JP2010251230A - Electric window glass - Google Patents

Abstract

A metal wire group is hardly visible and heat generation at a contact portion between the metal wire group and an electrode is suppressed at low cost.
An electrothermal window glass includes a heat generating portion formed along a longitudinal direction, and a first electrode and a second electrode formed above and below the heat generating portion. The heat generating portion 14 is formed with a heat generating area 43 composed of a mesh pattern 43A having a large fine wire interval between the fine metal wires 42. The first electrode 16 and the second electrode 18 are meshes having a small fine wire interval between the fine metal wires 42. An electrode area 44 made of a pattern 44A is formed. Assuming that the ratio of the area covered by the fine metal wires to the total area of each area is Ae% for the electrode area 44 and Ac% for the heat generation area 43,
Ac ≦ Ae, 5 ≦ Ae, and 0 <Ac ≦ 20 are satisfied.
[Selection] Figure 1

Description

  The present invention relates to an electrothermal window glass.

  2. Description of the Related Art Conventionally, an electric heating window is known in which an electrode wire is embedded in a window glass of an automobile, an aircraft, a ship, and the like, and an electric current is heated through the electrode wire.

  Patent Document 1 below discloses a structure in which electric heating wires are arranged at intervals of several mm on a three-dimensional curved glass so that the arrangement of the electric heating wires extends over substantially the entire transparent portion of the window.

JP-A-9-207718

  In Patent Document 1, the process of arranging the electric heating wires on the three-dimensional curved glass at intervals of several millimeters is complicated and expensive. If an electric heating window is provided in front of the driver's seat, the electric heating wire can be seen from the driver's seat and it is difficult to drive. Furthermore, the resistance of the contact portion between the electric heating wire and the electrode is large, and heat may be generated at the contact portion.

  The present invention has been made in consideration of such problems, and provides an electrically heated window glass in which the thin metal wire group is hardly visible and heat generation at the contact portion between the thin metal wire group and the electrode can be suppressed at a low cost. The purpose is to do.

The electrothermal window glass according to the first aspect of the present invention includes one or more glass layers made of a window glass material, and a conductive layer in which a number of fine metal wire groups are formed on a support supported by the glass layer. A pair of electrodes provided on both sides in the surface direction of the conductive layer and supplying electricity to the conductive layer, the conductive layer comprising an electrode area provided with the electrode, and the electrode A heating area where the metal thin wire group generates heat between the areas, and the area E covered by the metal thin wire group accounts for the area E of the electrode area as Ae% and the area C of the heating area When the ratio occupied by the area c covered with the metal thin wire group is Ac%,
Ac ≦ Ae, 5 ≦ Ae, and 0 <Ac ≦ 20
Meet.

  According to the above invention, the transparency of the heat generation area becomes higher than that of the electrode area when Ae, which is the ratio of the metal thin wire group in the electrode area, and Ac, which is the ratio of the metal thin wire group in the heat generation area, satisfy the above relational expression. The metal thin wire group is less visible from the driver's seat. Moreover, by satisfy | filling the said relational expression, the resistance of the contact part of a metal fine wire group and an electrode becomes small, and it can suppress the heat_generation | fever of a contact part. In addition, since the structure is such that Ae, which is the ratio of the metal thin wire group in the electrode area, and Ac, which is the ratio of the metal thin wire group in the heat generating area, manufacturing is easy and cost reduction is possible.

  According to a second aspect of the present invention, in the configuration of the first aspect, the support has a non-heat-generating area that is not covered with the metal thin wire group.

  According to said invention, the support body has the non-heat-generation area which is not covered with the metal fine wire group, It can comprise so that the unnecessary area | region of an electrothermal window glass may not be heated. In addition, although the area covered with the thin metal wire group is easily shielded from radio waves used in the ETC system or the like, shielding the radio waves is prevented by providing a non-heat generating area.

  According to a third aspect of the present invention, in the configuration of the first or second aspect, a conductive paste layer and a metal foil are sequentially laminated on the metal thin wire group in the electrode area, and the metal The foil is connected to an electric wire connected to an electric power source.

  According to the above invention, by sequentially laminating the conductive paste layer and the metal foil on the metal thin wire group in the electrode area, the resistance of the contact portion between the metal thin wire group and the electrode is reduced, and the heat generation in the contact portion is reduced. Can be suppressed.

  According to a fourth aspect of the present invention, in the configuration according to the first or second aspect, a metal foil is laminated on the thin metal wire group in the electrode area, and the thin metal wire group in the electrode area. The line width is larger than the line width of the metal thin wire group in the heat generating area, and the metal foil is connected to an electric wire connected to an electric supply source.

  According to the above invention, the metal foil is laminated on the metal wire group in the electrode area, and the line width of the metal wire group in the electrode area is made larger than the line width of the metal wire group in the heat generating area. The resistance of the contact portion between the thin wire group and the electrode is reduced, and heat generation at the contact portion can be suppressed.

  According to a fifth aspect of the present invention, in the configuration according to the first or second aspect, a metal foil is laminated on the metal thin wire group in the electrode area, and the unit per unit area of the electrode area. The number of metal thin wire groups is larger than the number of the metal thin wire groups per unit area of the heat generating area, and the metal foil is connected to an electric wire connected to an electric supply source.

  According to the above invention, the metal foil is laminated on the metal thin wire group in the electrode area, and the number of metal thin wire groups per unit area in the electrode area is larger than the number of metal thin wire groups per unit area in the heat generating area. By increasing the resistance, the resistance of the contact portion between the metal thin wire group and the electrode is reduced, and heat generation at the contact portion can be suppressed.

  According to a sixth aspect of the present invention, in the configuration according to any one of the first to fifth aspects, the metal fine wire group in the heat generation area is blackened, and the metal fine wire group in the electrode area Is not blackened.

  According to said invention, a metal fine wire group becomes difficult to visually recognize by carrying out the blackening process (for example, nickel plating etc.) of the metal fine wire group of an exothermic area. Moreover, it is possible to avoid an increase in the resistance of the thin metal wire group in the electrode area by not blackening the thin metal wire group in the electrode area.

  The invention according to claim 7 is the configuration according to any one of claims 1 to 6, wherein at least one of the pair of electrodes is bent halfway, and the distance between the pair of electrodes is different. 2 or more.

  According to said invention, it has two or more areas where the distance between a pair of electrodes differs, and the outer side of the area where the distance between a pair of electrodes is short is not covered with the metal fine wire group. For this reason, it is possible to prevent the radio waves used in the ETC system or the like from being shielded.

  According to an eighth aspect of the present invention, in the configuration according to the seventh aspect, a non-heat generation area not covered with the metal thin wire group is provided at a position adjacent to an area where the distance between the pair of electrodes is short. .

  According to the above invention, it is possible to shield radio waves used in an ETC system or the like by providing a non-heat generating area that is not covered with a thin metal wire group at a position adjacent to an area where the distance between the pair of electrodes is short. Can be blocked. Moreover, there are few positional restrictions which provide a non-heat-generating area, and the freedom degree of design improves.

  According to a ninth aspect of the present invention, in the configuration of the seventh or eighth aspect, when the voltage is applied to the pair of electrodes to cause the metal thin wire group in the heat generating area to generate heat, the heat generating area The surface resistance of the metal thin wire group in the heat generating area is controlled so that the heat generation amount per unit area of the heat generating area is uniform.

  According to the above invention, by controlling the surface resistance of the thin metal wire group in the heat generating area where the distance between the pair of electrodes is different, the heat generation amount per unit area of the heat generating area is made substantially uniform, and uneven heat generation is suppressed. Can do.

  A tenth aspect of the present invention is the configuration according to any one of the seventh to ninth aspects, wherein the line width of the thin metal wire group is changed in proportion to the distance between the pair of electrodes. .

  According to said invention, the line | wire width of a metal fine wire group is changed so that it may be proportional to the distance between a pair of electrodes. That is, by increasing the line width of the thin metal wire group as the distance between the pair of electrodes increases, the amount of heat generation per unit area of the heat generation area where the distance between the pair of electrodes is different can be made substantially uniform.

  According to an eleventh aspect of the present invention, in the configuration according to any one of the seventh to ninth aspects, the distance between the fine metal wires of the fine metal wire group is set to be inversely proportional to the distance between the pair of electrodes. Change.

  According to said invention, the distance between metal fine wires of a metal fine wire group is changed so that it may be inversely proportional to the distance between a pair of electrodes. That is, by reducing the distance between the fine metal wires of the fine metal wire group as the distance between the pair of electrodes becomes longer, the heat generation amount per unit area of the heat generation area where the distance between the pair of electrodes is different can be made substantially uniform. it can.

  According to a twelfth aspect of the present invention, in the configuration according to any one of the seventh to eleventh aspects, a high resistance having a resistance higher than that of the area at a boundary between areas where the distance between the pair of electrodes is different. There is an area.

  According to the above invention, by providing the high resistance area having higher resistance than the area at the boundary of the area where the distance between the pair of electrodes is different, it is possible to divide the area to generate heat on both sides of the high resistance area.

  According to a thirteenth aspect of the present invention, in the configuration according to any one of the seventh to eleventh aspects, an insulating layer is provided at a boundary between areas where the distance between the pair of electrodes is different.

  According to said invention, the insulating layer is provided in the boundary of the area where the distance between a pair of electrodes differs, and the area | region which generate | occur | produces heat | fever can be divided on both sides of an insulating layer.

  According to the electrothermal window glass of the present invention, the metal fine wire group is hardly visible, and heat generation at the contact portion between the metal fine wire group and the electrode can be suppressed at a low cost.

It is a top view which shows the whole structure of the electrothermal window glass which concerns on 1st Embodiment. It is sectional drawing which shows the heat_generation | fever area of the electroconductive film in the electrothermal window glass which concerns on 1st Embodiment. It is sectional drawing which shows the electrode area of the electroconductive film in the electrothermal window glass which concerns on 1st Embodiment. It is an expanded block diagram which shows the metal thin wire | line group of the heat_generation | fever area of an electroconductive film and the electrode area in the electrothermal window glass which concerns on 1st Embodiment. FIG. 5A to FIG. 5E are process diagrams showing an example (first method) of a method for forming a mesh pattern with fine metal wires according to the first embodiment. It is sectional drawing which shows the electroconductive film in the electrothermal window glass which concerns on 1st Embodiment. It is an expanded block diagram which shows the metal thin wire | line group of the heat_generation | fever area of an electroconductive film and an electrode area in the electrothermal window glass which concerns on 2nd Embodiment. It is a top view which shows the whole structure of the electrothermal window glass which concerns on 3rd Embodiment. It is an expanded block diagram which shows the metal thin wire | line group of the 1st heat_generation | fever area, 2nd heat_generation | fever area, and electrode area of the electroconductive film in the electrothermal window glass which concerns on 3rd Embodiment. It is an enlarged block diagram which shows the metal thin wire | line group of the 1st heat_generation | fever area, the 2nd heat_generation | fever area, and electrode area of the electroconductive film in the electrothermal window glass which concerns on 4th Embodiment. It is a top view which shows the whole structure of the electrothermal window glass which concerns on the modification of 3rd Embodiment.

[First Embodiment]
Hereinafter, the electric heating window glass which is 1st Embodiment of this invention is demonstrated, referring FIGS.

  FIG. 1 is a plan view showing the entire configuration of the electrothermal window glass. As shown in this figure, the heating window glass 10 has a substantially rectangular heating window glass body 12 in which the upper side and the lower side are substantially parallel and the lower side is longer than the upper side, and the length of the heating window glass body 12. A substantially rectangular heat generating part 14 formed in a strip shape along the direction, and a pair of upper and lower first electrodes 16 and second electrodes 18 disposed so as to oppose the heat generating part 14 are provided. . Furthermore, the non-heating part 20 is provided in the electrothermal window glass main body 12 along the up-down direction on the longitudinal direction both sides (left and right both sides in FIG. 1) of the heating part 14.

  The 1st electrode 16 and the 2nd electrode 18 are arrange | positioned along the edge part of the upper side of the electric heating window glass main body 12, and a lower side, and are formed in substantially parallel and substantially the same length. A power source 22 is connected to the first electrode 16 and the second electrode 18.

  In FIG. 2, the heat generating portion 14 of the electrothermal window glass 10 is shown in a sectional view. In FIG. 2, the cross-section of each member is schematically shown for easy understanding. As shown in this figure, the electrothermal window glass 10 includes two glasses 30 and 32 made of a window glass material, and one glass 30 is provided at a portion sandwiched between the two glasses 30 and 32. A resin layer 34 laminated on the resin layer 34, a conductive film 36 laminated on the resin layer 34, and a resin layer 38 interposed between the conductive film 36 and the other glass 32. A conductive layer 40 is formed on one surface (surface on the resin layer 38 side) of the conductive film 36. The resin layers 34 and 38 are formed of PVB (polyvinyl butyral) in this embodiment. PVB (polyvinyl butyral) is flexible in a normal state, but has a property of being hardened by being crosslinked by heat.

  FIG. 3 is a sectional view showing the first electrode 16 and the second electrode 18 of the electrothermal window glass 10. In FIG. 3, the cross-section of each member is schematically shown for easy understanding. As shown in this figure, the electric heating window glass 10 includes a resin layer 34 and a conductive film 36 sequentially laminated on the glass 30 at a portion sandwiched between two glasses 30 and 32, and A conductive paste layer 46 laminated on the conductive layer 40 of the conductive film 36 and a metal foil 48 laminated on the conductive paste layer 46 are provided. Furthermore, the electrothermal window glass 10 includes a resin layer 38 interposed between the metal foil 48 and the glass 32.

  As shown in FIG. 6, the conductive film 36 includes an insulating transparent film 50 as a support, and a conductive layer 40 formed on one surface of the transparent film 50. As shown in FIG. 4, the conductive layer 40 has a mesh-like pattern as a group of a plurality of fine metal wires having intersections of a large number of lattices formed of conductive metal fine wires 42, and is formed in the heat generating portion 14. The heat generating area 43 including the coarse mesh pattern 43A and the electrode area 44 including the fine mesh pattern 44A formed on the first electrode 16 and the second electrode 18 are provided. That is, a mesh pattern 43A in which the fine wire intervals of the fine metal wires 42 are large is formed in the heat generating area 43, and a mesh pattern 44A in which the fine wire intervals of the fine metal wires 42 are smaller than those in the heat generating area 43 is formed in the electrode area 44. Is formed. On one surface of the conductive film 36, a non-heat generation area 45 where the conductive layer 40 (mesh pattern) is not formed is provided, and the non-heat generation area 45 becomes the non-heat generation portion 20 of the electrothermal window glass 10.

  In the electrothermal window glass 10, the first electrode 16 and the second electrode 18 are configured by the mesh pattern 44 </ b> A of the electrode area 44, the conductive paste layer 46, and the metal foil 48. Although not shown, the metal foil 48 is connected to an electric wire connected to the power source 22.

  By applying a voltage from the power source 22 between the first electrode 16 and the second electrode 18 and energizing the fine metal wires 42 of the conductive layer 40, the mesh pattern 43A of the heat generating area 43 generates heat and becomes a heat generating area. .

  The electric heating window glass 10 is used, for example, for a window glass of a vehicle (for example, a rear glass or a windshield), and is formed in a curved shape that is symmetrical with respect to a center line along the vertical direction.

  Conventionally, the surface heating element used in the rear glass and the headlamp cover is usually heated by using one linear heating element for a small heater such as a headlamp cover, and no more than 10 linear heating elements for a rear glass having a large heater area. The wire heating element was drawn around the entire surface. Since the current flows along the line from one end of the wire heating element to the other end, if all the wire heating elements are the same material and have the same line width and thickness, the amount of heat generated depends on the existence density of the lines. Is decided. In other words, if a heating element is provided so as to have the same density everywhere, a uniform heat generation can be obtained regardless of the shape of the region to be heated.

  However, when the wire heating element is routed as described above, there is a problem that the line heating element can be easily visually recognized with the naked eye and obstructs the field of view when used in a window glass of a vehicle. Therefore, in the present embodiment, a highly heat-generating part 14 is configured by forming a mesh-like pattern 43A composed of fine metal wires 42 in the heat-generating area 43. However, in the highly transparent heat generating portion 14 having such a mesh pattern 43A, there are an infinite number of paths through which current flows, and the current concentrates on paths that have low surface resistance and are easy to flow. Therefore, it is necessary to devise in order to uniformly heat the region where heat generation is desired.

  A method for uniformly heating the heat generating portion 14 having high transparency can be achieved as follows. That is, the mesh pattern 43A is formed so that the heat generating area 43 has a substantially rectangular shape, the belt-shaped first electrode 16 and the second electrode 18 are provided along the longitudinal direction on both sides in the vertical direction of the heat generating area 43, and the first A voltage is applied between the electrode 16 and the second electrode 18 to pass a current. By making the heat generating area 43 in which the mesh pattern 43A is formed into a substantially rectangular shape, heat can be generated substantially uniformly.

  Further, in the case of the configuration in which the linear heating element is drawn in a zigzag manner, there is a problem that a potential difference is generated between adjacent conductive wires, causing migration, but in the present embodiment, the conductive metal thin wire 42 is used. The mesh pattern 43A has a large number of lattice intersections. Since adjacent metal thin wires are short-circuited from the beginning, there is no problem even if migration occurs.

  In addition, when the heat generating area is formed by the mesh pattern, the resistance of the contact portion between the mesh pattern and the pair of electrodes is increased, and heat may be generated at the contact portion. Therefore, a device is required to suppress the heat generation at the contact portion between the mesh pattern and the pair of electrodes.

A method for suppressing heat generation at the contact portion between the mesh pattern and the pair of electrodes can be achieved as follows. That is, the conductive layer 40 of the conductive film 36 is formed in the heat generation area 43 including the mesh pattern 43A in which the fine wire intervals of the metal thin wires 42 formed in the heat generating portion 14 are large, and in the first electrode 16 and the second electrode 18. The electrode area 44 is formed of a mesh pattern 44A in which the fine wire interval of the fine metal wires 42 is small. Further, the ratio of the area covered by the mesh pattern 44A to the entire area of the electrode area 44 (the ratio of the area covered by the mesh pattern 44A of the electrode area 44 to the area of the entire electrode area 44). Ae%, the ratio of the area covered by the mesh pattern 43A to the total area of the heat generation area 43 (the ratio of the area covered by the mesh pattern 43A of the heat generation area 43 to the area of the entire heat generation area 43 ) As Ac%,
Ac ≦ Ae, 5 ≦ Ae, and 0 <Ac ≦ 20
It is configured to satisfy.

  By setting Ac and Ae so as to satisfy the above relational expression, the transparency of the heat generation area 43 is increased, and the mesh pattern 43A of the heat generation area 43 is less likely to be visually recognized from the driver's seat. Further, by setting Ac and Ae so as to satisfy the above relational expression, the resistance of the contact portion between the mesh pattern 43A of the heat generating area 43 and the first electrode 16 or the second electrode 18, that is, the metal thin wire 42 and the metal Resistance between the foils 48 is reduced, and heat generation at the contact portion can be suppressed.

  In the present embodiment, a mesh pattern 43A having a fine wire interval of about 120 μm is formed in the heat generating area 43, and a mesh pattern 44A having a fine wire interval of about 600 μm is formed in the electrode area 44. ing. Since the fine line interval between the mesh pattern 43A of the heat generating area 43 and the mesh pattern 44A of the electrode area 44 is changed, the manufacturing is easy and the cost can be reduced.

  The electrothermal window glass 10 more preferably satisfies Ac <Ae, 10 ≦ Ae, and 0 <Ac <10, and more preferably satisfies Ac <Ae, 30 ≦ Ae, and 0 <Ac <7.

  Moreover, in this embodiment, it is preferable that the line | wire width of the metal fine wire 42 of the heat generation area 43 is 1 micrometer or more and 40 micrometers or less. Thereby, it becomes difficult to see the mesh pattern 43A of the heat generating area 43, and the transparency can be improved.

  The metal foil 48 is preferably a thin metal plate having a low specific resistance such as silver, copper, or aluminum. Moreover, it is preferable that the surface of the metal foil 48 is coated with tin or an alloy of tin and lead in order to prevent oxidation and impart solderability.

  The non-heat generating area 45 is an area without the mesh patterns 43A and 44A, and is not essential in the present invention.

  The electrode area 44 is an area for forming a bus bar for supplying current evenly to the mesh pattern 43A of the heat generation area 43. In this embodiment, a conductive paste layer is formed on the mesh pattern 44A of the electrode area 44. A metal foil 48 is laminated via 46.

  Next, a method for manufacturing the electrothermal window glass 10 will be described.

  First, as a conductive layer 40 on an insulating transparent film 50 (see FIG. 5), a heat generating area 43 composed of a mesh-shaped pattern 43A composed of a conductive fine metal wire 42 and an electrode area 44 composed of a mesh-shaped pattern 44A; Form. A method of forming the mesh patterns 43A and 44A will be described later. Further, a conductive paste layer 46 is formed by applying a conductive paste such as a silver paste on the mesh pattern 44A in the electrode area 44 and performing a heat treatment.

  Next, the PVB film (resin layer 34) on the glass 30, the conductive film 36, the conductive paste layer 46 of the conductive film 36, the metal foil tape (metal foil 48), the PVB film (resin layer 38). Then, the glass 32 is stacked in the order of description, put into a vacuum dryer, vacuum degassed, and then heated while keeping the vacuum to temporarily bond the laminated material of the electrothermal window glass. Furthermore, the laminated material of the electrothermal window glass is taken out from the vacuum dryer, transferred to an autoclave, and heat-treated at 120 to 150 ° C. under a pressure of 0.1 to 20 MPa. can get. The connection of the power source 22 to the first electrode 16 and the second electrode 18 of the electric heating window glass 10 is performed after the electric heating window glass 10 is attached to the window frame of the vehicle.

  Here, several methods (first method to fourth method) for forming the mesh patterns 43A and 44A by the fine metal wires 42 on the transparent film 50 will be described with reference to FIG. The mesh-shaped pattern 43A of the heat generating area 43 and the mesh-shaped pattern 44A of the electrode area 44 are the same in formation method except that the fine wire intervals of the metal thin wires 42 are different. Therefore, in FIG. 5, the heat generating area 43 and the electrode area 44 are distinguished. Explain without.

  The first method is a method in which the mesh-like patterns 43A and 44A are formed by metallic silver portions formed by exposing, developing and fixing a silver salt photosensitive layer provided on the transparent film 50.

  Specifically, as shown in FIG. 5A, a silver salt photosensitive layer 58 formed by mixing silver halide 54 (for example, silver bromide grains, silver chlorobromide grains or silver iodobromide grains) with gelatin 56, as shown in FIG. Is applied onto the transparent film 50. In FIGS. 5A to 5C, the silver halide 54 is expressed as “grains”, but is exaggerated to help the understanding of the present invention. It does not indicate sheath density.

  Thereafter, as shown in FIG. 5B, the silver salt photosensitive layer 58 is subjected to exposure necessary for forming the mesh pattern 43A in the heat generating area 43 and the mesh pattern 44A in the electrode area 44. Specifically, a mesh pattern having a large fine line interval is exposed in the heat generation area 43, and a mesh pattern having a fine line interval smaller than that in the heat generation area 43 is exposed in the electrode area 44. In the present embodiment, exposure for forming the heat generating area 43 and the electrode area 44 is performed simultaneously. The silver halide 54 is exposed to light energy and generates minute silver nuclei called “latent image” that cannot be observed with the naked eye.

  Thereafter, development processing is performed as shown in FIG. 5C in order to amplify the latent image into a visualized image that can be observed with the naked eye. Specifically, the silver salt photosensitive layer 58 on which the latent image is formed is developed with a developing solution (both alkaline solution and acidic solution, but usually alkaline solution is large). In this development process, silver ions supplied from silver halide grains or a developer are reduced to metallic silver by using a latent image silver nucleus as a catalyst nucleus by a reducing agent called a developing agent in the developer, and as a result Image silver nuclei are amplified to form a visualized silver image (developed silver 60).

  After the development processing is completed, silver halide 54 which can be exposed to light remains in the silver salt photosensitive layer 58. In order to remove this, a fixing processing solution (acid solution and alkaline solution is used as shown in FIG. 5D). Fixing is performed by using both solutions but usually there are many acidic solutions.

  By performing this fixing process, the metal silver portion 62 is formed in the exposed portion, and only the gelatin 56 remains in the non-exposed portion to become the light transmissive portion 64. That is, on the transparent film 50, a combination of the metallic silver portion 62 and the light transmissive portion 64 forms the heat generating area 43 made of the mesh pattern 43A and the electrode area 44 made of the mesh pattern 44A.

The reaction formula of the fixing process when silver bromide is used as the silver halide 54 and the fixing process is performed with thiosulfate is shown below.
AgBr (solid) + 2 S ₂ O ₃ ions → Ag (S ₂ O ₃ ) ₂
(Easily water-soluble complex)

That is, two thiosulfate ions S ₂ O ₃ and silver ions in gelatin 56 (silver ions from AgBr) form a silver thiosulfate complex. Since the silver thiosulfate complex is highly water-soluble, it is eluted from the gelatin 56. As a result, the developed silver 60 is fixed and remains as the metallic silver portion 62. The metallic silver portion 62 constitutes mesh patterns 43A and 44A.

  The developing process is a process of causing the developing agent to react with the latent image to precipitate the developed silver 60, and the fixing process is a process of eluting the silver halide 54 that has not become the developed silver 60 into water. For details, see T.W. H. James, The Theory of the Photographic Process, 4th ed. , Macmillan Publishing Co. , Inc, NY, Chapter 15, pp. 438-442. See 1977.

  Since the development process is often performed with an alkaline solution, when entering the fixing process from the development process, the alkaline solution adhering to the development process is brought into the fixing process solution (in many cases, an acidic solution). Therefore, there is a problem that the activity of the fixing processing solution changes. Further, there is a concern that an unintended development reaction may further progress due to the developer remaining in the film after leaving the development processing tank. Therefore, it is preferable to neutralize or acidify the silver salt photosensitive layer 58 with a stop solution such as an acetic acid (vinegar) solution after the development processing and before entering the fixing processing step.

  Of course, as shown in FIG. 5 (E), after forming the metallic silver portion 62 as described above, for example, a plating process (single or combined electroless plating or electroplating) is performed to obtain the metallic silver portion 62. Only the conductive metal 66 is supported on the metal silver portion 62 and the conductive metal 66 supported on the metal silver portion 62 may form the mesh patterns 43A and 44A.

  In the present embodiment, as shown in FIG. 6, after the metal silver portion 62 is formed by development and fixing, copper is electrolytically plated to form a copper plating layer 68. Further, the blackening layer 70 is formed on the surfaces of the metal silver portion 62 and the copper plating layer 68 by plating the nickel with the blackening layer. That is, the mesh pattern 43 </ b> A of the heat generating area 43 is formed by the copper plating layer 68 and the nickel black layer 70 carried on the metal silver portion 62. This is because the copper plating layer 68 is red, so that the mesh pattern 43 </ b> A is not easily seen by forming the nickel blackened layer 70. Further, in the electrode area 44, nickel blackening layer plating is not performed, and the mesh pattern 44 </ b> A of the electrode area 44 is formed by the copper plating layer 68 carried on the metal silver portion 62.

  Next, in the second method, for example, a photoresist film on a copper foil formed on a transparent film is exposed and developed to form a resist pattern, and the copper foil exposed from the resist pattern is etched to form a copper film. A mesh-like pattern is formed using foil.

  Next, the third method is a method of forming a mesh pattern by printing a paste containing metal fine particles on a transparent film. Of course, the printed paste may be subjected to metal plating to form a mesh pattern by the paste and metal plating.

  The fourth method is a method of forming a mesh pattern by printing a metal thin film on a transparent film with a screen printing plate or a gravure printing plate.

  Furthermore, as a method for forming a mesh pattern, a combination of a silver salt photograph and a calendar process can be employed. Here, the calendar process is a post-process after exposure / development and means a process of smoothing by applying pressure. The effect of the calendar process can be further brought out by bringing it into contact with steam having a temperature of 80 ° C. or more immediately before or after the calendar process.

  The electrothermal window glass 10 including the conductive layer 40 formed by the above method can improve the uniformity of heat generation in the heat generating area 43 and can eliminate the concern about migration.

Further, in the electrothermal window glass 10, the ratio of the area covered with the mesh pattern 44A of the electrode area 44 to the total area of the electrode area 44 is Ae%, and the heat generating area 43 is covered with the mesh pattern 43A. When the ratio of the area to the total area of the heat generating area 43 is Ac%,
Ac ≦ Ae, 5 ≦ Ae, and 0 <Ac ≦ 20
By satisfying the above, the transparency of the heat generating area 43 is increased, and the mesh pattern 43A of the heat generating area 43 is hardly visible from the driver's seat. Further, by setting Ac and Ae so as to satisfy the above relational expression, the resistance of the contact portion between the mesh pattern 43A of the heat generating area 43 and the first electrode 16 or the second electrode 18, that is, the metal thin wire 42 and the metal Resistance between the foils 48 is reduced, and heat generation at the contact portion can be suppressed.

  Furthermore, the electrothermal window glass 10 satisfies the following conditions.

(1) The visible light transmittance of the heat generating area 43 is set to 70% or more, preferably 80% or more, and more preferably 89% or more.

(2) As for the reflection chromaticity of the heat generation area 43 expressed in the CIE 1976 (L * a * b *) color system, L * is preferably 22 or less, more preferably 16 or less, and particularly preferably 12 or less. Further, both a * and b * are preferably from -4 to +4, particularly preferably from -2 to +2.

(3) The visible light reflectance is preferably 4% or less, more preferably 3% or less, and particularly preferably 2.4% or less.

(4) When the thin metal wire 42 is a straight line, a star mark due to light interference may occur in the light of an oncoming vehicle, which is annoying. The optical interference can be reduced by making the metal thin line into a curve or increasing the distance between the lines. The metal thin wire is preferably a wavy wire. Further, the fine metal wire can be a parallel wire that is not mesh-like and has no intersection.

(5) The conductive film 36 or the electrothermal window glass 10 includes at least one pair of electrodes and a set of heater groups each including a heat generation area existing between the electrodes. You may have two or more sets of heaters. When there are a plurality of heater groups in one conductive film or electric window glass, a heat generation distribution can be created in the electric window glass by changing the amount of heat generated in each heating area. For example, it is possible to make a setting such as rapidly heating the central portion of the conductive film or the electrothermal window glass to melt frost. The method of changing the calorific value can be implemented by changing the line width of the fine metal wires or changing the distance between the fine metal wires.

  Next, the method for forming the mesh patterns 43A and 44A using the silver halide photographic light-sensitive material which is a particularly preferable aspect in the conductive layer 40 according to this embodiment will be mainly described.

  As described above, the mesh patterns 43A and 44A according to the present embodiment expose the photosensitive material having the emulsion layer containing the photosensitive silver halide salt on the transparent film 50, and perform development processing to expose the exposed portion. And in the unexposed part, it can form by forming the metal silver part 62 and the light transmissive part 64, respectively (refer FIG. 5). Further, the metallic silver portion 62 may be subjected to physical development and / or plating treatment so that the conductive metal 66 is supported on the metallic silver portion 62.

  The method of forming the mesh patterns 43A and 44A includes the following three modes depending on the photosensitive material and the form of development processing.

(1) An embodiment in which a photosensitive silver halide black-and-white photosensitive material that does not contain physical development nuclei is chemically or physically developed to form a metallic silver portion 62 on the photosensitive material.

(2) A mode in which a photosensitive silver halide black-and-white photosensitive material containing physical development nuclei in a silver halide emulsion layer is physically developed to form a metallic silver portion 62 on the photosensitive material.

(3) A photosensitive silver halide black-and-white photosensitive material that does not contain physical development nuclei and an image-receiving sheet having a non-photosensitive layer that contains physical development nuclei are overlaid and diffused and transferred to develop a non-photosensitive image of the metallic silver portion 62 Form formed on a sheet.

  The aspect (1) is an integrated black-and-white development type, and a light-transmitting conductive film such as a light-transmitting electromagnetic wave shielding film or a light-transmitting conductive film is formed on the photosensitive material. The resulting developed silver is chemically developed silver or physical developed silver, and is highly active in the subsequent plating or physical development process in that it is a filament with a high specific surface.

  In the above aspect (2), the light-transmitting conductive film is formed on the photosensitive material by dissolving the silver halide near the physical development nucleus and depositing it on the development nucleus in the exposed portion. This is also an integrated black-and-white development type. Although the development action is precipitation on the physical development nuclei, it is highly active, but the specific surface of developed silver is a small sphere.

  In the aspect (3), the light-transmitting conductive film is formed on the image receiving sheet by dissolving and diffusing the silver halide in the unexposed area and depositing on the development nuclei on the image receiving sheet. This is a so-called separate type in which the image receiving sheet is peeled off from the photosensitive material.

  In either embodiment, either negative development processing or reversal development processing can be selected (in the case of the diffusion transfer method, negative development processing is possible by using an auto-positive type photosensitive material as the photosensitive material). .

  The chemical development, thermal development, dissolution physical development, and diffusion transfer development mentioned here have the same meanings as are commonly used in the industry, and are general textbooks of photographic chemistry such as Shinichi Kikuchi, “Photochemistry” (Kyoritsu Publishing) (Published in 1955), C.I. E. K. It is described in "The Theory of Photographic Processes, 4th ed." Edited by Mees (Mcmillan, 1977). Although this case is an invention related to liquid processing, a technique of applying a thermal development system as another development system can also be referred to. For example, the techniques described in Japanese Patent Application Laid-Open Nos. 2004-184893, 2004-334077, and 2005-010752, and Japanese Patent Application Nos. 2004-244080 and 2004-085655 can be applied. it can.

(Photosensitive material)
[Transparent film 50]
As the transparent film 50 used in the manufacturing method of the present embodiment, a flexible plastic film can be used.

  Examples of the raw material for the plastic film include polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyvinyl chloride, polyvinylidene chloride, polyvinyl butyral, polyamide, polyether, polysulfone, polyethersulfone, polycarbonate, and polyarylate. , Polyetherimide, polyetherketone, polyetheretherketone, polyolefins such as EVA, polycarbonate, triacetylcellulose (TAC), acrylic resin, polyimide, or aramid can be used.

  In the present embodiment, polyethylene terephthalate film is suitable as the plastic film from the viewpoint of translucency, heat resistance, ease of handling, and price, but it is appropriately selected depending on the necessity of heat resistance, thermoplasticity, etc. .

[Protective layer]
The photosensitive material used may be provided with a protective layer on the emulsion layer described later. In the present embodiment, the “protective layer” means a layer made of a binder such as gelatin or a high molecular polymer, and is formed in an emulsion layer having photosensitivity in order to exhibit an effect of preventing scratches and improving mechanical properties. The protective layer is preferably not provided for the plating treatment, and even if provided, the protective layer is preferably thin. The thickness is preferably 0.2 μm or less. The formation method of the coating method of the said protective layer is not specifically limited, A well-known coating method can be selected suitably.

[Emulsion layer]
The photosensitive material used in the production method of the present embodiment preferably has an emulsion layer (silver salt photosensitive layer 58) containing silver salt as a photosensor on the transparent film 50. In addition to the silver salt, the emulsion layer in this embodiment may contain a dye, a binder, a solvent, and the like as necessary.

<Silver salt>
The silver salt used in this embodiment is preferably an inorganic silver salt such as silver halide, and the silver salt is particularly preferably used in the form of silver halide grains for a silver halide photographic light-sensitive material. Silver halide is excellent in characteristics as an optical sensor.

  The silver halide preferably used in the form of a photographic emulsion of the silver halide photographic light-sensitive material will be described.

  In this embodiment, it is preferable to use silver halide in order to function as an optical sensor, and the technology used in silver halide photographic film, photographic paper, printing plate-making film, photomask emulsion mask, etc. relating to silver halide is used. The present embodiment can also be used.

  The halogen element contained in the silver halide may be any of chlorine, bromine, iodine and fluorine, or a combination thereof. For example, silver halide mainly composed of AgCl, AgBr, and AgI is preferably used, and silver halide mainly composed of AgBr or AgCl is preferably used. Silver chlorobromide, silver iodochlorobromide and silver iodobromide are also preferably used. More preferred are silver chlorobromide, silver bromide, silver iodochlorobromide and silver iodobromide, and most preferred are silver chlorobromide and silver iodochlorobromide containing 50 mol% or more of silver chloride. Used.

  Here, “silver halide mainly composed of AgBr (silver bromide)” refers to silver halide in which the molar fraction of bromide ions in the silver halide composition is 50% or more. The silver halide grains mainly composed of AgBr may contain iodide ions and chloride ions in addition to bromide ions.

  The silver halide emulsion used in this embodiment may contain a metal belonging to Group VIII or Group VIIB. In particular, it is preferable to contain a rhodium compound, an iridium compound, a ruthenium compound, an iron compound, an osmium compound or the like in order to obtain a gradation of 4 or more or to achieve low fog.

The amount of these compounds added is preferably 10 ⁻¹⁰ to 10 ⁻² mol / mol Ag per mol of silver halide, more preferably 10 ⁻⁹ to 10 ⁻³ mol / mol Ag.

  In this embodiment, in order to further improve the sensitivity as an optical sensor, chemical sensitization performed with a photographic emulsion can be performed. As the chemical sensitization method, sulfur sensitization, selenium sensitization, chalcogen sensitization such as tellurium sensitization, noble metal sensitization such as gold sensitization, reduction sensitization and the like can be used. These are used alone or in combination. When the above chemical sensitization methods are used in combination, for example, sulfur sensitization method and gold sensitization method, sulfur sensitization method and selenium sensitization method and gold sensitization method, sulfur sensitization method and tellurium sensitization. A combination of a method and a gold sensitization method is preferable.

<Binder>
In the emulsion layer, a binder can be used for the purpose of uniformly dispersing silver salt grains and assisting the adhesion between the emulsion layer and the support. In the present invention, as the binder, both a water-insoluble polymer and a water-soluble polymer can be used as a binder, but a water-soluble polymer is preferably used.

  Examples of the binder include polysaccharides such as gelatin, polyvinyl alcohol (PVA), polyvinyl pyrrolidone (PVP), starch, cellulose and derivatives thereof, polyethylene oxide, polysaccharides, polyvinylamine, chitosan, polylysine, polyacrylic acid, poly Examples include alginic acid, polyhyaluronic acid, and carboxycellulose. These have neutral, anionic, and cationic properties depending on the ionicity of the functional group.

  The content of the binder contained in the emulsion layer is preferably adjusted so that the Ag / binder volume ratio in the silver salt-containing layer is 1/4 or more, and is adjusted to be 1/2 or more. Is more preferable.

<Solvent>
The solvent used for the formation of the emulsion layer is not particularly limited. For example, water, organic solvents (for example, alcohols such as methanol, ketones such as acetone, amides such as formamide, dimethyl sulfoxide, etc. Sulphoxides, esters such as ethyl acetate, ethers, etc.), ionic liquids, and mixed solvents thereof.

  The content of the solvent used in the emulsion layer of the present invention is in the range of 30 to 90% by mass and in the range of 50 to 80% by mass with respect to the total mass of silver salt, binder and the like contained in the emulsion layer. Preferably there is.

  Next, each process for forming mesh pattern 43A, 44A is demonstrated.

[exposure]
In the present embodiment, the photosensitive material having the silver salt photosensitive layer 58 provided on the transparent film 50 is exposed. The exposure can be performed using electromagnetic waves. Examples of the electromagnetic wave include light such as visible light and ultraviolet light, and radiation such as X-rays. Furthermore, a light source having a wavelength distribution may be used for exposure, or a light source having a specific wavelength may be used.

  As an exposure method for forming a pattern image, a surface exposure method for irradiating a photosensitive surface with uniform light through a mask pattern to form a mask pattern imagewise, and a pattern irradiation unit by scanning a beam such as a laser beam There is a scanning exposure method in which is formed on the photosensitive surface.

  The exposure can be performed using various laser beams. For example, the exposure in this embodiment is a monochromatic light source such as a gas laser, a light emitting diode, a semiconductor laser, a semiconductor laser, or a second harmonic light source (SHG) that combines a solid state laser using a semiconductor laser as an excitation light source and a nonlinear optical crystal. A scanning exposure method using high-density light can be preferably used, and a KrF excimer laser, ArF excimer laser, F2 laser, or the like can also be used. In order to make the system compact and inexpensive, exposure is more preferably performed using a semiconductor laser, a semiconductor laser, or a second harmonic generation light source (SHG) that combines a solid-state laser and a nonlinear optical crystal.

  As a method for exposing the silver salt photosensitive layer 58 in a pattern, scanning exposure with a laser beam is also preferable. A capstan type laser scanning exposure apparatus described in Japanese Patent Application Laid-Open No. 2000-39677 is also preferable. Further, in this capstan method, a DMD described in Japanese Patent Application Laid-Open No. 2004-1224 is used as a light beam instead of beam scanning by rotation of a polygon mirror. It is also preferable to use it for a scanning system. In particular, when a long flexible film heater having a length of 3 m or more is produced, it is preferable to perform exposure with a laser beam while conveying the photosensitive material on a curved exposure stage.

  As will be described later, the mesh patterns 43A and 44A have lattice patterns such as triangles, quadrilaterals (diamonds, squares, etc.), hexagons formed by intersecting substantially parallel straight thin lines, parallel straight lines and zigzag lines. There is no particular limitation as long as the structure allows current to flow between electrodes to which a voltage is applied, such as a wavy line.

[Development processing]
In this embodiment, after the emulsion layer is exposed, further development processing is performed. The development processing can be performed by a normal development processing technique used for silver salt photographic film, photographic paper, printing plate-making film, photomask emulsion mask, and the like. The developer is not particularly limited, but a PQ developer, MQ developer, MAA developer and the like can also be used. Commercially available products include, for example, CN-16, CR-56, CP45X, and FD prescribed by FUJIFILM Corporation. -3, Papitol, a developer such as C-41, E-6, RA-4, D-19, D-72, etc. formulated by KODAK, or a developer included in the kit can be used. A lith developer can also be used.

  As the lith developer, D85 or the like prescribed by KODAK can be used. In the present invention, a metal silver portion, preferably a patterned metal silver portion, is formed in the exposed portion by performing the above exposure and development processing, and a light transmissive portion described later is formed in the unexposed portion.

  The developer used in the development process can contain an image quality improver for the purpose of improving the image quality. Examples of the image quality improver include nitrogen-containing heterocyclic compounds such as benzotriazole. Further, when a lith developer is used, it is particularly preferable to use polyethylene glycol.

  The mass of the metallic silver contained in the exposed portion after the development treatment is preferably a content of 50% by mass or more, and 80% by mass or more with respect to the mass of silver contained in the exposed portion before exposure. More preferably. If the mass of silver contained in the exposed portion is 50% by mass or more based on the mass of silver contained in the exposed portion before exposure, it is preferable because high conductivity can be obtained.

  The gradation after the development processing in this embodiment is not particularly limited, but is preferably more than 4.0. When the gradation after the development processing exceeds 4.0, the conductivity of the conductive metal portion can be increased while keeping the light transmissive property of the light transmissive portion high. Examples of means for setting the gradation to 4.0 or higher include the aforementioned doping of rhodium ions and iridium ions.

[Physical development and plating]
In the present embodiment, for the purpose of improving the conductivity of the metal silver portion 62 formed by the exposure and development processing described above, physical development and / or plating treatment for supporting the conductive metal particles on the metal silver portion 62 is performed. You may go. In this embodiment, the conductive metal particles can be supported on the metal silver portion 62 by only one of physical development and plating. However, the combination of physical development and plating is used to convert the conductive metal particles into metal. It can also be carried on the silver part 62.

  “Physical development” in the present embodiment means that metal particles such as silver ions are reduced with a reducing agent on metal or metal compound nuclei to deposit metal particles. This physical phenomenon is used for instant B & W film, instant slide film, printing plate manufacturing, and the like, and the technology can be used in the present invention.

  Further, the physical development may be performed simultaneously with the development processing after exposure or separately after the development processing.

  In addition, this invention can be used in combination with the technique of the public number described below suitably. JP 2004-221564 A, JP 2004-221565 A, JP 2007-200902 A, JP 2006-352073 A, International Publication No. 2006/001461 pamphlet, JP 2007-129205 A, JP 2007-235115, JP 2007-207987, JP 2006-012935, JP 2006-0110795, JP 2006-228469, JP 2006-332459, JP 2007. JP-A-207987, JP-A-2007-226215, WO2006 / 088059, JP-A-2006-261315, JP-A-2007-072171, JP-A-2007-102200, JP-A-2006. 228473 Gazette, JP-A-2006-26997, JP-A-2006-267635, JP-A-2006-267627, pamphlet of International Publication No. 2006/098333, JP-A-2006-324203, JP-A-2006-228478 JP, 2006-228836, JP, 2006-228480, WO 2006/098336, WO 2006/098338, JP 2007-009326, JP 2006-336057, JP, 2006-339287, JP, 2006-336090, JP, 2006-336099, JP, 2007-039738, JP, 2007-039739, JP, 2007-039740, JP 2 JP 07-002296 A, JP 2007-088886 A, JP 2007-092146 A, JP 2007-162118 A, JP 2007-200902 A, JP 2007-197809 A, JP 2007-2007 A. No. 270353, No. 2007-308761, No. 2006-286410, No. 2006-283133, No. 2006-283137, No. 2006-348351, No. 2007-270321. JP, 2007-270322, WO 2006/098335 pamphlet, JP 2007-088218, JP 2007-201378, JP 2007-335729, WO 2006/098334. Pamphlet, JP 2007-134439 A, JP 2007-149760 A, JP 2007-208133 A, JP 2007-178915 A, JP 2007-334325 A, JP 2007-310091 A, JP JP 2007-31646 A, JP 2007-013130 A, JP 2006-339526 A, JP 2007-116137 A, JP 2007-088219 A, JP 2007-207883 A, JP 2007-2007 A. No. 207893, JP 2007-207910, JP 2007-013130, WO 2007/001008, JP 2005-302508, JP 2005-197234.

  In the above embodiment, as shown in FIG. 1, the positions of the first electrode 16 and the second electrode 18 are arranged so as to face the top and bottom of the heat generating portion 14, but the present invention is not limited to this. You may arrange | position so that the right and left of the part 14 may be opposed.

  Moreover, in the said embodiment, as FIG.3 and FIG.4 shows, the electroconductive film 36 is the heat generating area 43 which consists of the mesh-shaped pattern 43A with a fine line space | interval, and the mesh pattern with a fine wire space | interval smaller than the heat generating area 43. The conductive paste layer 46 and the metal foil 48 are sequentially laminated on the mesh pattern 44A of the electrode area 44, but the present invention is not limited to this. The structure which laminates | stacks the foil 48 may be sufficient. A configuration in which only the conductive paste layer is laminated on the electrode area 44 may be employed.

[Second Embodiment]
Next, the electrothermal window glass according to the second embodiment of the present invention will be described below. In addition, the same code | symbol is attached | subjected to the member substantially the same as 1st Embodiment, and the overlapping description is abbreviate | omitted.

As shown in FIG. 7, the electrothermal window glass 90 is the same as the first embodiment in that it includes a conductive film 92 on which a conductive layer 94 is formed, but the configuration of the conductive layer 94 is different. That is, the conductive layer 94 includes a heat generation area 96 composed of a mesh pattern 96A composed of thin metal wires 42, and an electrode area 98 composed of a mesh pattern 98A composed of metal wires 97 thicker than the metal wires 42; I have. The thin wire width of the thin metal wire 42 is, for example, about 20 μm, and the thin wire width of the thin metal wire 97 is, for example, about 40 μm. As in the first embodiment shown in FIG. 3, the conductive paste layer 46 and the metal foil 48 are sequentially laminated on the mesh pattern 98 </ b> A of the electrode area 98 to form the first electrode 16 and the second electrode 18. Yes.
The fine wire width of the fine metal wire 42 is preferably 5 to 50 μm, and more preferably 10 to 30 μm. The fine wire width of the fine metal wire 97 is preferably 20 μm or more, and more preferably 40 μm or more. 40 μm or more includes infinity. An infinite line width represents a state where there is no space and the entire electrode area is covered with a metal layer.

In addition, the ratio of the area covered by the mesh pattern 98A made of the fine metal wires 97 to the electrode area 98 to the total area of the electrode area 98 is Ae%, and the mesh pattern made of the fine metal wires 42 for the heat generation area 96. When the ratio of the area covered with 96A to the total area of the heat generating area 96 is Ac%,
Ac ≦ Ae, 5 ≦ Ae, and 0 <Ac ≦ 20
Meet.

  In such an electrically heated window glass 90, by setting Ac and Ae so as to satisfy the above relational expression, the transparency of the heat generating area 96 is increased, and the mesh pattern 96A of the heat generating area 96 is less visible from the driver's seat. . Further, by setting Ac and Ae so as to satisfy the above relational expression, the resistance of the contact portion between the mesh pattern 96A of the heat generation area 96 and the first electrode 16 or the second electrode 18, that is, the metal thin wire 42 and the metal Resistance between the foils 48 is reduced, and heat generation at the contact portion can be suppressed.

  In the above embodiment, the conductive paste layer 46 and the metal foil 48 are sequentially laminated on the mesh pattern 98A in the electrode area 98. However, the present invention is not limited to this, and the mesh pattern 98A in the electrode area 98 is formed on the mesh pattern 98A. Only one of the conductive paste 46 and the metal foil 48 may be laminated.

[Third Embodiment]
Next, the electrothermal window glass of the third embodiment of the present invention will be described below. In addition, the same code | symbol is attached | subjected to the member substantially the same as 1st Embodiment and 2nd Embodiment, and the overlapping description is abbreviate | omitted.

  As shown in FIG. 8, the electrothermal window glass 100 is the same as the first embodiment in that the first electrode 106 and the second electrode 18 are provided above and below the heat generating portion 104 of the electrothermal window glass body 102. The configuration of the portion 104 and the first electrode 106 is different. That is, the first electrode 106 is formed such that both side portions 106A are formed in a horizontal line shape along the upper side of the electric heating window glass body 102, and the central portion 106B is bent in a substantially right angle in a concave shape inside the electric heating window glass body 102. Has become a department. The distance between the two side portions 106A of the first electrode 106 and the second electrode 18 is longer than the distance between the central portion 106B of the first electrode 106 and the second electrode 18.

  Above the central portion 106B of the first electrode 106, a non-heat generating area 108 is formed in a portion surrounded by the bent portion of the first electrode 106. In the non-heat generating area 108, a mesh-like pattern made of fine metal wires is not formed. When the heat generating portion 104 is formed in a mesh pattern using fine metal wires, there is a possibility that radio waves used in the ETC system or the like are shielded in these regions. For this reason, by providing a non-heat generating area 108 that does not form a mesh pattern of fine metal wires above the central portion 106B of the first electrode 106, the radio wave is prevented from being shielded.

  As shown in FIGS. 8 and 9, the heat generating part 104 includes a first heat generating area 110 sandwiched between both side parts 106 </ b> A of the first electrode 106 and the second electrode 18, and a central part of the first electrode 106. A second heat generation area 112 sandwiched between 106B and the second electrode 18. At the boundary between the first heat generating area 110 and the second heat generating area 112, a high resistance area 114 having a higher electrical resistance than the first heat generating area 110 and the second heat generating area 112 along the vertical direction of the electric heating window glass body 102. Is provided. It is desirable that the high resistance area 114 has an electrical resistance that is 3 times or more, preferably 10 times or more higher than that of the first heat generation area 110 and the second heat generation area 112. Further, an insulating layer may be applied to the high resistance area 114.

  The heat generating portion 104 changes the fine wire interval (interline distance) of the fine metal wires 116 so as to be inversely proportional to the distance between the first electrode 106 and the second electrode 18. That is, the first heat generating area 110 is formed with a mesh pattern 110 </ b> A in which the fine wire interval between the thin metal wires 116 is small. In the second heat generating area 112, the fine wire interval between the fine metal wires 116 is smaller than that in the first heat generating area 110. A large mesh pattern 112A is formed. In general, when regions having different distances between the first electrode and the second electrode are formed, current tends to flow in a region where the distance between the first electrode and the second electrode is short. For this reason, in this embodiment, the 1st heat_generation | fever area | region 110 and the 2nd heat_generation | fever area are adjusted by adjusting the fine wire space | interval of the metal fine wire 116 so that the surface resistance of the 1st heat_generation | fever area 110 and the 2nd heat_generation | fever area 112 may become the same. The calorific value per unit area of 112 is made substantially uniform.

  In the present embodiment, a mesh pattern 110A having a fine wire interval of about 650 μm is formed in the first heat generating area 110, and a mesh pattern having a fine wire interval of about 750 μm in the second heat generating area 112. 112A is formed. In the electrode area 44, a mesh pattern 44A in which the fine wire interval of the fine metal wires 42 is about 120 μm is formed.

  Such an electrically heated window glass 100 can more reliably prevent the radio waves used in the ETC system from being shielded by providing the non-heat generating area 108. Further, even when the central portion 106B of the first electrode 106 is bent in order to provide the non-heat generation area 108, the fine wires 116 are thin so that the surface resistances of the first heat generation area 110 and the second heat generation area 112 are the same. By adjusting the interval, the heat generation amount per unit area of the first heat generation area 110 and the second heat generation area 112 can be made substantially uniform. Moreover, since the thin wire | line space | interval of the metal fine wire 116 of the 1st heat_generation | fever area 110 and the 2nd heat_generation | fever area 112 is adjusted, manufacture is easy and cost reduction is possible.

[Fourth Embodiment]
Next, the electrothermal window glass of the fourth embodiment of the present invention will be described below. In addition, the same code | symbol is attached | subjected to the member substantially the same as 1st Embodiment-3rd Embodiment, and the overlapping description is abbreviate | omitted.

  As shown in FIG. 10, the electrothermal window glass 120 is the same as the third embodiment in that the first electrode 106 and the second electrode 18 are provided above and below the heat generating portion 104 of the electrothermal window glass body 102. 1 The structure of the heat generation area 122 and the electrode area 126 is different.

  In the electrothermal window glass 120, the thin wire widths of the thin metal wires 116 and 124 are changed so as to be proportional to the distance between the first electrode 106 and the second electrode 18. That is, the first heat generation area 122 and the second heat generation area 112 have the same surface resistance, and the first heat generation area 122 forms a mesh pattern 122A in which the fine wire width of the metal thin wire 124 is thick. Then, the mesh pattern 112A in which the fine wire width of the fine metal wire 116 is narrower than that of the first heat generating area 122 is formed.

  In the electrode area 126, a mesh pattern 126 </ b> A is formed in which the fine metal line 97 has a fine line width larger than that of the first heat generation area 122.

  In the present embodiment, the fine wire width of the fine metal wire 124 is set to about 40 μm, and the fine wire width of the fine metal wire 116 is set to about 20 μm.

  Such an electrically heated window glass 120 can more reliably prevent the radio wave used in the ETC system from being shielded by providing the non-heat generating area 108 as in the third embodiment. Further, the unit area of the first heat generation area 122 and the second heat generation area 112 is adjusted by adjusting the thin wire width of the metal thin wires 116 and 124 so that the surface resistances of the first heat generation area 122 and the second heat generation area 112 are the same. The amount of heat generated per hit can be made substantially uniform. In addition, since the fine wire widths of the thin metal wires 116 and 124 in the first heat generating area 122 and the second heat generating area 112 are adjusted, the manufacturing is easy and the cost can be reduced.

  Hereinafter, the present invention will be described more specifically with reference to examples of the present invention. In addition, the material, usage-amount, ratio, processing content, processing procedure, etc. which are shown in the following Examples can be changed suitably unless it deviates from the meaning of this invention. Accordingly, the scope of the present invention should not be construed as being limited by the specific examples shown below. In addition, in order to make the description easy to understand, the following examples are described using the same reference numerals as the configurations of the respective members of the electric heating window glass 10 shown in FIG. As described in Example 9.

[Example 1]
<Mesh formation>
An emulsion containing silver iodobromide grains (I = 2 mol%) having an average equivalent sphere diameter of 0.05 μm and containing 7.5 g of gelatin per 60 g of Ag in an aqueous medium was prepared. At this time, the Ag / gelatin volume ratio was 1/1, and a low molecular weight gelatin having an average molecular weight of 20,000 was used as the gelatin species.
In this emulsion, K ₃ Rh ₂ Br ₉ and K ₂ IrCl ₆ were added so as to have a concentration of 10 ⁻⁷ (mol / mol silver), and silver bromide grains were doped with Rh ions and Ir ions. . After adding Na ₂ PdCl ₄ to this emulsion and further performing gold-sulfur sensitization with chloroauric acid and sodium thiosulfate, together with the gelatin hardener, the coating amount of silver is 1 g / m ^2. It was coated on polyethylene terephthalate (PET). The PET used was hydrophilized before application. The dried coating film is exposed using a UV lamp through a photomask that can give a developed silver image as follows, developed at 25 ° C. for 45 seconds using the following developer, and further fixed solution (super Fuji Fix: Fuji Photo Film Co., Ltd.) was used for development processing, followed by rinsing with pure water.

[Mask mesh pattern]
The heat generating area 43 of the conductive film 36 was exposed to a mesh pattern having a line width of 17 μm and a pitch of 600 μm, and the electrode area 44 was exposed to a mesh pattern having a line width of 17 μm and a pitch of 600 μm.
[Developer composition]
The following compounds are contained in 1 liter of developer.
Hydroquinone 0.037mol / L
N-methylaminophenol 0.016 mol / L
Sodium metaborate 0.140 mol / L
Sodium hydroxide 0.360 mol / L
Sodium bromide 0.031 mol / L
Potassium metabisulfite 0.187 mol / L

  Next, copper is electroplated on the metal silver portion 62 formed by development and fixing to form a copper plating layer 68. The fine line width after copper plating was about 20 μm. Further, nickel is plated on the metal silver portion 62 and the copper plating layer 68 to form the blackened layer 70. The surface resistance of the mesh pattern 43A of the heat generating area 43 by the thin metal wire 42 thus formed was 0.34Ω / □. The size of the heat generating area 43 was 650 mm in width and 760 mm in length, and both of the electrode areas 44 were 650 mm in the horizontal direction and 25 mm in width. A silver paste ECM-100 AF4820 manufactured by Taiyo Ink Mfg. Co., Ltd. is applied on the electrode area 44 and heat-treated at 120 ° C. for 30 minutes to form a silver paste layer (conductive paste layer 46). At this time, the ratio Ae (%) of the fine metal wires 42 in the electrode area 44 and the ratio Ac (%) of the fine metal wires 42 in the heat generating area 43 were both 6.6%.

  A PVB film (resin layer 34) on the glass 30, the conductive film 36 described above, an aluminum foil tape AL-50BT (metal foil 48) manufactured by 3M on the electrode area 44 of the conductive film 36, a PVB film (resin Layer 38) and glass 32 are stacked in the order described, placed in a vacuum dryer, vacuum degassed, and heated to 110 ° C. with the vacuum maintained. When the PVB film (resin layers 34, 38) becomes transparent, it is taken out from the vacuum dryer, and each aluminum foil tape (metal foil 48) is connected to a DC constant voltage power supply so that the center of the heat generating area 43 is 45 ° C. Heat while adjusting. The heat generation state was observed with a radiation thermometer, and the heat generation of the first electrode 16 and the second electrode 18 was measured. For the measurement of the surface resistance, a MCP-T610 surface resistance meter manufactured by Mitsubishi Chemical Corporation was used.

[Example 2]
Nickel blackening layer plating was performed only in the heat generating area 43 and the electrode area 44 was not blackened layer plating. Further, no silver paste was applied to the electrode area 44. Otherwise, an electrically heated window glass was prepared in the same manner as in Example 1.

Example 3
An electrothermal window glass was prepared in the same manner as in Example 1 except that nickel black layer plating was performed only on the heat generating area 43 and the electrode area 44 was not black plated.

Example 4
An electrothermal window glass was prepared in the same manner as in Example 2 except that the exposure of the mesh pattern in the electrode area 44 was performed with a line width of 17 μm and a pitch of 120 μm. The ratio Ae (%) of the fine metal wires 42 in the electrode area 44 was 30.6%, and the ratio Ac (%) of the fine metal wires 42 in the heat generating area 43 was 6.6%.

Example 5
An electrothermal window glass was prepared in the same manner as in Example 2 except that the mesh pattern in the electrode area 44 was exposed to a line width of 36 μm and a pitch of 600 μm. The line width of the fine metal wire in the electrode area 44 after copper plating was 40 μm. The ratio Ae (%) of the fine metal wires 42 in the electrode area 44 was 12.9%, and the ratio Ac (%) of the fine metal wires 42 in the heat generating area 43 was 6.6%.

Example 6
An electrothermal window glass was prepared in the same manner as in Example 3 except that the exposure of the mesh pattern in the electrode area 44 was performed with a line width of 17 μm and a pitch of 120 μm. The ratio Ae (%) of the fine metal wires 42 in the electrode area 44 was 30.6%, and the ratio Ac (%) of the fine metal wires 42 in the heat generating area 43 was 6.6%.

[Comparative Example 1]
No silver paste was applied to the electrode area 44. Further, blackening layer plating was performed on the mesh pattern of the electrode area 44. Otherwise, an electrically heated window glass was prepared in the same manner as in Example 1.

The evaluation results of Examples 1 to 6 and Comparative Example 1 are shown in Table 1.

  The electric heating window glass having a large contact resistance between the thin metal wire 42 and the aluminum foil (metal foil 48) on the conductive film 36 generates heat at the boundary between the electrode area 44 and the heat generation area 43, and the electrode area 44 becomes high temperature. As shown in Table 1, in Comparative Example 1, it was confirmed that by not applying the silver paste to the electrode area 44, the electrode area 44 became hot and partially burned over 100 ° C.

  As shown in Examples 1 to 6, the ratio Ae of the fine metal wires 42 in the electrode area 44 is increased, or a silver paste layer (conductive paste layer 46) is provided between the fine metal wires 42 and the aluminum foil. As a result, the contact resistance between the fine metal wire 42 and the aluminum foil was reduced, and the heat generation in the electrode area 44 was reduced.

  According to Table 1, the ratio Ae (%) of the fine metal wires 42 in the electrode area 44 and the ratio Ac (%) of the fine metal wires 42 in the heat generating area 43 are

It is preferable to satisfy Ac ≦ Ae and 5 ≦ Ae. Further, in order to make the mesh pattern 43A of the heat generating area 43 less visible, it is preferable to satisfy 0 <Ac ≦ 20.

Example 7
<Mesh formation>
An emulsion containing silver iodobromide grains (I = 2 mol%) having an average sphere equivalent diameter of 0.05 μm and containing 5 g of gelatin per 80 g of Ag in an aqueous medium was prepared. At this time, the Ag / gelatin volume ratio was 2/1, and phthalated gelatin was used as the gelatin.
In this emulsion, K ₃ Rh ₂ Br ₉ and K ₂ IrCl ₆ were added so as to have a concentration of 10 ⁻⁷ (mol / mol silver), and silver bromide grains were doped with Rh ions and Ir ions. . After adding Na ₂ PdCl ₄ to this emulsion and further performing gold sulfur sensitization using chloroauric acid and sodium thiosulfate, the coating amount of silver becomes 1.5 g / m ² together with the gelatin hardener. It was coated on polyethylene terephthalate (PET). The PET used was hydrophilized before application. The electrode area 44 was exposed to a mesh pattern with a line width of 20 μm and a pitch of 100 μm, and the heat generation area 43 was exposed to a mesh pattern with a line width of 20 μm and a pitch of 600 μm. Thereafter, it was calendered at a linear pressure of 3000 N / cm and further exposed to water vapor at 100 ° C. for 1 minute for drying.
In the same manner as in Example 2, an aluminum foil tape was applied to the electrode area, and then the laminated glass was processed to prepare an electrically heated window glass of Example 7. The ratio Ae (%) of the fine metal wires 42 in the electrode area 44 was 36.0%, and the ratio Ac (%) of the fine metal wires 42 in the heat generating area 43 was 6.6%.

Example 8
An electrothermal window glass was prepared in the same manner as in Example 7 except that the electrode area 44 was exposed to a line width of 40 μm and a pitch of 600 μm.

The evaluation results of Example 7 and Example 8 are shown in Table 2.

  As shown in Table 2, heat generation in the electrode area 44 could be reduced by calendering the metallic silver portion after the exposure and development of the mesh pattern. This is considered to be because the metal silver part was compressed by the calendar process and the conductivity was increased.

Example 9
In Example 9, an electrothermal window glass 130 shown in FIG. 11 was created. In this electrically heated window glass 130, the first heat generating area 110 on both sides in the longitudinal direction has a mesh pattern with a thin wire width of 17 μm and a fine wire interval of 650 μm, and the second heat generating area 112 has a fine wire width of 17 μm and a fine wire interval of 750 μm. The electrode pattern 44 and the electrode area 44 were exposed to develop a mesh pattern having a fine line width of 17 μm and a fine line interval of 120 μm, and development and fixing were performed. An insulating film (corresponding to the high resistance area 114) was applied to the boundary between the first heat generation area 110 and the second heat generation area 112 to a width of about 1 mm. After that, by electroplating copper on the metal silver part, the fine metal wires 116 other than the part covered with the insulating film were covered with red copper.

  The fine wire width of the fine metal wire 116 after copper plating was about 20 μm. Furthermore, the blackening layer which consists of nickel was plated on copper. The size of the first heat generating area 110 was 600 mm wide and 750 mm long, and the size of the second heat generating area 112 was 200 mm wide and 650 mm long. The ratio Ae of the fine metal wires 42 in the electrode area 44 is 30.6%, the ratio Ac of the fine metal wires 116 in the first heat generating area 110 is 6.1%, and the ratio Ac of the fine metal wires 116 in the second heat generating area 112 is 5.3. %Met. The surface resistance of the first heat generation area 110 was 0.37Ω / □, and the surface resistance of the second heat generation area 112 was 0.42Ω / □. Silver paste ECM-100 AF4820 manufactured by Taiyo Ink Manufacturing Co., Ltd. was applied to the electrode area 44 and heat treated at 120 ° C. for 30 minutes to form a silver paste layer (conductive paste layer 46).

  A PVB film on the glass, the conductive film, and an electrode area 44 of the conductive film. 8701 copper foil tape (24 mm width), PVB film, and glass are stacked in the order of description and placed in a vacuum dryer. The bent portion 132A of the upper first electrode 132 was made of one copper foil tape by bending the copper foil tape. After degassing in vacuum, heat to 110 ° C. while maintaining the vacuum.

  When the PVB film becomes transparent, the PVD film is taken out from the vacuum dryer, and the first electrode 132 and the second electrode 18 (a pair of copper foil tapes) are connected to a DC 12 volt power source 22 to generate heat. was gotten. When the heat generation state was observed with a radiation thermometer, almost the entire area of the first heat generation area 110 and the second heat generation area 112 on both sides in the longitudinal direction except for the peripheral area of the heat generation portion 104 having the influence of heat dissipation was 45 ° C to 50 ° C. It was temperature.

  Moreover, when the test which receives the electromagnetic wave of an ETC system using the electrothermal window glass 130 was conducted, it was confirmed that an electromagnetic wave is not shielded.

  In addition, the manufacturing method of the electric heating window glass and electric heating window glass which concern on this invention is not restricted to the above-mentioned embodiment, Of course, various structures can be taken, without deviating from the summary of this invention.

DESCRIPTION OF SYMBOLS 10 Electric heating window glass 14 Heat generating part 16 First electrode (electrode)
18 Second electrode (electrode)
20 Non-heating part 22 Power supply (electric supply source)
30 glass (glass layer)
32 Glass (glass layer)
36 conductive film 40 conductive layer (conductive layer)
42 Fine metal wire 43 Heat generation area 43A Mesh pattern (metal fine wire group)
44 Electrode area 44A Mesh pattern (metal thin wire group)
45 Non-heating zone 46 Conductive paste layer 48 Metal foil 50 Transparent film (support)
90 electrothermal window glass 92 conductive film 94 conductive layer (conductive layer)
96 Heat generation area 96A Mesh pattern (metal thin wire group)
97 Metal fine wire 98 Electrode area 98A Mesh pattern (metal fine wire group)
100 Electric heating window glass 104 Heat generation part 106 1st electrode (electrode)
108 Non-heat generation area 110 First heat generation area (area where the distance between electrodes is different)
110A mesh pattern (metal fine wire group)
112 2nd heat generation area (area where distance between electrodes is different)
112A Mesh pattern (metal thin wire group)
114 High resistance area 116 Metal thin wire 120 Electric heating window glass 122 First heating area (area where the distance between the electrodes is different)
122A Mesh pattern (metal thin wire group)
124 Metal thin wire 126 Electrode area 126A Mesh pattern (metal thin wire group)
130 Electric window glass 132 First electrode (electrode)

Claims (13)

One or more glass layers made of window glass material;
A conductive layer in which a large number of fine metal wire groups are formed on a support supported by the glass layer;
A pair of electrodes provided on both sides in the surface direction of the conductive layer and supplying electricity to the conductive layer;
The conductive layer includes an electrode area in which the electrode is provided, and a heat generation area that is sandwiched between the electrode areas and generates heat from the metal wire group, and is covered with the metal wire group by the area E of the electrode area. The ratio of the area e occupied is Ae%, and the ratio of the area c covered with the metal thin wire group in the area C of the heat generation area is Ac%.
Ac ≦ Ae, 5 ≦ Ae, and 0 <Ac ≦ 20
Meet the electric heating window glass.   The said support body is an electrically heated window glass of Claim 1 which has a non-heat-generation area not covered with the said metal fine wire group. A conductive paste layer and a metal foil are sequentially laminated on the metal thin wire group in the electrode area,
The said metal foil is an electrically heated window glass of Claim 1 or Claim 2 connected to the electric wire connected with the electric power supply source. A metal foil is laminated on the metal wire group in the electrode area,
The line width of the said metal fine wire group of the said electrode area is larger than the line width of the said metal fine wire group of the said heat_generation | fever area, and the said metal foil is connected to the electric wire connected with the electric power supply source. Or the electrically heated window glass of Claim 2. A metal foil is laminated on the metal wire group in the electrode area,
The number of the fine metal wire groups per unit area of the electrode area is larger than the number of the fine metal wire groups per unit area of the heat generating area, and the metal foil is connected to an electric wire connected to an electric power source. The electrically heated window glass according to claim 1 or claim 2, wherein:   The electrothermal window glass according to any one of claims 1 to 5, wherein the thin metal wire group in the heat generating area is blackened, and the thin metal wire group in the electrode area is not blackened.   The electrothermal window glass according to any one of claims 1 to 6, wherein at least one of the pair of electrodes is bent in the middle and has two or more areas where the distance between the pair of electrodes is different.   The electrically heated window glass according to claim 7, wherein a non-heat generating area not covered with the thin metal wire group is provided at a position adjacent to an area where the distance between the pair of electrodes is short.   When the voltage is applied to the pair of electrodes to heat the metal thin wire group in the heat generating area, the heat generation amount of the metal thin wire group in the heat generating area is uniform so that the heat generation amount per unit area of the heat generating area is uniform. The electrothermal window glass according to claim 7 or 8, wherein the surface resistance is controlled.   The electrothermal window glass according to any one of claims 7 to 9, wherein a line width of the thin metal wire group is changed so as to be proportional to a distance between the pair of electrodes.   The electrothermal window glass according to any one of claims 7 to 9, wherein a distance between the fine metal wires of the fine metal wire group is changed so as to be inversely proportional to a distance between the pair of electrodes.   The electrothermal window glass according to any one of claims 7 to 11, wherein a high resistance area having a surface resistance higher than that of the area is provided at a boundary between areas where the distance between the pair of electrodes is different.   The electrothermal window glass according to any one of claims 7 to 11, wherein an insulating layer is provided at a boundary between areas having different distances between the pair of electrodes.

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