Abstract:
In an automotive window glass having a pair transparent sheet glasses that are stuck to each other with a transparent resin film, the inner surface of one of the pair of sheet glasses, which faces the transparent resin film, is coated with a heat-ray intercepting film that is composed of any one of the following chemical formulas whose atomic ratios are defined. 
     (A) ZrN x  O y  : 0.5≦x≦0.8, and 0.8≦x+y≦1.2 
     (B) TiN x  O y  : 0.2≦y≦0.8, and 1.4≦x+y≦1.8 
     (C) CrN x  O y  : 0.1≦y≦0.8, and 1.4≦x+y≦1.8

Description:
This is a continuation of application Ser. No. 07/837,158, filed Feb. 18, 1992 now abandoned. 
    
    
     BACKGROUND OF THE INVENTION 
     1. Field of the Invention 
     This invention relates generally to an automotive window glass, and particularly, but not exclusively, to an automotive window glass with a film for screening the inside of a car from solar radiation, and an antenna conductor. 
     2. Description of Related Art 
     Recently, there is a tendency that automotive window glasses increase in area, whereby solar radiation energy is given more in the inside of a car. Thus, the inside is air-conditioned to prevent it from a rise in temperature, and in order to reduce a cooling load, a film for screening the inside from the solar radiation has been used so far. 
     Moreover, in the automotive window glass, particularly in a windshield, it is required, from a security viewpoint, to use a laminated glass that transmits 70 percent or more of visible light, and it is also required, from a designing viewpoint, that if the glass is coated with a heat-ray intercepting film, the appearance of such glass is not so much different in color from that of a glass having no heat-ray intercepting film: the glass should appear nearly achromatic like the glass having no heat-ray intercepting film, and should be prevented from dazzling reflections of light. 
     It is further required that the radio waves radiating and receiving characteristics of antennas for a portable telephone or a global positioning system (GPS) set in the inside of the car, or the receiving characteristics of antenna conductors secured to the outer surface of the automotive window glass is not damaged due to a heat-ray intercepting film sandwiched in between laminated glasses of the automotive window glass. One example of the latter is disclosed in Japanese Laid Open Patent No. 177601/1990, in which the heat-ray intercepting film is made of chromium oxynitride (CrN x  O y ) or titanium oxynitride (TiN x  O y ), and it is reported that the antenna sensitivity was not damaged at all. 
     However, the disclosed automotive window glass is such that a surface of a single sheet glass is covered with a chromium or titanium oxynitride film. It is, therefore, not a laminated glass having a heat-ray intercepting film, and does not appear nearly achromatic, so that it is not usable for the car. 
     OBJECTS AND SUMMARY OF THE INVENTION 
     Accordingly, it is an object of the present invention to provide an automotive window glass which does not dazzle in light so as to match its color to that of a car, and screens the inside of the car from solar radiation so as to reduce a load for cooling the inside. 
     Another object of the invention is to provide an automotive window glass in which if an antenna is secured thereto, the radio waves receiving characteristic of the antenna is not damaged by a heat-ray intercepting film used therewith. 
     A further object of the invention is to provide an automotive window glass in which if an antenna is provided in the inside of a car, the radio waves radiating and receiving characteristic of the antenna is not damaged by a heat-ray intercepting film used therewith. 
     In accordance with an aspect of this invention, in an automotive window glass comprising a pair of transparent sheet glasses and a transparent resin film with which the pair of sheet glasses are stuck together, the window glass further comprises a second film sandwiched between one of said pair of sheet glasses and the transparent resin film so as to screen the inside of a car from solar radiation, the second film having any one of the following compositions represented by chemical formulas with which atomic ratios are defined. 
     (A) ZrN x  O y:  0.5≦x≦0.8 and, 0.8≦x+y≦1.2 
     (B) TiN x  O y:  0.2≦y≦0.8 and, 1.4≦x+y≦1.8 
     (C) CrN x  O y:  0.1≦y≦0.8 and, 1.4≦x+y≦1.8 
     When in Formula A, x is, and in formulas B and C, y are larger than 0.8, the characteristic of the heat-ray intercepting film deteriorates, and the window glass becomes so yellowish as not to be suitable for the car. When in Formula A, x is smaller than 0.5; in Formula B, y is smaller than 0.2; and in Formula C, y is smaller than 0.1, the film characteristic deteriorates, the absorption of visible light becomes high, whereby the window glass becomes not transparent enough, and the sheet resistivity becomes small, whereby it is impossible to obtain such a window glass as to be transparent enough, to have a good heat-ray intercepting characteristic, and to be transmissible of electromagnetic waves. 
     When in Formula A, x falls within 0.5-0.8, and (x+y) falls within 0.8-1.2; in Formula B, y falls within 0.2-0.8, and (x+y) falls within 1.4-1.8; and in Formula C, y falls within 0.1-0.8, and (x+y) falls within 1.4-1.8, the window glass of this invention, which includes the heat-ray intercepting film, was compared with a window glass which includes no such film but, as for the rest, is the same as that of this invention. Coordinates a and b of the two window glasses on the Hunter chromaticity plane were examined, respectively, and respective differences Δa and Δb between the two window glasses were calculated. As the result, it was possible to fall the differences Δa and Δb within -5-+5, and according to observation with the naked eye, there were scarcely any difference between the two window glasses. 
     Sheet resistivities of the heat-ray intercepting film are 1 kΩ/□ or more, so that respective antennas secured to the window glass of this invention, and loaded in the car to which such window glass is applied will be able to receive well, and radiate or receive well radio waves. 
     In a preferred embodiment of this invention, the second film has such a thickness as to transmit seventy percent or more of visible light. The thickness of the zirconium, titanium or chromium oxynitride film should be determined upon consideration of the visible-light transmissivity, heat-ray intercepting characteristic and colorific appearance of the window glass. In order to obtain seventy percent of more of the visible-light transmissivity, it is preferable to determine the thickness within a range of 3-15 nm, particularly, 5-10 nm. When the thickness is less than 3 nm, the heat-ray intercepting characteristic becomes not enough, and when it is more than 15 nm, the visible-light transmissivity deteriorates, whereby the window glass is not transparent enough. 
     Various kinds of sheet glasses can be used for the transparent sheet glass of this invention. For example, colorless sheet glasses or heat-ray intercepting sheet glasses of a bronze, grey or blue color, manufactured under the float process will be usable, and may also be treated under bending and/or tempering processes. The refractive index thereof is about 1.52. 
     As a material for the transparent resin film for sticking the pair of transparent sheet glasses to each other, it is preferable to use such a resin that the refractive index thereof is the same as that of the transparent sheet glasses. For example, it is preferable to use polyvinyl butyral whose refractive index is about 1.52, because it is excellent for the adhesive force and weatherproofness. 
     Moreover, in a preferred embodiment of this invention, an antenna conductor is provided on the outer surface of the other of the pair of sheet glasses, or between the inner surface of the other sheet glass and the transparent resin films. In this connection, the reception ability of the antenna conductor does not deteriorate, and the window glass appears nearly achromatic. The antenna conductor may be made, for example, by means of printing and then baking a silver paste on, or securing fine conductive wires to the surface of the sheet glass. 
     Various coating methods,such as a sputtering, ion-plating or vacuum arc-deposition method, of forming a film after atomizing a material therefor in a low atmospheric pressure are available for forming the heat-ray intercepting film of this invention. Particularly, the sputtering method is very suitable for a laminated glass that is very excellent in a heat-ray intercepting characteristic. The source of the sputtering method may be either direct or high frequency current. 
     When the zirconium, titanium or chromium oxynitride film is formed by the sputtering method, the targets used for the respective methods are made of zirconium, titanium or chromium, and the atmosphere during sputtering may include nitrogen and oxygen. The ratio between nitrogen and oxygen included in the formed film depends upon the composition and pressure of the atmosphere during sputtering. To stick the pair of transparent sheet glasses to each other with the transparent resin film, various well-known methods are available. 
     Respective amounts of nitrogen and oxygen in the heat-ray intercepting film of this invention are determined in relation to metals included in the film, so that the window glass is prevented from dazzling reflections of light, and has a high transmissivity of visible light and a high heat-ray intercepting characteristic. Further, if an antenna conductor is secured to the window glass of this invention, the reception ability of the antenna conductor does not deteriorate, because the window glass of this invention has a high electric resistance. 
     The invention will now be described by way of some examples with reference to the accompanying drawings, throughout which like parts are referred to like references. 
    
    
     BRIEF DESCRIPTION OF THE DRAWINGS 
     FIGS. 1-3 are fragmentary sectional views of automotive window glasses according to first to third embodiments of this invention, respectively; and 
     FIG. 4 is a perspective view of the automotive window glass of FIG. 2. 
    
    
     DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS 
     Referring initially to FIG. 1, it will be seen that an automotive window glass 6 comprises a pair of transparent sheet glasses: first sheet glass 2 and second sheet glass 3, a heat-ray intercepting film 1 and a transparent resin film 4. The outer surface of the first transparent sheet glass 2 faces the outdoors, and the inner surface thereof is coated with the heat-ray intercepting film 1. The transparent resin film 4 sandwiched between the heat-ray intercepting film 1 and the second transparent sheet glass 3 sticks the second transparent sheet glass 3 to the first transparent sheet glass 2 that is coated with the heat-ray preventing film 1. The outer surface of the second sheet glass faces the inside of a car. 
     In FIG. 2, the automotive window glass 6 has an antenna conductor 5 between the transparent resin film 4 and the second transparent sheet glass 3, the antenna conductor 5 being made of a fine copper wire that extends vertically downwards along the axis of the window glass 3 as illustrated in FIG. 4. In FIG. 3, the automotive window glass 6 has antenna conductors 5 secured to the outer surface of the second transparent sheet glass 3. 
     EXAMPLE 1 
     Both a heat absorbing glass (manufactured by Nippon Sheet Glass Co., Ltd., and sold under the name of &#34;BRONZEPANE&#34;), which is 2.1 mm in thickness, bronze in color, molded in a windshield size of a car and washed, and a 10 cm square of the glass for examining its composition and so forth are placed in a vacuum chamber of a sputtering device, from which air is exhausted to 0.004 Pa. 
     Then, a mixed gas having a ratio of 100 cc of argon to 180 cc of nitrogen is supplied to the vacuum chamber until its pressure becomes 0.4 Pa. 30 amperes of an electric current are supplied to the target of metallic zirconium to perform sputtering of predetermined duration, and obtain a film of 7 nm thickness on the concave surface of the heat absorbing glass and one surface of the 10 cm square of the glass. The latter is examined with an ESCA analyser, and it becomes clear that the film is of zirconium oxynitride. A result of its quantitative analysis is shown in Table 1. 
     
                                           TABLE 1__________________________________________________________________________Characteristics of Heat-ray Intercepting Films and ApplicationThereof to Laminated Glasses                Laminated Glass                Transmissivity    Reflectivity on                        Dif. bet. the outdoors sideHeat-ray Intercepting Film   glasses                             Diff.    Diff.        Sheet       Solar                        with and                             on the   on the    Atomic        resis-            Thick-                Visible                    radi-                        without                             Hunter                                  Visible                                      HunterTest    Chemical    ratio        tivity            ness                light                    ation                        the film                             plane                                  light                                      planeSeries    formula    x y (Ω/□)            (nm)                (%) Tg (%)                        ΔTg (%)                             Δa                                Δb                                  (%) Δa                                        Δb__________________________________________________________________________Ex. 1    ZrN.sub.x O.sub.y    0.6      0.4        3.4k            7   71.5                    59.6                        13.2 -1.2                                1.5                                  7.9 0.4                                        -3.1Ex. 2    TiN.sub.x O.sub.y    1.2      0.4        1.5k            7   71.7                    59.7                        13.1 -1.7                                2.5                                  7.7 0.5                                        -3.5Ex. 3    CrN.sub.x O.sub.y    1.2      0.4        50k 6   70.5                    62.8                        10.0 -1.2                                1.1                                  8.9 0.2                                        -2.3Ex. 4    ZrN.sub.x O.sub.y    0.8      0.2        80k 9   71.0                    62.3                        10.5 -1.4                                3.6                                  9.5 0.2                                        -5.1Ex. 5    TiN.sub.x O.sub.y    0.9      0.7        50k 8   70.9                    59.2                        13.6 -2.1                                4.1                                  8.9 0.2                                        -3.5Ex. 6    CrN.sub.x O.sub.y    0.8      0.8        500k            7   70.3                    63.7                         9.1 -1.3                                2.9                                  9.1 0.1                                        -3.1Comp.    ZrN.sub.x O.sub.y    0.9      0.3        500k            11  71.2                    65.3                         9.5 -1.3                                6.1                                  10.5                                      0.1                                        -6Ex. 1Comp.    TiN.sub.x O.sub.y    0.8      1.0        100k            10  71.8                    60.8                        12   -2.3                                6.5                                  10.6                                      0.3                                        -5.9Ex. 2Comp.    CrN.sub.x O.sub.y    0.5      1.1        &gt;2M 9   70.4                    66.3                         8.5 -1.2                                6.2                                  8.9 0.2                                        -4.1Ex. 3__________________________________________________________________________ 
    
     Oxygen in the film seems to have been supplied from the gas remained in the vacuum chamber before the sputtering is performed, or from the surface of the heat absorbing glass. It is noted that the sheet resistivity of the film is 3.4 k/Ω/□. 
     A transparent glass molded in the same size as that of the heat absorbing glass and having a thickness of 2.1 mm is stuck, with polyvinyl butyral, to the surface of the heat absorbing glass, which has been coated with the zirconium oxynitride film, and pressed under the pressure of 15 kg/cm 2  at temperature of 120° C. in an autoclave. An optical characteristics of a laminated glass thus obtained is also shown in Table 1. 
     Next, an antenna conductor made of copper is secured to the outer surface of the transparent glass, and various characteristics of the laminated glass: the transmissivity of visible light, the transmissivity of sun light, the reflectivity of visible light, and the difference with a filmless laminated-glass on the Hunter plane are examined and also shown is Table 1. 
     Moreover, the electromagnetic-wave transmission characteristic of the laminated glass is measured within a range of 1 kHz-1.575 GHz by a method proposed by &#34;Kansai Denshikogyo Shinko Center (denoted by KEC)&#34;, and shown in Table 2. 
     
                       TABLE 2______________________________________Transmissivity Reduction ofElectromagnetic Waves (dB)                          880 MHz 1.575 GHz    1       90     400 MHz                          for     for    kHz     MHz    for TV telephone                                  satellite    for     for    broad- communi-                                  communi-Frequency    AM      FM     casting                          cations cations______________________________________Example 1    ±0   ±0  ±0  ±0   ±0Example 2    ±0   ±0  ±0  ±0   -0.01Example 3    ±0   ±0  ±0  ±0   ±0Example 4    ±0   ±0  ±0  ±0   ±0Example 5    ±0   ±0  ±0  ±0   ±0Example 6    ±0   ±0  ±0  ±0   ±0Comp. Ex. 1    ±0   ±0  ±0  ±0   ±0Comp. Ex. 2    ±0   ±0  ±0  ±0   ±0Comp. Ex. 3    ±0   ±0  ±0  ±0   ±0______________________________________ 
    
     It will be seen that is no sensitivity reduction, if the heat-ray intercepting film is used. 
     EXAMPLE 2 
     In lieu of metallic zirconium, metallic titanium is used for the target of a magnetron sputtering-device, and by the same method as that used in Example 1 except supplying a mixed gas having a ratio of 100 cc of argon to 500 cc of nitrogen, a film having a thickness of 7 nm is formed on the concave surface of a heat absorbing glass and one surface of a 10 cm square of the glass. The film of the 10 cm square is examined by an ESCA analyser and it becomes clear that the film contains oxygen and is of titanium oxynitride. A result of its quantitative analysis is shown in Table 1. Oxygen in the film seems to have been supplied from the gas remained in the vacuum chamber before the sputtering is performed, or from the surface of the heat absorbing glass. It is noted that the sheet resistivity of the film is 1.5 kΩ/□. 
     A laminated glass with an antenna conductor is made by the same method as that used in Example 1, and its various characteristics are examined and shown in Tables 1 and 2. 
     EXAMPLE 3 
     In lieu of metallic zirconium, metallic chromium is used for the target of a magnetron sputtering-device, and by the same method as that used in Example 1 except supplying a mixed gas having a ratio of 100 cc of argon to 300 cc of nitrogen, a film having a thickness of 6 nm is formed on the concave surface of a heat absorbing glass and one surface of a 10 cm square of the glass. The film of the 10 cm square is examined by an ESCA analyser and it becomes clear that the film contains oxygen and is of chromium oxynitride. A result of its quantitative analysis is shown in Table 1. Oxygen in the film seems to have been supplied from the gas remained in the vacuum chamber before the sputtering is performed, or form the surface of the heat absorbing glass. It is noted that the sheet resistivity of the film is 50 kΩ/□. 
     A laminated glass with an antenna conductor is made by the same method as that used in Example 1, and its various characteristics are examined and shown in Tables 1  and 2. 
     EXAMPLE 4 
     By the same method as that used in Example 1 except supplying a mixed gas having a ratio of 100 cc of argon to 230 cc of nitrogen to a magnetron sputtering device, a film having a thickness of 9 nm is formed on the concave surface of a heat absorbing glass and one surface of a 10 cm square of the glass. The film of the 10 cm square is examined by an ESCA analyser and it becomes clear that the film contains oxygen and is of zirconium oxynitride. A result of its quantitative analysis is shown in Table 1. Oxygen in the film seems to have been supplied from the gas remained in the vacuum chamber before the sputtering is performed, or from the surface of the heat absorbing glass. It is noted that the sheet resistivity of the film is 80 kΩ/□. 
     A laminated glass with an antenna conductor is made by the same method as that used in Example 1, and its various characteristics are examined and shown in Tables 1 and 2. 
     EXAMPLE 5 
     In lieu of metallic zirconium, metallic titanium is used for the target of a magnetron sputtering-device, and by the same method as that used in Example 1 except supplying a mixed gas having a ratio of 100 cc of argon to 300 cc of nitrogen to 1 cc of oxygen, a film having a thickness of 8 nm is formed on the concave surface of a heat absorbing glass and one surface of a 10 cm square of the glass. The film of the 10 cm square is examined by an ESCA analyser and it becomes clear that the film contains oxygen and is of titanium oxynitride. A result of its quantitative analysis is shown in Table 1. It is noted that the sheet resistivity of the film is 50 kΩ/□. 
     A laminated glass with an antenna conductor is made by the same method as that used in Example 1, and its various characteristics are examined and shown in Tables 1 and 2. 
     EXAMPLE 6 
     In lieu of metallic zirconium, metallic chromium is used for the target of a magnetron sputtering-device, and by the same method as that used in Example 1 except supplying a mixed gas having a ratio of 100 cc of argon to 300 cc of nitrogen to 20 cc of oxygen, a film having a thickness of 7 nm is formed on the concave surface of a heat absorbing glass and one surface of a 10 cm square of the glass. The film of the 10 cm square is examined by an ESCA analyser and it becomes clear that the film contains oxygen and is of chromium oxynitride. A result of its quantitative analysis is shown in Table 1. It is noted that the sheet resistivity of the film is 500 kΩ/□. 
     A laminated glass with an antenna conductor is made by the same method as that used in Example 1, and its various characteristics are examined and shown in Tables 1 and 2. 
     COMPARATIVE EXAMPLE 1 
     By the same method as that used in Example 1 except supplying a mixed gas having a ratio of 100 cc of argon to 300 cc of nitrogen, a film having a thickness of 11 nm is formed on the concave surface of a heat absorbing glass and one surface of a 10 cm square of the glass. The film of the 10 cm square is examined by an ESCA analyser and it becomes clear that the film contains oxygen and is of zirconium oxynitride. A result of its quantitative analysis is shown in Table 1. Oxygen in the film seems to have been supplied from the gas remained in the vacuum chamber before the sputtering is performed, or from the surface of the heat absorbing glass. It is noted that the sheet resistivity of the film is 500 kΩ/□. 
     A laminated glass with an antenna conductor is made by the same method as that used in Example 1, and its various characteristics are examined and shown in Tables 1 and 2. 
     COMPARATIVE EXAMPLE 2 
     In lieu of metallic zirconium, metallic titanium is used for the target of a magnetron sputtering-device, and by the same method as that used in Example 1 except supplying a mixed gas having a ratio of 100 cc of argon to 300 cc of nitrogen to 30 cc of oxygen, a film having a thickness of 10 nm is formed on the concave surface of a heat absorbing glass and one surface of a 10 cm square of the glass. The film of the 10 cm square is examined by an ESCA analyser and it becomes clear that the film contains oxygen and is of titanium oxynitride. A result of its quantitative analysis is shown in Table 1. It is noted that the sheet resistivity of the film is 100 kΩ/□. 
     A laminated glass with an antenna conductor is made by the same method as that used in Example 1, and its various characteristics are examined and shown in Tables 1 and 2. 
     COMPARATIVE EXAMPLE 3 
     In lieu of metallic zirconium, metallic chromium is used for the target of a magnetron sputtering-device, and by the same method as that used in Example 1 except supplying a mixed gas having a ratio of 100 cc of argon to 300 cc of nitrogen to 100 cc of oxygen, a film having a thickness of 9 nm is formed on the concave surface of a heat absorbing glass and one surface of a 10 cm square of the glass. The film of the 10 cm square is examined by an ESCA analyser and it becomes clear that the film contains oxygen and is of chromium oxynitride. A result of its quantitative analysis is shown in Table 1. It is noted that the sheet resistivity of the film is 2 MΩ/□. 
     A laminated glass with an antenna conductor is made by the same method as that used in Example 1, and its various characteristics are examined and shown in Tables 1 and 2. 
     It will be seen that the respective laminated glasses disclosed in Examples 1-6 can transmit 70% or more of visible light, and have such characteristics that the respective differences Δa and Δb of the coordinates of the Hunter chromaticity plane between the laminated glasses disclosed in Example 1-6 and the laminated glasses having no heat-ray intercepting film are less than 5, so that the heat-ray intercepting film scarcely influences the color of the laminated glass. Further, it will be seen that the respective laminated glasses with antenna conductors disclosed in Examples 1-6 have the radio-waves transmitting characteristics similar to those having no heat-ray intercepting film. 
     Having described illustrative embodiments of this invention with reference to the accompanying drawings, it is to be understood that the invention is not limited to that precise embodiments, and that various changes and modifications may be effected therein by one skilled in the art without departing from the scope or spirit of the invention as defined in the appended claims.