JPH06144870A - Ultraviolet/heat ray-shielding film and glass provided therewith and method therefor - Google Patents

Abstract

PURPOSE:To obtain an ultraviolet/heat ray-shielding film with high visible ray transmittance, so durable as to be used as a single film by coating a substrate with a solution containing a cerium fatty acid salt or titanium fatty acid salt followed by baking in an oxidative atmosphere. CONSTITUTION:The objective multiple oxide film can be obtained by coating the surface of a substrate with the coating solution described below followed by drying, curing and baking in an oxidative atmosphere. The coating solution contains a cerium fatty acid salt or titanium fatty acid salt. The multiple oxide film is an ultraviolet/heat ray shielding film which consists of cerium oxide and titanium oxide, contains 30-80wt.% of cerium oxide, and has a thickness of 800-2000Angstrom . This shielding film is a single film, can simultaneously shield both ultraviolet and heat rays, is excellent in the adhesiveness to a substrate such as glass plate, surface wear resistance, and resistance to acids and alkalies, and also causes no problems in glass reinforcement.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ultraviolet and heat ray shielding glass used for vehicles such as automobiles and windows of buildings, and has a particularly high visible light transmittance and can be used as a single plate. TECHNICAL FIELD The present invention relates to a durable ultraviolet / heat ray shielding glass and a method for producing the same.

[0002]

2. Description of the Related Art In general, glass is provided with transparency, which is an excellent characteristic, and it has a function of selectively reflecting or absorbing ultraviolet rays and heat rays in order to prevent transmission of ultraviolet rays and heat rays. Must be applied to glass. The selective reflection property is obtained by the light interference effect by alternately laminating films having different refractive indexes on the glass surface, but it is technically difficult to apply it to a large area such as a window glass for a house. But the manufacturing cost is high. In addition, in order to give the glass the ability to block ultraviolet rays and heat rays, the glass itself must have a composition that absorbs ultraviolet rays and heat rays, or the glass sheet must be pasted with an organic film that has the ability to block ultraviolet rays and heat rays. Two methods are conceivable: laminated glass sandwiching an organic film.

The former glass that absorbs ultraviolet rays and heat rays is
It can be obtained by adding cerium oxide, iron oxide, titania, vanadium oxide, etc. to the usual glass composition, but since it has absorption in a part of the visible region, it is colored and absorbs heat rays, and the heat rays from the glass itself are absorbed. It emits secondary radiation, and its heat ray shielding ability is insufficient compared to heat ray reflective films.

As a method of installing the ultraviolet / heat ray shielding film on the outside of the glass, an organic polymer film containing an ultraviolet / heat ray shielding agent of an organic or inorganic compound is attached to the glass surface or inserted between two pieces of glass. Method, a method of adhering an ultraviolet or heat ray shielding agent of an organic or inorganic compound to the glass surface via a binder made of an organic or inorganic substance, or a method of forming a film of a substance itself having an ultraviolet or heat ray shielding ability on the glass surface. Can be taken.

Since the organic polymer film containing the ultraviolet / heat ray shielding agent adhered to the glass surface is soft, it is easily scratched, and there is a problem of deterioration over time such as coloring and peeling due to ultraviolet rays of sunlight. 2 organic polymer films
Laminated glass sandwiched between a plurality of glasses has excellent weather resistance and durability, but there are problems that laminated glass is thick and heavy and cannot be easily cut like single glass. The method is disclosed in Japanese Patent Application Laid-Open No. 2-75683 and the like, but it has a drawback that scratches are likely to occur as in the case of using an organic resin as a binder. Further, when an inorganic binder is used, it is difficult to obtain a required thick film having a defect of several tens of μm.

[0006]

SUMMARY OF THE INVENTION The present invention has been made by paying attention to such a conventional problem, and the first object of the present invention is to provide a single film having sufficient transmittance in the visible region and ultraviolet rays. It is intended to provide architectural / vehicle glass that can shield both heat and heat rays. Secondly, the present invention provides architectural / vehicle glass that is free from cracks and film peeling during the glass strengthening process and bending process. Third, it provides architectural / vehicle glass that allows radio waves to pass through inside buildings / vehicles. Further, the present invention provides inexpensive and large-area glass for construction and vehicles.

[0007]

The inventors of the present invention have found that cerium oxide (hereinafter
Also called CeO ₂ . ) Was studied as a basic component and capable of simultaneously shielding heat rays. As a result, by containing titanium oxide (hereinafter also referred to as TiO ₂ ) at the same time, it was possible to obtain a film having the desired ultraviolet / heat ray shielding ability. The inventors have found out what can be done and have reached the present invention.

That is, the ultraviolet / heat ray shielding film of the present invention specifies a composite metal oxide of cerium oxide and titanium oxide which contains cerium oxide having an ultraviolet absorbing ability and has a sufficiently high refractive index with respect to the substrate. It is characterized in that the heat ray is shielded at the same time by the interference reflection effect by setting the film thickness to.

For the film containing cerium oxide and titanium oxide, see Journal of Non-Cristalline Solids 121.
(1990) 315-318, and it is reported that it has an ultraviolet absorbing ability. However, in this document, it is essential to contain silicon oxide in addition to cerium oxide and titanium oxide, which is supposed to improve the film-forming property and maintain the stability of the precursor solution. Is unavoidable, which does not meet the purpose of the present invention.

Also, J. Am. Ceram. Soc., 69 (6) C-127-C-12
9 (1986), a method of forming a CeO ₂ —TiO ₂ coating film on the surface of a glass plate or an aluminum plate by a sol-gel method is reported. However, no reference is made to the method of exerting the ultraviolet / heat ray shielding effect which is the object of the present invention.

[0011] UV-heat-shielding single layer used in the present invention has been made to substantially block following ultraviolet and 700nm or more near infrared 380 nm, cerium oxide CeO ₂ and heat-reflecting ability excellent ultraviolet absorptivity It consists of a composite oxide film composed of a combination of excellent titanium oxide TiO ₂ . These thin films can be formed by any method selected from vacuum film forming methods such as sputtering method, vapor deposition method and chemical vapor deposition method, sol-gel method, flow coating method, spray method, dip coating method, spin coating method and wet method such as printing method. Can be formed with. The thin film used in the present invention needs to be laminated on at least one layer on one side, but it is also effective to form it on both sides in order to enhance the ultraviolet shielding effect and the heat ray reflection effect.

The film thickness of the film of the present invention is preferably 500 to 3000 angstroms in order to exert a sufficient ultraviolet shielding effect and to obtain sufficient durability. On the other hand, for the shielding of heat rays by the interference reflection effect, it is necessary that the refractive index of the coating is higher than that of the substrate, and according to the theory of interference, depending on the refractive index in the near infrared light region,
The film thickness is determined.

The coating of the present invention comprises cerium oxide 30-80.
Since it is a mixed metal oxide composed of cerium oxide and titanium oxide containing wt%, the refractive index is approximately 1.8 although it is slightly different depending on the method of forming the film, particularly the firing temperature.
Is about 2.7. Therefore, in order to reflect the near-infrared light of 1 μm, which is most effective in exerting the heat ray shielding effect, it is preferable that the film thickness of the coating film is 800 to 2000 angstrom.

When the content of cerium oxide is 30% by weight or less, the ultraviolet absorption effect is low, so that the film thickness becomes thicker and the optical thickness becomes thicker to obtain the necessary shielding effect, and a sufficient interference effect is expected. It is not possible and not preferable. Again 80
If it is more than 10% by weight, a uniform film suitable for optical use cannot be obtained.

In the present specification, “cerium oxide”, “titanium oxide”, “CeO ₂ ”, and “TiO ₂ ” all refer to cerium or a nonstoichiometric compound of titanium and oxygen in the film. The value indicating the composition ratio of each oxide is expressed by assuming that it is CeO ₂ or TiO ₂ in terms of stoichiometry.

The present invention will be described below by taking the case of using the dipping method, which is one method of forming the ultraviolet / heat ray shielding film of the present invention, as an example. In the dipping method, a thin film is formed by a method of applying a solution containing a cerium compound and a metal compound which is a titanium compound, and then baking the solution.

The metal compound used in the present invention includes:
Preferred are metal alkoxides, metal fatty acid salts, metal chlorides or metal nitrates. The metal alkoxide is represented by the general formula M (OR) n. Here, n is an integer and represents the coordination number of the alkoxyl group, and is generally 1-8. R
Is selected from any alkyl or alkoxyalkyl group. Examples of R include, for example, methyl group, ethyl group, i
-Propyl group, n-propyl group, n-butyl group, sec
-Butyl group, methoxyethyl group, ethoxyethyl group, n
-Propoxyethyl group, i-propoxyethyl group and the like. R may be the same or different.

The method of applying the solution of the metal compound may be according to the method known as the so-called Sol-Gew method, and the solvent of the solution is methanol, ethanol or i.
-Propanol, n-propanol, n-butanol,
Most preferred are alcohols such as sec-butanol, t-butanol, methyl cellosolve, and ethyl cellosolve, and if necessary, esters, ethers, ketones,
It is also possible to add a hydrocarbon solvent, a halogenated hydrocarbon solvent, an aromatic solvent and the like.

The metal concentration of the solution should be appropriately adjusted depending on the desired film thickness of the coating film, the type of solvent, the type of alkoxide or the presence or absence of the addition of a viscosity modifier, but usually 0.1 to 3 mol. / L is preferable, and it is difficult to obtain a sufficient film thickness at a concentration of 0.1 mol / L or less, and if it exceeds 3 mol / L, it is not preferable in terms of preparation and storage of the coating solution.

The metal fatty acid salt has the general formula M (CxHyCOO).
It is represented by n. Here, n represents the valence of the metal. CxHy
COO is preferably a saturated or unsaturated fatty acid group in which x is 3 to 23 and y is 7 to 47. As the fatty acid, 2-ethylhexanoic acid, naphthenic acid, etc. are preferably used. Preferable examples of the metal fatty acid salt include titanium 2-ethylhexanoate and cerium 2-ethylhexanoate. In the case of a combination of a metal fatty acid salt and an unsaturated fatty acid, an aromatic compound such as benzene, toluene, xylene, etc., or ethyl acetate, butyl acetate, etc., is used as a diluting solvent in order to adjust the viscosity and the solute concentration optimum for coating. Ester compounds, alcohols such as ethanol and butanol are preferably used. It is also desirable to add a leveling agent such as dimethyl silicone so that a good coating film can be obtained. The unsaturated fatty acid used in the present invention is most preferably linoleic acid, and for example, dehydrated castor oil fatty acid, which is inexpensive as a linoleic acid-containing compound, can be applied. As the leveling agent, dimethyl silicone oils such as TSF400 and TSF401 of Toshiba Silicone Co., KF96 of Shin-Etsu Chemical Co., Ltd. and SH200 of Toray Silicone Co., Ltd. are effective. The mixing ratio of these compounds may be arbitrary, but preferably 60 to 100 parts by weight of unsaturated fatty acids such as linoleic acid and 0.1 to 5 parts by weight of a leveling agent such as dimethyl silicone oil to 100 parts by weight of metal fatty acid salt. By weight, the organic solvent is 150-850 parts by weight.

By subjecting the solution applied onto the glass to drying and baking treatment, a desired strong coating film can be obtained. The drying temperature is preferably in the range of 70 to 200 ° C. Firing should be at a temperature at which organic compounds are removed, preferably 400 ° C. or higher, and firing time is 10 to 10.
60 minutes is enough. The upper limit of the firing temperature varies depending on the type of glass, but in the case of ordinary soda lime glass, when simultaneously strengthened, it can be up to about 720 ° C.

The veneered glass to be mounted on a vehicle requires tempered glass to ensure the safety of passengers, and the window needs to have a curved shape depending on the shape of the vehicle.
For that purpose, the glass plate is heated and bent at a temperature of at least 600 ° C. or higher, and is then quenched and then strengthened. This step is performed after forming the ultraviolet / heat ray shielding film on the glass plate. The heating time may be 2 to 30 minutes. The substrate to be applied is selected from transparent glass substrates and usually silica coated or untreated soda lime glass is used.

[0023]

EXAMPLES The present invention will be further described below with reference to examples, but the present invention is not limited to these examples. The test results obtained in the examples and comparative examples are summarized in Table 1. (Example 1) 75 g of cerium nitrate hexahydrate was dissolved in 290 ml of ethylene glycol monoethyl ether, and 49 g of tetraisopropoxytitanium was added dropwise thereto over 30 minutes so that the molar ratio to cerium was 1 and mixed and stirred. did. 290 ml of ethanol to improve the quick-drying property of this homogeneous solution
Was added and mixed and stirred to obtain a coating liquid for cerium oxide-titanium oxide coating. 100 × 100 × 4 in this coating liquid
A plate of soda lime glass having a masking film attached to one surface thereof was dipped in mm and pulled up at a speed of 20 cm / min to form a coating film on one surface. The coating is 1 at 100 ° C
Dry in an electric furnace for 0 minutes, then 700 in an electric furnace
After baking at 4 ° C for 4 minutes, it was taken out and rapidly cooled with warm air at 60 ° C to carry out a strengthening treatment to obtain a uniformly transparent cerium oxide-titanium oxide film.

The following measurements were carried out on the coated glass, and the evaluation results are shown in Table 1. "UV cut rate" indicates the absorption rate at 300 to 380 nm measured by a spectrophotometer U-4000 (Hitachi). "Visible transmittance" and "solar transmittance" are JIS
Spectrophotometer U-400 according to R3106 (1985)
0 (Hitachi) was measured and calculated. The “transmitted color” and the “reflected color” are hues visually observed. “Taber wear” is the number of wear wheels. The CS-10F was applied with a load of 500 g, and the change in the haze ratio after 1000 rotations was measured with a haze meter. The "acid resistance" was evaluated by immersing the glass in a 10% aqueous hydrochloric acid solution at room temperature for 24 hours and then evaluating the optical characteristics and durability. "Alkali resistance" means the optical characteristics after immersing glass in a 10% sodium hydroxide aqueous solution at room temperature for 24 hours.
The durability was evaluated. In the "strengthening treatment", after putting in a muffle furnace at 700 ° C for 4 minutes, it was taken out, rapidly cooled by hot air at 60 ° C for 1 minute, and then naturally cooled. (Example 2) 43 g of cerium nitrate hexahydrate was dissolved in 436 ml of ethylene glycol monoethyl ether, and 85 g of tetraisopropoxytitanium was added dropwise thereto over 30 minutes so that the atomic ratio of cerium / titanium was 1/3. Mix and stir. In order to improve the quick-drying property of this uniform solution, 436 ml of ethanol was added and mixed and stirred to obtain a coating liquid for cerium oxide-titanium oxide coating.

A uniform transparent cerium oxide-titanium oxide film was formed by the same method as in Example 1 using this coating solution.
The evaluation results are shown in Table 1. (Example 3) A coating liquid prepared in the same manner as in Example 1 was used, except that 64 g of cerium chloride heptahydrate was used and the atomic ratio of cerium to titanium was 1/1. A uniform transparent cerium oxide-titanium oxide coating was formed by the method. The evaluation results are shown in Table 1.

[0026]

[Table 1] (Example 4) A method similar to that of Example 1 using a coating solution prepared in the same manner as in Example 1 except that 96 g of diammonium cerium nitrate was used and the atomic ratio of cerium to titanium was 1/1. To form a uniform transparent cerium oxide-titanium oxide film. The evaluation results are shown in Table 1.

(Example 5) Tetra-isopropoxytitanium 2 was added to 100 g of a 0.8 mol / kg ethyl cellosolve solution of tetra-n-butoxycerium [Ce (OBu ⁿ ) ₄ ].
3 g was gradually added and mixed and stirred. To improve the quick-drying property of this uniform solution, 157 ml of ethanol was added, and the mixture was mixed and stirred to obtain a coating liquid for cerium oxide-titanium oxide film. This solution has an atomic ratio of cerium to titanium of 1/1
Then, the concentration of the metal component was 0.5 mol / L.

A uniform and transparent cerium oxide-titanium oxide film was formed by the same method as in Example 1 using this coating solution.
The evaluation results are shown in Table 1. (Example 6) Cerium 2-ethylhexanoate (8% toluene solution) 87.5 g was dissolved in xylene 300 ml,
Titanium 2-ethylhexanoate (10% toluene solution) 62 was added to this so that the molar ratio was 1 with respect to cerium.
While adding 78 g of dehydrated castor oil fatty acid as a curing agent and 5 g of dimethyl silicone TSF400 (Toshiba Silicone) as a leveling agent, the mixture is heated to 60 ° C.
A uniform transparent coating liquid for cerium oxide-titanium oxide coating was obtained by mixing and stirring for a minute. 100 × 10 for this coating liquid
A soda lime glass plate having a masking film attached on one side at 0 × 4 mm was dipped and pulled up at a speed of 5 cm / min to form a coating film on one side. The coating film is 100 ° C
Dry in an electric furnace for 10 minutes, and then in an electric furnace for 7 minutes.
After calcining at 00 ° C. for 4 minutes, it was taken out and rapidly cooled with warm air to carry out a strengthening treatment to obtain a uniformly transparent cerium oxide-titanium oxide film. The evaluation results are shown in Table 1.

Comparative Example For comparison, untreated glass on which no coating was formed was also measured, and the results are shown in Table 1.

[0030]

According to the results of Table 1, the coating film of the present invention can simultaneously block ultraviolet rays and heat rays with a single film, and further has an adhesion property to a substrate such as glass and a surface abrasion resistance. It is clear that it has excellent properties, acid resistance, and alkali resistance, and that it does not cause any problems when strengthening glass, and is characterized by the fact that glass is strengthened and / or bent It is especially useful for UV and heat ray shielding glass.

Therefore, according to the present invention, firstly, there can be provided an ultraviolet / heat ray shielding glass for a vehicle, which is durable against up / down movement of a window, scratched and rubbed, that is, excellent in scratch resistance. 2) We can provide UV / heat ray shielding glass for vehicles that does not crack or peel off in the strengthening process or bending process, and 3rd, we can also provide UV / heat ray shielding glass for vehicles that allows radio waves to penetrate into the vehicle interior. With the remarkable effect that it is possible to provide a large area ultraviolet and heat ray shielding glass for vehicles.

Continuation of front page (51) Int.Cl. ⁵ Identification code Office reference number FI Technical display area E06B 5/18

Claims (5)

[Claims] 1. A composite oxide film composed of cerium oxide and titanium oxide formed on a substrate, wherein the composite oxide film contains 30 to 80% by weight of cerium oxide and has a film thickness of 800 to 2000 angstroms. An ultraviolet / heat ray shielding film having: 2. A method for forming a complex oxide film, which comprises applying a coating solution onto a surface of a substrate and then drying and curing in an oxidizing atmosphere, followed by baking, wherein the coating solution is a cerium fatty acid salt or a titanium fatty acid salt. The method for forming an ultraviolet / heat ray shielding film according to claim 1, further comprising: 3. A method for forming a complex oxide film, which comprises applying a coating solution onto a surface of a substrate, and then drying and curing the composition in an oxidizing atmosphere, wherein the coating solution contains a cerium alkoxide. The method for forming an ultraviolet / heat ray shielding film according to claim 1, which is characterized in that. 4. An ultraviolet / heat ray shielding glass obtained by forming the ultraviolet / heat ray shielding film according to claim 1 on a glass plate. 5. An ultraviolet / heat ray-shielding glass having an ultraviolet / heat ray-shielding film formed by the method according to claim 2 or 3.