JP7409205B2 - Glass with heat reflective film - Google Patents

Description

The present invention relates to glass with a heat ray reflective film.

BACKGROUND ART Glass with a heat ray reflection film, which is formed by installing a heat ray reflection film (so-called Low-E film) on the surface of a glass substrate, is widely used, for example, in window glasses of buildings and glass members for vehicles.

Glass with a heat ray reflective film exhibits good heat insulation and heat shielding properties due to the effect of the heat ray reflective film. That is, in the summer, solar heat is prevented from entering the room, and in the winter, the movement of heat from the room to the outside is suppressed. As a result, a comfortable indoor environment can be maintained for a year.

Japanese Patent Application Publication No. 2011-157241

The inventors of the present application have noticed that when glass with a heat ray reflective film is applied as a glass member for a vehicle, a water film is often formed on the surface of the heat ray reflective film, especially in winter. If such a water film is formed on the heat ray reflective film, the effect of the heat ray reflective film in reflecting heat rays may be reduced or eliminated.

Further, in the case of a vehicle, a shielding film may be installed on the periphery of the glass member in order to make various terminals and the like provided on the periphery of the glass member difficult to see from the outside. In a humid environment where water droplets adhere to the surface of the heat ray reflective film of the glass member, there is a risk that this shielding film will malfunction. In other words, since the shielding film is originally constructed with the assumption that it will be installed on a glass substrate, if the shielding film is installed on top of the heat ray reflective film, in a humid environment, the shielding film will be damaged due to the influence of moisture. There is an increased risk of peeling.

The present invention was made in view of this background, and the present invention makes it possible to significantly suppress the deterioration of the heat ray reflection function even in a humid environment, and also to significantly suppress the peeling of the shielding film. The purpose of the present invention is to provide glass with a heat ray reflective film.

In the present invention, a glass with a heat ray reflective film is provided, comprising:
a glass substrate having a first surface and having at least three sides when viewed from above;
a heat ray reflective film installed on the first surface of the glass substrate;
A shielding film installed at the peripheral edge of the first surface along at least one of the at least three sides on the first surface side of the glass substrate, the shielding film having an outer edge and an inner edge. a shielding membrane having a portion;
a water-repellent film disposed on the heat ray reflective film;
has
When viewed from above, a glass with a heat ray reflective film is provided, in which the water-repellent film is disposed to cover the inner end portion of the shielding film.

According to the present invention, it is possible to provide a glass with a heat ray reflective film that can significantly suppress deterioration of the heat ray reflection function and also significantly suppress peeling of the shielding film even in a humid environment.

FIG. 1 is a schematic top view of glass with a heat ray reflective film according to an embodiment of the present invention. 2 is a diagram schematically showing a cross section taken along line II in FIG. 1. FIG. FIG. 3 is an enlarged view schematically showing an example of a cross section of a shielding film. FIG. 7 is an enlarged view schematically showing another example of a cross section of a shielding film. FIG. 3 is a top view for explaining the positional relationship between a water-repellent film and a shielding film. FIG. 7 is a top view for explaining another positional relationship between the water-repellent film and the shielding film. FIG. 7 is a top view for explaining still another positional relationship between the water-repellent film and the shielding film. 1 is a diagram schematically showing an example of an enlarged cross section of a glass with a heat ray reflective film according to an embodiment of the present invention. 1 is a diagram schematically showing a flow of a method for manufacturing glass with a heat ray reflective film according to an embodiment of the present invention.

An embodiment of the present invention will be described below.

As mentioned above, the inventors of the present application have noticed that when glass with a heat ray reflective film is applied as a glass member for a vehicle, a water film is formed on the surface of the heat ray reflective film in a humid environment. If such a water film is formed on the heat ray reflective film, the effect of the heat ray reflective film in reflecting heat rays may be reduced or eliminated. Furthermore, the shielding film provided on the peripheral edge of the glass member is originally designed to be installed on a glass substrate. For this reason, when a shielding film is installed on a heat ray reflective film, there is a high risk that the shielding film will peel off due to the influence of moisture.

In contrast, the present invention provides glass with a heat ray reflective film,
a glass substrate having a first surface and having at least three sides when viewed from above;
a heat ray reflective film installed on the first surface of the glass substrate;
A shielding film installed at the peripheral edge of the first surface along at least one of the at least three sides on the first surface side of the glass substrate, the shielding film having an outer edge and an inner edge. a shielding membrane having a portion;
a water-repellent film disposed on the heat ray reflective film;
has
When viewed from above, a glass with a heat ray reflective film is provided, in which the water-repellent film is disposed to cover the inner end portion of the shielding film.

In one embodiment of the present invention, a water-repellent film is installed on the heat ray reflective film. Due to the effect of this water-repellent film, in one embodiment of the present invention, formation of a water film on the heat ray reflective film can be significantly suppressed even in a humid environment. Moreover, as a result, it is possible to significantly suppress the deterioration of the heat ray reflection function of the heat ray reflection film.

Furthermore, in one embodiment of the present invention, the water-repellent film is arranged to cover the inner end of the shielding film. In this case, the problem of peeling of the shielding film due to moisture entering from the inner end of the shielding film can be significantly suppressed.

As a result of these effects, an embodiment of the present invention provides a glass with a heat ray reflective film that can significantly suppress a decline in heat ray reflection function and significantly suppress peeling of the shielding film even in a humid environment. can be provided.

(Glass with a heat ray reflective film according to an embodiment of the present invention)
EMBODIMENT OF THE INVENTION Hereinafter, with reference to FIG. 1 and FIG. 2, the glass with a heat ray reflective film according to one embodiment of the present invention will be described in more detail. FIG. 1 schematically shows a top view of a glass with a heat ray reflective film according to an embodiment of the present invention. Further, FIG. 2 schematically shows a cross-sectional view taken along the line II shown in FIG. 1.

As shown in FIGS. 1 and 2, a glass with a heat ray reflective film (hereinafter referred to as "first glass member") 100 according to an embodiment of the present invention has a substantially rectangular shape when viewed from above. This "substantially rectangular shape" includes a configuration in which the four corners of the rectangle in the first glass member 100 are rounded or chamfered.

The first glass member 100 includes a glass substrate 110, a heat ray reflective film 120, a shielding film 130, and a water-repellent film 160.

Glass substrate 110 has a first surface 112 and a second surface 114 facing each other. Further, the glass substrate 110 has a first side 115, a second side 116, a third side 117, and a fourth side 118 when viewed from above. The first side 115 and the third side 117 are opposite sides. Similarly, the second side 116 and the fourth side 118 are also mutually opposing sides.

Note that in the present application, a "side" is not necessarily limited to a "line segment" in the form of a straight line. That is, the term "side" includes a curved shape.

The heat ray reflective film 120 has a function of reflecting infrared rays (heat rays), and is installed on the first surface 112 side of the glass substrate 110.

In addition, in the example shown in FIG. 1 and FIG. 2, the heat ray reflective film 120 is installed over the entire first surface 112. However, this is just an example, and there may be a portion of the heat ray reflective film 120 that is not placed directly under the shielding film 130.

Shielding film 130 is installed on at least a portion of the peripheral edge of first surface 112 of glass substrate 110 . The shielding film 130 is installed to make it difficult for various members placed adjacent to the first glass member 100 to be visually recognized from the outside. For example, when using the first glass member 100 with the side on which the shielding film 130 is installed as the "inside", a member disposed on the inner side (upper side in the example shown in FIG. 2) than the shielding film 130 can be made difficult to see from the outside.

As shown in FIG. 1, the shielding film 130 is arranged, for example, along the first side 115 to the fourth side 118 of the glass substrate 110 at the periphery of the first surface 112 in a substantially “frame-like” manner. may be done.

Shielding membrane 130 has an inner end 132 and an outer end 134. Hereinafter, the distance between the inner end 132 and the outer end 134 that face each other will be referred to as "width" and will be represented by the symbol Ws.

Note that when the shielding film 130 is arranged in a frame shape, the width Ws between the inner end 132 and the outer end 134 of the shielding film 130 may be the same or different on each side 115 to 118. You can leave it there.

The water-repellent film 160 is arranged on the heat ray reflective film 120 and the shielding film 130. The water-repellent film 160 has a function of repelling water droplets adhering to the heat-ray reflective film 120 and suppressing formation of a water film on the heat-ray reflective film 120. Therefore, in the first glass member 100, it is possible to significantly avoid a decrease in the heat ray reflection function due to the formation of a water film.

Further, the water-repellent film 160 is arranged to cover at least the inner end portion 132 of the shielding film 130 when viewed from above. For example, in the example shown in FIGS. 1 and 2, the water-repellent film 160 has a peripheral edge 162 located at a position between the inner end 132 and the outer end 134 of the shielding film 130 when viewed from above. (excluding the position overlapping with the inner end portion 132).

By arranging the water-repellent film 160 in this manner, it is possible to significantly suppress moisture from entering through the gap between the inner end 132 of the shielding film 130 and the heat ray reflective film 120. Moreover, with this, in the first glass member 100, peeling of the shielding film 130 can be significantly suppressed even in a humid environment.

(Each component)
Next, each component included in the glass with a heat ray reflective film according to an embodiment of the present invention will be described in more detail. Here, the constituent members will be explained using the first glass member 100 as an example. Therefore, in the following description, the reference numerals shown in FIGS. 1 and 2 will be used to represent each member.

(Glass substrate 110)
The glass substrate 110 may have any shape as long as it has three or more sides when viewed from above.

For example, in the example shown in FIGS. 1 and 2, the glass substrate 110 has a substantially rectangular shape when viewed from above. Therefore, first surface 112 and second surface 114 each have first to fourth sides 115 to 118.

However, the glass substrate 110 may have a substantially triangular shape when viewed from above, and may have three sides. Alternatively, the glass substrate 110 may have a substantially n-gonal shape (n is an integer of 4 or more and 10 or less) when viewed from above, and may have four or more sides.

In the present application, the term "approximately square shape" includes a form in which at least one of the intersections between sides is rounded or chamfered.

The composition of the glass substrate 110 is not particularly limited. The glass substrate 110 may be, for example, soda lime glass, aluminosilicate glass, lithium silicate glass, or alkali-free glass.

Note that a second glass substrate may be provided on the second surface 114 side of the glass substrate 110 to form a laminated glass. In this case, the glass substrate 110 and the second glass substrate may be bonded to each other via an intermediate film.

The thickness of the glass substrate 110 is not particularly limited. The thickness of the glass substrate 110 may range, for example, from 1.6 mm to 5.0 mm.

(Heat ray reflective film 120)
The heat ray reflective film 120 may have any configuration as long as it can reflect infrared rays.

For example, the heat ray reflective film 120 may include at least one selected from the group including silver (Ag), gold (Au), copper (Cu), aluminum (Al), platinum (Pt), and ion-doped metal oxides. can include.

In particular, it is preferable to use ion-doped metal oxides. Ion-doped metal oxides include, for example, indium tin oxide (ITO), fluorine-doped tin oxide (FTO), aluminum-doped zinc oxide (AZO), and gallium zinc oxide (GZO). etc.

The thickness of the heat ray reflective film 120 is not particularly limited, but is, for example, in the range of 100 nm to 1000 nm.

As described above, the heat ray reflective film 120 does not necessarily need to be installed on the entire first surface 112. For example, the heat ray reflective film 120 does not need to be disposed directly under the shielding film 130.

(Shielding film 130)
The shielding film 130 is usually made of colored ceramics or colored resin. For example, the shielding film 130 is formed by printing a black ceramic paste on the peripheral edge of the heat ray reflective film 120 and firing it. If the black ceramic paste is replaced with a black resin composition, the shielding film 130 can be made of a colored resin.

The ceramic paste contains, as a solid content, 20% to 90% by mass of glass powder and 10% to 40% by mass of inorganic pigment including a filler, and is constituted by adding an organic binder and an organic solvent to these. Ru.

The thickness of the shielding film 130 is not particularly limited, but is, for example, in the range of 5 μm to 30 μm.

The width Ws of the shielding film 130, that is, the distance between the inner end 132 and the outer end 134, is not particularly limited, but is, for example, in the range of 10 mm to 50 mm.

In the example shown in FIG. 2, the inner end 132 and outer end 134 of the shielding film 130 both have walls extending in the vertical direction when viewed in cross section. However, in reality, the shielding film 130 may have a profile in which the thickness decreases toward the tip when viewed in cross section.

FIGS. 3 and 4 show an example of an enlarged cross section of such a shielding film. Note that in these figures, the water-repellent film 160 is omitted for clarity.

In the example shown in FIG. 3, the thickness of the shielding film 130 decreases linearly toward the inner end 132 near the inner end 132, and the thickness reaches zero (0) at the inner end 132. It has a profile of

FIG. 4 shows another example of the cross section of the shielding film 130 in an enlarged manner. In the example shown in FIG. 4, the thickness of the shielding film 130 decreases in a curved manner toward the inner end 132 near the inner end 132, and the thickness reaches zero (0) at the inner end 132. It has a profile of

Here, in the cross section of the shielding film 130, the slope of the tangent at a position of 0.2×Ws from the inner end 132 toward the outer end 134 is, for example, in the range of 50 μm/mm to 200 μm/mm. Good too.

Generally, when the shielding film 130 has such a "slanted" inner end 132, peeling at the inner end 132 may become more noticeable in a humid environment. This is because moisture is more likely to enter such an inner end portion 132.

However, in the first glass member 100, the water-repellent film 160 is arranged so as to cover the inner end portion 132 of the shielding film 130, as described above. Therefore, in the first glass member 100, peeling of the shielding film 130 can be significantly suppressed even when the shielding film 130 has the "slanted" inner end portion 132.

The inner end 132 of the shielding film 130 may have various shapes other than the cross-sectional shapes shown in FIGS. 3 and 4. Furthermore, like the inner end 132, the outer end 134 can have various forms.

As described above, the shielding film 130 is disposed at the periphery of the first surface 112 of the glass substrate 110 along at least one side of the first surface 112 .

For example, as shown in FIG. 1 described above, when the first surface 112 of the glass substrate 110 has a substantially rectangular shape when viewed from above, the shielding film 130
(i) may be arranged at the peripheral edge of the first surface 112 along any one of the first sides 115 to the fourth sides 118;
(ii) may be arranged at the periphery of the first surface 112 along any two sides of the first side 115 to the fourth side 118;
(iii) may be disposed at the periphery of the first surface 112 along any three sides of the first side 115 to the fourth side 118; or (iv) the first side 115 to the fourth side The first surface 112 may be disposed along all four sides 118 at the periphery of the first surface 112 .

Among these, in the case of form (i), it is preferable that the side on which the shielding film 130 is arranged is the longest side. For example, when the first surface 112 has a shape as shown in FIG. It is preferable that the

Furthermore, in the case of the form (ii), the shielding film 130 may be arranged at the peripheral edge of the first surface 112 along a pair of mutually opposing sides. Moreover, in this case, it is preferable that the pair of mutually opposing sides be long sides. For example, when the first surface 112 has a shape as shown in FIG. may be placed in

Moreover, in the case of the form (iv), the form of the shielding film 130 becomes a frame shape as shown in FIG. 1 described above.

It is also possible that the first surface 112 of the glass substrate 110 has other shapes.

(Water repellent film 160)
The material for the water-repellent film 160 is not particularly limited as long as it can suppress the formation of a water film. For example, it may be made of fluororesin.

For example, a compound having a perfluoroalkyl group can be used as the water-repellent film 160.

Examples of the compound having a perfluoroalkyl group include perfluoroalkyltrialkoxysilane and perfluoroalkyltrichlorosilane. Specific examples include perfluorohexylethyltrimethoxysilane, perfluorohexylethyltriethoxysilane, perfluorohexylethyltrichlorosilane, or combinations thereof.

Furthermore, a compound having a perfluoropolyether group can also be used as the water-repellent film 160.

The perfluoropolyether group has moieties represented by -(OC ₄ F ₈ )s-, -(OC ₃ F ₆ )a-, and -(OC ₂ F ₄ )b-.

The subscripts a, b, c, and s each represent the number of four types of repeating units of perfluoropolyether that constitute the main skeleton of the polymer. Subscripts a, b, c, and s may independently be integers from 0 to 200, for example, from 1 to 200. The sum of the subscripts a, b, c and s is at least 1, preferably from 20 to 100, more preferably from 30 to 50, typically about 40. The repeating units attached with subscripts a, b, c, and s and enclosed in parentheses can be present in any order in the formula.

Among these repeating units, -(OC ₄ F ₈ )s- is -(OCF ₂ CF ₂ CF ₂ CF ₂ )-, -(OCF(CF ₃ )CF ₂ CF ₂ )-, -(OCF ₂ CF( CF ₃ )CF ₂ )-, -(OCF ₂ CF ₂ CF(CF ₃ ))-, -(OC(CF ₃ ) ₂ CF ₂ )-, -(OCF ₂ C(CF ₃ ) ₂ )-, and - (OCF(CF ₃ )CF(CF ₃ ))-, preferably -(OCF ₂ CF ₂ CF ₂ CF ₂ )-. -(OC ₃ F ₆ )- may be any of -(OCF ₂ CF ₂ CF ₂ )-, -(OCF(CF ₃ )CF ₂ )- and -(OCF ₂ CF(CF ₃ )). , preferably -(OCF ₂ CF ₂ CF ₂ )-. -(OC ₂ F ₄ )s- may be either -(OCF ₂ CF ₂ )- or -(OCFCF ₃ )-, but preferably -(OCF ₂ CF ₂ )-.

The thickness of the water-repellent film 160 may range, for example, from 1 nm to 10 nm.

The water-repellent film 160 is arranged to cover the heat ray reflective film 120 in areas where the shielding film 130 is not arranged.

Further, the water-repellent film 160 is arranged to cover the inner end portion 132 of the shielding film 130 in the region where the shielding film 130 is arranged.

For example, when the shielding film 130 is arranged in the above-described manner (i), the water-repellent film 160 may be arranged in the manner shown in FIG. 5. That is, as shown in FIG. 5, the water-repellent film 160 is installed such that the peripheral edge 162 is disposed between the inner end 132 and the outer end 134 of the shielding film 130 when viewed from above. (excluding the arrangement where the peripheral edge 162 overlaps the inner edge 132 of the shielding membrane 130).

Further, for example, when the shielding film 130 is arranged in the above-described manner (ii), the water-repellent film 160 may be arranged in the manner shown in FIG. 6.

In this case, a first shielding film 130-1 is formed along the first side 115, and a second shielding film 130-2 is formed along the third side 117. Therefore, when viewed from above, the water-repellent film 160 has a first peripheral end 162-1 disposed between the inner end 132-1 and the outer end 134-1 of the first shielding film 130-1, and the first peripheral end 162-1 of the water-repellent film 160. The peripheral end 162-2 of the second shielding film 130-2 is disposed between the inner end 132-2 and the outer end 134-2 of the second shielding film 130-2 (however, the first peripheral end 162-1 overlaps the inner end 132-1 of the first shielding film 130-1, and the second peripheral end 162-2 overlaps the inner end 132-2 of the second shielding film 130-2. (excluding placement).

Further, when the shielding film 130 is arranged in the above-described manner (iii), the water-repellent film 160 may be arranged in the manner shown in FIG. 7.

In this case, a first shielding film 130-1 is formed along the first side 115, a second shielding film 130-2 is formed along the second side 116, and a second shielding film 130-2 is formed along the second side 117. A third shielding film 130-3 is formed along. Therefore, the water-repellent film 160 is arranged such that the first peripheral end 162-1 is disposed between the inner end 132-1 and the outer end 134-1 of the first shielding film 130-1 when viewed from above. (However, excluding the arrangement where the first peripheral end 162-1 overlaps the inner end 132-1 of the first shielding film 130-1). In addition, the water-repellent film 160 has a second peripheral end 162-2 disposed between the inner end 132-2 and the outer end 134-2 of the second shielding film 130-2 when viewed from above. However, this excludes the arrangement in which the second peripheral end 162-2 overlaps the inner end 132-2 of the second shielding film 130-2). Further, the water-repellent film 160 is arranged such that the third peripheral end 162-3 is disposed between the inner end 132-3 and the outer end 134-3 of the third shielding film 130-3 when viewed from above. (However, the arrangement in which the third peripheral end 162-3 overlaps the inner end 132-3 of the third shielding film 130-3 is excluded).

Furthermore, when the shielding film 130 is arranged in the manner (iv) described above, the water-repellent film 160 may be arranged in the manner shown in FIG. 1 described above. In this case, the water-repellent film 160 is arranged so that the peripheral end 162 has a loop shape passing between the inner end 132 and the outer end 134 of the shielding film 130 (however, the water-repellent film 160 is 130).

Note that when the first glass member 100 is used, for example, as a glass member for a vehicle, a step of incorporating the first glass member 100 into the body of the vehicle is performed. In this process, an adhesive is often placed on the shielding film 130 to bond it to the body. However, if the water-repellent film 160 is present on the entire upper surface of the shielding film 130, a problem may arise in that the adhesive becomes difficult to adhere to.

For this reason, when the width of the overlapping portion of the water-repellent film 160 and the shielding film 130 is defined as Wp, the width Wp is preferably 0.4 times or less than the width Ws. By setting Wp≦0.4×Ws, the adhesive can be reliably applied onto the shielding film 130. In particular, it is more preferable that Wp≦0.3×Ws.

On the other hand, the width Wp is preferably 0.04 times or more the width Ws. By setting Wp≧0.04×Ws, the water-repellent film 160 can be reliably placed over the shielding film 130. In particular, it is more preferable that Wp≧0.2Ws.

Further, on the side of the first glass member 100 where the shielding film 130 is installed, at a position of 0.2×Ws toward the inside from the outer end 134 of the shielding film 130 (hereinafter referred to as "position Q1"). The contact angle α _o of the water droplet to be measured is preferably 70° or less. In this case, at the position Q1 of the first glass member 100, the influence of water repellency by the water repellent film 160 can be reduced. Therefore, the problem of insufficient adhesion between the shielding film 130 and the adhesive as described above can be significantly suppressed.

The contact angle α _o is preferably 60° or less.

On the other hand, on the side where the shielding film 130 of the first glass member 100 is installed, the measurement was performed at a position of 0.2×Ws outward from the inner end 132 of the shielding film 130 (referred to as "position Q2"). The contact angle α _i of the water droplets is preferably 90° or more. In this case, the water-repellent effect of the water-repellent film 160 can be reliably exhibited at the position Q2 of the first glass member 100.

The contact angle α _i is preferably 95° or more.

FIG. 8 schematically shows an example of an enlarged cross section of a glass with a heat ray reflective film according to an embodiment of the present invention. In FIG. 8, various dimensions and positions used in the evaluation of the above items are collectively shown.

(First glass member 100)
The first glass member 100 can be applied to, for example, a roof glass of a vehicle.

The first glass member 100 does not necessarily have to have a flat shape, and may be curved.

Note that when the first glass member 100 is applied to the roof glass of a vehicle, the first glass member 100 may be applied so that the water-repellent film 160 side is on the inside of the vehicle.

(Method for manufacturing glass with a heat ray reflective film according to an embodiment of the present invention)
Next, a method for manufacturing glass with a heat ray reflective film according to an embodiment of the present invention will be described.

FIG. 9 schematically shows a flow of a method for manufacturing glass with a heat ray reflective film (hereinafter referred to as "first method") according to an embodiment of the present invention.

As shown in FIG. 9, the first method is
forming a heat ray reflective film on the glass substrate (S110);
forming a shielding film on the heat ray reflective film (S120);
forming a water-repellent film on the heat ray reflective film and the shielding film (S130);
has.

Each step will be explained below. Note that each process will be described here, taking as an example the method for manufacturing the first glass member 100 described above. Therefore, when representing each member, the reference numerals shown in FIGS. 1 and 2 will be used.

(Step S110)
First, a glass substrate 110 is prepared. Further, a heat ray reflective film 120 is formed on the first surface 112 of the glass substrate 110.

The heat ray reflective film 120 may be formed by sequentially forming a plurality of layers on the first surface 112 using a sputtering method.

(Step S120)
Next, a shielding film 130 is formed on the heat ray reflective film 120.

For this purpose, first, a shielding film paste is placed at a predetermined position by screen printing. As described above, the shielding film paste contains glass particles, black pigment, binder resin, and solvent.

Thereafter, the paste is fired to form the shielding film 130. The firing conditions also vary depending on the composition of the shielding film paste. For example, the firing temperature is in the range of 600°C to 700°C, and the firing time is in the range of 2 minutes to 10 minutes.

The shielding film 130 may be formed in a frame shape along the peripheral edge of the first surface 112 on which the heat ray reflective film 120 is provided.

Thereafter, the glass substrate 110 may be subjected to bending processing, if necessary. Through the bending process, a glass substrate 110 having a desired curved surface is obtained. Moreover, thereby, the first glass member 100 having a desired curved surface shape can finally be obtained.

The bending process may be performed, for example, by holding the glass substrate 110 at a temperature of 600° C. to 700° C. for 2 minutes to 10 minutes.

Note that the bending process and the baking process of the shielding film paste may be performed simultaneously. In this case, the shielding film 130 can be obtained upon completion of the bending process.

However, the bending process is a process that is performed when necessary, and may be omitted when unnecessary.

(Step S130)
Next, a water-repellent film 160 is formed on the heat ray reflective film 120 and the shielding film 130.

The water-repellent film 160 is formed by applying a water-repellent liquid to a predetermined area. The water repellent liquid includes, for example, 1H, 1H, 2H, 2H tridecafluoro-n-octyltrimethoxysilane. The water repellent liquid is installed so as to cover the inner end 132 of the shielding film 130 when viewed from above. The method of applying the water repellent liquid is not particularly limited, and conventional methods such as brush coating may be used.

After that, a drying process may be performed in a drying oven. The drying process may be carried out, for example, at a temperature of 60° C. to 110° C. for 5 minutes to 1 hour.

A water-repellent film 160 is formed by drying the water-repellent liquid.

Through the above steps, the first glass member 100 having the configuration shown in FIGS. 1 and 2, for example, is manufactured.

Examples of the present invention will be described below. In the following description, Examples 1 to 9 are examples, and Examples 11 to 12 are comparative examples.

(Example 1)
Glass with a heat ray reflective film was manufactured by the following method.

First, a glass substrate (UVFL; manufactured by AGC) having a length of 300 mm, a width of 300 mm, and a thickness of 3.5 mm was prepared. Next, a heat ray reflective film was formed on one surface (first surface) of this glass substrate over the entire surface.

The heat ray reflective film had a four-layer structure of the first layer to the fourth layer, and was formed by a sputtering method.

First, a first layer was formed on a first surface of a glass substrate. The first layer was made of titanium oxide containing silica (the amount of silica was 8% by mass). A silica-doped titania target containing 8% by mass of silica was used for film formation. The film thickness was targeted to be 10 nm. Next, a second layer was formed on the first layer. The second layer was a silica layer. The film thickness was targeted to be 35 nm. Next, a third layer was formed on the second layer. The third layer was an amorphous ITO transparent conductive layer. The film thickness was targeted at 150 nm. Note that the glass substrate was not heated during film formation. Next, a fourth layer was formed on the third layer. The fourth layer was a silica layer. The film thickness was targeted at 55 nm.

Next, paste for a shielding film was screen printed in the shape of a frame on the peripheral edge of the first surface of the glass substrate on which the heat ray reflective film was formed. Thereafter, after drying the paste, the glass substrate was heated at 650° C. for 7 minutes to form a shielding film. The width Ws on each side of the obtained shielding film was 25 mm.

Note that this treatment crystallized the third layer included in the heat ray reflective film, that is, the ITO layer.

Next, 2 ml of the water repellent liquid was dropped onto the heat ray reflective film under an environment of a temperature of 25° C. and a relative humidity of 60%. Further, the water repellent liquid was spread over the entire heat ray reflective film using a cotton cloth (trade name: Bencot).

The water repellent solution was a solution in which 0.1 g of 1H, 1H, 2H, 2H tridecafluoro-n-octyltrimethoxysilane was dissolved in 20 g of Asahiklin AE3000. The water-repellent liquid was applied so as to cover the inner end of the shielding film, but not the outer end, when viewed from above.

Thereafter, the water repellent liquid was dried for 5 minutes, and then the glass substrate was placed in a hot air circulation oven at 100° C. and heat treated for 5 minutes.

As a result, a water-repellent film was formed. The thickness of the water-repellent film was about 5 nm. On either side of the glass substrate, the distance from the peripheral edge of the water-repellent film to the inner end of the shielding film, that is, the width Wp, was 6 mm (=0.24×Ws).

Through the above processing, a glass with a heat ray reflective film (hereinafter referred to as "Sample 1") was manufactured.

(Example 2 to Example 5)
Glass with a heat ray reflective film was manufactured in the same manner as in Example 1. However, in these Examples 2 to 5, the thickness of the water-repellent film was changed from that in Example 1. Other manufacturing conditions are the same as in Example 1.

As a result, glasses with heat ray reflective films (hereinafter referred to as "Samples 2 to 5", respectively) were manufactured.

(Example 11)
Glass with a heat ray reflective film was manufactured in the same manner as in Example 1. However, in this Example 11, no water-repellent film was provided.

As a result, a glass with a heat ray reflective film (hereinafter referred to as "Sample 11") was manufactured.

(evaluation)
The following evaluations were conducted using Samples 1 to 5 and Sample 11.

(Measurement of contact angle)
The contact angle was measured for each sample. The measurement location was the central part of the sample on the side where the heat ray reflective film was formed. The contact angle was measured using a contact angle meter (DMs-401; manufactured by Kyowa Kaimen Kagaku).

(Measurement of emissivity)
Emissivity was measured in each sample.

The emissivity was measured using an emissivity meter (TSS-5X-2; manufactured by Japan Sensor Co., Ltd.). The obtained emissivity is referred to as "initial emissivity."

In addition, each sample was placed on a water bath heated to 35° C. with the heat ray reflective film side facing downward, steam was applied to the sample for 10 seconds, and then similar evaluations were performed. The obtained emissivity is referred to as "wetting emissivity".

Table 1 below summarizes the evaluation results obtained for Samples 1 to 5 and Sample 11.

この結果から、サンプル１～サンプル５では、接触角が１００゜を超えており、熱線反射膜の側に撥水性が得られていることがわかった。一方、撥水膜を有しないサンプル１１では、接触角が５０゜しかなく、撥水性が得られていないことがわかった。

From this result, it was found that Samples 1 to 5 had a contact angle of more than 100°, indicating that water repellency was obtained on the side of the heat ray reflective film. On the other hand, in Sample 11, which did not have a water-repellent film, the contact angle was only 50°, indicating that water repellency was not obtained.

In addition, in sample 11, the wet emissivity was higher than the initial emissivity, and it was found that the heat ray radiation function deteriorates in a humid environment. On the other hand, in Samples 1 to 5, the wet emissivity showed a value equivalent to the initial emissivity, and it was found that the deterioration of the heat ray reflection function was suppressed even in a humid environment.

(Example 6)
Glass with a heat ray reflective film was manufactured in the same manner as in Example 1.

However, in this Example 6, the installation area of the water-repellent film was changed from that in Example 1. Specifically, the water-repellent film was formed such that the distance between the peripheral edge of the water-repellent film and the inner end of the shielding film, that is, the width Wp, was 1 mm on each side when viewed from above. Therefore, Wp=0.04×Ws.

As a result, a glass with a heat ray reflective film (hereinafter referred to as "Sample 6") was manufactured.

(Example 7)
Glass with a heat ray reflective film was manufactured in the same manner as in Example 1.

However, in this Example 7, the installation area of the water-repellent film was changed from that in Example 1. Specifically, the water-repellent film was formed such that the distance between the peripheral edge of the water-repellent film and the inner end of the shielding film, that is, the width Wp, was 5 mm on each side when viewed from above. Therefore, Wp=0.2×Ws.

As a result, a glass with a heat ray reflective film (hereinafter referred to as "Sample 7") was manufactured.

(Example 8)
Glass with a heat ray reflective film was manufactured in the same manner as in Example 1.

However, in this Example 8, the installation area of the water-repellent film was changed from that in Example 1. Specifically, the water-repellent film was formed such that the distance between the peripheral edge of the water-repellent film and the inner end of the shielding film, that is, the width Wp, was 8 mm on each side when viewed from above. Therefore, Wp=0.32×Ws.

As a result, a glass with a heat ray reflective film (hereinafter referred to as "Sample 8") was manufactured.

(Example 9)
Glass with a heat ray reflective film was manufactured in the same manner as in Example 1.

However, in this Example 9, the installation area of the water-repellent film was changed from that in Example 1. Specifically, the water-repellent film was formed such that the distance between the peripheral edge of the water-repellent film and the inner end of the shielding film, that is, the width Wp, was 12 mm on each side when viewed from above. Therefore, Wp=0.48×Ws.

As a result, a glass with a heat ray reflective film (hereinafter referred to as "Sample 9") was manufactured.

(Example 12)
Glass with a heat ray reflective film was manufactured in the same manner as in Example 1.

However, in this Example 12, the installation area of the water-repellent film was changed from that in Example 1. Specifically, the water-repellent film was formed so that the peripheral edge of the water-repellent film coincided with the inner end of the shielding film on each side when viewed from above, that is, the width Wp=0.

As a result, a glass with a heat ray reflective film (hereinafter referred to as "Sample 12") was manufactured.

(evaluation)
The following evaluations were conducted using Samples 6 to 9 and Sample 12.

(Measurement of contact angle)
The contact angle was measured using each sample.

For each sample, measurements were performed at two locations:
(1) Position Q1, that is, a position on the shielding film, 0.2×Ws (=5 mm) from the outer end toward the inner end, and (2) Position Q2, that is, on the shielding film, A position of 0.2 x Ws (=5 mm) from the inner end toward the outer end.

In addition, the above-mentioned contact angle meter was used for the measurement.

(Shielding film adhesion evaluation test)
A shielding film adhesion evaluation test was conducted using each sample.

The adhesion evaluation test was carried out by placing each sample in a test tank maintained at a temperature of 85° C. and a relative humidity of 85%, and observing the state of the shielding film after 500 hours had elapsed. Specifically, the presence or absence of peeling at the inner end of the shielding film was visually evaluated.

(Adhesion evaluation test between shielding film and adhesive)
Using samples cut out from each sample, an adhesion evaluation test between the shielding film and the adhesive was conducted.

The test was conducted as follows.

First, in each sample, a portion including the shielding film (25 mm in length x 25 mm in width) was cut out and a sample was collected. Next, an adhesive (WS242; manufactured by Yokohama Rubber) was applied onto the shielding film of the collected sample. Further, an adhesive (WS242; manufactured by Yokohama Rubber) was similarly applied onto a separately prepared stainless steel plate of the same size.

Next, the sample and the stainless steel plate were crimped together so that their respective adhesives were in contact with each other. After curing this at a temperature of 60° C. for 30 minutes, it was kept in an environment of a temperature of 20° C. and a relative humidity of 60% for 72 hours to prepare a test body.

Using this test specimen, shear strength was measured.

When the obtained shear strength was 3.0 MPa or more and the damage occurred on the adhesive side, it was determined that the adhesion between the shielding film and the adhesive was good (◯). In addition, cases in which only one of the items was satisfied were judged to be acceptable (△), and cases in which neither of the items were satisfied were judged to be unacceptable (×).

Table 2 below summarizes the evaluation results obtained for Samples 6 to 9 and Sample 12.

サンプル６～サンプル８およびサンプル１２では、位置Ｑ１における接触角は、低い値を示した。すなわち、遮蔽膜上の位置Ｑ１では、撥水効果が生じていないことが示唆された。一方、サンプル９では、位置Ｑ１における接触角は、高い値（９０゜）を示した。これは、サンプル９では、撥水膜の周端が遮蔽膜の内端部から１２ｍｍ外側にまで延在しており、他のサンプルに比べて、遮蔽膜のより外側にまで、撥水機能が及ぶためであると考えられる。

In samples 6 to 8 and sample 12, the contact angle at position Q1 showed a low value. That is, it was suggested that no water repellent effect was produced at position Q1 on the shielding film. On the other hand, in sample 9, the contact angle at position Q1 showed a high value (90°). This is because in sample 9, the peripheral edge of the water-repellent film extends 12 mm outward from the inner edge of the shielding film, and compared to other samples, the water-repellent function extends further to the outside of the shielding film. This is thought to be due to the spread of the virus.

On the other hand, the contact angle at position Q2 was as high as 90° or more in all of Samples 6 to 9. However, in sample 12, the contact angle at position Q2 was as low as 60°.

From this result, it was found that in Samples 6 to 9, the water-repellent film produced a water-repellent effect at position Q2, and the inner end of the shielding film tended to be easily protected from the outside world.

Next, as a result of the shielding film adhesion evaluation test, it was observed that in sample 12, the shielding film had peeled off. On the other hand, in Samples 6 to 9, no peeling was observed in the shielding film. From this result, it was found that in Samples 6 to 9, the problem of peeling of the shielding film was significantly suppressed even in a humid environment.

The results of the adhesion evaluation test between the shielding film and the adhesive revealed that samples 6 to 8 had good adhesion between the shielding film and the adhesive. On the other hand, in Sample 9, it was found that the adhesion between the shielding film and the adhesive tended to decrease. This is considered to be because, in Sample 9, the adhesive was unable to exhibit appropriate adhesive strength due to the influence of the water-repellent film that covered about half the width of the shielding film.

100 Glass with heat ray reflective film (first glass member)
110 Glass substrate 112 First surface 114 Second surface 115 First side 116 Second side 117 Third side 118 Fourth side 120 Heat ray reflective film 130 (130-1 to 130-3) Shielding film 132 (132-1 to 132-3) Inner end 134 (134-1 to 134-3) Outer end 160 Water-repellent film 162 (162-1 to 162-3) Peripheral end

Claims (10)

Glass with a heat ray reflective film,
a glass substrate having a first surface and having at least three sides when viewed from above;
a heat ray reflective film installed on the first surface of the glass substrate;
A shielding film installed at the peripheral edge of the first surface along at least one of the at least three sides on the first surface side of the glass substrate, the shielding film having an outer edge and an inner edge. a shielding membrane having a portion;
a water-repellent film disposed on the heat ray reflective film;
has
The shielding film has a portion installed on the heat ray reflective film,
When viewed from above, the water-repellent film is arranged to cover the inner end of the shielding film, and the glass has a heat-reflecting film. The glass substrate has two sides facing each other when viewed from above,
The glass with a heat ray reflective film according to claim 1, wherein the shielding film is disposed at a peripheral edge of the first surface along each of the two mutually opposing sides. The glass with a heat ray reflective film according to claim 2, wherein the glass substrate has a rectangular shape when viewed from above. The glass with a heat ray reflective film according to claim 3, wherein the two mutually opposing sides are two long sides. The glass with a heat ray reflective film according to any one of claims 1 to 4, wherein the shielding film is arranged in a frame shape over the peripheral edge of the first surface. When the distance between the outer end and the inner end of the shielding film is defined as the width Ws, the width Wp of the overlapping portion of the water-repellent film and the shielding film is 0.4×Ws when viewed from above. The glass with a heat ray reflective film according to any one of claims 1 to 5, which is as follows. When the distance between the outer end and the inner end of the shielding film is the width Ws, on the side of the glass with a heat ray reflective film where the shielding film is installed,
A contact angle α _o of the water droplet measured at a position of 0.2×Ws from the outer end toward the inner end of the shielding film is 70° or less,
Any one of claims 1 to 6, wherein a contact angle α _i of a water droplet measured at a position of 0.2×Ws from the inner end to the outer end of the shielding film is 90° or more. Glass with a heat ray reflective film described in . The shielding film according to any one of claims 1 to 7, wherein the slope of a tangent at a position 100 μm from the inner end toward the outer end is in the range of 50 μm/mm to 200 μm/mm when viewed in cross section. Glass with a heat ray reflective film as described in . The glass substrate has a second surface opposite to the first surface,
The glass with a heat ray reflection film according to any one of claims 1 to 8, wherein the glass with a heat ray reflection film has another glass substrate on the second surface side. The glass with a heat ray reflection film according to any one of claims 1 to 9, wherein the glass with a heat ray reflection film is roof glass for a vehicle.

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