopropyl group, normal butyl group, secondary group
Cyl, methoxyethyl, ethoxyethyl or fluoro
Indicates any of the phenyl groups. ) Alkoxylation
Among the compounds, tetraethoxysilane, tetramethoxysilane
Orchid, methyltriethoxysilane, methyltrimethoxy
Silane, dimethyldimethoxysilane, dimethyldietoxy
Sisilane, phenyltriethoxysilane, phenyltri
Methoxysilane and the like can be mentioned.

As Ti raw material, TiCl ₄ , TiOCl ₂ , Ti (NO ₃ ) ₄ ,
Ti salts such as TiO (NO ₃ ) ₂ or hydrous salts thereof, or general formulas Ti (0R ¹ ) (0R ² ) (0R ³ ) (0R ⁴ ), TiCl (0R ¹ ) (0R ² ) (0R ³ ).
, TiCl ₂ (0R ¹ ) (0R ² ), or TiCl ₃ (0R ¹ ), where R
¹ and R ^{2 each} represent a methyl group, an ethyl group, a normal propyl group, an isopropyl group, a normal butyl group, a secondary butyl group, a methoxyethyl group, an ethoxyethyl group or a phenyl group. Among the alkoxy compounds represented by), tetraethoxy titanium, tetranormal propoxy titanium, tetraisopropoxy titanium, tetranormal butoxy titanium, chlorotriethoxy titanium, dichlorodinormal butoxy titanium, trichloro normal butoxy titanium, etc. or dibutoxy titanium acetyl. Examples include acetonate and isopropoxydititanium octylene glycolate.

ZrCl ₄ , ZrOCl ₂ , Zr (N
_{O 3) 4, ZrO (NO} 3) 2, zirconium stearate, zirconium naphthenate, 2-ethylhexanoate, zirconium, Zr salt or a hydrated salt such as zirconium acetylacetonate or general formula Zr (0R ^1,) ( 0R ² ) (0R ³ )
(0R ⁴ ), ZrCl (0R ¹ ) (0R ² ) (0R ³ ), ZrCl ₂ (0R ¹ ) (0R ² ), or ZrCl ₃ (0R ¹ ) (wherein R ¹ and R ² are methyl groups, An ethyl group, a normal propyl group, an isopropyl group, a normal butyl group, a secondary butyl group, a methoxyethyl group, an ethoxyethyl group or a phenyl group), among the alkoxy compounds represented by tetraethoxyzirconium and tetranormal Propoxyzirconium, tetraisopropoxyzirconium, tetranormalbutoxyzirconium, chlorotriethoxyzirconium,
Examples thereof include dichlorodinormal butoxy zirconium and trichloro normal butoxy zirconium.

The concentration of the coating chemical solution used for forming the oxide film is 0.01 to 5 mol as the ratio of metal in the solution.
l / l is preferred, but 0.1-2 mol / l is more preferred.
When the metal concentration is lower than 0.1% by weight, the film formed in one coating operation becomes thin, and the number of times of repeated coating increases, which is practically inconvenient. On the other hand, if the metal concentration is too high, cracks, peeling, devitrification, etc. occur, making it difficult to obtain a smooth and uniform film. However, it is not always necessary that this concentration condition be satisfied, and adjustment is possible depending on the types of additives and solvents.

The thickness of the oxide film obtained at this time is 0.
1-2 μm is preferable, and 0.5-1.5 μm is more preferable. If the film is thinner than 0.1 μm, the effect of protecting the ultraviolet absorbing film is not sufficient. On the other hand, if the film is thicker than 2 μm, cracks are likely to occur and it is desirable to avoid it. The oxide film can be formed by coating once or plural times, and it is also effective to form a film having a different composition for each film.

For example, as shown in the examples, a film made of tetraethoxysilane is once coated on a zinc oxide film, and a protective film containing titanium, zirconium or silicon is further formed on the film to form a remarkable film. Shows a protective effect. This avoids the problem that the zinc oxide film is dissolved or peeled off when a chlorine-containing alkoxide having a low pH is used in the film forming method of the present invention, so-called sol-gel method. As a result, a protective film was obtained that facilitated the formation of the film and was excellent in smoothness, uniformity, adhesion, and chemical stability.

Application of the chemical solution onto the ultraviolet absorbing film is carried out by dipping method, spraying method, roller coating method, flow coating method,
It is performed by a method such as a screen printing method. The coating film formed by various methods is dried at 70 to 250 ° C for 5 to 15 minutes and baked in an electric furnace at 400 ° C or higher for 10 to 30 minutes to obtain an excellent protective film as an oxide or oxide glass. Become.

As described above, the ultraviolet absorbing glass of the present invention is used for buildings such as windows and show windows of buildings, greenhouses, vehicles such as automobiles, railways and ships, stained glass,
It has various applications in interior decoration such as showcases and lighting fixture covers, and in the electronics field such as solar cell covers, and can protect plants, animals, and articles inside glass from deterioration or damage due to ultraviolet rays.

[0033]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

Preparation Example 1 100 g of zinc 2-ethylhexanoate, 80 g of linoleic acid and mixed xylene as a solvent 500 ml with a stirrer and a reflux device
The mixture was placed in a round bottom flask and stirred for 2 hours while maintaining at 190 to 220 ° C. in an oil bath to obtain a brownish viscous liquid. This liquid was further distilled under a reduced pressure of 5 to 20 mmHg to remove the mixed xylene used as a solvent to obtain 185 g of a brown solid substance.

52.5 g of the above solid substance was added to 46.5 g of toluene,
Dimethyl silicone compound (TSF-
400) It was possible to prepare a zinc oxide film forming chemical solution by pouring it into 1 g of a mixed solution and stirring it.

A 100 × 100 × 3 mm raw plate glass of soda lime glass having a masking film on one side was dipped in this chemical solution and pulled up at a rate of 30 cm / min to form a coating film on one side. The coating film is dried in a far infrared oven at 200 ° C for 15 minutes to remove the solvent and oxidatively harden the film, and then baked in an electric furnace at 550 ° C for 15 minutes to give a 1.1 μm thick gauze-like wrinkle pattern. A transparent and uniform thickness zinc oxide film showing no interference fringe pattern was obtained.

The ultraviolet absorbing glass obtained in this adjustment example is
It was found that almost 100% of ultraviolet rays with a wavelength of 370 nm or less are absorbed and the transmittance is almost the same as that of the raw glass plate in the visible region.

Examples 1 to 5 and 8 , Comparative Example 1 The glass plate having the zinc oxide coating obtained in Preparation Example 1 was further coated with a liquid having the composition shown in Table 1 by a dipping method.

That is, the above glass plate was immersed in a solution containing a compound having a composition shown in Table 1 at a concentration of 0.5 mol / l and using normal butanol as a solvent, and pulled up at a speed of 27 cm / min.
Heat treated at 150 ° C for 15 minutes and baked at 500 ° C for 15 minutes, then
An oxide film having a film thickness shown in was obtained. It was found that the obtained ultraviolet absorbing glass absorbs almost 100% of ultraviolet rays having a wavelength of 370 nm or less, and its transmittance is almost the same as that of the raw glass plate in the visible region.

Various physical property tests were conducted on the obtained ultraviolet absorbing glass. (1) The acid resistance test was carried out by immersing the sample in a 1% hydrochloric acid aqueous solution at 30 ° C. for 24 hours and then measuring the change in wavelength absorption characteristics.

(2) The alkali resistance test was carried out at 30 ° C. for the sample.
Was immersed in a 1% aqueous sodium hydroxide solution for 24 hours, and then the change in wavelength absorption characteristics was measured.

(3) The weather resistance test was carried out by measuring changes in appearance and wavelength absorption characteristics after exposing the sample to ultraviolet rays of 3 mW / cm ² for 2000 hours using a high pressure mercury lamp.

(4) Regarding the haze ratio, in a wear resistance test in accordance with JIS R-3212, the test piece was worn by a specified wear wheel, and it was expressed by the scattering transmittance / total transmittance (%). Table 1 shows the difference before and after the abrasion resistance test. Regarding the number of rotations, in Examples 3 and 5 in which peeling was performed at 1000 rotations defined by JIS, the change value at 100 rotations was shown for reference.

(5) The solvent resistance test was carried out by measuring changes in appearance and wavelength absorption characteristics after the sample was immersed in acetone at 20 ° C. for 720 hours. (6) The boiling resistance test was carried out by measuring changes in the appearance and wavelength absorption characteristics after the sample was immersed in boiling pure water for 50 hours.

(7) The humidity resistance test was carried out at a temperature of 50 ° C.
(48 to 52 ° C.) and humidity of 98% (96 to 100%) were measured by measuring changes in appearance and wavelength absorption characteristics after installation in a thermo-hygrostat for 2 weeks.

(8) The adhesion test was conducted by a 1 mm square cross-cut tape test and evaluated by n / 100 (n is the number not peeled). The results are shown in Table 1.

Example 6 Tetraethoxysilane was added to normal butanol at 0.1 mol /
The glass plate having the zinc oxide coating obtained in Preparation Example 1 was dipped in the coating chemical solution dissolved so that it was pulled up at a rate of 27 cm / min and heat-treated at 150 ° C. for 15 minutes. Then, a glass plate having a zinc oxide coating obtained in Preparation Example 1 in a coating solution prepared by dissolving chlorotriethoxytitanium and tetraethoxysilane in normal butanol at 0.25 mol / each and having been subjected to the above-mentioned treatment Was dipped, pulled up at a speed of 27 cm / min, and heat-treated at 150 ° C. for 15 minutes. After that, 500 ℃
And baked for 15 minutes to obtain an oxide film having a film thickness shown in Table 1. It was found that the obtained ultraviolet absorbing glass absorbs almost 100% of ultraviolet rays having a wavelength of 370 nm or less, and has almost the same transmittance as that of the raw glass plate in the visible region. The same test as in Example 1 was performed. The results are shown in Table 1.

Example 7 The same experiment and test as in Example 6 were carried out except that chlorotriethoxyzirconium was used instead of chlorotriethoxytitanium. The results are shown in Table 1.

Comparative Examples 2 and 3 Comparative Examples 2 are glass plates coated with only the zinc oxide film obtained in Preparation Example 1, and Comparative Example 3 is a green glass plate not coated with zinc oxide and a protective film. is there. Example 1
The same test was performed. However, regarding the abrasion resistance test (fogging rate) of Comparative Example 2, peeling occurred at 100 rotations as well as 1000 rotations specified in JIS. The results are shown in Table 1.

[0050]

[Table 1]

A detailed examination of the results in Table 1 revealed that the acid resistance was not sufficient and that the haze was slightly inferior to that of uncoated glass, but the protective film was peeled off in the above test. It is clear that it has much higher mechanical and chemical strength than the zinc oxide film alone.

[0052]

The UV-absorbing glass of the present invention exhibits optical characteristics that it hardly absorbs visible light and selectively absorbs UV light, and further, it is one of Si, Ti and Zr on the zinc oxide coating. By coating the above oxide film,
It becomes a mechanically excellent UV absorbing glass.

Claims (3)

[Claims] 1. An ultraviolet absorbing glass having an ultraviolet absorbing film on glass and an oxide coating as an outer coating. 2. The ultraviolet absorbing glass according to claim 1, wherein the ultraviolet absorbing film contains at least zinc oxide. 3. The ultraviolet absorbing glass according to claim 1, wherein the outer coating is made of at least one oxide of silicon, zirconium or titanium.