JPWO2007081025A1 - VEHICLE GLASS PLATE HAVING COATING AND METHOD FOR MANUFACTURING SAME - Google Patents

Abstract

It is a glass plate for vehicles provided with the film which formed the water repellent film and the infrared cut film in the main surface of the glass substrate. For example, a water-repellent film is formed on the main surface of the glass substrate that becomes the outside of the vehicle when attached to the vehicle, and an infrared cut film is formed on the main surface of the glass substrate that becomes the inside of the vehicle when attached to the vehicle. 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. An object of this invention is to provide the glass plate for vehicles suitable for the window glass for vehicles which has water-repellent property and infrared cut property as several functions.

Description

  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.

2. Description of the Related Art Conventionally, an automotive glass plate in which a water-repellent coating containing silica as a main component and containing fluorine is formed on the surface of an automotive glass is known. (For example, see Patent Document 1).
Also known is 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 doped tin oxide) is formed on the surface of glass for automobiles. ing. (For example, see Patent Documents 2 and 3)

JP 2001-010337 A International Publication No. 2004/011381 Pamphlet International Publication No. 2005/095298 Pamphlet

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.
An object of this invention is to provide the glass plate for vehicles optimal for the window glass for vehicles which has water repellency and infrared cut property as several functions, and its manufacturing method.

In order to solve the above-mentioned problems, the present invention provides (1) a vehicle glass plate comprising a film in which a water-repellent film and an infrared cut film 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 which is the outside of the vehicle when attached to the vehicle, and the infrared cut coating is formed on the main surface of the glass substrate which is the inside of the vehicle when attached to the vehicle. A glass plate for a vehicle provided with the coating film according to (1) above, which is formed;
(3) The said infrared cut film is formed in the main surface of the glass substrate used as a vehicle exterior when it attaches to a vehicle, The said water-repellent film is formed on the said infrared cut film, The said characterized by the above-mentioned. (1) Glass plate for vehicles provided with the coating according to the description,
(4) The water-repellent film is a film containing a fluoroalkyl group and / or an alkyl group, and the infrared cut film is a film containing silica as a main component and containing infrared cut fine particles. A glass plate for a vehicle comprising the coating film according to any one of (1) to (3),
(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 vehicles provided with a coating of
(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 is formed on a surface substantially free of tin. A glass plate for a vehicle, comprising the coating according to any one of (1) to (6),
(8) A glass plate for vehicles provided with the coating according to (7) above, wherein a difference in refractive index at a wavelength of 550 nm between the surface of the glass substrate substantially not containing tin and the infrared cut coating is less than 0.04.
(9) A first cleaning step of cleaning the main surface of the glass substrate that is the inside of the vehicle when attached to the vehicle, and an application liquid for forming an infrared cut film on 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 a main surface of the glass substrate which is the outside of the vehicle when attached to a vehicle; A method of manufacturing 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) Attached to a vehicle A cleaning step of cleaning the main surface of the glass substrate that is outside the vehicle, a step of applying an infrared cut coating forming coating solution to the main surface cleaned in the cleaning step to form an infrared cut coating, and the glass Heating the substrate A vehicle comprising a film having a step of firing the infrared cut coating, and a step of applying a water repellent coating forming coating liquid on the infrared cut coating forming surface and forming the water repellent coating on the infrared cut coating forming surface. Glass plate manufacturing method,
Is to provide.

  ADVANTAGE OF THE INVENTION According to this invention, the glass plate for vehicles provided with the film which has the function of both water repellency and infrared rays cut property can be obtained.

It is sectional drawing of the glass plate for vehicles provided with the film of this invention. It is sectional drawing of the glass plate for vehicles provided with the film of this invention, Comprising: It is a figure which shows the example which formed the base film between the water-repellent film and the glass plate for vehicles. It is sectional drawing of the other form of the glass plate for vehicles provided with the film of this invention. It is the figure which showed the result of having measured the light transmittance in wavelength 300-2500nm in Example 1 and 2. FIG. It is a figure which shows the result of having measured the reflectance of the light of wavelength 370-780 nm. It is a figure which shows the atomic concentration of indium (In), tin (Sn), and silicon (Si) in Example 1.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Glass plate for vehicles provided with film 2 Glass substrate 2a Main surface of glass substrate which becomes vehicle exterior when attached to vehicle 2b Main surface of glass substrate which becomes vehicle interior when attached to vehicle 3 Water repellent coating 4 Infrared cut Coating 5 Base film 11 Glass plate for vehicle 13 with coating 13 Water-repellent coating 14 Infrared cut coating

The 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 the 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. 1 includes a water-repellent coating 3 formed on the main surface 2a of the glass substrate 2 that is the exterior of the vehicle when attached to the vehicle, and the interior of the vehicle when attached to the vehicle. An infrared cut coating 4 formed on the main surface 2b of the glass substrate 2 is provided. In the first embodiment, since the infrared cut film is formed on the main surface of the glass substrate which is the inside of the vehicle when attached to the vehicle, the infrared cut film is exposed to wind and rain, dust and sand outside the vehicle, and the like. It is possible to prevent the infrared cut film from being deteriorated.

  Although the glass substrate 2 which comprises this invention will not be restrict | limited especially if it is a glass plate used for vehicles, Soda lime silica glass generally used for vehicles is preferable. Soda lime silica glass includes colorless glass, colored glass such as green, gray, and blue, glass that has the function of cutting ultraviolet rays, and low transmittance of visible light to maintain privacy. There are suppressed glass and the like, and these are suitable as the glass substrate of the glass plate for vehicles of the present invention.

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 tin.
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. Changes depending on the angle with respect to the glass plate, or even if the angle to the glass plate is the same, there is a problem of appearance that the reflected color changes if there is a difference in film thickness on the infrared cut film formed on the glass plate surface May occur. 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.

  Generally, since the bottom surface contains tin, the refractive index is higher than that of the top surface that does not substantially contain tin. When the glass plate is soda lime silica glass, specifically, the refractive index at a wavelength of 550 nm on the top surface is 1.50 to 1.52, whereas the refractive index at a wavelength of 550 nm on the bottom surface is 1.53 to 1. .55. The said malfunction can be reduced, so that the refractive index difference of an infrared cut film and the glass plate surface is small. More specifically, when the infrared cut film (refractive index: 1.48 to 1.52) of the present invention is formed on the glass plate surface, the difference in refractive index is greater when formed on the top surface than when formed on the bottom surface. It can be made smaller, and the above-mentioned 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 with respect to the glass plate and the film thickness difference of the infrared cut coating will be described.
FIGS. 5 (A) to 5 (D) show the reflection of the glass plate surface on which the coating film is formed when the infrared cut coating film and the coating film having different refractive index differences are formed on the glass plate surface. FIG. 5A shows a case where the film thickness of the infrared cut film is about 500 nm, and FIG. 5B shows a case where the film thickness of the infrared cut film is about 500 nm. FIG. 5C shows the case where the film thickness of the infrared cut film is about 1000 nm, and FIG. 5D shows the case where the film thickness of the infrared cut film is about 2000 nm. The thick solid line shows the case where the refractive index difference at a wavelength of 550 nm is about 0.01, 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. Show. In addition, about the reflectance, the reflectance of the incident light whose incident angle is 12 degrees was measured.

5A to 5D, in any infrared cut film having any film thickness and refractive index difference, an increase / decrease behavior in which the reflectance of light repeatedly increases and decreases according to the variation of the wavelength of light. Is shown. However, the infrared cut film having a refractive index difference of about 0.10 on the glass plate surface at a wavelength of 550 nm is compared with the infrared cut film having a refractive index difference of about 0.01 on the glass plate surface at a wavelength of 550 nm, The fluctuation cycle 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, an infrared cut film having a large refractive index difference of about 0.10 with respect to the glass plate surface at a wavelength of 0.10 nm greatly changes the reflectance increasing / decreasing 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 at a wavelength of 550 nm with respect to the glass plate surface of about 0.10 is likely to change due to a change in the film thickness of the infrared cut film.
Here, the larger the angle of incident light (incident angle) with respect to the normal of the glass plate, the longer the path of light passing through the infrared cut film. 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 surface 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, the minimum value, and the difference between the maximum value and the minimum value of the reflectance of light having a wavelength of 400 to 600 nm at each film thickness obtained by FIGS. 5 (A) to 5 (D) are shown in Table 1. Shown in

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

Moreover, in this invention, it is preferable that the refractive index difference of an infrared cut film and a glass substrate surface is less than 0.04. When 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 is glass. Even if it is formed on the surface of the substrate, the change in the 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.
Here, the reason that the “refractive index at a wavelength of 550 nm” is a representative value of the refractive index in the visible light region is that the wavelength 550 nm is almost the center of the visible light region and has the highest sensitivity in the human eye. .

As the water-repellent coating 3, a known water-repellent coating can be used. Among them, a water-repellent coating containing a fluoroalkyl group and / or an alkyl group is preferable. Among these, a silicon compound containing a fluoroalkyl group having high water repellency is more preferable.
The fluoroalkyl group-containing silicon compound is a silicon compound containing a fluoroalkyl group and containing an alkoxy group, an acyloxy group, or a chlorine group. For example, CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si ( OCH ₃ ) ₃ , CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ Si (OCH ₃ ) ₃ , CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ SiCl ₃ , CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ SiCl ₃ , etc. can be exemplified.
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 being hydrolyzed using a catalyst such as an acid or a base, if necessary. A silicon compound may be used as a siloxane compound by hydrolysis and condensation reaction.

  The film thickness of the water repellent coating 3 is preferably 0.1 to 300 nm. When the film thickness is 0.1 nm or more, sufficient water repellency can be obtained, and when it is 300 nm or less, the film is excellent in abrasion resistance and scratch resistance, and the water-repellent film 3 can be made hard and hard. .

Further, in order to prevent the water-repellent coating 3 from being deteriorated by an alkaline component eluted from the glass substrate 2, it is preferable to form a base film mainly composed of silica between the water-repellent coating 3 and the glass substrate 2. .
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, the term “main component” is used as a term indicating a content rate of 50% or more.

Examples of the raw material of silica constituting the base film 5 include silicon alkoxides and tetrachlorosilanes such as tetraethoxysilane, tetramethoxysilane, tetrapropoxysilane, and tetrabutoxysilane, SiHCl ₃ and SiH ₂ Cl _2. And silicon compounds having a chlorosilyl group in the molecule. 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 coating 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 from the glass substrate described above, and when it is 300 nm or less, the wear resistance and scratch resistance are excellent.

Next, the infrared cut coating 4 in the present invention preferably contains silica as a main component and contains infrared cut fine particles. The infrared cut film 4 composed of these compositions can easily form a transparent film on a glass substrate by a simple method such as a sol-gel method.
Various kinds 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 zinc oxide ( IZO) fine particles, tin-doped zinc oxide fine particles, silicon-doped zinc oxide fine particles, lanthanum hexaboride fine particles, cerium hexaboride fine particles, and the like.
Among these, in the present invention, it is preferable to contain at least one of ITO (indium doped tin oxide) fine particles and ATO (antimony doped tin oxide) fine particles from the viewpoint of excellent infrared cut property. In addition, ITO fine particles and / or ATO fine particles are used dispersed in an infrared cut film.

  Hereinafter, ITO fine particles and / or ATO fine particles will be described as examples. However, the present invention is not limited to these, and instead of or together with them, aluminum-doped zinc oxide (AZO) fine particles, indium-doped zinc oxide ( IZO) fine particles, tin-doped zinc oxide fine particles, silicon-doped zinc oxide fine particles, lanthanum hexaboride fine particles, cerium hexaboride fine particles and the like may be used.

The particle diameter of the ITO fine particles and / or ATO fine particles is 100 nm or less, preferably 40 nm or less, and more preferably 1 to 40 nm. Thereby, the efficiency of infrared cut is good and the generation of haze due to the large particle size of the fine particles can be suppressed.
In addition, by using a material having excellent infrared cut performance, such as ITO fine particles and / or ATO fine particles, and having a relatively high refractive index at a wavelength of 550 nm, the content of ITO fine particles and / or ATO fine particles is compared. 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 with respect to the glass substrate is the same, there is a difference in film thickness between 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 presence of the light.

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

  Further, when the thickness of the infrared cut film 4 is increased, the total content of ITO fine particles and / or ATO fine particles dispersed in the film in the thickness direction can be increased, and thus a film having excellent infrared cut performance can be obtained. Obtainable. Therefore, the thickness of the infrared cut film 4 is preferably 300 nm or more. However, when the thickness of the film increases, the wear resistance and scratch resistance of the film deteriorate, and when the infrared cut film 4 is formed on the glass substrate 2, there is a problem that the film tends to crack. Therefore, the thickness of the infrared cut film 4 is preferably 3000 nm or less.

(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, the glass plate 11 for vehicles provided with a coating is on the glass substrate 2, the infrared cut coating 14 formed on the main surface 2a of the glass substrate which is the vehicle exterior when attached to the vehicle, and the infrared cut coating 14 The 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 a 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.
Moreover, since the water-repellent coating 13 is formed on the infrared cut coating 14, the water-repellent coating 13 functions as a protective film for the infrared cut coating 14. Specifically, the water-repellent coating 13 is, in the case where the infrared cut coating is a door window glass of an automobile such as moisture and dust, in addition to the two described above, a door window lifting device, a window frame and Protects against direct contact with weatherstrip etc.

  As described above, by adopting the second embodiment, a vehicle having an infrared cut film that can prevent deterioration of the water-repellent film due to alkali without providing a base film and that is less deteriorated due to wear, damage, etc. It can be used as a glass plate.

Next, the manufacturing method of the glass plate for vehicles provided with the film of this invention is demonstrated.
(Production method of the first embodiment)
The manufacturing method of the glass plate for vehicles provided with the film of 1st form wash | cleaned in the 1st washing | cleaning process which wash | cleans the main surface of the glass substrate used as a vehicle inside, when it attaches to a vehicle, and this 1st washing | cleaning process Applying a coating liquid for forming an infrared cut film on the main surface to form an infrared cut film, heating the glass substrate, firing the infrared cut film, and the outside when mounted on a vehicle A second cleaning step of cleaning the main surface of the glass substrate; and a step of applying a water-repellent coating forming coating liquid to the main surface cleaned in the second cleaning step to form a water-repellent coating.

  The glass substrate which comprises the 1st form of this invention wash | cleans the main surface of the glass substrate used as a vehicle inside, when it attaches to a vehicle in a 1st washing | cleaning process. As cleaning, a known method can be used. For example, glass is placed in an alkaline solution or an organic solvent, and if necessary, the surface of the glass plate is removed by heating and applying ultrasonic waves. Examples thereof include a method, a method of removing dirt on the surface of the glass plate by polishing the glass surface using an aqueous polishing solution.

  Next, an infrared cut film forming coating solution is applied to the surface cleaned in the first cleaning step, and the infrared cut film is formed by a spray method, a dip method, a roll coat method, a spin coat method, a screen, or the like. Examples thereof include a printing method, a flexographic printing method, and a flow coating method.

  The glass substrate on which the infrared cut film is 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 the film is formed by the sol-gel method, the firing temperature is preferably about 100 to 750 ° C.

When applying to the glass plate and / or tempered glass which have a curved surface as a glass plate for vehicles provided with the film of the present invention, it is necessary to perform bending processing and / or tempering processing of a glass plate further. In the case where the firing temperature for curing the above-described infrared cut film is a relatively high temperature (for example, 550 to 750 ° C.), once the bending treatment and / or the strengthening treatment are performed with the heat at the time of firing described above, It is economical because the coating can be baked and bent and / or strengthened by heating.
Moreover, when the temperature of baking for hardening an infrared cut film is a comparatively low temperature (for example, 100-550 degreeC), when a bending process and / or a reinforcement process are performed before forming an infrared cut film on a glass substrate. Good.

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

  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. In the case of forming a base film 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. Moreover, after forming a water-repellent film, you may bake as needed.

  By manufacturing a 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 is the exterior of the vehicle when mounted on the vehicle, and is attached to the vehicle. In this case, a vehicle glass plate having a coating in which an infrared cut coating is formed on the main surface of the glass substrate that becomes the inside of the vehicle can be obtained.

(Manufacturing method of 2nd form)
The manufacturing method of the glass plate for vehicles provided with the film of a 2nd form is a washing | cleaning process which wash | cleans the main surface of the glass substrate used as a vehicle outside when it attaches to a vehicle, and infrared rays are wash | cleaned in the main surface wash | cleaned by this washing | cleaning process A step of applying a coating solution for forming a cut film to form an infrared cut coating, a step of heating the glass substrate and firing the infrared cut coating, and a coating solution for forming a water repellent coating on the surface of the infrared cut coating And forming the water-repellent film on the infrared cut film-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 that is on the outside of the vehicle is cleaned in the cleaning step. As the cleaning method, the same method as described in the cleaning step of the first embodiment can be used.

  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 application method is as described in the manufacturing method of the first embodiment.

  The glass substrate on which the infrared cut film is 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.

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

  An infrared cut film is formed on the main surface of the glass substrate on the outside of the vehicle when the vehicle glass plate provided with the film is manufactured by the manufacturing method according to the second embodiment described above, and the infrared cut film is formed on the infrared cut film. A glass plate for vehicles provided with a coating having a water-repellent coating formed thereon can be obtained.

  Moreover, in the glass plate for vehicles provided with the film of this invention, you may add additives, such as organic substance, in addition to ITO microparticles | fine-particles and a silica component in an infrared cut film. 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 a sol-gel method, it is possible to obtain an effect such as not generating cracks in the film. Although it does not specifically limit as content of organic substance, 60 mass% or less is preferable with respect to the total mass of a thin film. If it exceeds 60% by mass, the content of the organic substance 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 1
(1) Preparation of infrared cut film forming solution 0.036 g of polyethylene glycol (PEG400: manufactured by Kanto Chemical Co., Inc.), 5.86 g of pure water, polyether phosphate ester surfactant (Solsperse 41000: A solution containing 0.162 g of Nippon Lubrizol Co., Ltd. and 12.44 g of denatured alcohol (Solmix (registered trademark) AP-7: manufactured by Nippon Alcohol Sales Co., Ltd. (hereinafter referred to as “AP-7”)) for 1 minute. After stirring, 3.00 g of AP-7 (hereinafter referred to as “1% by mass AP-7”) to which 1% by mass of concentrated hydrochloric acid (manufactured by Kanto Chemical Co., Ltd.) was added was added to the above solution and stirred for 1 minute.

  Then, 6.25 g of tetraethoxysilane (KBE-04: manufactured by Shin-Etsu Chemical Co., Ltd., silica component content = 28.8% by mass) was added to the above solution and stirred at room temperature for 4 hours. Thereafter, 2.25 g of ITO dispersion obtained by mixing ITO fine particles and ethanol in a mass ratio of 2: 3 and stirring for 4 hours was added to the above solution, stirring was performed for 30 minutes, and infrared rays were cut. A solution for forming a film was obtained. Further, as the ITO fine particles in the ITO dispersion liquid, fine particles having a diameter of about 10 to 20 nm were used.

(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 for side glass of an automobile and then reinforced 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, after drying the glass substrate coated with the infrared cut film forming solution at room temperature for about 5 minutes, the glass substrate is put in an oven preheated to 200 ° C. and heated for 10 minutes, and then cooled to form an infrared cut film. A formed glass substrate was obtained. The film thickness of the infrared cut film was about 1500 nm.

(3) Preparation of base treatment liquid (for base film formation) and water repellent film formation solution To 100 g of ethanol (manufactured by Nacalai Tesque), 0.01 g of chlorosilane (SiCl ₄ , manufactured by Shin-Etsu Silicone) was added with stirring. A ground treatment solution was obtained.
Also, 1.3 g of CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (OCH ₃ ) ₃ (heptadecafluorodecyltrimethoxysilane, manufactured by Toshiba Silicone) was dissolved in 40.6 g of ethanol and stirred for 1 hour. Thereafter, 0.808 g of ion-exchanged water and 1.0 g of 0.1N hydrochloric acid were added, and the mixture was further stirred for 1 hour to obtain a water repellent film forming solution.

(4) Formation of water-repellent coating The main surface (bottom surface) of the glass substrate that becomes the exterior of the vehicle when the glass substrate on which the infrared cut coating is formed is attached to a vehicle using a polishing aqueous solution and then with water Washed off 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 containing 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 was 10 nm or less when observed with a scanning electron microscope (SEM, “S-4700 type” manufactured by Hitachi, Ltd., acceleration voltage 5 kV, emission current 10 μA, measurement magnification 100,000 times). It was.

  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 is the outside of the vehicle when attached to the vehicle, and is attached to the vehicle. An infrared cut film is provided on the main surface of the glass substrate on the inside of the vehicle.

(5) Content of ITO fine particle content in infrared cut coating (hereinafter referred to as “ITO content”) and content ratio of silica component in infrared cut coating (hereinafter referred to as “silica content”) ITO content And the content ratio of silica content detects the photoelectron intensity (Intensity) of indium (In), tin (Sn), and silicon (Si), and uses the detected photoelectron intensity and the relative sensitivity coefficient value in the device used, It is obtained by calculating the atomic concentration% value of the atomic concentration ratio (In + Sn: Si) between the sum of indium (In) and tin (Sn) and silicon (Si).

Here, the analysis method is as follows.
As a pretreatment, a sample of an appropriate size was cut from the vehicle glass plate provided with the coating obtained in Example 1, and then the sample was fixed to the sample table using a molybdenum mask. Thereafter, composition analysis in the depth direction by X-ray photoelectron spectroscopic analysis was performed using the following analyzer, analysis conditions, and etching conditions.
As an analyzer, an X-ray photoelectron spectrometer “ESCA-5600ci” manufactured by ULVAC-PHI Co., Ltd. was used.
Regarding the analysis conditions, a monochromatic X-ray source (Al Monochromated 2 mm Filament) was used as the X-ray source (Current X-Ray anode), the anode energy (Anode Energy) was set to 2.3828 J (1486.6 eV), and the power The amount (Anode Power) was 150 W, the voltage (X-Ray Voltage) was 14 kV, and the take-out angle (Stage Angle) was 45 degrees.
As for the etching conditions, the etching method is sputtering with Ar ions, the acceleration voltage (Beam Voltage) is 3.0 kV, the raster is 4 × 4 mm, and the sputtering rate is about 1.9 nm / It was a min (SiO ₂ film equivalent).
The composition of the infrared cut film, specifically, the ITO content and the silica content are 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 infrared. It was expressed as a component of the film near the center in the depth direction of the cut film.

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 the sputtering time (min. ).
In FIG. 6, since the atomic concentration ratio (In + Sn: Si) between indium (In) and tin (Sn) and silicon (Si) is about 1: 9, the ITO content and the silica content are contained. It can be seen that the ratio is about 1: 9 in molar ratio.

  Moreover, the refractive index in wavelength 550nm of the infrared cut film obtained in Example 1 was measured using the spectroscopic ellipsometer (JA Woollam VASE). The refractive index at a wavelength of 550 nm on the surface of the glass plate was calculated from the transmittance and reflectance measured using a spectrophotometer (Hitachi Ltd. spectrophotometer U-4000). 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 optical model parameters so as to reproduce Psi (ψ) and Delta (Δ) obtained from a spectroscopic ellipsometer, and optical constants (refractive index, extinction coefficient). Was evaluated by ellipsometry (spectral ellipsometry). Table 2 shows the results of the refractive index of the glass plate surface at a wavelength of 550 nm, the refractive index of the infrared cut coating at a wavelength of 550 nm, the difference in refractive index of the infrared cut coating and the glass plate surface at a wavelength of 550 nm, and the degree of light interference. .

Example 2
Similarly to Example 1, a 4 mm thick glass substrate (green soda-lime silica glass having an ultraviolet absorbing function) which was cut and polished for automobile side glass and then bent and strengthened 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, the glass substrate is put in an oven preheated to 200 ° C. and heated for 10 minutes, and then cooled to form an infrared cut film. A formed glass substrate was obtained.

3 ml of the water repellent film forming solution used in Example 1 was applied to a cotton cloth, applied on the surface of the glass substrate on which the infrared cut film was formed, on which the infrared cut film was formed, and then the water repellent film forming solution adhered excessively. 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 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 becomes the outside of the vehicle when attached to the vehicle, and a water repellent coating is formed on the infrared cut coating. ing.

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. evaluated. The results are shown in Table 2.

Example 4
In Example 1, when the glass substrate was attached to the vehicle, the same solution as in Example 1 was applied except that the infrared cut film forming solution was applied to the main surface (bottom surface) that was the inside of the vehicle by the flow coating method. Thus, a glass plate for a vehicle having a coating film was obtained and evaluated in the same manner as in Example 1. The results are shown in Table 2.

ITO content in the infrared cut film of the vehicle glass plate provided with the film obtained in Examples 1, 2, and 4, the content of organic matter in the infrared cut film (hereinafter referred to as "organic content"), As a result of calculating the silica content from the mass of each material component added to the coating solution, the ITO content is 31% by mass, the organic content is 7% by mass, and the silica content Was 62% by mass.
Moreover, as a result of calculating | requiring the ITO content, organic content, and silica content in the infrared cut film of the glass plate for vehicles provided with the film obtained in Example 3 by the same method, ITO content is 42. The organic content was 7% by mass, and the silica content was 51% by mass.
In the calculation, the mass of the ITO fine particles is 40% by mass of the ITO dispersion liquid, the mass of the organic substance is the mass of the polymer dispersant and polyethylene glycol, and the mass of the silica component is the tetraethoxysilane. Based on the content of silica component of 28.8% by mass.

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

  As a water-repellent performance of a 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, Kyowa Interface Science Co., Ltd.). Product) and measured as a 2 mg water drop static contact angle. Furthermore, a critical inclination angle was measured as a scale indicating 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 inclined, 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 adhering to the glass window of a running car are more likely to scatter and the driver's vision is not obstructed.

Moreover, the transmittance | permeability of the light in wavelength 300-2500nm was measured as infrared cut performance of the sample for a test (glass plate for vehicles provided with a film) obtained by the method similar to Example 1 and 2. FIG. In the measurement, a spectrophotometer (manufactured by Shimadzu Corporation: model number UV-3100PC) was used. The obtained results are shown in FIGS. 4 (a) and 4 (b).
FIG. 4A shows the result of measuring the light transmittance at a wavelength of 300 to 2500 nm in Example 1, and FIG. 4B shows the result of measuring the light transmittance at a wavelength of 300 to 2500 nm in Example 2. is there.
The contact angle of the surface on which the water repellent film of the test sample (vehicle glass plate provided with a coating) obtained in Examples 1 and 2 was formed was 108 degrees, and the critical inclination angle was 13 degrees. It was confirmed that the glass plate was excellent in water repellency. Moreover, the infrared transmittance | permeability of the test sample (vehicle glass plate provided with a film) obtained in Example 1 and 2 is clear as FIG. 4 (a) and (b) shows. It was confirmed that it was kept low.

  Also in Examples 3 and 4, glass plates for vehicles having the same excellent water repellency performance as in Examples 1 and 2 and having a coating with low infrared transmittance were obtained.

  ADVANTAGE OF THE INVENTION According to this invention, the glass plate for vehicles provided with the film which has the function of both water repellency and infrared cut property can be provided, and it is useful especially as a window glass for vehicles.

Claims (10)

  A glass plate for a vehicle, comprising a film in which a water repellent film and an infrared cut film are formed on a main surface of a glass substrate.   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 formed on 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.   2. The infrared cut film is formed on a main surface of a glass substrate that becomes an outside of the vehicle when attached to a vehicle, and the water repellent film is formed on the infrared cut film. The glass plate for vehicles provided with the film of this.   2. The water repellent coating film is a film containing a fluoroalkyl group and / or an alkyl group, and the infrared cut film is a film containing silica as a main component and containing infrared cut fine particles. The glass plate for vehicles provided with the film of any one of thru | or 3.   The glass plate for vehicles having a coating according to claim 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.   The film according to claim 1, wherein the water repellent film has a thickness of 0.1 to 300 nm, and the infrared cut film has a thickness of 300 to 3000 nm. Glass plate for vehicles.   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 is formed on a surface containing substantially no tin. A glass plate for a vehicle, comprising the coating according to any one of claims 1 to 6.   The glass plate for vehicles provided with the film of Claim 7 whose refractive index difference in wavelength 550nm of the surface which does not contain tin of the said glass substrate substantially, and the said infrared cut film is less than 0.04.   A first cleaning step for cleaning the main surface of the glass substrate which is the inside of the vehicle when attached to the vehicle, and an infrared cut coating forming coating solution is applied to the main surface cleaned in the first cleaning step. A step of heating the glass substrate and firing the infrared cut film, a second cleaning step of cleaning the main surface of the glass substrate which is the exterior of the vehicle when attached to a vehicle, and the second The manufacturing method of a glass plate for vehicles provided with the film which has the process of apply | coating the coating liquid for water-repellent film formation to the main surface wash | cleaned at the washing | cleaning process, and forming a water-repellent film.   A cleaning process for cleaning the main surface of the glass substrate that is the outside of the vehicle when attached to the vehicle, and a process for forming an infrared cut film 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 liquid on the infrared cut coating forming surface to form 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 to do.

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