JPH10152349A - Colored glass absorbing ultraviolet light - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a ultraviolet absorbing colored glass plate improved in weather resistance in a state enlarged in a long wavelength ultraviolet light- absorbing force by coating the surface of a transparent glass substrate with a silicon primer coating solution containing a fluorescent brightening agent, a ultraviolet light absorbent and a metal chelate compound and subsequently curing the coated solution to form a ultraviolet absorbing colored film. SOLUTION: The fluorescent brightening agent absorb light in a ultraviolet light region, generates fluorescent light in a visible light region, can be dissolved in a silicon primer coating solution, is thermally not denaturated on the thermal curing of a coating film, is good in thermal stability, and has absorbing wavelengths at a place (400nm) near to the boundary between the ultraviolet light region and the visible light region. The coexisting ultraviolet absorbent includes a benzophenone ultraviolet absorbent and a benzotriazole ultraviolet adsorbent. The metal chelate compound is preferably a transtion metal chelate also useful for quenching the fluorescent brightening agent, and the stable chelate compound of Ni, Fe or Mn in the fourth period. The ligand of the chelate compound is preferably acetyl acetone, cyclohexyl butyrate, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a glass having a colored coating film excellent in ultraviolet absorption, and a film formed by laminating this film with a protective coating film having excellent durability such as abrasion resistance and chemical resistance. It relates to an ultraviolet absorbing colored glass having excellent properties.

[0002] The present invention relates to a UV-absorbing filter member having a design property, which is useful as a window material for various windows, for example, a building, a house, a vehicle such as an automobile, a ship, an aircraft, or various display devices. Provide colored glass.

[0003]

2. Description of the Related Art Conventionally, as a treatment method for imparting ultraviolet absorption to a glass substrate or the like, for example, a soda lime silica glass in which a metal oxide such as iron oxide, cerium oxide or titanium oxide is dissolved and added ( For example, JP-A-4-224133
JP-A-6-321577) or a glass substrate on which a film of zinc oxide, titanium oxide, silicon nitride, or the like is formed by a vapor-phase film forming method such as a CVD method or a sputtering method (for example, JP-A-5-321577). -152213, Japanese Patent Publication No. 4-44721),
Alternatively, a film formed of titanium oxide, cerium oxide, zinc oxide, or the like by liquid phase film formation such as a sol-gel method (for example,
JP-A-4-97103, JP-A-5-345638) or a film formed by dispersing ultrafine particles such as titanium oxide, cerium oxide and zinc oxide in a resin matrix by liquid phase film forming such as sol-gel method ( For example, there are JP-A-2-265976 and JP-A-5-222338.

[0004] Since all of these use an inorganic ultraviolet absorber, they have insufficient long-wavelength ultraviolet (UVA) absorption power, and can be used for bulk glass and vapor-phase film-formed products in a wide variety of small-lot production. There is a weak point that it is difficult to perform interference coloring, and in a vapor-phase film-formed product and a liquid-phase film-formed product, it is necessary to strictly control interference coloring caused by a difference in refractive index and film thickness. Further, it is difficult to form a film directly on a bent plate by a method requiring high-temperature baking such as a sol-gel method. In addition, when zinc oxide is used, it is weak in moisture resistance and chemical resistance, so that protection measures are required.

On the other hand, a film formed by dissolving an organic ultraviolet absorbent in a resin matrix is disclosed in, for example, the above-mentioned Japanese Patent Application Laid-Open No. 2-265976, which has a long wavelength ultraviolet absorbing power. Because of its heat resistance, it can inevitably be cured at low temperatures, so it is easy to handle bent plates and reinforced plates, and it is easy to cope with high-mix low-volume production. Absent.

[0006] As described above, it is not suitable for small-quantity multi-product production, and has insufficient long-wavelength ultraviolet ray absorbing power, or has concerns about chemical resistance, moisture resistance, scratch resistance, durability or weather resistance. Improve the inferior or conventional technology,
By combining an organic UV absorber and a fluorescent whitening agent, the applicant has obtained glass that has improved long-wavelength UV absorptivity and improved durability or weather resistance by using a silicone resin. Application has already been filed (for example,
145837, Japanese Patent Application No. 6-318625).

[0007]

Recently, with increased long-wavelength ultraviolet absorption, it is durable even in harsher environments that require superior weather resistance in harsh environments. It is desired to provide an inexpensive, simple, and efficient UV-absorbing colored glass that can be used sufficiently and that can be produced in small quantities and in various types.

[0008]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above-mentioned problems, and has been made in combination with a metal chelate compound while maintaining a longer-wavelength ultraviolet ray absorbing power in a more improved state. In this case, a useful ultraviolet absorbing colored glass capable of improving weather resistance more effectively with a trace amount of the metal chelate compound, although accompanied by pale coloring, is provided at low cost, simply and efficiently.

That is, according to the present invention, an optical brightener, an ultraviolet absorber and a metal cleaner are provided on the surface of a transparent glass substrate.
A silicone-based primer coating solution obtained by dissolving and adding a silicon compound, and applying heat to cure an ultraviolet-absorbing colored film, and further applying a silicone-based hard coating solution on the ultraviolet-absorbing colored film to form a coating. An ultraviolet-absorbing colored glass, wherein the protective film is laminated and formed, and the above-mentioned ultraviolet-absorbing colored glass, wherein the silicone-based primer is an organopolysiloxane-based solution, Further, the above-mentioned ultraviolet absorbing colored glass, wherein the metal chelate compound is at least one kind of transition metal chelate compound, and the silicone-based hard coating solution comprises an organopolysiloxane-based solution. An object of the present invention is to provide the ultraviolet absorbing colored glass described above, which is a solution mainly used.

[0010]

Here, as described above, the fluorescent whitening agent absorbs in the ultraviolet region, emits fluorescence in the visible region, and can be dissolved and added to a silicone-based primer coating solution, Any material may be used as long as it does not undergo thermal denaturation at the time of heat curing of the coating film. In addition, it has appropriate heat resistance, and has an absorption wavelength at the boundary between the ultraviolet and visible regions (around 400 nm). For example, Uvitex-OB ( 2,5 bis (5'-tert-butylbenzoxazolyl) thiophene manufactured by Ciba Geigy, or EB-501 (manufactured by Mitsui Toatsu Dyestuffs), and Nikkafluor SB, KB, EFS, OB (Nippon Chemical Industry Co., Ltd.) Manufactured).

Examples of the ultraviolet absorber to be coexistent include benzophenone type, benzotriazole type, cyanoacrylate type, salicylate type and indole type.

The metal chelate compound is not particularly limited as long as it can be dissolved and added to a silicone-based primer coating solution, but it is a transition metal chelate which is also useful for quenching the fluorescent brightener. Is preferred. The stability of the liquid is also good, and particularly preferable are Ni, Fe,
Chelate compounds such as Mn, Co, and Cr are exemplified.

Examples of the chelate ligand include β-diketones such as acetylacetone and thenoyltrifluoroacetone, aliphatic carboxylic acids such as cyclohexylbutyric acid, oxines, dithizones, cuperones, and α-dioximes. Most preferred are acetylacetone, cyclohexylbutyric acid and the like, which are easily available and have good solubility in silicone-based primer coating solutions.

Although the action of the metal chelate is not clear, it is speculated that a more stable chelate may be formed with the ultraviolet absorber to prevent its deterioration as a new ultraviolet absorber.

The weight ratio of the fluorescent whitening agent to the ultraviolet absorber is about 1: 0.5 to 1:10, and a preferable range for ensuring more stable is 1: 3 to 1: 1. The ratio is about 1: 6, and when the amount of the fluorescent whitening agent is increased, the transparency deteriorates due to the fluorescence. When the amount is too small, the desired UVA absorbing power cannot be obtained. These are preferably used in a total amount of 0.1 to 10% by weight of the primer coating solution, and it is uneconomical to add more than necessary even if there is a margin in solubility.

Next, considering the limits of solubility and coloring tolerance of the metal chelate, 0.1 to 5 parts by weight per 100 parts by weight of the primer coating solution to which the fluorescent brightener and the ultraviolet absorber are added. Parts by weight, preferably 0.5 to 3 parts by weight.
It is about part by weight and improves weather resistance and coloring is also yellowish, greenish, brownish pale tone, if too small, there is no effect on weatherability improvement, and if it is too large, coloring becomes severe,
The stability of the liquid also deteriorates.

Further, as for the silicone primer, since it is necessary to sufficiently dissolve the above-mentioned fluorescent whitening agent, ultraviolet absorber and metal chelate, a ketone-based solvent such as cyclohexanone or xylene, which has solubility, is used. It is preferable to use a solvent in which an aromatic solvent such as the above is mixed with an ether alcohol-based solvent such as cellosolve or an alcohol-based solvent such as butanol.

Further, the silicone-based primer
Examples of the resin component include those composed of only an organosiloxane polymer and copolymers with an acrylic resin, a urethane resin, a fluorine resin, a polyester resin, and the like. In order to improve the properties, adhesion and transparency, for example, commercially available silicone varnishes for coatings or silicone-modified varnishes (eg, manufactured by Toshiba Silicone Co., Ltd. or Shin-Etsu Chemical Co., Ltd.) or Bellclean [manufactured by NOF CORPORATION] ] And OS-800 [Daichi Chemical Co., Ltd.]
And the thickness, viscosity or thickness of the film may be adjusted, and ultrafine oxide particles such as silica and alumina may be added. 5 as solids concentration
About 50 wt%, viscosity about 2-100 cP, thickness of UV-absorbing colored film with primer of 0.5-10 μm
The thickness is preferably about 1 to 5 μm, and the total thickness is preferably about 1.5 to 15 μm.

Particularly, for example, a preferable concentration (for a silicone-based primer solution) of Bellclean (silicone-modified acrylic polymer) is about 10 to 30% by weight,
If it is less than about 10% by weight, the coating film tends to be whitened, and if it is more than about 30% by weight, the adhesion is deteriorated and cracks appear. For example, the preferable concentration of OS800 (silicone-based polymer) is about 5 to 30% by weight, and when the concentration is gradually reduced to less than about 5% by weight, it affects the hot water resistance and the adhesion to the silicone-based hard coat film mainly coated. If too little, the effect of adhesion will be lost and 30
If the amount exceeds about wt%, whitening is apt to occur.

Further, for example, the preferred concentration of colloidal silica XBA (xylene, n-butanol-dispersed silica ultrafine particle organosol) is about 20 to 50 wt%, and when the concentration is gradually reduced to less than about 20 wt%, generation of cracks may be observed. If the content exceeds about 50% by weight, whitening tends to occur. Furthermore, for example, it is a silane coupling agent for further improving adhesion.
The addition amount of S510 (epoxysilane) is about 0.
It is preferable to add about 5 to 20 wt%, and 0.5 wt%
When the amount is less than the degree, the adhesiveness to glass is mainly affected. When the amount is too small, the adhesion effect is lost. When the amount exceeds about 20% by weight, the amount is uneconomical.

Further, the above-mentioned ultraviolet-absorbing silicone primer prepared as described above may have a uniform film thickness, for example, by dipping, spraying, flow coating, spin coating, roll coating, or screen coating. It is applied by a printing method such as printing, flexo, gravure, offset, etc. to form a film. For example, it is heated and dried at about 80 ° C. or more for about 1 hour. The primer component is eluted to easily develop, for example, cloudiness or cracks, and the hot water resistance deteriorates. Excessive heating leads to coloring due to burning and a decrease in ultraviolet absorption performance.

Further, as an application environment, for example, a temperature of about
A temperature of about 15 to 25 ° C., a humidity of about 40 to 50 RH%, and a cleanness of about 10,000 or less are preferred from the viewpoint of preventing coating film defects. It goes without saying that a flow improver or a rheology control agent may be appropriately added in order to improve the coating performance.

Further, the silicone-based primer
The silicone-based hard coating solution that is most suitable as a protective film for a colored film formed by a coloring solution is an organopolysiloxane-based material that can be expected to have a high crosslink density siloxane bond such as tetraethoxysilane hydrolyzate or colloidal silica. Is preferably based on an alcohol solution of a siloxane prepolymer obtained by hydrolyzing a trifunctional organoalkoxysilane such as methyltriethoxysilane. For example, Japanese Patent Application Laid-Open No. 622-220531 has already been filed by the present applicant. The one containing colloidal silica as a coating composition described in the gazette is preferable, and further containing a large amount of an epoxysilane component is useful for improving adhesiveness and crack resistance. Commercially available products include, for example, Tosgard 510 (manufactured by Toshiba Silicone Co., Ltd.) and Si Coat 2 (manufactured by Daihachi Chemical Co., Ltd.).

The silicone hard coating solution may be formed into a film having a uniform thickness by, for example, dipping, spraying, flow coating, spin coating, roll coating, screen or flexo. Printing method such as gravure or offset can be used, and the film thickness is preferably about 1.0 to 5.0 μm.The thinner film reduces the effect of strengthening the surface protection, and the thicker film is more likely to develop cracks during heat drying and curing. It is not economic. Further, for heat drying and curing, the first layer contains an organic UV absorber, a fluorescent whitening agent and a resin, so that the temperature is about 100 ° C.
It is necessary to process at a temperature of about 250 ° C. or less, preferably about 13 ° C. when the transparent substrate is a glass plate or the like.
The treatment is performed at about 0 to 230 ° C. for about 10 to 60 minutes, preferably about 30 minutes, in order to increase the surface hardness.

The environment for the application is the same as that of the silicone primer, for example, at a normal temperature of about 25 ° C. and a relative humidity of about 20 to 50% RH, preferably about 40% RH.
It is preferable to carry out in an air-conditioned environment of about front and rear. Needless to say, a flow improver or a rheology control agent may be appropriately added to improve the coating function.

Further, the transparent glass substrate is preferably an inorganic glass such as a float glass, and is not particularly limited to a shape or the like, but may be formed into various shapes or having a size or configuration such as a bent glass. It goes without saying that it can be used not only as a sheet glass, but also as various strengthened glass, strengthened glass, a flat plate or a single plate, and also as a double-layer glass or a laminated glass.

As described above, according to the present invention, a light-colored coating film excellent in ultraviolet-ray shielding properties and having a unique constitution is a silicone primer solution in which a fluorescent whitening agent, an ultraviolet absorber, and a metal chelate compound coexist. This is a laminated film in which a silicone hard coat film with excellent surface hardness is formed as a protective film on the surface of the film, so it can be formed at a relatively low temperature as a film in which the fluorescence of the fluorescent whitening agent is also inconspicuous, and has excellent UV absorption , Although the effect of absorption slightly extends to the visible region, it can significantly block ultraviolet rays including UVA,
Moreover, the pencil hardness becomes 9H or more without occurrence of defects such as cracks, excellent in adhesion, chemical resistance, scratch resistance or durability, film strength and smoothness are improved, and long-term weather resistance is improved. It is also significantly improved, and it is possible to sufficiently secure the field of view even though it is accompanied by pale coloration, dramatically enhance the livability, and it is of course possible to use it for buildings, houses, vehicles or various window materials such as veneers and exteriors, In particular, long-term use is possible under harsher operating conditions and environments such as windshields for automobiles, rear glass and side door glass that goes up and down, sunroof glass, window materials for ships and aircraft, and more. Is a transparent coat of transparent UV-absorbing colored glass that can be used as a useful UV-shielding window without glare due to visible light reflection or radio wave shielding due to radio wave reflection. Easily can be obtained efficiently and inexpensively by grayed process, there is provided.

[0028]

The present invention will be described below in detail with reference to examples. However, the present invention is not limited to such an embodiment.

(Preparation of UV-absorbing silicone primer) 10.0 g of S510 (manufactured by Chisso) was added as a silane coupling agent to 10.1 g of hexanone while stirring at room temperature, and then organocolloidal silica XBA (manufactured by Nissan Chemical) was added. 37.3 g, 0.7 g of UVITEX-OB (manufactured by Ciba Geigy) as a fluorescent whitening agent, and TINUVIN90 as an ultraviolet absorber
2.8 g of 0 (made by Ciba-Geigy), plus Bellclean No1
15.8g of 000 (manufactured by NOF CORPORATION) and OS-800
By adding 23.3 g of [Daihachi Chemical Co., Ltd.], an ultraviolet absorbing silicone primer was obtained. Further, a colored ultraviolet absorbing silicone primer was obtained by adding various chelate in the ratio shown in Table 1 to 100 parts by weight of the ultraviolet absorbing silicone primer.

(Preparation of Silicone Hard Coating Solution) A 500 ml round bottom flask equipped with a stirrer was charged with 100 g of methyltriethoxysilane, 43 g of tetraethoxysilane, and 18 g of 3-glycidoxypropyltrimethoxysilane, and 0.45 g of phthalic anhydride. After addition, the mixture was heated to about 40 ° C. in a hot water bath and dissolved, and then an organocolloidal silica solution IPA-ST [manufactured by Nissan Chemical Co., Ltd., average particle size of about 15 μm, S
iO ₂ content about 20%] 143 g, water 98 g is added little by little, and the reaction is carried out at about 40 ° C for about 2 days.
[Number average molecular weight by Tosoh Corporation, ULC802A)
A composition having about 1000 and a solid content of about 28 wt% was obtained.

To this, 163 g of isopropyl alcohol was added to obtain a composition having a solid content of about 20% by weight. About 0.1 part of dicyandiamide was added as a curing catalyst to the composition to obtain a silicone-based hard coating solution.

(Performance Evaluation Method) Ultraviolet Absorption: Absorption spectrum pattern is measured with a spectrophotometer. (Eg Hitachi-U4000) Fluorescence: Visual observation under natural sunlight outdoors. (No worrisome light emission and no cloudiness.) Abrasion resistance: Conforms to JIS R 3221, wear wheel CS-10F, load 500 g, ΔH (haze) value after 1000 rotations (%).

Surface hardness: Pencil hardness. Adhesion: Based on JIS K5400, the number of tape peeling (1 mm square) tape peeling remaining is indicated by / 100.

Hot water resistance: Appearance and adhesion after boiling water (100 ° C.) for about 2 hours. Chemical resistance: Acid resistance -------- 24 hours in -1N HCl immersion test. Alkali resistance --- 4 hours in 1N NaOH immersion test.

Solvent resistance ----- 100% ethanol 24 hours in immersion test. Weather resistance: Based on JIS D0205, time until visual abnormalities (film cracks, peeling, noticeable yellowing) are observed with a sunshine carbon weather meter. (However, irradiation on the glass surface) Ultraviolet absorption performance (based on ISO9050) Investigation was also made on changes in Tuv (%), visible light transmittance Tv (%), and solar transmittance Ts (%).

Example 1 A clear float glass substrate having a size of about 300 mm × 300 mm and a thickness of about 3.5 mm was washed sequentially with a neutral detergent, water rinse, and alcohol, dried, and then wiped with acetone to form a glass substrate for coating. did.

In a clean room air-conditioned at about 25 ° C. and about 40% RH, one surface of the coating glass substrate was subjected to film masking, and as shown in Table 1, Ni-acetylacetonate was used as a metal chelate. Immersed in the above-prepared colored ultraviolet-absorbing silicone-based primer solution to which 1 part by weight was added, and pulled up at a speed of about 1 cm / sec.
After drying and curing for about 1 hour, an ultraviolet absorbing colored film having a thickness of about 6 μm was formed.

Next, the glass surface of the glass substrate with the ultraviolet absorbing colored film is film-masked, immersed in the prepared silicone hard coat solution described above, applied only to the film surface, and air-dried for about 10 minutes. Subsequently, the mixture was placed in a hot air circulating drier at about 175 ° C. for about 1 hour and cured to obtain a silica-based protective film of about 3 μm. The film was colored and transparent and had no cracks. In the case of drying treatment in a far-infrared furnace, curing was possible at about 200 ° C. for about 15 minutes.

The obtained ultraviolet absorbing colored glass was evaluated according to the performance evaluation method described above. As a result, as shown in FIG. 1 showing the transmittance (%) in the spectrophotometric curve and the appearance and the optical characteristics in Table 1, the visible light transmittance was 85.8%, which was slightly colored with a transparent pale yellow color tone. However, it shields almost 100% of UVA, has an ultraviolet transmittance Tuv of 0.8% or less at 1% or less, has a pencil hardness of 9H or more and is hard, and has a haze value (△ H) of 4.2 after Taber test. As shown in Table 2, the weather resistance (SWM: 1000Hr) was sufficiently excellent, and the weather resistance was 1000 hours or more, there was no visual abnormality, and the decrease in ultraviolet absorption performance was only 0.8% to 1.3%. Thus, an ultraviolet-absorbing colored glass having sufficient long-term weather resistance in a harsh environment, excellent adhesion, hot water resistance and chemical resistance, and excellent durability for outdoor use was obtained.

Examples 2 to 5 On the same glass substrate as in Example 1, the prepared colored ultraviolet-absorbing silicone-based primer solution containing various metal chelates and the added amounts shown in Table 1 was used, and By the same film formation as in Example 1, an ultraviolet absorbing colored film having a thickness of about 6 to 7 μm was formed.

Next, the glass surface of the glass substrate with the ultraviolet absorbing colored film is film-masked, immersed in the prepared silicone hard coat solution described above, applied only to the film surface, and air-dried for about 10 minutes. It was placed in a hot air circulating drier at about 175 ° C. for about 1 hour to cure, and a silica-based protective film of about 3 μm was obtained.

The obtained ultraviolet absorbing colored glass was used in Example 1.
Was evaluated in the same way as As a result, Tables 1 and 2 (Example 2)
As shown in FIG. 1), the hue value (ΔH) after Taber test is 4.6 in Example 2, 4.5 in Example 3, 4.5 in Example 4, 4.3, and Example 5 after the Taber test. Is 4.2 and the abrasion resistance is sufficiently excellent, and the weather resistance test (SWM: 10
00Hr), as shown in Table 2, the weather resistance was 1000 hours or more, there was no visual abnormality, and the ultraviolet absorption performance was reduced by 0.7 in Example 2.
% To 3.2%, Example 3 is 1.1% to 3.6%, Example 4
Was 2.0% to 8.5%, and Example 5 was 1.4% to 8.9%.
% Or less, and there was long-term weather resistance in a harsh environment, and other evaluations resulted in the same results as in Example 1. As in Example 1, the expected ultraviolet absorbing colored glass was excellent. .

Comparative Example 1 As shown in Table 1, an ultraviolet absorbing glass substrate was obtained in the same manner as in Example 1 except that an ultraviolet absorbing silicone primer prepared without adding a metal chelate was used.

The obtained ultraviolet-absorbing glass substrate was transparent in appearance as shown in FIG. 1 and Table 1, but blocked the visible region near ultraviolet, but as shown in Table 2, Tuv is about 13% in about 1000 hours in sex test
The degree of change also increased, and it was not suitable for long-term outdoor use, and it was hard to say that it was the expected ultraviolet absorbing colored glass.

[0045]

[Table 1]

[0046]

[Table 2]

[0047]

As described above, according to the present invention,
Without impairing the optical properties, it is transparent and shields ultraviolet rays, especially UVA can be almost completely shielded, drastically improves weather resistance, dramatically improves the habitability of lightly colored items, and improves adhesion In addition, it can be used as a single panel or exterior for window materials of buildings, houses, vehicles, etc., as well as those with excellent chemical resistance, scratch resistance or durability. It is possible to easily and inexpensively provide useful ultraviolet-absorbing colored glass that can be widely used in various fields, such as being able to be used for a long period of time under use conditions and environments.

[Brief description of the drawings]

FIG. 1 shows UV-absorbing colored glasses of Examples 1 and 2 of the present invention (curves 1 and 2), UV-absorbing glass of Comparative Example 1 (curve 3) and a conventional glass substrate (float glass 3 mm).
Thickness, curve 4) shows transmittance (%).

────────────────────────────────────────────────── ─── Continued on the front page (51) Int.Cl. ⁶ Identification code FI E06B 9/24 E06B 9/24 Z (72) Inventor Toshikazu Nagashima 1510 Oguchicho, Matsusaka-shi, Mie Central Glass Inside Glass Research Laboratory Co., Ltd.

Claims (5)

[Claims] An ultraviolet ray cured by applying a silicone-based primer coating solution obtained by dissolving and adding a fluorescent whitening agent, an ultraviolet absorber and a metal chelate compound onto the surface of a transparent glass substrate. An ultraviolet absorbing colored glass having an absorbing colored film. 2. An ultraviolet ray cured by heating by applying a silicone-based primer coating solution obtained by dissolving and adding a fluorescent whitening agent, an ultraviolet absorber and a metal chelate compound onto the surface of a transparent glass substrate. 2. The ultraviolet absorbing colored glass according to claim 1, wherein an absorbing colored film and a protective film formed by applying a silicone hard coating solution on the ultraviolet absorbing colored film to form a coating are laminated. 3. The ultraviolet absorbing colored glass according to claim 1, wherein the silicone-based primer is an organopolysiloxane-based solution. 4. The ultraviolet absorbing colored glass according to claim 1, wherein said metal chelate compound is at least one kind of transition metal chelate compound. 5. The ultraviolet absorbing colored glass according to claim 1, wherein the silicone-based hard coating solution is a solution mainly composed of an organopolysiloxane.