WO2007081025A1

WO2007081025A1 - Glass plate with film for vehicle and process for producing the same

Info

Publication number: WO2007081025A1
Application number: PCT/JP2007/050515
Authority: WO
Inventors: Takashi Muromachi; Hisashi Ogawa; Mamoru Yoshida; Nobuki Iwai
Original assignee: Nippon Sheet Glass Co., Ltd.
Priority date: 2006-01-16
Filing date: 2007-01-16
Publication date: 2007-07-19
Also published as: JP5156393B2; JPWO2007081025A1

Abstract

This invention provides a glass plate with a film for a vehicle, comprising a glass substrate and a water-repellent film and an infrared-cut film provided on a main surface of the glass substrate. For example, a water-repellent film is provided on a glass substrate on its main surface which, when the film is mounted on a vehicle, is on the vehicle exterior side, and an infrared-cut film is provided on the glass substrate on its main surface which, when the film is mounted on a vehicle, is on the vehicle interior side. In recent years, an automobile glass having a plurality of functions has become demanded for meeting the requirement that persons, who ride in the automobile, enjoy better comfort within the automobile. The glass plate for a vehicle according to the present invention has water-repellent properties and infrared-cut properties as the plurality of functions and is suitable for an window glass for a vehicle.

Description

Specification

VEHICLE GLASS PLATE HAVING COATING AND METHOD FOR MANUFACTURING SAME

Technical field

[0001] The present invention relates to a glass plate for vehicles provided with a water-repellent coating and an infrared cut coating, and a method for producing the same.

Background art

[0002] Conventionally, an automotive glass plate is known in which a water-repellent coating containing silica as a main component and containing fluorine is formed on the surface of an automotive glass. (For example, refer to Patent Document 1).

There is also an automotive glass plate in which an infrared cut film containing silica as a main component and containing infrared cut fine particles such as ITO (indium-doped tin oxide) and ATO (antimony tin oxide) is formed on the surface of an automotive glass. Known. (For example, see Patent Documents 2 and 3)

[0003] Patent Document 1: Japanese Patent Application Laid-Open No. 2001-010337

Patent Document 2: Pamphlet of International Publication No. 2004Z011381

Patent Document 3: International Publication No. 2005Z095298 Pamphlet

Disclosure of the invention

[0004] In recent years, there has been a demand for glass for automobiles having a plurality of functions so that passengers who ride in automobiles can board more comfortably.

It is an object of the present invention to provide a vehicle glass plate that is optimal for a vehicle window glass having water repellency and infrared cutting properties as a plurality of functions, and a method for manufacturing the same.

In order to solve the above-described problems, the present invention

(1) A vehicle glass plate comprising a coating having a water repellent coating and an infrared cut coating formed on the main surface of the glass substrate,

(2) The water-repellent coating is formed on the main surface of the glass substrate that becomes the outside of the vehicle when attached to a vehicle, and the infrared cut coating is formed on the main surface of the glass substrate that becomes the inside of the vehicle when attached to the vehicle. A glass plate for vehicles provided with the coating according to (1) above, characterized in that it is formed, (3) The infrared cut film is formed on a main surface of a glass substrate which is an outside of the vehicle when attached to a vehicle, and the water repellent film is formed on the infrared cut film. A glass plate for a vehicle comprising the coating film according to (1),

(4) The water-repellent film is a film containing a fluoroalkyl group and Z or an alkyl group, and the infrared cut film is a film containing silica as a main component and containing infrared cut fine particles. (1) to (3) a glass plate for a vehicle comprising the coating according to any one of the above,

(5) The vehicle glass provided with the coating according to (4), wherein the infrared cut fine particles are at least one of indium-doped tin oxide (ITO) fine particles and antimony-doped tin oxide (ATO) fine particles. Board,

(6) The film thickness of the water-repellent film is 0.1 to 300 nm, and the film thickness of the infrared cut film is 300 to 3000 nm. A glass plate for a vehicle comprising the film described above,

(7) The glass substrate is a soda lime silica glass plate containing tin on one surface and substantially free of tin on the other surface, and the infrared cut film substantially contains tin. The glass plate for vehicles provided with the coating according to any one of the above (1) to (6), characterized in that it is formed on the surface,

(8) An automotive vehicle comprising the coating according to (7) above, wherein the glass substrate substantially does not contain tin, and the refractive index difference at a wavelength of 550 nm between the surface and the infrared cut coating is less than 0.04. Glass plate,

(9) A first cleaning step for cleaning the main surface of the glass substrate that is the inside of the vehicle when it is attached to the vehicle, and a coating solution for forming an infrared cut film is applied to the main surface cleaned in the first cleaning step. A step of forming an infrared cut film, a step of heating the glass substrate and firing the infrared cut film, and a second cleaning step of cleaning the main surface of the glass substrate that is the outside of the vehicle when attached to the vehicle. A method for producing a glass plate for a vehicle, comprising: a step of applying a water-repellent coating-forming coating solution to the main surface cleaned in the second cleaning step, and forming a water-repellent coating

(10) a cleaning process for cleaning the main surface of the glass substrate that is outside the vehicle when attached to the vehicle; Applying a coating solution for forming an infrared cut film on the main surface washed in the washing step to form an infrared ray cut film; heating the glass substrate; and firing the infrared cut film; A method for producing a glass plate for a vehicle, comprising: a step of applying a water-repellent coating-forming coating solution on the infrared cut coating-forming surface and forming the water-repellent coating on the infrared cut coating-forming surface;

Is to provide.

[0006] According to the present invention, it is possible to obtain an automotive glass plate provided with a coating film having both functions of water repellency and infrared ray cutting.

Brief Description of Drawings

[0007] FIG. 1 is a cross-sectional view of a glass plate for vehicles provided with a coating film of the present invention.

FIG. 2 is a cross-sectional view of a vehicle glass plate provided with the coating film of the present invention, showing an example in which a base film is formed between the water-repellent coating film and the vehicle glass plate.

FIG. 3 is a cross-sectional view of another embodiment of a vehicle glass plate provided with the coating of the present invention.

FIG. 4 is a diagram showing the results of measuring the light transmittance at wavelengths of 300 to 2500 nm in Examples 1 and 2.

FIG. 5 is a diagram showing the results of measuring the reflectance of light having a wavelength of 370 to 780 nm.

FIG. 6 shows the atomic concentrations of indium (In), tin (Sn), and silicon (Si) in Example 1.

Explanation of symbols

[0008] 1 Glass plate for vehicles provided with coating

2 Glass substrate

2a Main surface of the glass substrate on the outside of the vehicle when attached to the vehicle

2b Main surface of the glass substrate that is the inside of the vehicle when it is mounted on the vehicle

3 Water repellent coating

4 Infrared cut film

5 Underlayer

11 Vehicle glass plate with coating

13 Water repellent coating 14 Infrared cut film

BEST MODE FOR CARRYING OUT THE INVENTION

[0009] A glass plate for vehicles provided with the coating of the present invention is characterized in that a water-repellent coating and an infrared cut coating are formed on the main surface of a glass substrate.

The present invention will be described below with reference to the drawings.

(First form)

FIG. 1 is a cross-sectional view showing one embodiment of a glass plate for vehicles provided with the coating of the present invention. The vehicle glass plate 1 having the coating shown in FIG. 1 includes a water-repellent coating 3 formed on the main surface 2a of the glass substrate 2 that becomes the outside of the vehicle when attached to the vehicle, and the inside of the vehicle when attached to the vehicle. An infrared cut film 4 formed on the main surface 2b of the glass substrate 2 is provided. In this first embodiment, the infrared cut film is formed on the main surface of the glass substrate that is the inside of the vehicle when attached to the vehicle. Therefore, the infrared cut film can be prevented from being deteriorated.

[0010] The glass substrate 2 constituting the present invention is not particularly limited as long as it is a glass plate used for vehicles, but soda lime silica glass generally used for vehicles is preferred. Soda lime silica glass includes colorless glass, colored glass such as green, gray, and bunole, and Sarasako is a glass that has the function of cutting ultraviolet rays, and visible light transmittance to maintain privacy. And the like, and these are suitable as the glass substrate of the vehicle glass plate of the present invention.

[0011] Further, as the glass substrate 2, a glass plate manufactured by a float process can be used. The glass plate produced by the float process has a glass plate surface (bottom surface) containing tin and a glass plate surface (top surface) substantially free of tin. In the present invention, it is preferable to provide an infrared cut film on the glass plate surface (top surface) substantially free of soot.

When the infrared cut film is provided on the surface of the glass plate, since the infrared cut film is relatively thick, the reflection color of the glass plate surface on which the film is formed due to the difference in refractive index between the infrared cut film and the glass plate surface. Varies depending on the angle with respect to the glass plate, or the glass plate Even if the angle with respect to is the same, if the infrared cut film formed on the surface of the glass plate has a difference in film thickness, there may be a problem that the reflected color changes. On the other hand, these problems can be reduced by providing the infrared cut film on the glass plate surface (top surface) substantially free of tin.

[0012] Generally, since the bottom surface contains tin, the refractive index is higher than that of the top surface that does not substantially contain tin. In the case of glass lime glass, specifically, the refractive index at the top surface wavelength of 550 nm is 1.50 to L 52, whereas the refractive index at the bottom surface wavelength of 550 nm is 1 53 ~: L 55. The smaller the difference in refractive index between the infrared cut film and the glass plate surface, the more the above problems can be reduced. More specifically, when the infrared cut film of the present invention (refractive index: 1.48 to: L 52) is formed on the glass plate surface, the refractive index is higher when formed on the top surface than when formed on the bottom surface. The difference can be reduced, and the above-described problems can be reduced.

Hereinafter, based on FIG. 5, the relationship between the refractive index difference between the infrared cut coating and the glass plate surface and the change in the reflected color due to the angle to the glass plate and the film thickness difference of the infrared cut coating will be described. .

Fig. 5 (A) to Fig. 5 (D) show the surface of the glass plate on which the coating was formed when different coatings with different refractive indices between the infrared cut coating and the glass plate were formed on the surface of the glass plate. The reflectance was measured in the wavelength range of 370 m to 780 nm. Fig. 5 (A) shows the case where the thickness of the infrared cut film is about 500 nm, and Fig. 5 (B) shows the film thickness of the infrared cut film. Fig. 5 (C) shows the case where the film thickness of the infrared cut film is about lOOOnm, and Fig. 5 (D) shows the case where the film thickness of the infrared cut film is about 2000 nm. Show. The thick solid line shows the case where the refractive index difference is about 0.01 at a wavelength of 550 nm, the thin solid line shows the case where the refractive index difference is about 0.03, and the broken line shows the case where the refractive index difference is about 0.10. Indicates. The reflectivity of incident light with an incident angle of 12 ° was measured.

[0014] In FIGS. 5A to 5D, in the infrared cut film having any film thickness and refractive index difference, the reflectance of light repeatedly increases and decreases according to the variation of the wavelength of light. The increase / decrease behavior is shown. However, an infrared cut film with a refractive index difference of about 0.10 at a wavelength of 550 nm on the glass plate surface has a refractive index at a wavelength of 550 nm with respect to the glass plate surface. Compared with an infrared cut film having a difference of about 0.01, the fluctuation period of the light reflectance is short, and the difference between the maximum value of the refractive index and the minimum value adjacent to the maximum value is large. In addition, the infrared cut coating with a large refractive index difference of about 0.10 at a wavelength of 550 nm with respect to the glass plate surface also greatly changes the reflectance increase / decrease behavior with respect to the change in film thickness. This means that the reflected color of an infrared cut film having a large refractive index difference of about 0.10 at a wavelength of 550 nm with respect to the glass plate surface is likely to change due to a change in the film thickness of the infrared cut film.

Here, as the angle of incident light (incident angle) with respect to the normal of the glass plate increases, the path of light passing through the infrared cut film becomes longer. Therefore, when the incident angle is large, the optical characteristics are the same as when the infrared cut film is thick.

As the refractive index difference between the infrared cut coating and the glass plate at a wavelength of 550 nm increases to about 0.03 and about 0.10, the reflected color tends to change due to the change in film thickness. Makes it easy to change the reflected color.

Next, the maximum value, minimum value, and difference between the maximum value and the minimum value of the reflectance of light having a wavelength of 400 to 600 nm in each film thickness obtained by FIGS. 5 (A) to 5 (D) are shown. Table 1 shows.

[0016] [Table 1] Table 1

In the present invention, even if the reflection color of the glass plate surface on which the infrared cut film is formed varies depending on the angle with respect to the glass plate or the angle with respect to the glass plate is the same, In order to reduce defects in appearance such as the reflection color changes if there is a difference in film thickness in the formed infrared cut film, the reflectance of light with a wavelength of 400 to 600 nm on the surface of the glass substrate on which the infrared cut film is formed The difference between the maximum value and the minimum value is preferably 1.5% or less, and more preferably 1.0% or less.

In the present invention, the difference in refractive index between the infrared cut film and the glass substrate surface is 0.04. It is preferable that it is less than. If this difference is less than 0.04, it is possible to reduce the change in the reflected color due to the change in the angle with respect to the glass substrate surface on which the infrared cut film is formed, and the non-uniform infrared cut film having a film thickness difference. Even if it is formed on the surface of the glass substrate, the change in reflected color can be reduced. From the above viewpoint, the difference in refractive index between the infrared cut film and the glass substrate surface is more preferably 0.02 or less.

Note that the “refractive index at a wavelength of 550 nm” is a representative value of the refractive index in the visible light region, where the wavelength of 550 nm is almost the center of the visible light region, and the human eye has the highest sensitivity! This is because the wavelength is low.

[0019] As the water-repellent coating 3, a known water-repellent coating can be used, and among them, a water-repellent coating containing a fluoroalkyl group and Z or an alkyl group is preferable. Among these, silicon compounds containing a high water repellency and containing a fluoroalkyl group are more preferred.

The fluoroalkyl group-containing silicon compound is a silicon compound that contains a fluoroalkyl group and also contains an alkoxy group, an acyloxy group, or a chlorine group. For example, CF (CF) (CH) Si (OCH), CF ( CF) (CH) Si (OCH), CF (CF) (

3 2 7 2 2 3 3 3 2 5 2 2 3 3 3 2 7

CH) SiCl, CF (CF) (CH) SiCl, etc. can be shown in the f column.

2 2 3 3 2 5 2 2 3

Among these, a plurality of materials selected from a fluoroalkyl group and an alkyl group can be used in combination or alone.

These water repellents may be used after hydrolysis using a catalyst such as an acid or a base, if necessary. Alternatively, a silicon compound may be used as a siloxane compound by hydrolysis and condensation.

[0020] The film thickness of the water-repellent coating 3 is preferably 0.1 to 300 nm. If the film thickness is 0.1 nm or more, sufficient water repellency can be obtained, and if it is 300 nm or less, it has excellent wear resistance and scratch resistance, and the water-repellent coating 3 can be damaged to make it a strong film. it can.

[0021] In order to prevent the water-repellent coating 3 from being deteriorated by an alkali component eluted from the glass substrate 2, a base film mainly composed of silica is formed between the water-repellent coating 3 and the glass substrate 2. Preferably.

FIG. 2 is a cross-sectional view of a vehicle glass plate having a coating according to the present invention, which is an example in which a base film is formed between a water-repellent coating and a glass substrate. In this specification, ぉ and “main component” Is used as a word indicating a content rate of 50% or more.

[0022] As the raw material of silica constituting the undercoat film 5, for example, silicon alkoxide represented by tetraethoxysilane, tetramethoxysilane, tetrapropoxysilane, tetrabutoxysilane and the like, and tetrachlorosilane, SiHCl, SiHCI, etc. Chlorosilyl group

3 2 2

The silicon compound which has in a molecule | numerator is mentioned. The chlorosilyl group has a very high reactivity and forms a dense base film by self-condensation or condensation reaction with the substrate surface. Therefore, it is preferable to use a silicon compound having a chlorosilyl group in the molecule because a dense film can be formed without heating after the film is formed.

When forming the base film 5, the thickness of the base film 5 is preferably 5 to 300 nm. When the thickness is 5 nm or more, the water-repellent coating can be prevented from being deteriorated by the alkali component of the glass substrate force described above, and when it is 300 nm or less, the wear resistance and scratch resistance are excellent.

[0024] Next, the infrared cut film 4 in the present invention preferably contains silica as a main component and contains infrared cut fine particles. The infrared cut film 4 having such a composition can easily form a transparent film on a glass substrate by a simple method such as a sol-gel method.

Various types of infrared cut fine particles can be selected. For example, ITO (indium doped tin oxide) fine particles, ATO (antimony doped tin oxide) fine particles, aluminum doped zinc oxide (AZO) fine particles, indium doped Examples include zinc oxide (IZO) fine particles, tin doped zinc oxide fine particles, silicon-doped zinc oxide fine particles, lanthanum hexaboride fine particles, and cerium hexaboride fine particles.

Among these, in the present invention, it is preferable that the point power excellent in the infrared cut-off property also includes at least one of ITO (indium doped tin oxide) fine particles and ATO (antimony doped tin oxide) fine particles. ITO fine particles and Z or ATO fine particles are dispersed in the infrared cut film.

[0025] In the following, the force described by taking ITO fine particles and Z or ATO fine particles as examples. Instead of these, or in addition to these, aluminum-doped zinc oxide (AZO) fine particles, indium Doped acid-zinc (IZO) fine particles, tin-doped zinc oxide fine particles, silicon-doped zinc oxide fine particles, lanthanum hexaboride fine particles, cerium hexaboride fine particles, etc. May be.

[0026] The particle diameters of the ITO fine particles and the Z or ATO fine particles are lOOnm or less, preferably 40nm or less, more preferably l to 40nm. Thereby, generation | occurrence | production of the haze resulting from the efficiency of infrared cut being good and the particle size of microparticles | fine-particles being large can be suppressed.

Further, by using a material having excellent infrared cut performance, such as ITO fine particles and Z or ATO fine particles, and having a relatively high refractive index at a wavelength of 550 nm, as the infrared cut fine particles, the content of ITO fine particles and Z or ATO fine particles can be reduced. Even with a relatively low infrared cut film, the infrared cut performance can be maintained. Furthermore, even if the reflection color of the glass substrate surface on which the infrared cut film is formed changes depending on the angle with respect to the glass substrate or the angle to the glass substrate is the same, the infrared cut film formed on the glass substrate surface It is possible to reduce the appearance defect that the reflected color changes due to the difference in film thickness.

[0027] The content of ITO fine particles and / or ATO fine particles is preferably 20 to 45 mass% with respect to the total mass of the infrared cut coating 4. When the content is 20% by mass or more, sufficient infrared hot-cut performance can be obtained, and when it is 45% by mass or less, the hardness of the infrared cut coating 4 can be increased.

[0028] In addition, when the thickness of the infrared cut film 4 is increased, the total content of the ITO fine particles and Z or ATO fine particles dispersed in the film in the thickness direction can be increased, so that the infrared cut A film having excellent performance can be obtained. Therefore, the thickness of the infrared cut film 4 is preferably 300 ηm or more. However, when the thickness of the film increases, the abrasion resistance and scratch resistance of the film deteriorate, and when the infrared cut film 4 is formed on the glass substrate 2, defects such as film cracks are likely to occur. Therefore, the thickness of the infrared cut film 4 is preferably 3000 nm or less.

[0029] (Second form)

FIG. 3 is a cross-sectional view of another embodiment of a vehicle glass plate provided with a coating according to the present invention. In FIG. 3, a vehicle glass plate 11 having a coating is formed on a glass substrate 2, an infrared cut coating 14 formed on the main surface 2a of the glass substrate that is the exterior of the vehicle when attached to the vehicle, and an infrared cut coating 14 on the infrared cut coating 14. A formed water repellent coating 13 is provided. As the glass substrate 2, the infrared cut film 14 and the water repellent film 13 used in the second embodiment of the present invention, the glass plate and the film described in the first embodiment can be used.

In FIG. 3, an infrared cut film 14 exists between the water repellent film 13 and the glass substrate 2. Therefore, the infrared cut film 14 has the function as the base film described in the first embodiment. Specifically, the infrared cut film 14 prevents the water-repellent film 13 from being deteriorated by an alkali component eluted from the glass substrate 2.

In addition, since the water repellent coating 13 is formed on the infrared cut coating 14, the water repellent coating 13 has a function as a protective film for the infrared cut coating 14. Specifically, the water-repellent coating 13 is the same as the above-mentioned two when the infrared cut coating is an automobile door window glass such as moisture and dust. Protected against direct contact with other frames and weather strips.

[0031] As described above, by adopting the second form, it is possible to prevent deterioration of the water-repellent coating due to alkali even without providing a base film, and to reduce infrared rays due to wear, damage, etc. It can be set as the glass plate for vehicles provided with a cut film.

Next, a method for producing a vehicle glass plate provided with the coating of the present invention will be described.

(Production method of the first form)

The method for manufacturing a glass plate for a vehicle having a coating film according to the first aspect includes a first cleaning step of cleaning a main surface of a glass substrate that is the inside of a vehicle when attached to the vehicle, and cleaning in the first cleaning step. Applying a coating solution for forming an infrared cut film on the main surface to form an infrared cut film; heating the glass substrate; and firing the infrared cut film; and A second cleaning step of cleaning the main surface of the glass substrate, and a step of applying a water-repellent coating forming coating solution to the main surface cleaned in the second cleaning step to form a water-repellent coating.

[0033] In the first cleaning step, the glass substrate constituting the first embodiment of the present invention cleans the main surface of the glass substrate that becomes the interior of the vehicle when mounted on the vehicle. For cleaning, a known method can be used. For example, glass is placed in an alkali solution or an organic solvent, and if necessary, the surface of the glass plate is removed by heating and applying ultrasonic waves. how to For example, a method of removing dirt on the surface of the glass plate by polishing the glass surface with an aqueous polishing solution.

[0034] Next, as a coating method for applying the infrared cut film forming coating solution to the surface cleaned in the first cleaning step and forming the infrared cut film, a spray method, a dipping method, a roll coat method, Examples include spin coating, screen printing, flexographic printing, and flow coating.

[0035] The glass substrate on which the infrared cut film has been formed is heated (fired) at a predetermined temperature in order to cure the infrared cut film. The firing temperature is appropriately determined according to the characteristics of the coating solution for forming an infrared cut film. When forming a film by the sol-gel method, the firing temperature is preferably about 100-750 ° C! /.

When applied to a glass plate having a curved shape and Z or tempered glass as a glass plate for vehicles provided with the coating of the present invention, it is necessary to further perform bending treatment and Z or tempering treatment of the glass plate. If the firing temperature for curing the infrared cut film described above is relatively high (for example, 550 to 750 ° C), if the bending process and Z or strengthening process are performed with the heat during the firing process described above, 1 It is economical because the coating can be baked, bent and Z or strengthened by multiple heating.

Also, when the firing temperature for curing the infrared cut film is relatively low and the temperature (for example, 100 to 550 ° C), bending treatment and Z or strengthening treatment are performed before forming the infrared cut film on the glass substrate. It is good to do.

[0037] After the formation and heating (firing) of the infrared cut film, the main surface of the glass substrate that is outside the vehicle when attached to the vehicle is cleaned (second cleaning step). As the cleaning method, the same method as the first cleaning step described above can be used.

[0038] Next, a water-repellent coating-forming coating solution is applied to the glass substrate surface cleaned in the second cleaning step to form a water-repellent coating. As a coating method, the same method as described in the method of forming an infrared cut film can be used, and a hand coating method, a brush coating method, and the like are also suitable. When a base film is formed between the water repellent film and the glass substrate, it is preferable to form the base film before forming the water repellent film and to form the water repellent film thereon. Further, after forming the water repellent coating, firing may be performed as necessary. [0039] By manufacturing the glass plate for a vehicle having a coating film by the manufacturing method of the first embodiment described above, a water-repellent coating film is formed on the main surface of the glass substrate that becomes the outside of the vehicle when attached to the vehicle. Thus, it is possible to obtain a glass plate for a vehicle provided with a coating in which an infrared cut coating is formed on the main surface of the glass substrate that is the inside of the vehicle when attached to the vehicle.

[0040] (Manufacturing method of the second embodiment)

A method for manufacturing a glass plate for a vehicle having a coating of the second form includes a cleaning step for cleaning a main surface of a glass substrate that is an outside of a vehicle when attached to a vehicle, and an infrared ray on the main surface cleaned in the cleaning step. Applying a coating liquid for forming a cut film to form an infrared cut film, heating the glass substrate and firing the infrared cut film, and forming a water-repellent film on the surface where the infrared ray cut film is formed And applying a coating solution for forming the water-repellent coating on the infrared cut coating forming surface.

When the glass plate for a vehicle constituting the second embodiment of the present invention is attached to the vehicle, the main surface of the glass substrate on the outside of the vehicle is cleaned in the cleaning step. As a cleaning method, the same method as described in the cleaning step of the first embodiment can be used.

[0041] Next, an infrared cut film-forming coating solution is applied to the surface cleaned in the cleaning step to form an infrared cut film. The coating method is as described in the manufacturing method of the first embodiment.

[0042] The glass substrate on which the infrared cut film has been formed is heated (fired) at a predetermined temperature in order to cure the infrared cut film. The firing method is as described in the manufacturing method of the first embodiment.

[0043] Next, a water-repellent film-forming coating solution is applied to the surface on which the infrared cut film is formed, and a water-repellent film is formed on the infrared ray cut film-formed surface. The application method is as described in the manufacturing method of the first embodiment.

[0044] By manufacturing a glass plate for a vehicle having a coating film by the manufacturing method of the second embodiment described above, an infrared cut coating film is formed on the main surface of the glass substrate that is the outside of the vehicle when attached to the vehicle. In addition, it is possible to obtain a glass plate for a vehicle having a coating formed by forming a water-repellent coating on the infrared cut coating.

[0045] Further, in the glass plate for vehicles provided with the coating of the present invention, ITO is contained in the infrared cut coating. In addition to the fine particles and the silica component, additives such as organic substances may be added. By adding an organic substance, it is possible to improve the dispersibility of fine particles such as ITO, and when the thin film is formed by the sol-gel method, it is possible to obtain such effects as not generating cracks in the film. The content of the organic substance is not particularly limited, but is preferably 60% by mass or less with respect to the total mass of the thin film. If it exceeds 60% by mass, the content of organic matter in the thin film is too large, and sufficient thin film hardness cannot be obtained. The organic content is preferably 15% by mass or less. Example

[0046] Example 1

(1) Preparation of infrared cut film forming solution

Polyethylene glycol (PEG400: manufactured by Kanto Chemical Co., Ltd.) 0.036 g, pure water 5.86 g, polyether phosphate ester surfactant as a polymer dispersant (Solsperse 41000: manufactured by Nippon Lubrizol) 0.162 g, Modified alcohol (Solmix (registered trademark) AP-7: manufactured by Nippon Alcohol Sales Co., Ltd. (hereinafter referred to as “AP-7”)) 12. A solution containing 44 g in order was stirred for 1 minute, and then concentrated hydrochloric acid (Kanto Chemical) AP-7 (hereinafter referred to as “1% by mass AP-7”) added by 1% by mass was added to the above solution and stirred for 1 minute.

[0047] Thereafter, tetraethoxysilane (KBE-04: manufactured by Shin-Etsu Chemical Co., Ltd., silica component content = 28.

(8% by mass) 6.25 g was added to the above solution and stirred at room temperature for 4 hours. Thereafter, ITO fine particles and ethanol were mixed at a mass ratio of 2: 3 and stirred for 4 hours, and 2.25 g of the ITO dispersion liquid obtained was added to the above solution and stirred for 30 minutes to cut off infrared rays. A film forming solution was obtained. In addition, fine particles having a diameter of about 10 to 20 nm were used as ITO fine particles in the ITO dispersion.

[0048] (2) Formation of infrared cut film

A 4 mm thick glass substrate (green soda-lime silica glass having an ultraviolet absorption function) which was cut and polished and then reinforced after being cut and polished for an automobile side glass was prepared. The main surface (top surface) that becomes the inside of the vehicle when the glass substrate was attached to the vehicle was polished with an aqueous polishing solution, rinsed with water, and dried. The infrared cut film forming solution was applied to the cleaned surface by a flow coating method.

Next, boil the glass substrate coated with this infrared cut film forming solution at room temperature for about 5 minutes. After drying, the glass substrate was put in an oven preheated to 200 ° C. and heated for 10 minutes, and then cooled to obtain a glass substrate on which an infrared cut film was formed. The film thickness of the infrared cut film was about 1500 nm.

[0049] (3) Preparation of base treatment liquid (for base film formation) and water repellent film formation solution

Ethanol (Nacalai Testa) lOOg and chlorosilane (SiCl, Shin-Etsu Silicone) 0

Four

Olg was added with stirring to obtain a surface treatment solution.

CF (CF) (CH) Si (OCH) (heptadecafluorodecyltrimethoxysilane

3 2 7 2 2 3 3

(Toshiba Silicone Co., Ltd.) 1. Dissolve 3 g in 40.6 g of ethanol and stir for 1 hour, then add 0.880 g of ion-exchanged water and 1. Og of 0.1N hydrochloric acid, and stir for an additional hour. A water repellent film-forming solution was obtained.

[0050] (4) Formation of water-repellent coating

The main surface (bottom surface) of the glass substrate, which becomes the outside of the vehicle when the glass substrate with the infrared cut film formed thereon was attached to the vehicle, was polished with an aqueous polishing solution, rinsed with water, and dried. The surface treatment solution was applied to the cleaned glass surface by flow coating at a humidity of 40% and room temperature. After drying for about 1 minute to obtain a base film, 3 ml of the water-repellent film-forming solution prepared above was applied to a cotton cloth and applied onto the surface of the base film. Thereafter, the excessively water-repellent film-forming solution was wiped off with a new cotton cloth soaked in ethanol to form a water-repellent film, and a vehicle glass plate provided with the film was obtained. The film thickness of the water-repellent coating is 10 nm when observed with a scanning electron microscope (SEM, “S-4700” manufactured by Hitachi, Ltd., acceleration voltage 5 kV, emission current 10 μΑ, measurement magnification 100,000 times) It was the following.

[0051] As described above, the glass plate for vehicles provided with the coating obtained in Example 1 is provided with a water-repellent coating on the main surface of the glass substrate that becomes the outside of the vehicle when attached to the vehicle. An infrared cut film is provided on the main surface of the glass substrate that is the inside of the car when it is installed.

[0052] (5) Content of ITO fine particles in infrared cut coating (hereinafter referred to as “ITO content”) and content of silica component in infrared cut coating (hereinafter referred to as “silica content” t) Content ratio

The content ratio of ITO content and silica content is the detection of photoelectron intensity (Intensity) of indium (In), tin (Sn), and silicon (Si), and the detected photoelectron intensity and relative sensitivity in the device used. Using the coefficient value, the sum of indium (In) and tin (Sn) and the atomic concentration of silicon (Si) It is obtained by calculating the atomic concentration% value of the degree ratio (In + Sn: Si).

Here, the analysis method is as follows.

As a pretreatment, a sample of an appropriate size, such as a vehicle glass plate provided with the coating obtained in Example 1, was cut, and then the sample was fixed to a sample table using a molybdenum mask. Then, composition analysis in the depth direction was performed by X-ray photoelectron spectroscopy analysis using the following analyzer, analysis conditions, and etching conditions.

As an analyzer, an X-ray photoelectron spectrometer “ESCA-5 600ci” manufactured by ULVAC FUAI Co., Ltd. was used.

Regarding the analysis conditions, a monochromatic X-ray source (Al Monochromated 2mm Filament) is used as the X-ray source (Current X-Ray anode), and the anode energy (Anode

Energy) was 2.3828J (1486. 6eV), the power (Anode Power) was 150W, the voltage (X-Ray Voltage) was 14kV, and the extraction angle (Stage Angle) was 45 degrees. As for the etching conditions, the etching method is Ar ion sputtering, the acceleration voltage (Beam Voltage) is 3. OkV, the raster (Raster) is 4 X 4 mm, and the sputtering rate (Etching Rate) is about 1.9 nmZmin. (SiO film equivalent).

2

The composition of the infrared cut film, specifically the ITO content and the silica content, is obtained from the composition analysis result in the depth direction of the infrared cut film by X-ray photoelectron spectroscopy, and the composition (content) is It was expressed as a component of the film near the center in the depth direction of the infrared cut film.

FIG. 6 is a graph showing the atomic concentrations of indium (In), tin (Sn), and silicon (Si) in Example 1, the vertical axis indicates the atomic concentration (%), and the horizontal axis indicates In Fig. 6, which shows the sputter time (min), the atomic concentration ratio (In + Sn: Si) of indium (In) and tin (Sn) to silicon (Si) is about 1: 9. It can be seen that the content ratio of ITO content and silica content is about 1: 9 in mole ratio.

[0055] The refractive index of the infrared cut film obtained in Example 1 at a wavelength of 550 nm was measured using a spectroscopic ellipsometer (VASE manufactured by JA Woollam). The refractive index of the surface of the glass plate at a wavelength of 550 nm is measured using a spectrophotometer (Hitachi Ltd. spectrophotometer U-4000). The transmittance and reflectance measured using the above were calculated. The degree of light interference of the vehicle glass plate provided with the coating obtained in Example 1 was visually observed. The refractive index of the infrared cut film at a wavelength of 550 nm is optimized for the optical model parameters to reproduce the Psi (φ) and Delta (Δ) obtained from the spectroscopic ellipsometer, and the optical constants (refractive index, extinction coefficient). Was evaluated by ellipsometry (spectral ellipsometry). The refractive index at the wavelength of 550 nm on the surface of the glass plate, the refractive index at the wavelength of 550 nm of the infrared cut coating, the refractive index difference at the wavelength of 550 nm between the infrared cut coating and the glass plate, and the degree of interference of light Shown in Table 2.

[0056] Example 2

In the same manner as in Example 1, a 4 mm thick glass substrate (green soda lime silica glass having an ultraviolet absorbing function) that was cut and polished and then reinforced after being cut for a side glass of an automobile was prepared. The main surface (top surface) that becomes the outside of the vehicle when the glass substrate was attached to the vehicle was polished with an aqueous polishing solution, rinsed with water, and dried. The infrared cut film forming solution used in Example 1 was applied to the cleaned surface by a flow coating method. Next, after drying the glass substrate coated with the infrared cut film forming solution at room temperature for about 5 minutes, put it in an oven preheated to 200 ° C and heat for 10 minutes, then cool And the glass substrate in which the infrared cut film was formed was obtained.

[0057] 3 ml of the water-repellent film-forming solution used in Example 1 was applied to a cotton cloth, applied to the surface of the glass substrate on which the infrared-cut film was formed, and then applied to the surface of the glass substrate. The forming solution was wiped off with a new cotton cloth soaked in ethanol to form a water-repellent coating, and a vehicle glass plate provided with the coating was obtained.

The glass plate for vehicles provided with the coating obtained in Example 2 is provided with an infrared cut coating on the main surface of the glass substrate that is the outside of the vehicle when attached to the vehicle, and a water-repellent coating is formed on the infrared cut coating. Has been.

[0058] Example 3

In Example 1, a vehicle glass plate provided with a coating film was obtained in the same manner as in Example 1 except that the ITO dispersion was 3.07 g and tetraethoxysilane was 5.13 g. And evaluated. The results are shown in Table 2. [0059] Example 4

In Example 1, the same method as in Example 1 was applied except that the infrared cut film forming solution was applied to the main surface (bottom surface) that became the inside of the vehicle when the glass substrate was attached to the vehicle by the flow coating method. Thus, a vehicle glass plate provided with a coating was obtained and evaluated in the same manner as in Example 1. The results are shown in Table 2.

[0060] [Table 2] Table 2 1

[0061] [Table 3] Table 2 1

[0062] The ITO content in the infrared cut film of the vehicle glass plate provided with the film obtained in Examples 2 and 4, the organic content in the infrared cut film (hereinafter referred to as "organic content"). ), And the silica content was calculated from the mass of each material component added to the coating solution. As a result, the ITO content was 31% by mass and the organic content was 7% by mass. The content was 62% by mass. Further, the ITO content, the organic content, and the silica content in the infrared cut film of the vehicle glass plate provided with the film obtained in Example 3 were determined by the same method. As a result, the ITO content Was 42 mass%, the organic content was 7 mass%, and the silica content was 51 mass%.

In the calculation, the mass of the ITO fine particles is 40% by mass of the ITO dispersion, the mass of the organic substance is the mass of the polymer dispersant and polyethylene glycol, and the mass of the silica component is tetraethoxysilane. Based on the content of 28.8% by mass of the silica component.

[0063] The water-repellent performance and infrared cut performance of the vehicle glass plate provided with the obtained coating were confirmed. For the confirmation, a test sample in which an infrared force coating and a water-repellent coating were formed in the same manner as the glass plate for vehicles provided with the coating of Examples 1 and 2 was used. This is because when measuring the water-repellent performance and infrared ray cutting performance of a bent glass for a vehicle, it is difficult to measure with good measurement accuracy because it is a simple method.

[0064] As the water repellency of the test sample (vehicle glass plate provided with a coating) obtained by the same method as in Examples 1 and 2, the contact angle with water droplets was measured using a contact angle meter (CA-DT, Using Kyowa Interface Science Co., Ltd.), water droplets were measured as 2 mg static contact angle. Furthermore, the critical tilt angle was measured as a measure of water repellency. In order to measure the ability of water droplets to roll on the surface of the water-repellent coating, when a water droplet with a diameter of 5 mm is placed on the surface of a horizontally placed glass plate and the water-repellent glass plate is gradually tilted, the water droplet placed on the surface begins to roll. The inclination angle (critical inclination angle) of the glass plate was measured. The smaller the critical inclination angle, the better the dynamic water repellency. For example, raindrops attached to the glass window of a running car are more likely to scatter and the driver's vision is not obstructed.

[0065] Further, the light transmittance at a wavelength of 300 to 2500 nm was measured as an infrared cut performance of a test sample (vehicle glass plate provided with a coating) obtained by the same method as in Examples 1 and 2. In the measurement, a spectrophotometer (manufactured by Shimadzu Corporation: model number UV-3100PC) was used. The results obtained are shown in Figs. 4 (a) and (b).

Fig. 4 (a) shows the results of measuring the light transmittance at a wavelength of 300 to 2500 nm in Example 1, and Fig. 4 (b) shows the light transmittance at a wavelength of 300 to 2500 nm in Example 2. It is the result of measurement.

The contact angle of the surface on which the water repellent film of the test sample (vehicle glass plate provided with a film) obtained in Examples 1 and 2 was formed was a deviation of 108 degrees, the critical inclination angle was a deviation of 13 degrees. It was confirmed that the glass plate was excellent in water repellency. In addition, the infrared transmittance of the test samples (vehicle glass plates provided with a coating) obtained in Examples 1 and 2 is as shown in FIGS. 4 (a) and (b). It was confirmed that it was kept low.

[0066] Also in Examples 3 and 4, there is obtained a glass plate for a vehicle having the same excellent water repellency performance as in Examples 1 and 2 and having a coating with a low infrared transmittance. It was. Industrial applicability

[0067] According to the present invention, it is possible to provide an automotive glass plate provided with a coating film having both functions of water repellency and infrared cutting property, and it is particularly useful as a vehicle window glass.

Claims

The scope of the claims

[1] An automotive glass plate provided with a coating in which a water repellent coating and an infrared cut coating are formed on the main surface of the glass substrate.

[2] The water-repellent coating is formed on the main surface of the glass substrate that becomes the outside of the vehicle when attached to the vehicle, and the infrared cut coating is the main surface of the glass substrate that becomes the inside of the vehicle when attached to the vehicle. The glass plate for vehicles provided with the film of Claim 1 characterized by the above-mentioned.

[3] The infrared cut film is formed on a main surface of a glass substrate which is an outside of the vehicle when attached to a vehicle, and the water repellent film is formed on the infrared cut film. A glass plate for a vehicle, comprising the coating according to claim 1.

[4] The water-repellent film is a film containing a fluoroalkyl group and Z or an alkyl group, and the infrared cut film is a film containing silica as a main component and containing infrared cut fine particles. Item 4. A vehicle glass plate comprising the coating according to any one of Items 1 to 3.

[5] The infrared cut fine particles are at least one of indium-doped tin oxide (ITO) fine particles and antimony-doped tin oxide (ATO) fine particles.

A glass plate for vehicles comprising the coating according to 4.

[6] The film thickness of the water repellent film is 0.1 to 300 nm, and the film thickness of the infrared cut film is 3

The glass plate for vehicles provided with the coating according to any one of claims 1 to 5, wherein the glass plate has a thickness of 00 to 3000 nm.

[7] The glass substrate is a soda-lime-silica glass plate containing tin on one surface and substantially not containing tin on the other surface, and the infrared cut film substantially does not contain tin. The glass plate for vehicles provided with the film of any one of Claim 1 thru | or 6 characterized by the above-mentioned.

[8] Wavelength of the surface of the glass substrate substantially free of tin and the infrared cut film

The glass plate for vehicles provided with the film of Claim 7 whose refractive index difference in 550nm is less than 0.04.

[9] A first cleaning step for cleaning the main surface of the glass substrate that is the inside of the vehicle when attached to the vehicle; Applying a coating solution for forming an infrared cut film on the main surface cleaned in the first cleaning step, forming an infrared cut film, heating the glass substrate, and firing the infrared cut film; A second cleaning step for cleaning the main surface of the glass substrate that is the outside of the vehicle when attached to the vehicle, and a coating liquid for forming a water-repellent film is applied to the main surface cleaned in the second cleaning step, The manufacturing method of the glass plate for vehicles provided with the film which has a process of forming a water-repellent film.

A cleaning process for cleaning the main surface of the glass substrate on the outside of the vehicle when it is mounted on a vehicle, and an infrared cut coating film is formed by applying a coating solution for forming an infrared cut film on the main surface cleaned in the cleaning process. Heating the glass substrate and firing the infrared cut coating; and applying a water repellent coating forming coating solution to the infrared cut coating forming surface; and forming the water repellent coating on the infrared cut coating forming surface. The manufacturing method of the glass plate for vehicles provided with the film which has a process of forming a film.