JP2002274892A - Automotive window glass having shade band - Google Patents

Abstract

PROBLEM TO BE SOLVED: To solve the problem that light leaks through a crack of a ceramic color print at an edge part of a dot, which crack is generated at a part where the ceramic color print and the dot are overlapped in an automotive window glass having a picture frame-like part of the ceramic color print provided at the indoor side and the shade band constituted of a dot pattern using noble metal colloidal time particles as a coloring source. SOLUTION: The automotive window glass having the shade band is obtained by carrying out the ceramic color print at the indoor side in a picture frame-like form, then printing the shade band of a plurality of dots, which is made of the transparent color film using the noble metal as the coloring source on one and the same surface by screen printing and baking. The size of the dot, overlapped with the ceramic color print, of the shade band comprising the plurality of dots is set in such a manner that when the dot is rectangular, the length of one side is >=0.5 mm, and when the dot is a circular form, the diameter is >=0.5 mm.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a window glass for a vehicle with a shade band having a shade band formed by a dot pattern formed of a frame portion formed by ceramic color printing and a transparent coloring film using noble metal fine particles as a coloring source.

[0002]

2. Description of the Related Art Conventionally, a ceramic color paste obtained by adding powder of a heat-resistant pigment (metal oxide), which is an inorganic component, and powder of a glass frit to a resin and a solvent is kneaded around a window glass of an automobile. After being applied to the surface of a glass plate by screen printing, dried, and then heated and baked in a heating bending process or the like for forming into a window glass, a frame-shaped black frame made of ceramic color print is provided.

[0003] Usually, ceramic color paste is prepared by kneading a powder of low melting glass frit (low melting point lead glass), a powder of pigment (metal oxide), a resin such as acryl, resin, ethylcellulose and the like in a solvent such as terpineol. ,
For example, to prevent transmission of visible light and ultraviolet light,
Adjusted to black or gray.

[0004] The purpose of providing a ceramic color print on a window glass of an automobile is to prevent the urethane-based adhesive from being deteriorated due to solar radiation from the outside when the window glass is bonded to the window frame, and to provide a surface of the window glass on the inner side of the vehicle. Hiding the terminal portion of the formed conductive thin film electrode or heating wire from the outside may be mentioned.

On the other hand, in order to prevent glare of the driver and improve decorativeness, the upper part of the window glass of recent automobiles has a certain degree of transmission of visible light and moderately suppresses transmission of solar light. A shade band is formed.

Generally, in a laminated glass used for a windshield of an automobile, a shade band is formed by partially dyeing polyvinyl butyral which is an interlayer film of the laminated glass. The gradation is obtained by continuously changing the visible light transmittance by decreasing the degree of dyeing of polyvinyl butyral from the upper part of the window glass for automobiles to the lower part.

[0007] However, in single-pane tempered glass usually used for side and rear glass of automobiles,
Shade band is obtained by screen printing. Even if a transparent colored film is formed by screen printing, it is difficult to obtain a gradation by changing the color tone,
The gradation is obtained by making the shade band entirely a dot type and gradually reducing the dots downward. For example, Japanese Unexamined Utility Model Publication No. 7-18930 and Japanese Unexamined Patent Application Publication No. 11-335141 disclose a shade band using a colored dot pattern (dot gradation) by screen printing.

FIG. 3 is a schematic plan view of an automobile rear glass provided with a frame-shaped ceramic color print 3 and a shade band 2.

On the side and rear glass of a car made of single-panel tempered glass, a shade band 2 of a dot pattern is provided on the same surface as the above-mentioned ceramic color print 3, that is, on the indoor side of the window glass of the car. .

On the other hand, in recent years, regarding shade bands,
Bright color tones are being preferred, and are being addressed by, for example, a colored dot pattern of a transparent colored film utilizing colloidal resonance absorption of precious metal colloid fine particles.

For example, a noble metal fine particle or a compound for providing noble metal fine particles, a fixing material comprising an organometallic compound,
A method for obtaining a vivid transparent colored glass by forming a transparent coloring film by screen-printing the glass coloring colorant on a glass substrate by mixing the paste (binder resin) and an organic solvent or the like with the glass coloring colorant is described in detail. Kaihei 7-2564
1, JP-A-2000-185942 and JP-A-20
No. 00-247686 and the like.

[0012]

However, a ceramic color paste is screen-printed on a glass substrate cut into the shape of an automobile window and dried, and gold, that is, a noble metal colloidal particle of Au or the like is used as a coloring source. A glass colorant is screen-printed to form a dot pattern, dried, and baked to make a window glass for automobiles.When the ceramic color print and the dot pattern of the transparent color film overlap, the ceramic color print is There was a problem that cracks occurred. Even when the glass is mounted on an automobile, there is a problem in that when a ceramic color print in which cracks occur is viewed from the indoor side, light leaks and it is difficult to sell as a product.

For example, Japanese Patent Application Laid-Open No. 11-335141 discloses a glass plate with a colored film having a gradation in which the degree of coloring changes very naturally by a screen-printed dot pattern. Although used for automotive glass, there is a problem that cracks occur after baking at the overlapping portion of the ceramic color print and the lower part of the shade band where the size of each dot is reduced.

The cracks in the ceramic color print are:
When a ceramic color paste and a colorant for glass coloring using noble metal colloidal fine particles as a color source are screen-printed on a glass substrate and then baked to form a dot pattern of a ceramic color paint and a transparent coloring film, respectively, heat is applied to each other. It is thought to occur due to different shrinkage rates,
Occurs in the ceramic color print just below the edge of each dot made of a transparent colored film.Even if it is cooled slowly after baking, or if it is quenched by blowing air to make the glass substrate tempered glass I do.

In order to avoid cracks, the ceramic color print and the dot need not be overlapped, and a pattern in which the ceramic color print and the transparent colored film portion are not overlapped is disclosed in JP-A-5-286358. . FIG. 4 is a partially enlarged view showing an example of a boundary between a ceramic color print 3 and a shade band 2 made of a transparent coloring film described in Japanese Patent Application Laid-Open No. 5-286358.

However, when a dot pattern composed of a ceramic color print and a transparent colored film as a shade band is not overlapped, if the gap at the boundary is enlarged, light enters from there, and the dot pattern has a meaning as a shade band. Therefore, it is necessary to perform screen printing with high positional accuracy so that a large gap does not occur between the ceramic color print and the dot pattern. In actual production, if the ceramic color print and the dot pattern are printed separately and the positional accuracy is strictly adjusted for each sheet, the tact time becomes slow, so that a displacement of several millimeters must occur. Therefore, it is not realistic in mass production as an automobile window glass with a shade band, and it is necessary to overlap a ceramic color print with a shade band.

[0017]

Means for Solving the Problems The inventors of the present invention have prepared a ceramic color paste obtained by kneading terpineol with powder of low melting point glass frit, pigment, acryl, resin and ethyl cellulose on a glass substrate. Screen printing was performed to form a ceramic color paint, and then a noble metal fine particle or a compound providing noble metal fine particles, a fixing material made of an organometallic compound, and a commercially available colorant for glass coloring obtained by kneading ethyl cellulose with terpineol were screen printed as a dot pattern. Thereafter, an attempt was made to suppress the occurrence of cracks, which was the above problem, at the portion where dots were overlapped with the baked ceramic color print. As a result, the dot size of the portion where the shade band and the ceramic color print overlap, for a rectangular dot, 0.5 mm or more on one side, preferably 0.8 mm or more, for a circular dot, a diameter of 0.5 mm or more, preferably , 0.8m
It was found that cracks did not occur after baking by setting m or more.

According to the present invention, a frame-shaped ceramic color print is provided on the inner peripheral side surface, and a plurality of dots of a transparent colored film made of a noble metal as a color source are printed on the same surface by screen printing. Then, in a window glass for a vehicle with a shade band that is baked, the dot size of the portion overlapping the ceramic color print of the shade band composed of a plurality of dots is 0.5 mm or more on a side of a rectangular dot, and a circular shape. With dots,
A window glass for an automobile with a shade band, having a diameter of 0.5 mm or more.

Further, in the present invention, the transparent colored film is preferably made of Au,
The above-mentioned window for a vehicle with a shade band, comprising a noble metal compound and / or a noble metal fine particle selected from Ag, Pt, Pd, and Rh, a fixing agent composed of an organometallic compound, and a binder resin as main components. It is glass.

Further, the present invention provides the above-mentioned automobile with a shade band, wherein the dot pattern of the shade band portion is large at a portion overlapping the ceramic color print at the periphery of the glass, and becomes smaller toward the center of the glass. Window glass.

FIG. 2 shows a dot pattern 1 formed by printing on a ceramic color print 3 on a glass substrate G by using a screen printing machine and printing at a high temperature. It is explanatory drawing of the crack generation mechanism of No. 3.

FIG. 2A is a schematic sectional view immediately after printing of the small-sized dot 1, and FIG. 2B is a schematic sectional view after leveling. FIG. 2C is a schematic cross-sectional view of the large dot 1 immediately after printing.
FIG. 2D is a schematic sectional view after the leveling.

The reason why cracks occur at the edge of the dot 1 is that when the dot 1 is formed by screen printing using a gauze, that is, a screen composed of the mesh 4 and the emulsion hardened layer 5, when the dot 1 is formed on the emulsion hardened layer, This is considered to be due to the edge effect in screen printing, where the paste thickness is increased only in the portion. The edge effect is described in JP-A-6-295.
No. 781.

As shown in FIG. 2A, when the size of the dot 1 is small, if the film thickness at the edge of the dot 1 made of the coloring agent for coloring glass containing noble metal colloidal fine particles is increased by the edge effect, Then, as shown in FIG.
Even if leveling is performed, the dot 1 remains small in thickness because the size of the dot 1 is small. When printing is performed at a high temperature in this state, cracks occur in the ceramic color print 3 ′ immediately below the dot 1 due to the contraction force of the dot 1.

As shown in FIG. 2 (c), when the dot 1 'is large, the film thickness at the edge of the paste, that is, the dot 1' made of a coloring agent for glass coloring containing noble metal colloid fine particles has an edge. Even if the thickness is increased due to the effect, as shown in FIG. In this state, even when printing is performed at a high temperature, the contraction force of the dot 1 'is small, so that no crack occurs in the ceramic color print 3' immediately below the edge of the dot 1 '.

The present inventors have conducted intensive studies and found that, in the color former for glass coloring containing noble metal colloid fine particles adjusted to the viscosity used for screen printing, in the case of a rectangle, one side, less than 0.5 mm, a circle If diameter, 0.
When the thickness is less than 5 mm, it has been found that the thickness after baking is nearly double the desired thickness.

Therefore, when the size of the dot 1 overlapping the ceramic color print 3 is rectangular, one side is 0.5 mm
Or more, preferably 0.8 mm or more, in the case of a circle, the diameter,
It was found that by setting the thickness to 0.5 mm or more, and preferably 0.8 mm or more, no cracks occur in the ceramic color print 3 ′ immediately below the dot 1 after printing.

Conventionally, when a shade band 2 is applied to a window glass for an automobile by screen printing, visible light is continuously increased by decreasing the size of the dot 1 from the upper portion to the lower portion of the dot pattern. However, in order to prevent the cracks, the dots 1 forming the shade band 2 are large in a portion overlapping the ceramic color print 3 on the peripheral portion of the glass substrate G, and are small toward the center of the glass substrate G. It is preferred that it is.

[0029]

FIG. 1 is a partially enlarged view of an example of a window glass for a vehicle having a shade band according to the present invention. Figure 1
As shown in the figure, the dots 1 forming the shade band 2 are large at the portion overlapping the ceramic color print 3 at the periphery of the glass, and become smaller toward the center of the glass.

Dot pattern 1 forming shade band 2
Is formed on the indoor glass surface by screen printing.The paste used is mainly a precious metal colloid fine particle that gives a transparent colored film with a vivid color tone, a coloring agent, a fixing agent composed of an organic metal, a binder resin, etc. It is preferable to use a colorant for glass coloring prepared in an organic solvent as a component, for example, as a commercially available one,
High Color T (manufactured by Mitsuboshi Belting Co., Ltd., trade name) and the like can be mentioned.

The coloring source of the colorant for coloring glass is gold (A).
u) If it is a colloidal fine particle, a different color such as red, orange, blue, and violet is exhibited by adjusting the refractive index and the particle diameter of the matrix in a transparent matrix.
In addition, silver (Ag) colloidal fine particles exhibit a yellow color by themselves, and exhibit vivid green by coexisting with gold colloidal fine particles. In addition, examples of the noble metal colloid fine particles exhibiting vivid colors by colloid resonance absorption include platinum (Ag) colloid fine particles, palladium (Pd) colloid fine particles, and rhodium (Rh) colloid fine particles.

The organometallic fixing agent as a composition component of the glass colorant includes Al, Si, Ti, C
r, Mn, Fe, Co, Ni, Cu, Y, Zr, Nb,
Ethoxides such as In, Sn, and Sb; alkoxides such as propoxide; organic acid salts such as naphthenates and acetates; acetylacetone complex salts; oxy complex salts; and the like; binder resins such as nitrocellulose, ethyl cellulose, and acetic acid; Cellulose such as cellulose and butylcellulose, acrylics such as methyl acrylate, polyamides such as nylon 6, nylon 11, nylon 12, polyethers such as polyethylene terephthalate and polycaprolactone, polycarbonates, polystyrene, polybutadiene, polyisoprene, etc. And organic solvents such as meta-cresol, dimethylformamide, carbitol, terpinol, diacetone alcohol, triethylene glycol, and para-xylene. Solvent and the like.

The ceramic color paste 3 is formed into a frame-shaped ceramic color print 3 on the inside of a glass room for an automobile by screen printing, and then the ceramic color paste to be baked at a high temperature is composed of a powder of a heat-resistant pigment (metal oxide) and a glass frit of a low melting point. Powder and acrylic, resin, or a resin such as ethyl cellulose and kneaded in a solvent such as terpineol, light, for example, preferably dark color so as not to transmit visible light and ultraviolet light, for example,
Adjusted to black or gray.

In the manufacture of a window glass for a vehicle having a shade band according to the present invention, a ceramic color paste is screen-printed on a glass substrate and dried as a ceramic color paint 3, and then on the same surface as a colorant for glass coloring. It is preferable that the paste is screen-printed so as to form the shade band 3 by the dot pattern 1 and baked, and at the same time, the glass substrate G is bent and air is blown to the glass substrate G to strengthen the air-cooling, thereby improving the production efficiency. If it is soda lime silicate glass manufactured by the normal float method, the baking temperature is
600-750 ° C, preferably 620-670 ° C
Can be set in the range.

Hereinafter, the present invention will be described in detail with reference to examples. Hereinafter, the present invention is not limited to the examples.

[0036]

EXAMPLE (Preliminary test) A black ceramic color paste was applied to the entire surface of a glass substrate G of 3.5 mm thick float plate glass (soda lime silicate glass), and the drying temperature was adjusted to 120 ° C. in a drying furnace. And dried for 10 minutes. From above, mesh size, # 250
High color T which is a colorant for glass coloring using commercially available noble metal colloid fine particles as a color source.
(Trade name, manufactured by Mitsuboshi Belting Co., Ltd.)
From 0.4 to 0.4 mm, applied by a screen printer so as to form a dot pattern of square dots 1 changed by 0.02 mm, and dried at a drying temperature of 150 ° C. for 5 minutes, and then heated to 650 ° C. in a firing furnace. After heating and curing for 3 minutes, the mixture was allowed to stand still and gradually cooled.

The glass substrate G after the baking was visually observed by transmission using a fluorescent lamp in a dark room.
Light leakage was observed at the edge of the dot 1 having a size of less than 0.5 mm. When the magnified observation was performed using a loupe under reflected light, cracks were observed in the black ceramic color paint 3 which caused light leakage. Dot 1 of 0.5mm or more on one side
No light leakage was observed at the edge. Example 1 FIG. 3 is a schematic plan view of a rear glass for an automobile. A rear glass for an automobile was produced according to the following procedure.

The thickness of the black ceramic color paste cut into the shape of the rear glass of a sedan type passenger car,
A 3.5 mm float glass sheet (soda lime silicate glass), which was a glass substrate G, was applied to a frame shape and dried for 10 minutes in a drying furnace adjusted to a drying temperature of 120 ° C. Using a screen with a mesh size of # 250, a high-color T (trade name, manufactured by Mitsuboshi Belting Co., Ltd.), which is a colorant for glass coloring using commercially available noble metal colloid fine particles as a coloring source, was placed on one side thereof. 1.0mm to 0.4
mm was applied by a screen printer so as to form a dot pattern 1 of square dots 1 changed by 0.02 mm at a time. At this time, the dot pattern 1 gradually becomes smaller from the periphery of the glass substrate G toward the center.
The size of the square dot 1 in the portion overlapping the black ceramic color print 3 was 0.5 mm or more on one side. Then, the drying temperature 15
After drying at 0 ° C. for 5 minutes, it was heated at 650 ° C. in a firing furnace for 3 minutes.
After baking for minutes, it was air-cooled for strengthening to obtain an automobile rear glass.

When the obtained rear glass for an automobile was visually observed by transmission in a dark room using a fluorescent lamp, no light leakage was observed at the portion where the black ceramic color print 3 and the dot 1 overlapped. Appearance was good as a rear glass. Example 2 A rear glass for an automobile was prepared in the same manner as in Example 1 except that the shape of the dot 1 was changed from a square to a circle, and the size of the dot 1 overlapping the black ceramic color print 3 was 0.5 mm in diameter. It was above.

When the obtained rear glass for an automobile was visually observed by transmission using a fluorescent lamp in a dark room, no light leakage was observed at the portion where the black ceramic color print 3 and the dot 1 overlapped. Appearance was good as a rear glass. Comparative Example 1 Black ceramic color paste 3 cut into a rear glass shape of a sedan type passenger car, 3.5 mm in thickness.
Float glass (soda lime silicate glass)
Is applied to the frame shape of the glass substrate G which is
It dried for 5 minutes in the drying furnace adjusted to ° C. From above, one side, from 0.8 mm to 0.4 mm, 0.02 m
Using a screen of mesh size # 250 having a square pattern changed by m, one side, 1.0 m
High Color T (Mitsuboshi Belt Co., Ltd.) is a colorant for glass coloring using commercially available noble metal colloidal fine particles as a coloring source so as to form a dot pattern 1 of square dots 1 changed from m to 0.4 mm by 0.02 mm in steps of 0.02 mm. ), Trade name) was applied by a screen printing machine. At this time, when the rear glass for an automobile is used, the shade band 2 is formed by a conventional dot pattern 1 that gradually decreases downward from the upper portion of the glass substrate G. Unlike the first embodiment, the size is gradually reduced from the upper part to the lower part. Then, after drying at a drying temperature of 120 ° C. for 5 minutes, baking at 650 ° C. for 3 minutes in a firing furnace,
Air-cooled rear glass for automobiles was obtained for strengthening.

When the obtained rear glass for an automobile was visually observed by transmission in a dark room using a fluorescent lamp, a portion smaller than 0.5 mm on one side at a portion where the black ceramic color print 3 and the dot 1 overlapped each other. Dot 1
In this case, light leakage was observed, which was not preferable as a rear glass for an automobile. Comparative Example 2 A rear glass for an automobile was prepared in the same manner as in Comparative Example 1 except that the shape of the dot 1 was changed from a square to a circle, and the circular dot 1 overlapping the black ceramic print 3 was formed.
The size of was gradually reduced from the upper part to the lower part.

When the obtained rear glass for an automobile was visually observed by transmission in a dark room using a fluorescent lamp, a diameter smaller than 0.5 mm was found at a portion where the black ceramic color print 3 and the dot 1 overlapped. Light leakage was observed at the edge of the dot, which was not preferable as a rear glass for automobiles.

[0043]

According to the present invention, there is provided an automotive glass with a shade band having a frame-shaped portion formed of a ceramic color print on a surface on the indoor side and a shade band formed of a dot pattern using noble metal colloid fine particles as a coloring source. In the overlapping portion, if the size of the dot is rectangular, one side is 0.5 mm or more, if it is circular, the diameter is 0.5 mm or more. Light leakage due to cracks in the ceramic print at the dot portions generated at the overlapping portions can be eliminated.

[Brief description of the drawings]

FIG. 1 is a partial enlarged view of an example of a window glass for a vehicle with a shade band according to the present invention.

FIG. 2 is a diagram illustrating a mechanism of occurrence of cracks in a ceramic color print at a dot edge portion. (A) It is a schematic sectional drawing immediately after printing of the dot of a small size. FIG. 4B is a schematic cross-sectional view of a small-sized dot after leveling. (C) is a schematic sectional view immediately after printing of a large-sized dot. (D) is a schematic sectional view of a large-sized dot after leveling.

FIG. 3 is a schematic plan view of a frame-shaped ceramic color print and an automobile rear glass provided with a shade band.

FIG. 4 is a partially enlarged portion showing a boundary example of a shade band composed of a ceramic color print and a transparent coloring film described in JP-A-5-286358.

[Explanation of symbols]

 1 dot (dot pattern) 2 shade band 3 ceramic color paint 4 mesh 5 emulsion layer

Claims (3)

[Claims] 1. A frame-shaped ceramic color print is applied on the inner peripheral side surface, and a plurality of dots of a transparent colored film made of a noble metal as a color source are printed on the same surface by screen printing. In a car window glass with a shade band that is baked, the dot size of the portion overlapping the ceramic color print of the shade band made up of a plurality of dots is a rectangular dot, one side, 0.5 mm or more, a circular dot , Diameter, 0.5m
m or more, and a window glass for an automobile with a shade band. 2. The method according to claim 2, wherein the transparent colored film is made of Au, Ag, Pt, Pt.
The vehicle window with a shade band according to claim 1, wherein the main component is a precious metal compound and / or precious metal fine particles selected from d and Rh, a fixing agent composed of an organometallic compound, and a binder resin. Glass. 3. The method according to claim 1, wherein the dot pattern of the shade band portion is large at a portion overlapping the ceramic color print at the periphery of the glass, and becomes smaller toward the center of the glass. Automotive window glass with shade band.