JPWO2020141601A1 - UV shielding glass - Google Patents

Abstract

Provided is an ultraviolet shielding glass having excellent ultraviolet shielding properties and appearance. It is an ultraviolet shielding glass that includes a glass plate and an ultraviolet shielding film provided on the main surface of the glass plate and can be opened and closed at the opening of the vehicle body. The ultraviolet shielding film is continuous without any sudden change in the film thickness. It is a film, and the UV shielding film is a peripheral region which is a region having a width of 1 mm inward from the outer peripheral edge of the UV shielding film and an intermediate region which is a region having a width of 59 mm inward from the inner peripheral edge of the peripheral region in a plan view. And a central region surrounded by an intermediate region, the maximum film thickness of the ultraviolet shielding film in the central region is 1 μm to 10 μm, and when the ultraviolet shielding glass is attached to the opening of the vehicle body, the ultraviolet shielding film is formed. In the peripheral region where 70% or more of the surface of the vehicle body opening is present and at least a part of the peripheral region is present in the vehicle body opening and is present in the vehicle body opening, the maximum film thickness of the ultraviolet shielding film is 0. Ultraviolet shielding glass with a size of 4 μm to 1.0 μm.

Description

The present invention relates to ultraviolet shielding glass.

An ultraviolet shielding glass having an ultraviolet shielding film on the surface of a glass plate is known.
When the glass with a coating film is used as a window glass that can be opened and closed, the coating film is provided with a predetermined width from the end of the window glass, and the thickness of the coating film is 1 μm or more. Document 1) has been proposed. Further, there has been proposed a glass with a coating film (Patent Document 2) in which the angle formed by the glass plate and the coating film is within a predetermined range.

Japanese Unexamined Patent Publication No. 2013-129576 JP-A-2018-104218

When the ultraviolet shielding film having a film thickness of 1 μm or more is provided with a predetermined width from the end portion of the window glass as in Patent Document 1, the outer peripheral edge of the ultraviolet shielding film is easily noticeable. In order to improve that the outer peripheral edge of the ultraviolet shielding film is easily noticeable visually, as in Patent Document 2, a film thickness gradually changing portion is provided at the end of the ultraviolet shielding film, and the angle formed by the glass plate and the coating film is determined. The present inventors have found that when the range is set to the above range, visual distortion is likely to occur in the vicinity of the outer periphery of the ultraviolet shielding film. Therefore, an object of the present invention is to provide an ultraviolet shielding glass having excellent ultraviolet shielding properties and appearance.

The present inventors have found that the strain generated in the vicinity of the outer periphery of the ultraviolet shielding film is caused by the cross-sectional structure of the end portion of the ultraviolet shielding film, and completed the present invention.

That is, it was found that the above problem can be solved by the following configuration.
An ultraviolet shielding glass provided with a glass plate and an ultraviolet shielding film provided on the main surface of the glass plate, which can be opened and closed at the opening of the vehicle body.
The ultraviolet shielding film is a continuous film having no sudden change in the film thickness.
The ultraviolet shielding film includes a peripheral region having a width of 1 mm inward from the outer peripheral edge of the ultraviolet shielding film and an intermediate region having a width of 59 mm inward from the inner peripheral edge of the peripheral area in a plan view. , With a central region surrounded by the intermediate region
The maximum film thickness of the ultraviolet shielding film in the central region is 1 μm to 10 μm.
When the ultraviolet shielding glass is attached to the vehicle body opening, the ultraviolet shielding film is present on 70% or more of the surface of the vehicle body opening, and at least a part of the peripheral region is present in the vehicle body opening. death,
An ultraviolet shielding glass having a maximum film thickness of 0.4 μm to 1.0 μm in the peripheral region existing in the vehicle body opening.

According to the present invention, it is possible to provide an ultraviolet shielding glass having excellent ultraviolet shielding properties and appearance.

It is a top view which shows an example of the ultraviolet ray shielding glass 10 of this invention. It is a top view which shows an example of the ultraviolet shielding film 12 of this invention. It is a top view of the cut portion of the AA'line of FIG.

Hereinafter, the present invention will be described in detail.
The description of the constituent elements described below in the present specification may be based on a representative embodiment of the present invention, but the present invention is not limited to such an embodiment. Further, the dimensional ratios in FIGS. 1 to 3 are different from the actual ones for convenience of explanation.
Hereinafter, the present invention will be described in detail.

(UV shielding glass)
The ultraviolet shielding glass of the present invention is an ultraviolet shielding glass provided with a glass plate and an ultraviolet shielding film provided on the main surface thereof, and which can be opened and closed at an opening of a vehicle body.
The ultraviolet shielding film of the ultraviolet shielding glass of the present invention is a continuous film having no sudden change in the film thickness, and is one of the two main surfaces of the glass plate (when attached to the opening of the vehicle body). It is provided on almost the entire surface of the inner surface).
In the present invention, the ultraviolet shielding film includes a peripheral region having a width of 1 mm inward from the outer peripheral edge of the ultraviolet shielding film and an intermediate region having a width of 59 mm inward from the inner peripheral edge of the peripheral region in a plan view. It shall have a central region surrounded by an intermediate region. In the ultraviolet shielding glass of the present invention, the maximum film thickness of the ultraviolet shielding film in the central region is 1 μm to 10 μm.

Further, when the ultraviolet shielding glass of the present invention is attached to the vehicle body opening, the peripheral edge of the ultraviolet shielding glass exists in the glass storage portion around the vehicle body opening. Therefore, when the ultraviolet shielding film extends to the peripheral edge of the glass plate, the peripheral edge of the ultraviolet shielding film in that portion exists in the glass storage portion. When the UV shielding film is separated from the peripheral edge of the glass plate by a distance exceeding the depth of the glass storage portion, the UV shielding film is formed between the UV shielding film peripheral edge of the UV shielding glass attached to the vehicle body opening and the periphery of the vehicle body opening. There will be parts that do not exist. In the ultraviolet shielding glass of the present invention, when it is attached to the vehicle body opening, the ultraviolet shielding film is present on 70% or more of the surface of the vehicle body opening. The ratio of the ultraviolet shielding film present in the car body opening to the car body opening surface is preferably 80% or more, more preferably 90% or more, and may be 100%. Due to this large area, the function as an ultraviolet shielding glass is fully exhibited.

In addition, in the ultraviolet shielding glass of the present invention, when the ultraviolet shielding glass is attached to the vehicle body opening, at least a part of the peripheral region of the ultraviolet shielding film is present in the vehicle body opening. That is, when the ultraviolet shielding glass is attached to the opening of the vehicle body, the ultraviolet shielding film is separated from the glass storage portion around the opening of the vehicle body at least a part of the peripheral edge of the ultraviolet shielding glass, or the width of the peripheral region is 1 mm. As a result, it exists in the glass storage portion with a width of less than 1 mm. In the present invention, the maximum film thickness of the peripheral region away from the glass storage portion and the peripheral region existing in the glass storage portion with a width of less than 1 mm is 0.4 μm to 1.0 μm.
The peripheral area existing in the vehicle body opening or the peripheral area existing in the glass storage portion having a width of less than 1 mm is the glass storage portion when the ultraviolet shielding glass attached to the opening of the vehicle body is opened. It is preferable that the peripheral region is along the peripheral edge of the ultraviolet shielding glass away from. For example, when a substantially quadrilateral UV-shielding glass is attached to the opening of the vehicle body so as to be openable and closable in the vertical direction and opened, the upper side of the UV-shielding glass usually moves downward away from the glass storage and both sides. And the lower side is in the glass storage part and moves downward. In such an ultraviolet shielding glass, it is preferable that at least a part of the peripheral region of the ultraviolet shielding film along the upper side is present in the vehicle body opening. In addition, peripheral regions along at least a portion of both sides and the lower side may also be present in the vehicle body meatus as well as the upper side.

The general shape of the flat glass in the ultraviolet shielding glass of the present invention is preferably quadrilateral, but is not limited to this, and may be a shape such as a quadrilateral or a pentagon. Further, all the sides may be linear, but a part of the sides may be curved or uneven. Hereinafter, ultraviolet rays that are opened and closed in the vertical direction using a flat glass having a roughly quadrilateral shape, a curved shape whose upper side is convex upward, and a convex portion on the lower side for attachment to a car body opening, etc. The present invention will be described by taking a shielding glass as an example.

FIG. 1 is a plan view showing an example of the ultraviolet shielding glass 10 of the present invention. The ultraviolet shielding glass 10 attached to the opening of the vehicle body so as to be openable and closable in the vertical direction has a glass plate 11 and an ultraviolet shielding film 12 provided on the main surface of the glass plate 11. The glass plate 11 has an outer circumference composed of four sides, an upper side 31, a lower side 32, a front side side 33, and a rear side side 34.

FIG. 2 is a plan view schematically showing an example of the ultraviolet shielding film 12 in the ultraviolet shielding glass of the present invention. The ultraviolet shielding film 12 is a continuous film having no sudden change in film thickness, and has a peripheral region 21, an intermediate region 22, and a central region 23. The peripheral edge region 21 is a region having a width of 1 mm inward from the outer peripheral edge of the ultraviolet shielding film 12 in a plan view. In the present invention, the inside of the glass plate means the direction of the center of gravity in the plane of the glass plate. The intermediate region 22 is a region having a width of 59 mm inward from the inner peripheral edge of the peripheral edge region 21. The central region 23 is an region surrounded by the intermediate region 22. The maximum film thickness of the ultraviolet shielding film 12 in the central region 23 is 1 μm to 10 μm.

The ultraviolet shielding film 12 in the ultraviolet shielding glass 10 shown in FIG. 1 is provided along the upper side 31 of the glass plate 11 with a certain width from the upper side 31 and below it, and has a constant width along the upper side 31. There is a membrane-absent part. The width of the film-absent portion is preferably 5 mm to 25 mm. Since the width of the peripheral region 21 of the ultraviolet shielding film 12 is 1 mm, when the ultraviolet shielding glass 10 is attached to the opening of the vehicle body, when the width of the film absent portion exceeds the depth of the glass storage portion minus 1 mm, the upper side At least a part of the peripheral region 21 along the 31 in the width direction exists in the vehicle body opening. When the width of the film absent portion exceeds the depth -1 mm of the glass storage portion and is less than the depth of the glass storage portion, a part of the peripheral region 21 along the upper side 31 in the width direction exists in the glass storage portion. However, since the width is narrow, the smooth movement of the ultraviolet shielding glass 10 can be maintained.

FIG. 3 is a part of the end view of the A-A'line cut portion of FIG. 1 that crosses the upper side 31. The ultraviolet shielding film 12 provided directly on the main surface of the glass plate 11 has a peripheral region 21, an intermediate region 22, and a central region 23. At least a part of the peripheral region 21 shown in the figure along the upper side 31 in the width direction exists in the car body opening when the ultraviolet shielding glass 10 is attached to the car body opening.

In the ultraviolet shielding glass 10 shown in FIGS. In the existing peripheral region 21, the maximum film thickness (L) of the ultraviolet shielding film 12 is 0.4 μm to 1.0 μm.

As shown in FIG. 1, the ultraviolet shielding film 12 is provided close to each other along the front side side 33 and the rear side side 34, and there is substantially no film-absent portion along those sides. Therefore, when attached to the vehicle body opening, the peripheral region 21 along the front side side 33 and the rear side side 34 is usually always present in the glass storage portion around the vehicle body opening regardless of the opening and closing of the ultraviolet shielding glass 10. .. Further, also in the lower side 32, the ultraviolet shielding film 12 is provided close to the lower side 32 except for the portion protruding downward, and there is substantially no film absent portion along the lower side 32. Therefore, as in the case of the side side, the peripheral region 21 along the lower side 32 is usually always present in the glass storage portion around the opening of the vehicle body regardless of the opening and closing of the ultraviolet shielding glass 10.
However, the ultraviolet shielding glass of the present invention is not limited to the one shown in the figure. For example, a film absent portion similar to the membrane absent portion along the upper side 31 may be provided along at least one side selected from the front side side 33, the rear side side 34, and the lower side 32. When the film absent portion is provided, it is preferable that at least a part of the peripheral region along the side where the film absent portion is provided is present in the vehicle body opening when the ultraviolet shielding glass is attached to the vehicle body opening.
Further, when the ultraviolet shielding glass attached to the vehicle body opening is opened, when at least a part of the front side 33 or the rear side 34 is separated from the glass storage portion together with the upper side 31 (for example, the ultraviolet shielding glass is slanted). (If it has a structure that can be moved downward), in addition to the upper side, a film absent part along the side side away from the glass storage part is provided, and at least the peripheral area along the side side is provided in addition to the peripheral area along the upper side. It is also preferable that a part thereof is also present in the opening of the vehicle body.

(Glass plate)
Examples of the glass plate 11 include soda lime glass, aluminosilicate glass, and non-alkali glass, and soda lime glass is preferable.
The thickness of the glass plate 11 is preferably 0.5 mm to 5.0 mm, more preferably 1.5 mm to 4.5 mm, and particularly preferably 2.0 to 4.0 mm.
Further, even if the glass plate has an intermediate layer on a part of the main surface on which the ultraviolet shielding film is formed so that an intermediate layer such as a black ceramic layer exists between the glass plate and the ultraviolet shielding film. good.

(UV shielding film)
As shown in FIG. 2, the ultraviolet shielding film 12 has a peripheral region 21 which is a region having a width of 1 mm inward from the outer peripheral edge of the ultraviolet shielding film 12 and 59 mm inward from the inner peripheral edge of the peripheral region 21 in a plan view. It has an intermediate region 22 which is a width region and a central region 23 surrounded by the intermediate region 22.
The ultraviolet shielding film is a continuous film having no sudden change in the film thickness, and the film thicknesses of two adjacent regions at the boundary between the peripheral region 21 and the intermediate region 22 and the boundary between the intermediate region 22 and the central region 23 are the same. be. However, the film thickness at these boundaries may change in the length direction of the boundaries.
Further, as described later, the cross-sectional shape of the ultraviolet shielding film 12 in the peripheral region 21 preferably has an upwardly convex curve, and the cross-sectional shape of the ultraviolet shielding film 12 in the intermediate region 22 also has an upwardly convex curve. Is preferable. The film thickness of the central region 23 is preferably constant, but there may be some change in the film thickness.

The maximum film thickness of the ultraviolet shielding film 12 in the central region 23 is 1 μm to 10 μm. When the maximum film thickness of the ultraviolet shielding film 12 in the central region 23 is within the range, the ultraviolet shielding glass 10 can secure excellent ultraviolet shielding property and abrasion resistance. The maximum film thickness of the ultraviolet shielding film 12 in the central region 23 is preferably 1.5 μm to 6 μm, more preferably 2 μm to 5 μm, and particularly preferably 2 μm to 4 μm. The minimum film thickness of the ultraviolet shielding film 12 in the central region 23 is preferably 0.8 μm, more preferably 1 μm.

At least a part of the peripheral region 21 of the ultraviolet shielding film 12 (the peripheral region portion along the upper side 31 in FIG. 1 or a part thereof) is formed in the vehicle body opening when the ultraviolet shielding glass 10 is attached to the vehicle body opening. exist. The maximum film thickness of the ultraviolet shielding film 12 in the peripheral region 21 existing in the vehicle body opening is 0.4 μm to 1.0 μm. When the maximum film thickness of the ultraviolet shielding film 12 is 0.4 μm to 1.0 μm in the peripheral region 21 existing in the vehicle body opening, it is possible to suppress the occurrence of distortion in the vicinity of the outer periphery of the ultraviolet shielding glass 10. Although the details are not clear, when the maximum film thickness of the ultraviolet shielding film 12 in the peripheral region 21 is 0.4 μm or more, leveling during formation of the ultraviolet shielding film in the intermediate region 22 is likely to occur, and the smoothness of the intermediate region 22 is enhanced. The present inventors believe that the occurrence of distortion is suppressed. When the maximum film thickness of the ultraviolet shielding film 12 in the peripheral region 21 is 1.0 μm or less, the outer periphery of the ultraviolet shielding film 12 becomes less noticeable visually. In the peripheral region 21 existing in the vehicle body opening, the maximum film thickness of the ultraviolet shielding film 12 is preferably 0.4 μm to 0.9 μm, more preferably 0.4 μm to 0.8 μm, and 0. It is particularly preferably 4 μm to 0.7 μm.

The peripheral edge region 21 existing in the vehicle body opening when attached to the vehicle body opening is along at least a part of one or more sides selected from the upper side 31, the front side side 33, and the rear side side 34 of the glass plate 11. It is preferably the peripheral region 21 that is present. When the peripheral region 21 existing in the vehicle body opening of the ultraviolet shielding film 12 exists along at least a part of one or more sides selected from the upper side 31, the front side side 33, and the rear side side 34 of the glass plate 11, ultraviolet rays are emitted. The appearance of the shielding glass 10 can always be excellent.

The cross-sectional shape of the ultraviolet shielding film 12 in the peripheral region 21 preferably has a convex curve upward when the substrate 11 is on the lower side and the ultraviolet shielding film 12 is on the upper side. When the cross-sectional shape of the ultraviolet shielding film 12 in the peripheral region 21 has an upwardly convex curve, the maximum film thickness in the peripheral region 21 becomes 0.4 μm or more, and distortion occurs in the vicinity of the outer periphery of the ultraviolet shielding film 12. It can be suppressed. In the convex curve, the inclination of the straight line connecting the outer peripheral edge of the ultraviolet shielding film and the upper surface of the film at a position 0.1 mm inward from the outer peripheral edge is preferably 6 μm / mm or less. When this inclination is 6 μm / mm or less, the outer periphery of the ultraviolet shielding film 12 becomes inconspicuous. This inclination is more preferably 4 μm / mm or less, and particularly preferably 3 μm / mm or less.

The film thickness on the intermediate region side at the boundary between the peripheral region 21 and the intermediate region 22 is the same as the film thickness on the peripheral region side. Since the film thickness on the peripheral region side at this boundary is usually within the range of the maximum film thickness of the peripheral region, the film thickness on the intermediate region side at this boundary is also within the range of the maximum film thickness of the peripheral region. Is preferable.
The average film thickness of the ultraviolet shielding film 12 in the intermediate region 22 is preferably 1 μm to 3 μm. In the present invention, the average film thickness is the average value of the film thickness at five randomly selected places. When the average film thickness of the ultraviolet shielding film 12 in the intermediate region 22 is 1 μm to 3 μm, leveling at the time of forming the ultraviolet shielding film in the intermediate region 22 is likely to occur, and distortion occurs in the vicinity of the outer periphery of the ultraviolet shielding film 12. Can be suppressed. The average film thickness of the ultraviolet shielding film 12 in the intermediate region 22 is more preferably 1 μm to 2 μm.

The cross-sectional shape of the ultraviolet shielding film 12 in the intermediate region 22 preferably has a convex curve upward when the substrate 11 is on the lower side and the ultraviolet shielding film 12 is on the upper side. When the cross-sectional shape of the ultraviolet shielding film 12 in the intermediate region 22 has an upwardly convex curve, leveling at the time of forming the ultraviolet shielding film in the intermediate region 22 is likely to occur, the smoothness of the intermediate region 22 is enhanced, and the ultraviolet shielding film is enhanced. It is possible to suppress the occurrence of distortion in the vicinity of the outer periphery of the twelve. The slope of the tangent line tangent to the convex curve is preferably 2 μm / mm or less. When the inclination of the tangent line in contact with the convex curve is 2 μm / mm or less, leveling at the time of forming the ultraviolet shielding film in the intermediate region 22 is likely to occur, and it is possible to suppress the occurrence of distortion in the vicinity of the outer periphery of the ultraviolet shielding film 12. The slope of the tangent line tangent to the convex curve is more preferably 1 μm / mm or less, and particularly preferably 0.5 μm / mm or less.

The maximum film thickness of the ultraviolet shielding film in the central region 22 is 1 μm to 10 μm.
Further, the film thickness on the central region side at the boundary between the intermediate region 22 and the central region 23 is the same as the film thickness on the intermediate region side. The film thickness of the ultraviolet shielding film 12 on the outer peripheral edge of the central region 23, which is the boundary line, is preferably 1 μm to 3 μm. The film thickness of the central region 22 may exceed 3 μm except in the vicinity of this boundary line.
When the maximum film thickness of the ultraviolet shielding film 12 in the central region 23 is 1 μm to 10 μm, the ultraviolet shielding glass 10 ensures excellent ultraviolet shielding property because the central region 23 is the main region of the ultraviolet shielding film 12. can.

The ultraviolet shielding film 12 is preferably provided directly on the main surface of the glass plate 11. By providing the ultraviolet shielding film 12 directly on the main surface of the glass plate 11, excellent adhesion to the glass can be ensured.

The ultraviolet shielding film 12 preferably has an ultraviolet light transmittance of 0% to 15%, more preferably 0% to 10%, and further preferably 0% to 5% in the central region 22. It is preferably 0 to 1%, and particularly preferably 0 to 1%. In the present invention, the ultraviolet light transmittance refers to a value measured in accordance with ISO13837: 2008A.

(Composition for Forming UV Shielding Film 12)
The UV shielding film 12 of the peripheral region 21 existing in the vehicle body opening is appropriately designed with the surface tension of the liquid composition forming the UV shielding film 12, the contact angle of the composition with respect to the glass plate 11, and the viscosity of the composition. Obtained at. The liquid composition adjusted for the surface tension, the contact angle, and the viscosity is also used for forming the ultraviolet shielding film 12 other than the peripheral region 21 existing in the vehicle body opening. That is, usually, the entire ultraviolet shielding film 12 is formed by using this liquid composition.

The surface tension of the composition forming the ultraviolet shielding film 12 is preferably 22 mN / m to 30 mN / m. In the present invention, the surface tension of the composition refers to a value when the composition having a solid content concentration of 30% by mass is measured at 20 ° C. When the surface tension of the composition is 22 mN / m or more, the maximum film thickness in the peripheral region 21 of the ultraviolet shielding film 12 can be 0.4 μm or more. When the surface tension of the composition is 30 mN / m or less, the maximum film thickness in the peripheral region 21 of the ultraviolet shielding film 12 can be 1.0 μm or less. The surface tension of the composition can be designed by the material constituting the ultraviolet shielding film 12, the surface conditioner, the solvent, the concentration and the like. The surface tension of the composition is more preferably 23 mN / m to 28 mN / m, and particularly preferably 24 mN / m to 27 mN / m.

The contact angle of the composition forming the ultraviolet shielding film 12 with respect to the glass plate 11 is preferably 18 ° to 35 °. In the present invention, the contact angle of the composition refers to a value when the composition having a solid content concentration of 30% by mass is measured at 20 ° C. When the contact angle of the composition with respect to the glass plate 11 is 18 ° or more, the maximum film thickness in the peripheral region 21 of the ultraviolet shielding film 12 can be 0.4 μm or more. When the contact angle of the composition with respect to the glass plate 11 is 35 ° or less, the maximum film thickness in the peripheral region 21 of the ultraviolet shielding film 12 can be 1.0 μm or less. The contact angle of the composition with respect to the glass plate 11 can be designed by cleaning the glass, the material contained in the composition, the surface conditioner, the solvent, the concentration, and the like. The contact angle of the composition with respect to the glass plate 11 is more preferably 20 ° to 30 °, and particularly preferably 21 ° to 27 °.

The viscosity of the composition forming the ultraviolet shielding film 12 is preferably 0.5 mPa · s to 5 mPa · s. In the present invention, the viscosity of the composition is a value when the composition having a solid content concentration of 30% by mass is measured at 25 ° C. using an E-type viscometer (RE-85, manufactured by Toki Sangyo Co., Ltd.). Point to. When the viscosity of the composition is 0.5 mPa · s or more, the yield value of the composition can be controlled within an appropriate range, and the maximum film thickness in the peripheral region 21 of the ultraviolet shielding film 12 can be 0.4 μm or more. .. When the viscosity of the composition is 5 mPa · s or less, the yield value of the composition can be controlled within an appropriate range, and the maximum film thickness in the peripheral region 21 of the ultraviolet shielding film 12 can be made 1.0 μm or less. The viscosity of the composition can be designed by the material constituting the ultraviolet shielding film 12, the surface conditioner, the solvent, the concentration and the like. The viscosity of the composition is more preferably 1 mPa · s to 3 mPa · s, and particularly preferably 1.4 mPa · s to 2.5 mPa · s.

The composition forming the ultraviolet shielding film 12 preferably contains an ultraviolet absorber and a curable silane. The curable silane is a silicon compound having at least one hydroxyl group or hydrolyzable group bonded to a silicon atom and having one or more such silicon atoms. The hydrolyzable group is a group that can be hydrolyzed to become a hydroxyl group, and examples thereof include an alkoxy group, a chlorine atom, an acyl group, and an acyloxy group. The curable silane is preferably an alkoxysilane having at least two alkoxy groups bonded to a silicon atom, and the alkoxy group is preferably an alkoxy group having 1 to 4 carbon atoms.

UV absorbers include triazine-based UV absorbers, benzotriazole-based UV absorbers, benzophenone-based UV absorbers, azomethine-based UV absorbers, indol-based UV absorbers, benzodithiol-based UV absorbers, and oxazolone-based UV absorbers. Can be mentioned. In particular, the ultraviolet absorber is preferably one or more selected from azomethine-based ultraviolet absorbers, indole-based ultraviolet absorbers, and benzodithiol-based ultraviolet absorbers. When the ultraviolet absorber is one or more selected from azomethine-based ultraviolet absorbers, indole-based ultraviolet absorbers, and benzodithiol-based ultraviolet absorbers, ultraviolet rays of 380 nm to 400 nm can be efficiently shielded, and ISO13837: The ultraviolet transmittance of the ultraviolet shielding film 12 measured according to 2008A can be 0% to 5% at a film thickness of 1.5 μm.

As the curable silane, tetraalkoxysilane and bisalkoxysilane are preferable. Examples of the tetraalkoxysilane include tetraethoxysilane and tetramethoxysilane. The bisalkoxysilane is preferably a compound represented by the following formula (1).
R ¹ _n X ¹ _3-n Si-Q-SiR ² _m X ² _3-m (1)
R ¹ and R ² are independently monovalent hydrocarbon groups having 1 to 3 carbon atoms, X ¹ and X ² are independently alkoxy groups, and Q is a carbon atom. It is a linear or branched divalent hydrocarbon group of the number 3 to 8, and n and m are independently 0, 1 or 2, respectively.

The composition forming the ultraviolet shielding film 12 contains an ultraviolet absorber and silane, and the ultraviolet absorber is one or more selected from an azomethine-based ultraviolet absorber, an indole-based ultraviolet absorber, and a benzodithiol-based ultraviolet absorber. When the silane is a tetraalkoxysilane or a bisalkoxysilane represented by the formula (1), it becomes easy to set the surface tension of the composition forming the ultraviolet shielding film 12 to 22 mN / m to 30 mN / m. , It is possible to suppress the occurrence of distortion in the vicinity of the outer periphery of the ultraviolet shielding film 12.

The composition forming the ultraviolet shielding film 12 preferably contains both tetraalkoxysilane and bisalkoxysilane represented by the formula (1) as the curable silane. In this case, the ratio of the bisalkoxysilane represented by the formula (1) to the tetraalkoxysilane is preferably 0.05 to 0.2 by mass ratio. When the ratio of the bisalkoxysilane represented by the formula (1) to the tetraalkoxysilane is 0.05 or more, the elution of the ultraviolet shielding film 12 when immersed in an alkaline solution can be suppressed. When the ratio of the bisalkoxysilane represented by the formula (1) to the tetraalkoxysilane is 0.2 or less, the hardness of the ultraviolet shielding film 12 increases, and the ultraviolet shielding glass 10 has excellent wear resistance and scratch resistance. .. The ratio of the bisalkoxysilane represented by the formula (1) to the tetraalkoxysilane is more preferably 0.05 to 0.15, and particularly preferably 0.06 to 0.13.

When tetraalkoxysilane and bisalkoxysilane represented by the formula (1) are used in combination as the curable silane, the ratio of the bisalkoxysilane represented by the formula (1) to the ultraviolet absorber is 0.5 by mass ratio. It is preferably ~ 2. When the ratio of the bisalkoxysilane represented by the formula (1) to the ultraviolet absorber is 0.5 or more, the ultraviolet shielding film 12 in which the ultraviolet absorber is uniformly dispersed can be obtained. When the ratio of the bisalkoxysilane represented by the formula (1) to the ultraviolet absorber is 2 or less, the hardness of the ultraviolet shielding film 12 increases, and the ultraviolet shielding glass 10 has excellent weather resistance and scratch resistance. The ratio of the bisalkoxysilane represented by the formula (1) to the ultraviolet absorber is more preferably 0.6 to 1.7, and particularly preferably 0.7 to 1.5.

The composition forming the ultraviolet shielding film 12 preferably further contains an infrared absorber, a resin, a surface conditioner, a chelating agent, an acid and a solvent.

(Manufacturing method of ultraviolet shielding glass 10)
The ultraviolet shielding film 12 is preferably formed on the surface of the glass plate 11 by applying the obtained composition, drying it, and curing it. Examples of the method for applying the composition include a flow coating method, a dip coating method, a spin coating method, a spray coating method, a flexographic printing method, a screen printing method, a gravure printing method, a roll coating method, a meniscus coating method and a die coating method.

Examples of the method for drying the composition include heat treatment and vacuum drying treatment. When the method for drying the composition is heat treatment, it is preferable to dry the composition at 20 ° C. to 100 ° C. for 3 seconds to 60 seconds. Under these drying conditions, it becomes easy to obtain an ultraviolet shielding film 12 having a maximum film thickness of 0.4 μm to 1.0 μm in at least a part of the peripheral region 21 of the ultraviolet shielding film 12.

Examples of the curing method of the composition include heat treatment and vacuum drying treatment. When the curing method of the composition is heat treatment, it is preferable to cure the composition at 60 ° C. to 230 ° C. in 2 to 20 minutes.

The components and manufacturing method of the ultraviolet shielding glass 10 according to the embodiment of the present invention have been described above. These are merely examples, and it will be apparent to those skilled in the art that the UV shielding glass 10 of the present invention may have other embodiments.

Hereinafter, the present invention will be described in detail by way of examples, but the present invention is not limited thereto. Examples 1 to 5 are examples, and examples 6 to 8 are comparative examples.

(Example 1)
In a round bottom flask, 2.09 g of a benzophenone-based ultraviolet absorber (BASF, Uvinul3050), 5.24 g of epoxysilane (KBM-403, manufactured by Shin-Etsu Chemical), 4.25 g of butyl acetate, and benzyltriethylammonium chloride. 0.03 g was added, and the mixture was heated to 105 ° C. and stirred for 4 hours to obtain a formulation A.
In the obtained preparation solution A, 39.44 g of methyl ethyl ketone, 8.87 g of methanol, 13.80 g of pure water, 10.80 g of tetraethoxysilane, and 0.86 g of bisalkoxysilane (KBM3066 manufactured by Shin-Etsu Chemical Co., Ltd.) were added. , 9.52 g of acetic acid aqueous solution (90% by mass), 0.95 g of epoxy resin (Sakamoto Yakuhin Kogyo Co., Ltd., SR-SEP), 0.17 g of polymaleic acid aqueous solution (Nippon Oil Co., Ltd., non-pole PMA-50W), 0.01 g of maleic acid and 0.06 g of a surface conditioner (BYK377 manufactured by Big Chemie) were added, and the mixture was stirred at 50 ° C. for 2 hours. Finally, 3.87 g of an ITO dispersion (manufactured by Mitsubishi Materials Corporation, 30% by mass ITO dispersion) was added to obtain a composition 1 having a solid content concentration of 12.5%.
The composition 1 is applied to the concave surface of the glass plate by pouring the coating liquid along the upper side of the glass plate with a gap of several mm to several tens of mm from the upper end of the glass plate in a state where the glass plate is erected vertically. , The mixture was heated at 200 ° C. for 20 minutes in an air atmosphere to obtain an ultraviolet shielding glass 1 having an ultraviolet shielding film. As the glass plate, a glass plate having a size of 670 mm (length) × 910 mm (horizontal) × 3.1 mm (thickness) (high heat absorption green glass manufactured by AGC Inc.) was used.

(Examples 2 to 8)
Instead of the compounding liquid A described in Example 1, the compounding solutions B to D were prepared. Table 1 shows the composition of the preparations B to D together with the preparation A (the unit of the numerical value is g). The ultraviolet absorbers used in the preparations B to D are as follows.
Benzodithiol-based UV absorber: 1,2-dibutyl-4- (4,7-dihydroxy-1,3-benzodithiol-2-iriden) Pyrazolidine-3,5-dione Azomethine-based UV absorber: Orient Chemical Industry Co., Ltd. Made by BONASORB UA-3701
Indole-based UV absorber: BONASORB UA-3911 manufactured by Orient Chemical Industry Co., Ltd.

Compositions 2 to 8 were produced in the same manner as in Composition 1 of Example 1 using the preparations A to D. Table 2 shows the compositions of compositions 2 to 8 together with composition 1 (the unit of numerical value is g). The surface conditioners used in the compositions 2 to 8 are as follows.
BYK307: BYK-307 manufactured by Big Chemie Japan
DN900: Disparon DN-900 manufactured by Kusumoto Kasei Co., Ltd.
BYK302: BYK-302 manufactured by Big Chemie Japan
BYK348: BYK-348 manufactured by Big Chemie Japan
BYK3811: BYK-381 manufactured by Big Chemie Japan

The surface tensions, contact angles and viscosities of the obtained compositions 1 to 8 with respect to the glass plate were as shown in Table 3. The surface tension, the contact angle with respect to the glass plate, and the viscosity were measured using a composition having a solid content concentration of 30% by mass.

UV shielding glasses 2 to 8 were obtained in the same manner as in Example 1 except that the compositions 2 to 8 shown in Table 2 were used and the leaning angle of the glass plate was changed. Table 4 shows the evaluation results of the obtained ultraviolet shielding glasses 1 to 8.
The leaning angle of the glass plate is 0 ° when the coating surface is facing upward and placed horizontally.
The state in which the glass was erected vertically was expressed as 90 °, and the state in which the coated surface was placed horizontally with the coated surface facing down was expressed as 180 °. The inclination in the peripheral region means the inclination of a straight line connecting the outer peripheral edge of the ultraviolet shielding film and the upper surface of the film at a position 0.1 mm inward from the outer peripheral edge.

(Film thickness in each area)
The film thickness (μm) of the ultraviolet shielding film in each region on the upper end side of the ultraviolet shielding glass was measured using a stylus type surface shape measuring device (Dektake 150 manufactured by ULVAC, Inc.).
(Evaluation of visibility on the outer circumference)
Those whose outer circumference was clearly confirmed by visual observation were marked with x, and those other than that were marked with ○.

(Distortion evaluation near the outer circumference)
When the surface of the obtained UV-shielding glass was irradiated with the light of a projector (EB-1776W, manufactured by EPSON) from a position 7 m away, the one in which distortion was visible near the outer periphery of the UV-shielding film was marked with x. Other than that, it was marked as ○. However, if the strain evaluation near the outer periphery cannot be visually determined, the peripheral region and the intermediate region are measured using a stylus type surface shape measuring instrument (Dectak150, manufactured by ULVAC), and the maximum cross-sectional height is increased. When there was unevenness of 100 nm or more, it was evaluated as x, and when it was not, it was evaluated as ◯.

Since the ultraviolet shielding glass of the present invention is an ultraviolet shielding glass having excellent ultraviolet shielding properties and appearance, it is applied to vehicles such as automobiles and railways, and is particularly preferably applied to automobiles.
The entire contents of the specification, claims, abstract and drawings of Japanese Patent Application No. 2019-000196 filed on January 04, 2019 are cited here as disclosure of the specification of the present invention. It is something to incorporate.

10: UV shielding glass 11: Glass plate 12: UV shielding film 21: Peripheral region 22: Intermediate region 23: Central region 31: Upper side 32: Lower side 33: Front side side 34: Rear side side

Claims (11)

An ultraviolet shielding glass provided with a glass plate and an ultraviolet shielding film provided on the main surface of the glass plate, which can be opened and closed at the opening of the vehicle body.
The ultraviolet shielding film is a continuous film having no sudden change in the film thickness.
The ultraviolet shielding film includes a peripheral region having a width of 1 mm inward from the outer peripheral edge of the ultraviolet shielding film and an intermediate region having a width of 59 mm inward from the inner peripheral edge of the peripheral area in a plan view. , With a central region surrounded by the intermediate region
The maximum film thickness of the ultraviolet shielding film in the central region is 1 μm to 10 μm.
When the ultraviolet shielding glass is attached to the vehicle body opening, the ultraviolet shielding film is present on 70% or more of the surface of the vehicle body opening, and at least a part of the peripheral region is present in the vehicle body opening. death,
An ultraviolet shielding glass having a maximum film thickness of 0.4 μm to 1.0 μm in the peripheral region existing in the vehicle body opening. The peripheral region existing in the vehicle body opening when the ultraviolet shielding glass is attached to the vehicle body opening is the vehicle body opening when the ultraviolet shielding glass attached to the vehicle body opening on the outer peripheral edge of the ultraviolet shielding glass is opened. The ultraviolet shielding glass according to claim 1, which is a peripheral region portion along a portion away from a surrounding glass storage portion. The ultraviolet shielding glass is a substantially quadrilateral ultraviolet shielding glass attached to the opening of the vehicle body so as to move in the vertical direction to open and close, and the peripheral edge region portion is a peripheral edge along the upper side of the ultraviolet shielding glass. The ultraviolet shielding glass according to claim 2, which is a region portion. The ultraviolet shielding glass according to claim 3, further comprising a film absent region having a width of 5 mm to 25 mm between the outer peripheral edge of the peripheral edge region portion along the upper side of the ultraviolet shielding glass and the outer peripheral edge of the glass plate. The ultraviolet shielding glass according to any one of claims 1 to 4, wherein the cross-sectional shape of the ultraviolet shielding film in the peripheral region has an upwardly convex curve. The ultraviolet shielding glass according to claim 5, wherein in the convex curve, the inclination of the straight line connecting the outer peripheral edge of the ultraviolet shielding film and the upper surface of the film at a position 0.1 mm inward from the outer peripheral edge is 6 μm / mm or less. .. The ultraviolet shielding glass according to any one of claims 1 to 6, wherein the average film thickness of the ultraviolet shielding film in the intermediate region is 1 μm to 3 μm. The ultraviolet shielding glass according to any one of claims 1 to 7, wherein the cross-sectional shape of the ultraviolet shielding film in the intermediate region has an upwardly convex curve. The ultraviolet shielding glass according to claim 8, wherein the inclination of the tangent line in contact with the curve is 2 μm / mm or less. The ultraviolet shielding glass according to any one of claims 1 to 9, wherein the film thickness of the ultraviolet shielding film on the outer peripheral edge of the central region is 1 μm to 3 μm. The ultraviolet shielding glass according to any one of claims 1 to 10, wherein the ultraviolet shielding film is directly provided on the main surface of the glass plate.

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