JP2500117B2 - Glass with a functional coating with a protective coating - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention relates to an electromagnetic shield, heat ray reflection and low heat radiation on a glass substrate used as a window material for buildings and the like.
(Low Emission), a glass with a functional film for the purpose of anti-fogging with electricity, etc., and a glass with a functional film having a protective coating thereon.

[0002]

2. Description of the Related Art The functional film is a transparent metal film (eg, silver, copper, zinc, etc.) or a transparent metal oxide film (eg, zinc oxide, tin oxide, indium oxide-tin oxide, etc.) on a glass substrate. Or transparent metal non-oxide film (eg, silicon nitride, titanium nitride, titanium boride, silicon nitride, etc.), etc., especially those with three or more alternating layers are computers in broadcasting rooms or offices. As a window material for electromagnetic shielding in a room, general house, building, etc., or as a window material for efficiently heating by reflecting far infrared rays inside the building or in the room, as a conductive anti-fog window material in a vehicle, etc. Demand has been increasing in recent years.

Since these films are insufficient in weather resistance and scratch resistance, they are used by arranging them on the inner surface side of at least one glass such as double glazing or laminated glass (for example, JP-A-64-5099). No.). However, making the form of the above-mentioned double glazing or laminated glass requires a large number of steps, costs and the like, and the production efficiency is not good.

On the other hand, Japanese Patent Laid-Open No. 2-248344 discloses a water repellent mirror in which a reflecting metal layer and a silicone water repellent layer are laminated on a glass substrate with a transparent oxide layer interposed therebetween. The prior art is to give water repellency and antifouling property to the metal film surface of the mirror,
Unlike what is intended for the glass with a functional film of the present invention, and as shown in the specific examples, the silicone water repellent layer is formed by simply applying a solution prepared by diluting dimethylsiloxane with an n-hexane solvent. However, it is easily inferred that it is difficult to obtain a film having excellent film adhesion, weather resistance and scratch resistance with this structure.
A temperature of ℃ or higher is required, but there is a risk that the film performance will be impaired at that temperature depending on the type of functional film.

The present invention solves the above-mentioned problems and provides a functional film-coated glass which has a technically easy structure in which a film having excellent weather resistance and scratch resistance is coated and which can be produced at low cost. .

[0006]

SUMMARY OF THE INVENTION The present invention relates to a glass with a functional film, in which a glass substrate is provided with two or more layers of a transparent metal thin film and a transparent metal compound film on the outer surface of the functional film. In the film-coated glass having a protective coating formed of a coalescence, the protective coating is a coating of a transparent silicone composition containing colloidal silica, a partial condensate of an organoalkoxysilane, and an alcohol-water solvent, which is cured. Preferably, the outermost layer of the functional film is a metal oxide film, and the silicone composition is RSi.
(OR ') _{3 In the} formula, R represents a methyl group or an ethyl group, and R'represents a methyl group, an ethyl group or a propyl group, and includes a partial condensate of organotrialkoxysilane, colloidal silica and an alcohol-water solvent. , A polyvalent carboxylic acid anhydride having a cyclic structure is added.

As described above, the functional film is a transparent metal film such as silver, copper or zinc on a glass substrate, a transparent metal oxide film such as zinc oxide, tin oxide, indium oxide-tin oxide or the like, or a transparent film. Metal non-oxide film, for example, two or more layers of silicon nitride, titanium nitride, silicon carbide, etc., preferably three or more layers of alternating layers, which are known vacuum deposition method, sputtering method, chemical vapor deposition method, etc. To form a laminate. The outermost layer of the film may be a metal having excellent stability, such as aluminum, but more preferably coating of the subsequent coating composition,
A film of a metal oxide is provided which reacts with this upon curing, changes in quality, and improves adhesion.

The protective coating employs a hard coating agent which is excellent in weather resistance, scratch resistance, and adhesion to the above-mentioned metals and metal oxides, especially metal oxides. As mentioned above, colloidal silica and organoalkoxy are used. A material obtained by applying and curing a transparent silicone composition containing a partial condensate of silane and an alcohol-water solvent can be recommended. More preferably, it is preferable to employ the specific silicone hard coat composition described in Japanese Patent Application No. 61-63899 filed by the applicant. In the above-mentioned invention, a specific silicone-based hard coat composition that adheres well to resins and the like, has high hardness, and is excellent in weather resistance was proposed, but with regard to adhesion with metals and oxides thereof, especially metal oxides, Does not suggest mentioning.

In the above silicone-based hard coat composition, it is preferable to use a methyltriethoxysilane partial condensate as the organotrialkoxysilane partial condensate and a weakly basic colloidal silica aqueous solution as the colloidal silica. An anhydride of a polyvalent carboxylic acid having a cyclic structure has the advantage that the hydrolysis reaction proceeds mildly and reproducibly and the silanol partial condensation polymer produced is stabilized. Specifically, phthalic acid, trimellitic acid,
Pyromellitic acid, benzophenone tetracarboxylic acid,
Anhydrides of polybasic acids such as alicyclic tetrahydrophthalic acid, hexahydrophthalic acid, het acid, cyclopentanoic acid and tetracarboxylic acid can also be used.

The mixing reaction of the organotrialkoxysilane, the acid anhydride and the aqueous colloidal silica solution is carried out at about 30 to 50 ° C. for several tens of hours to several days until the number average molecular weight reaches about 1,000. The reaction product is isopropyl alcohol or
Add n-propyl alcohol to adjust the solvent, and further concentrate by ultrafiltration to adjust the solid concentration to about 10-40%.
The obtained liquid is excellent in storage stability, but on the contrary, it lacks fast hardening, so alkali metal salts of organic carboxylic acids, organic amine compounds, etc. as curing catalysts are added so that the pH of the liquid will be about 6 to 7. This completes the adjustment of the coating liquid. An ultraviolet absorber, a flow improver and the like can be added as appropriate.

The means for applying these silicone-based compositions is not specified, and any suitable means such as a dipping method, a casting method, a spraying method, or the like can be adopted. Usually, it is 1 μm to several tens μm, preferably 3 μm. -4 μm or 10-15 μm. The protective coating thus obtained is a functional film, that is, excellent adhesion to a metal film, particularly excellent adhesion to a metal oxide film,
Of course, it has excellent properties as a hard coat agent, that is, excellent weather resistance, scratch resistance, and the like, and has the effect of suppressing functional deterioration of the film.

The present invention can be widely applied not only to low heat radiation and electromagnetic shielding glass but also to high performance heat ray reflecting glass such as Sky Cool manufactured by Central Glass Co., Ltd.

[0013]

EXAMPLES The present invention will be described below based on examples. Example 1 70 cm × 7 ocm × 4 mm (thickness) float plate glass with zinc oxide,
Silver, zinc, zinc oxide, silver and zinc were sequentially laminated by a sputtering method, and a zinc oxide film was sputtered thereon to obtain an electromagnetic shielding film.

Separately, 0.2 part by weight of phthalic anhydride was added to 100 parts by weight of methyltriethoxysilane, and a weakly basic colloidal silica aqueous solution (manufactured by Nissan Kagaku Co., Ltd., trade name Snowtex C SiO ₂ content 20 wt%) 100 40 parts by weight
The reaction was carried out at 0 ° C for 10 days to obtain an ethanol-water mixed solution of a siloxane prepolymer. Isopropanol 140
A part by weight was added, and the solid content was concentrated to 25 wt% by ultrafiltration (molecular weight cut off: 1000). Further, 0.1 part by weight of sodium acetate as a curing catalyst was added to 100 parts by weight of the concentrated solution to prepare a silicone-based hard coat stock solution for protective coating.

The silicone hard coat stock solution was applied onto the plate glass having the electromagnetic shielding film formed thereon by a flow coating method, dried at room temperature, and then cured at 120 ° C. for 90 minutes. The film thickness of the hard coat is 10 μm.

The obtained coated glass was measured for visible light average transmittance with a photometer, and for electromagnetic shielding effect with a known KEC method. After standing for 6 months, the average visible light transmittance and the electromagnetic shielding effect were measured, and in addition, it was lightly rubbed with steel wool # 0000 to observe the scratched condition (surface hardness).
Then, perform a cross-cut peeling test with mending tape, and
The number of residual stitches per 0 squares was measured (adhesion). Initial visible light average transmittance; 68% Electromagnetic shielding effect; 100MHZ: -58dB, 500MHZ: -41dB, 1G
HZ: -31dB Visible light average transmittance after 6 months ; 67% Electromagnetic shielding effect; 100MHZ: -58dB, 500MHZ: -40dB, 1G
HZ: -30dB surface hardness; scratch-free adhesion; 100 residual stitches

Example 2 As a silicone type hard coat liquid, a hard coat agent manufactured by Toshiba Silicone Co., Ltd., which is composed of a partial condensate of organoalkoxysilane containing colloidal silica and an alcohol-water solvent, under the trade name Tosguard was prepared.

A glass with a coated film was obtained in the same manner as in Example 1 except that Tosugad manufactured by Toshiba Silicone Co., Ltd. was used instead of the silicone type hard coat of Example 1. The thickness of the toss guard is 8 μm. This was tested as in Example 1. Initial visible light average transmittance; 68% Electromagnetic shielding effect; 100MHZ: -58dB, 500MHZ: -41dB, 1G
HZ: -31dB Visible light average transmittance after 6 months ; 65% Electromagnetic shielding effect; 100MHZ: -58dB, 500MHZ: -38dB, 1G
HZ: -28 dB Surface hardness; Almost no scratches Adhesion; Residual number 98 In this example, although weather resistance durability, scratch resistance, and film adhesion were slightly inferior to those in Example 1, deterioration was generally suppressed, It can be said that the functional film is protected at a high level.

Comparative Example 1 A functional film was formed on a float glass plate in the same manner as in Example 1,
The same test as in Example 1 was carried out as it was without applying the protective coating. Initial visible light average transmittance; 69% Electromagnetic shielding effect; 100MHZ: -57dB, 500MHZ: -41dB, 1G
HZ: -31dB Visible light average transmittance after 6 months ; 41% Electromagnetic shielding effect; 100MHZ: -47dB, 500MHZ: -15dB, 1G
HZ: 0dB (Since the protective coating was omitted, surface hardness and adhesion were not measured.) In this comparative example, the visible light transmittance and the electromagnetic shielding effect suddenly declined in a short period because the protective coating was not applied. Is clear.

Comparative Example 2 A commercially available coating agent composed of an ultraviolet curable acrylic resin liquid was used as the hard coat liquid. A glass with a coating film was obtained by the same treatment as in Example 1 except that the above-mentioned hard coat liquid was used instead of the silicone type hard coat in Example 1 (however, curing was carried out by ultraviolet irradiation). The hard coat film thickness is 12 μm. This was tested as in Example 1. Initial visible light average transmittance; 67% Electromagnetic shielding effect; 100MHZ: -58dB, 500MHZ: -41dB, 1G
HZ: -31dB Visible light average transmittance after 6 months ; 65% Electromagnetic shielding effect; 100MHZ: -54dB, 500MHZ: -33dB, 1G
HZ: -20 dB Surface hardness; Clear scratches Adhesion; Residual number: 55 In this comparative example, deterioration in visible light transmittance and electromagnetic shielding effect was obvious as compared with Examples 1 and 2, and film hardness and adhesion It is clear that the sex is getting worse.

As described above, in Examples 1 and 2, it is clear that the visible light average transmittance and the electromagnetic shielding effect are suppressed from being deteriorated, and the surface hardness and the adhesiveness are excellent.

[0022]

EFFECTS OF THE INVENTION According to the present invention, by providing a protective coating, the deterioration of the functional film such as the visible light average transmittance and the electromagnetic shielding effect can be suppressed, and the protective coating is excellent in surface hardness and adhesion. Play.

Claims (3)

(57) [Claims] 1. A film-coated glass in which a protective film made of an organic polymer is applied to the outer surface of a functional film in which two or more layers of a transparent metal thin film and a transparent metal compound film are formed on a glass substrate. Is a glass with a functional film coated with a transparent silicone composition containing colloidal silica, a partial condensate of organoalkoxysilane, and an alcohol-water solvent, and cured. 2. The glass with a functional film provided with the protective coating according to claim 1, wherein the outermost layer of the functional film is a metal oxide film. 3. A silicone composition is RSi (OR ') _{3 wherein} R is
Represents a methyl group or an ethyl group, R'represents a methyl group, an ethyl group or a propyl group, and is a partial condensate of organotrialkoxysilane, colloidal silica, and an alcohol-water-based solvent. The functional film-attached glass provided with the protective coating according to claim 1 or 2, wherein an anhydride of a carboxylic acid is added.