JP2007237807A - Vehicle windowpane and manufacturing method therefor - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a vehicle windowpane and the manufacturing method wherein electric conductors such as a snow melting heater or a communications antenna or the like are sandwiched in a laminated glass and which is excellent in see-through property (to be invisible) and does not cut off the view. <P>SOLUTION: In the vehicle window 11 having the electric conductors therein, the electric conductor 14 composed of a wiring pattern 17 made of conductive metal and metal plated layers 18a, 18b laminated thereon is attached to the one side of a first plate glass 12 composing the windowpane 11 by a transcription, and sandwiched between the first plate glass 12 and the second plate glass 16 to form the laminated glass 11. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a window glass for vehicles such as trains and automobiles. In more detail, for vehicles that have excellent transparency (not visible) and that do not block the field of view, in which conductors such as a snow melting heater and communication antenna are sandwiched between two glass sheets of laminated glass. It is related with a window glass and its manufacturing method.

In cold regions, in the winter, snow and icing adhere to the windshield surface of automobiles parked outdoors at night, and anti-fogging glass that melts and removes this with a heater is known (for example, Patent Documents). 1-3).
In addition, a vehicle antenna is attached to a part of a vehicle window glass to receive radio waves (see, for example, Patent Document 4).

Patent Document 1 discloses a vehicle in which a plurality of heating metal wires are disposed on an intermediate film of laminated glass obtained by bonding two plate glasses with an intermediate film, and a heating transparent conductive film is formed on almost the entire surface of one of the plate glasses. An anti-fogging glass is disclosed.
Patent Document 2 discloses an electric heating window glass for a vehicle using a transparent conductive film provided on one surface of two plate glasses.
Patent Document 3 discloses a vehicle electric window glass that adjusts a voltage by dividing a conductive film into a plurality of areas.
Patent Document 4 discloses a vehicle antenna having a cutout portion in a part of a transparent conductive film of a vehicle window glass having a transparent conductive film formed on the entire surface, and an antenna that receives radio waves in the cutout portion. Is disclosed.
In Patent Document 5 and Patent Document 6, as a method for producing an electromagnetic wave shielding material using a conductive metal mesh, a thin line pattern is formed with developed silver produced by a photographic method, and then the developed silver thin film is formed on the developed silver thin film. A photographic silver-plating method is disclosed in which a conductive metal pattern is formed by plating.
JP 2000-128588 A Japanese Patent Laid-Open No. 8-119065 JP 2003-163071 A JP 2004-040571 A JP 2004-221564 A International Publication No. 2004/007810 Pamphlet

As shown in Patent Document 1, when a plurality of heating metal wires are embedded in a rectangular shape in the longitudinal direction in an interlayer film of laminated glass, the visibility of the heating metal wires to the driver (not visible) is ensured. In order to achieve this, it is necessary to reduce the width of the metal line to about 60 μm or less. However, in order to embed a thin metal wire in this manner, the metal wire cannot be visually observed, so that there is a problem that work is difficult and workability is low.
In the electric heating window glass made of a transparent conductive film provided on one surface of two sheet glasses shown in Patent Document 2, in order to avoid a local temperature rise on the glass surface, the transparent electric heating of the electric heating window glass Although the resistance of the film is increased stepwise or continuously from the upper side toward the lower side, there is a problem that it is difficult to change the film thickness stepwise or continuously. Furthermore, in the case of a transparent conductive film, it is necessary to reduce the film thickness in order to increase the visible light transmittance. However, when the film thickness is decreased, there is a problem that the resistance increases and the heater output decreases.

The electric window glass shown in Patent Document 3 that divides the conductive film into a plurality of areas and adjusts the voltage is performed by coating the conductive film using sputtering, and is similar to Patent Document 2. In addition, in order to increase the visible light transmittance, it is necessary to reduce the film thickness. However, when the film thickness is decreased, there is a problem in that the resistance increases and the heater output decreases.
In Patent Document 4, a vehicle window glass having a transparent conductive film formed on the entire surface thereof is provided with a notch in a part of the transparent conductive film, and the vehicle antenna having an antenna for receiving radio waves in the notch. Is disclosed. However, since the color tone is different between the part with the transparent conductive film and the part without the transparent conductive film, it is necessary to make the dimensions of the notch as small as possible. There is a problem in that the appearance of the image is conspicuous due to the difference in color tone and the aesthetic appearance is impaired.

  The present invention has been made in view of the above circumstances, and a conductor such as a snow melting heater and a communication antenna is sandwiched between two laminated glasses, and has excellent transparency (not visible) and has a field of view. It is an object of the present invention to provide a vehicle window glass that is not obstructed and a manufacturing method thereof.

In order to solve the above-mentioned problems, the present invention provides a vehicle window glass provided with a conductor, wherein the conductor comprising a conductive metal wiring pattern and a metal plating layer laminated thereon is provided on the window glass. A window glass for a vehicle is provided, which is attached to one side of a first plate glass constituting the sheet by transfer and is sandwiched between the first plate glass and the second plate glass.
The conductive metal wiring pattern is preferably a developed silver wiring pattern produced by a photographic method.
The metal plating layer preferably includes an electroless copper plating layer and / or an electrolytic copper plating layer laminated on and in contact with the developed silver wiring pattern.
The developed silver wiring pattern is preferably generated by a positive photographic process or a negative photographic process.

In order to solve the above-described problems, the present invention is a method for manufacturing a window glass for a vehicle in which a conductor is disposed, and a wiring pattern generation step of generating a developed silver wiring pattern by a photographic method on a supporting substrate. And a plating step of forming a conductor with a conductive metal plating layer on the developed silver wiring pattern, and a step of transferring the conductor to one side of a plate glass constituting the window glass. The manufacturing method of the window glass for vehicles characterized by these is provided.
Prior to the plating step and the transfer step, the conductor formed on the support substrate is immersed in a strong alkaline solution having a pH of 11 to 13 to reduce the adhesion between the conductor and the support substrate. It is preferable to include an alkali treatment step.
The developed silver wiring pattern is preferably produced by a positive photographic process or a negative photographic process.

Preferably, the wiring circuit pattern of the conductor is a mesh pattern, and a slit (opening) for transmitting electromagnetic waves of a predetermined frequency is disposed in the mesh pattern.
Preferably, the wiring circuit pattern of the conductor is a lattice pattern, and slits (openings) for transmitting electromagnetic waves of a predetermined frequency are disposed in the lattice pattern.
The metal plating layer of the conductor is preferably a copper plating layer and / or a nickel plating layer.
The conductor is preferably disposed with a line width of 20 to 60 μm, which is a thickness that cannot be visually recognized by a viewer.
The outermost surface of the metal plating layer of the conductor is preferably blackened to prevent reflection of light due to the gloss of the plated metal.

  According to the vehicle window glass of the present invention and the method for manufacturing the same, since a conductor having an ultrathinness of 20 to 60 μm, which is a thickness that cannot be visually recognized by a viewer, is provided, the visibility (not visually observed) is excellent. Thus, it is possible to provide a vehicle window glass that does not obstruct the field of view.

  In the present invention, a copper plating layer is laminated by electroless plating and / or electrolytic plating in contact with a developed silver wiring pattern produced by a photographic process on a supporting substrate. Due to the phenomenon of diffusion transfer to the copper plating layer, the adhesion between the developed silver wiring pattern and the supporting substrate is reduced, and the conductor can be lifted from the supporting substrate, and the conductor is easily peeled off from the substrate. .

Moreover, since the said conductor formed on the support base material is immersed in the strong alkaline liquid of pH 11-13, this invention has reduced the adhesive force of a conductor and a support base material, It becomes easy to peel from the support substrate.
For this reason, in this invention, in the process which peels a conductor from a support base material and transfers to the single side | surface of one plate glass of the two plate glasses which comprise a laminated glass, the electroconductivity formed on the support base material After the body is pressure-bonded to one side of the plate glass via the adhesive layer, the transfer work performed by peeling off the conductor having a reduced adhesion to the supporting substrate can be carried out smoothly.

The vehicle window glass of the present invention will be described in detail below based on the best mode.
FIG. 1 is a front view schematically showing an example of a vehicle window glass of the present invention. FIG. 2 is a front view schematically showing another example of the vehicle window glass of the present invention. FIG. 3 is a schematic cross-sectional view showing an example of the configuration of the vehicle window glass of the present invention. FIG. 4 is a schematic cross-sectional view showing an example of a laminate in which a conductor is provided on a support base material. FIG. 5A is a schematic cross-sectional view illustrating a state in which a conductor provided on a supporting base material is transferred to a plate glass, and FIG. 5B illustrates a state in which the supporting base material is peeled from the conductor. It is typical sectional drawing to do.
In FIG. 1 and FIG. 2, the circuit wiring pattern of the conductor region 2 is shown only in a part of the conductor region 2 in order to simplify the drawing. However, in an actual vehicle window glass, the circuit wiring pattern is a conductor. It is provided in the entire area 2.

A vehicle window glass 10 shown in FIG. 1 is provided with a conductor region 2 on one side of one plate glass of a window glass 1 made of laminated glass, and upper and lower ends of the conductor region 2 are an upper bus bar (bus bar) 3 and a lower bus bar. (Bus) is connected to two lead wires 5 and 6 through 4. In this example, the circuit wiring pattern of the conductor region 2 is a mesh pattern.
It is preferable that a slit (opening) for transmitting electromagnetic waves of a predetermined frequency is disposed in the mesh pattern (not shown).

As in FIG. 1, the vehicle window glass 20 shown in FIG. 2 is provided with a conductor region 2 on one surface of one plate glass 1 made of laminated glass, and upper and lower ends of the conductor region 2 are respectively upper bus bars. It is connected to two lead wires 5 and 6 through a (bus) 3 and a lower bus bar (bus) 4. In this example, the circuit wiring pattern of the conductor region 2 is a lattice pattern in which a plurality of fine lines connecting the upper and lower bus bars 3 and 4 in the vertical direction are arranged in the left and right directions.
It is preferable that a slit (opening) for transmitting electromagnetic waves of a predetermined frequency is disposed in the mesh pattern (not shown).

  As shown in the sectional view of FIG. 3, these vehicle window glasses 10 and 20 have a structure in which a conductor (circuit wiring pattern) 14 is sandwiched between two sheet glasses 12 and 16 constituting a laminated glass 11. Have. That is, the conductor 14 is attached to the one surface (inner surface) of the first glass sheet 12 disposed on the outdoor side by the adhesive layer 13, and the second resin disposed on the indoor side with the transparent resin layer 15 interposed therebetween. The plate glass 16 is bonded together. The conductor 14 includes a conductive metal wiring pattern 17 and metal plating layers 18a and 18b laminated thereon.

(Metal wiring pattern manufacturing method)
In the method for producing a window glass for a vehicle according to the present invention, a supporting base material is used by using any one of two different silver salt photographic development methods (positive photographic method-plating method, negative photographic method-plating method). A thin film of developed wiring pattern 17 made of developed silver is formed on the developed silver film, and conductive metal layers 18a and 18b are laminated on the developed silver wiring pattern by plating to form a conductor 14, The conductor is transferred to the plate glass 12.

  One of the silver salt photographic development methods used in the present invention is a method (negative type photographic production method) performed using a conventional so-called silver salt photographic film that has been known for a long time. A silver salt-containing layer containing a silver salt provided on a support is exposed and developed to form a metallic silver part and a light-transmitting part, and the metallic silver part This is a method of forming a conductive metal part in which conductive metal particles are supported on the metal silver part by physical development and / or plating.

  Another silver salt photographic developing method (positive type photographic method) used in the present invention is a method described in Patent Document 6, that is, the silver salt photographic developing method is applied, and silver halide is dissolved in soluble silver. This is a method of dissolving a complex salt forming agent to form a soluble silver complex salt, and simultaneously reducing with a reducing agent (developing agent) such as hydroquinone to deposit metal silver having an arbitrary wiring pattern on the development nucleus.

Hereinafter, since the description overlaps in the positive type photographic method-plating method and the negative type photographic method-plating method, a wiring pattern is formed with developed silver generated by the photographic method, mainly using the positive type photo-plating method described above. A method will be described. In the present invention, the negative photographic method-plating method can be basically carried out according to the positive photographic method-plating method.
That is, the present invention can be applied to either a positive photographic process or a negative photographic process.

(Positive photographic process-plating method: physical development nucleus)
The transparent base material (support base material S shown in FIGS. 4 and 5) on which the developed silver wiring pattern is formed is preferably provided with a physical development nucleus layer in advance. The transparent substrate is not particularly limited. For example, polyester resin such as polyethylene terephthalate (PET) or polyethylene naphthalate (PEN), diacetate resin, triacetate resin, acrylic resin, polycarbonate resin, triacetyl cellulose, Examples thereof include a plastic film (single layer or composite film) made of polystyrene, polyolefin, polyurethane resin, polyvinyl chloride, polyimide resin, polyamide resin or the like.

  As the physical development nuclei, fine particles (having a particle size of about 1 to several tens of nm) made of heavy metals or sulfides thereof are used. Examples thereof include colloids such as gold and silver, metal sulfides obtained by mixing water-soluble salts such as palladium and zinc and sulfides, and the like. The fine particle layer of these physical development nuclei can be provided on the transparent substrate by a vacuum deposition method, a cathode sputtering method, a coating method or the like. From the viewpoint of production efficiency, a coating method is preferably used. The content of physical development nuclei in the physical development nuclei layer is suitably about 0.1 to 10 mg per square meter in solid content.

  An adhesive layer of a polymer latex layer such as vinylidene chloride or polyurethane can be provided on the transparent substrate, and an intermediate layer made of a hydrophilic binder such as gelatin is provided between the adhesive layer and the physical development nucleus layer. You can also.

  The physical development nucleus layer preferably contains a hydrophilic binder. The amount of the hydrophilic binder is preferably about 10 to 300% by mass with respect to the physical development nucleus. As the hydrophilic binder, gelatin, gum arabic, cellulose, albumin, casein, sodium alginate, various starches, polyvinyl alcohol, polyvinyl pyrrolidone, polyacrylamide, a copolymer of acrylamide and vinyl imidazole, and the like can be used. The physical development nucleus layer may also contain a hydrophilic binder crosslinking agent.

  The physical development nucleus layer and the intermediate layer can be applied by an application method such as dip coating, slide coating, curtain coating, bar coating, air knife coating, roll coating, gravure coating, spray coating, and the like. In the present invention, the physical development nucleus layer is preferably provided as a continuous and uniform layer by the above-described coating method.

  In the present invention, the supply of silver halide for precipitating metallic silver on the physical development nucleus layer is performed by a method in which the physical development nucleus layer and the silver halide emulsion layer are integrally provided in this order on a transparent substrate, or by another method. There is a method of supplying a soluble silver complex salt from a silver halide emulsion layer provided on a substrate such as paper or a plastic resin film. From the viewpoint of cost and production efficiency, the former physical development nucleus layer and the silver halide emulsion layer are preferably provided integrally.

(Negative photographic process-plating method: silver halide emulsion)
In the present invention, the silver halide emulsion can be produced according to a general method for producing a silver halide emulsion of a silver halide photographic light-sensitive material. The silver halide emulsion is usually prepared by mixing and ripening an aqueous silver nitrate solution, an aqueous halogen solution of sodium chloride or sodium bromide in the presence of gelatin.
The silver halide composition of the silver halide emulsion layer used in the present invention preferably contains 80 mol% or more of silver chloride, and more preferably 90 mol% or more is silver chloride. The conductivity of the physically developed silver formed by increasing the silver chloride content is improved.

  The silver halide emulsion layer used in the present invention is sensitive to various light sources. As one method for producing a conductor region disposed inside a laminated glass, for example, formation of physically developed silver having a fine line pattern such as a mesh shape can be mentioned. In this case, the silver halide emulsion layer is exposed in the form of a fine line pattern. As an exposure method, a method in which a transparent original having a fine line pattern and the silver halide emulsion layer are in close contact with each other and exposed with ultraviolet light, or various laser beams are used. Scanning exposure method. The former contact exposure using ultraviolet light is possible even if the silver halide has relatively low photosensitivity, but in the case of scanning exposure using laser light, relatively high photosensitivity is required. Therefore, when the latter exposure method is used, the silver halide may be subjected to chemical sensitization or spectral sensitization with a sensitizing dye in order to increase the sensitivity of the silver halide. Chemical sensitization includes metal sensitization using a gold compound or silver compound, sulfur sensitization using a sulfur compound, or a combination thereof. Gold-sulfur sensitization using a gold compound and a sulfur compound in combination is preferable. In the exposure method using the laser beam described above, a laser beam having an oscillation wavelength of 450 nm or less, for example, a blue semiconductor laser (also referred to as a violet laser diode) having an oscillation wavelength of 400 to 430 nm is used. It can be handled even under a yellow fluorescent lamp.

  In the present invention, an arbitrary position on the transparent substrate on which the physical development nucleus layer is provided, for example, an adhesive layer, an intermediate layer, a physical development nucleus layer or a silver halide emulsion layer, or a backing layer provided with a support interposed therebetween A dye or pigment for preventing halation or irradiation may be contained.

(Positive photographic process-plating method: exposure and development)
When producing a fine line pattern using a photosensitive material in which a silver halide emulsion layer is coated directly on the physical development nucleus layer or via an intermediate layer, a transparent original having an arbitrary fine line pattern and the photosensitive material described above are used. Exposure with close contact, or after scanning exposure of the above-mentioned photosensitive material with a laser beam output device with a digital image of an arbitrary fine line pattern, and processing in an alkaline solution in the presence of a soluble silver complexing agent and a reducing agent. Silver complex diffusion transfer development (DTR development) occurs, the silver halide in the unexposed area is dissolved to form a silver complex salt, which is reduced on the physical development nuclei to deposit metal silver to form a finely patterned physical development silver thin film. Obtainable. The exposed portion is chemically developed in the silver halide emulsion layer to become blackened silver. After development, the silver halide emulsion layer and intermediate layer, or the protective layer provided as necessary, are washed away with water, and a physically developed silver thin film having a fine line pattern is exposed on the surface.

  After DTR development, the silver halide emulsion layer or the like provided on the physical development nucleus layer may be removed by washing with water or transferring and peeling to a release paper or the like. There are two methods for removing the water washing: a method of removing hot water using a scrubbing roller or the like while jetting it with a nozzle or the like, and a method of removing hot water by jetting with a nozzle or the like.

  On the other hand, when the soluble silver complex salt is supplied from a silver halide emulsion layer provided on a substrate different from the transparent substrate on which the physical development nucleus layer is coated, the silver halide emulsion layer is exposed as described above. After that, a transparent substrate coated with a physical development nucleus layer and another photosensitive material coated with a silver halide emulsion layer are superposed in an alkaline solution in the presence of a soluble silver complexing agent and a reducing agent. After several tens of seconds to several minutes after taking out from the alkaline solution, the both are removed to obtain a physically developed silver thin film having a fine line pattern deposited on the physical development nuclei.

  Next, a soluble silver complex salt forming agent, a reducing agent, and an alkali solution necessary for silver complex diffusion transfer development will be described. The soluble silver complex salt forming agent is a compound that dissolves silver halide to form a soluble silver complex salt, and the reducing agent is a compound that reduces this soluble silver complex salt to precipitate metallic silver on physical development nuclei. These actions are performed in an alkaline solution.

  Examples of the soluble silver complex forming agent used in the present invention include sodium thiosulfate, thiosulfate such as ammonium thiosulfate, thiocyanate such as sodium thiocyanate and ammonium thiocyanate, alkanolamine, sodium sulfite, and potassium bisulfite. Sulfites such as T. H. Examples include the compounds described in 474-475 (1977) of James The Theory of the Photographic Process 4th edition.

  As the reducing agent, a developing agent known in the field of photographic development can be used. For example, hydroquinone, catechol, pyrogallol, methylhydroquinone, polyhydroxybenzenes such as chlorohydroquinone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-3-pyrazolidone, 1-phenyl-4-methyl- Examples include 3-pyrazolidones such as 4-hydroxymethyl-3-pyrazolidone, paramethylaminophenol, paraaminophenol, parahydroxyphenylglycine, paraphenylenediamine, and the like.

  The above-mentioned soluble silver complex salt forming agent and reducing agent may be applied to the transparent substrate together with the physical development nucleus layer, added to the silver halide emulsion layer, or contained in the alkaline solution. It may be allowed to be contained, and may be further contained in a plurality of positions, but is preferably contained at least in the alkaline liquid.

  The content of the soluble silver complex salt forming agent in the alkaline solution is suitably used in the range of 0.1 to 5 mol per liter of the developer, and the reducing agent is 0.05 to 1 per liter of the developer. It is suitable to use in the molar range.

  The pH of the alkaline solution is preferably 10 or more, and more preferably in the range of 11-14. Application of the alkaline solution for silver complex diffusion transfer development may be an immersion method or a coating method. The immersion method is, for example, transporting while immersing a transparent substrate provided with a physical development nucleus layer and a silver halide emulsion layer in an alkaline solution stored in a large amount in a tank. For example, about 40 to 120 ml of an alkaline solution per square meter is applied on the silver halide emulsion layer.

(Dimensions of metal wiring pattern)
As described above, some vehicle window glasses using conductive wires are provided with conductive wires having a thickness of, for example, about 40 to 100 μm. Even in the case where the metal wiring pattern is formed as in the present invention, it is not visually recognized by the viewer if the thin line width is reduced. In particular, when the line width is about 60 μm or less, visual observation becomes difficult, but the conductivity becomes low. On the other hand, when the thin line width is increased, it becomes easier for a viewer to visually recognize, but the conductivity increases.
As a conductor of the window glass for a vehicle of the present invention, it is preferable to dispose a conductor having a line width of 20 to 60 μm, which is a thickness that cannot be visually recognized by a viewer. The wiring interval of the conductor is preferably 0.15 to 5 mm in order to increase the total light transmittance.

(Plating of wiring pattern on metallic silver)
In the step of forming a wiring pattern made of the developed silver layer 17 on the supporting substrate S by a photographic method and then conducting conductive metal plating on the developed silver wiring pattern, the plating thickness of the conductor is as desired. Although it can be arbitrarily changed depending on the conductivity characteristics, it is in the range of 0.5 to 15 μm, preferably 2 to 12 μm.

(Plating method)
In the present invention, the method of plating the developed silver layer having a fine line pattern is as follows.
A thin line pattern of developed silver 17 generated by a photographic method is formed on one side of the supporting substrate S, and one or more conductive metals 18a and 18b are plated on the developed silver layer 17.
The fine line pattern of physically developed silver can be plated by any of electroless plating, electrolytic plating, or a combination of both. However, when creating a circuit wiring pattern on a supporting substrate, From the viewpoint that a roll-like long web provided with a physical development nucleus layer and a silver halide emulsion layer can be subjected to at least a series of treatments such as exposure of a fine line pattern, development treatment and plating treatment. A method in which electrolytic plating is combined with it is preferable.

In the present invention, the metal plating method can be performed by a known method. For example, the electrolytic plating method is a conventionally known method such as copper, nickel, silver, gold, solder, or a multilayer or composite system of copper / nickel. For these, reference can be made to documents such as “Surface Treatment Technology Overview; Technical Data Center, Inc., December 21, 1987, first edition, pages 281 to 422”.
A thin line pattern of a developed silver layer generated by a photographic method is formed on one side of the supporting substrate, and copper (Cu) and / or nickel (Ni) is plated on the developed silver layer. It is preferable to use copper and / or nickel for reasons such as easy plating, excellent electrical conductivity, plating on a thick film, and low cost.
In this embodiment, the conductor 14 is attached to one side of the plate glass 12 on the outdoor side on the metal plating layer 18b side by transfer, so that the blackened plating layer 18b can be arranged on the outdoor side.

(Electroless copper plating)
The electroless copper plating solution preferably has a metal copper (Cu) concentration of 0.5 to 10 g / liter, more preferably 2 to 3 g / liter.
As temperature of a plating process liquid, 30-80 degreeC is preferable, More preferably, it is 40-50 degreeC. If the temperature of the plating solution is lower than 30 ° C., the copper deposition rate is slow, and if it is 80 ° C. or higher, the energy cost increases, which is not preferable.
The plating thickness is preferably 0.01 to 1 μm, and more preferably 0.05 to 0.2 μm. Further, the electroless copper plating solution may be any solution as long as it is a known plating solution.

(Electrolytic copper plating)
In the case of electrolytic copper plating, any plating solution such as copper sulfate, copper cyanide, and copper pyrophosphate may be used, but copper sulfate is preferable from the viewpoint of cost. In these electrolytic copper plating solutions, the concentration of copper (Cu) may be set to an appropriate concentration.
When using a copper sulfate plating bath, the sulfuric acid concentration is preferably 20 to 400 g / liter, more preferably 70 to 300 g / liter. If the sulfuric acid concentration is lower than 20 g / liter, the plating solution becomes unstable, and if it is higher than 300 g / liter, abnormalities occur in the plating particles.
The plating temperature is preferably 10 to 60 ° C, more preferably 20 to 40 ° C. If the temperature of the plating solution is lower than 10 ° C., the plating time will be longer and the cost will be increased.
The current density of electrolytic plating is preferably 0.05 to 20 A / cm ² , more preferably 0.5 to 8 A / cm ² . When the current density of electrolytic plating is lower than 0.05 A / cm ² , the plating time becomes longer and the cost increases. Moreover, if the current density of electrolytic plating is higher than 20 A / cm ² , the appearance of the plating film is deteriorated, which is not preferable.

(Electrolytic nickel plating)
When performing electrolytic nickel plating, any plating bath such as watt bath (nickel sulfate, nickel chloride, boric acid), nickel sulfamate bath (nickel sulfamate, nickel chloride, boric acid), etc. But you can.

(Blackening treatment)
The outermost surface of the plating layer (the surface of the plating layer 18b in FIG. 3) is preferably blackened to prevent reflection of light due to the gloss of the plated metal. As a method of blackening treatment on the surface of nickel plating, there is no particular limitation on the type of blackening treatment film and the composition of the blackening treatment solution to be used. As a preferable example, when black nickel is used, The concentration is preferably 10 to 50 g / liter, and more preferably 20 to 40 g / liter. When the concentration of nickel sulfate is lower than 10 g / liter, plating deposition is delayed and the cost is increased, and when it is higher than 50 g / liter, the finished color of the blackening treatment is not stable.

(Alkali treatment of support substrate)
After the step of producing a developed silver wiring pattern generated by a photographic method on a support substrate, conductive metal plating is performed on the developed silver wiring pattern to form a conductor (circuit wiring pattern). However, in the process of transferring the subsequent conductor to one side of the plate glass constituting the vehicle window glass, the base material S on which the conductor 14 is formed (see FIG. 4) is treated with an alkali.
The alkali treatment is performed by immersing the support substrate on which the conductor is formed in a strong alkaline solution (for example, sodium hydroxide aqueous solution or potassium hydroxide aqueous solution) having a pH of 11 to 13. By this alkali treatment, the adhesive force between the conductor 14 and the support substrate S is reduced, and the conductor 14 is easily separated from the support substrate S. After the support substrate S on which the conductor 14 is formed is alkali-treated, the excess chemical solution adhering to the support substrate S is sufficiently washed and removed by neutralization, water washing, etc., and then drained and dried. I do.

(Vehicle window glass manufacturing method)
In the present invention, any one of two different silver salt photographic development methods (positive type photographic method-plating method, negative type photographic method-plating method) is used on the supporting substrate S by a photographic method. The conductive film 14 formed by forming the thin film 17 of the generated wiring pattern made of developed silver and laminating the metal layers 18a and 18b on the wiring pattern by plating is used.
The conductor 14 formed on the support substrate S by the photographic method-plating method is transferred to one surface of the plate glass 12 to form wiring of the window glass for the vehicle.
In addition, in the manufacturing method of the window glass for vehicles of this invention, the conductor is manufactured on the roll-shaped support base film, and this roll-shaped support base film is laminated to laminated glass according to demand. The window glass for a vehicle can also be manufactured by transferring a conductor.

  Although the manufacturing method of the window glass for vehicles shown in FIGS. 1-3 is not specifically limited, For example, the method shown below can be used. In addition, in order to protect an adhesive bond layer during a manufacturing process or after a process, you may laminate | stack release paper arbitrarily.

(1) As shown in FIG. 4, a developed silver layer 17 formed on a support substrate S produced by a photographic method and plated layers 18a and 18b laminated thereon, preferably copper A conductor 14 having a metal wiring pattern including a plating layer 18a (by electroless copper plating and / or electrolytic copper plating) and / or a nickel plating layer 18b is prepared.
The conductor 14 formed on the support substrate S is immersed in a strong alkaline solution having a pH of 11 to 13 to reduce the adhesion between the conductor 14 and the support substrate S, and the conductor 14 is supported by the support base. It is preferable to make it easy to peel from the material S.
(2) The adhesive layer 13 is provided on one side of the first glass sheet 12. After the conductor 14 on the support base material S is bonded and pressure-bonded on the adhesive layer 13 as shown in FIG. 5A, the support base material S is peeled off as shown in FIG. 5B. Then, the conductor 14 is transferred onto the adhesive layer 13, and the conductor 14 of the vehicle window glass 1 is formed by the conductor 14.
(3) The transparent resin layer 15 is formed by embedding and smoothing a transparent resin in the depression of the conductor 14 transferred onto the first glass plate 12.
(4) A second glass sheet 16 is further laminated on the transparent resin layer 15 to obtain the vehicle window glass 11 of this embodiment (see FIG. 3).

  When transferring the conductor 14 to the plate glass 12, an adhesive layer 13 is provided on one side of the plate glass 12 in order to transfer the conductor 14 to the plate glass 12 reliably. As the adhesive, a pressure-sensitive adhesive having an appropriate adhesive force, or a curable adhesive that is cured by light, ionizing radiation, heat, or the like can be used. In the present invention, an acrylic-based thermosetting adhesive is particularly preferable because it is cured after bonding and the shape is stabilized.

  According to the window glass for a vehicle of this embodiment, an ultra fine conductor having a thickness of 20 to 60 μm, which is not visible to the viewer, is transferred and fixed to the inner surface of any one of the laminated glass. Because it is installed, it has excellent transparency (not visible) and does not obstruct the field of view.

  In the present invention, since the copper plating layer is laminated by electroless plating and / or electrolytic plating in contact with the developed silver mesh pattern formed by the photographic method formed on the supporting base, Due to the phenomenon that the metallic silver on the material diffuses and migrates to the copper plating layer, the adhesion between the developed silver metal wiring pattern and the supporting substrate is reduced, and the conductor floats from the supporting substrate. It becomes easy to peel from the material.

Moreover, in this invention, since the said conductor formed on the support base material is immersed in the strong alkaline liquid of pH 11-13, the adhesive force of a conductor and a support base material is reduced, Therefore Conductor Is easily peeled off from the support substrate.
For this reason, in the present invention, in the step of peeling the conductor from the support base material and transferring it to the laminated glass constituting the vehicle window glass, the conductor formed on the support base material is replaced with the vehicle window glass. After the pressure-bonding to the laminated glass that constitutes, through the adhesive layer, the work of peeling and transferring the conductor whose adhesion with the supporting base material has been reduced can be smoothly performed.

  The present invention is a vehicle window in which a conductor such as a snow melting heater and a communication antenna is sandwiched between two glass plates constituting laminated glass, and has excellent transparency (not visible) and does not obstruct the view. Can be used for glass.

It is a front view showing roughly an example of the window glass for vehicles of the present invention. It is a front view which shows roughly the other example of the window glass for vehicles of this invention. It is typical sectional drawing which shows an example of a structure of the window glass for vehicles of this invention. It is typical sectional drawing which shows an example of the laminated body in which the conductor was provided on the support base material. (A) is typical sectional drawing explaining a mode that the conductor provided on the support base material is transcribe | transferred to plate glass, (b) is a typical cross section explaining a mode that the support base material is peeled from a conductor. FIG.

Explanation of symbols

DESCRIPTION OF SYMBOLS S ... Support base material, 1 ... Window glass (front glass), 2 ... Conductor area | region, 3 ... Upper bus bar (bus), 4 ... Lower bus bar (bus), 5 ... Lead wire connected to upper bus bar, 6 ... Lead wires connected to the lower bus bar, 10 ... window glass for vehicle, 11 ... laminated glass, 12 ... first plate glass, 13 ... adhesive layer, 14 ... conductor (circuit wiring pattern), 15 ... transparent resin layer, 16 ... second plate glass, 17 ... developed silver layer (development silver wiring pattern), 18a ... first metal plating layer (copper plating layer), 18b ... second metal plating layer (nickel plating layer), 20 ... Vehicle window glass.

Claims (7)

  In a window glass for a vehicle in which a conductor is disposed, a conductor composed of a conductive metal wiring pattern and a metal plating layer laminated thereon is transferred onto one surface of the first plate glass constituting the window glass. A window glass for vehicles, which is stuck and sandwiched between the first plate glass and the second plate glass.   2. The vehicle window glass according to claim 1, wherein the conductive metal wiring pattern is a developed silver wiring pattern generated by a photographic process. 3.   3. The vehicle window glass according to claim 2, wherein the metal plating layer has an electroless copper plating layer and / or an electrolytic copper plating layer laminated on and in contact with the developed silver wiring pattern. .   4. The vehicle window glass according to claim 2, wherein the developed silver wiring pattern is generated by a positive photographic method or a negative photographic method. 5.   A method for producing a window glass for a vehicle in which a conductor is disposed, wherein a wiring pattern generation step for generating a developed silver wiring pattern on a supporting substrate by a photographic method, and a conductive pattern on the developed silver wiring pattern. The manufacturing method of the window glass for vehicles characterized by including the plating process which forms a conductor with an electroconductive metal plating layer, and the process of transferring the said conductor to the single side | surface of the plate glass which comprises the said window glass.   Prior to the plating step and the transfer step, the conductor formed on the support substrate is immersed in a strong alkaline solution having a pH of 11 to 13 to reduce the adhesion between the conductor and the support substrate. The method for producing a vehicle window glass according to claim 5, further comprising an alkali treatment step.   7. The method for producing a window glass for a vehicle according to claim 5, wherein the developed silver wiring pattern is generated by a positive photographic method or a negative photographic method.

Images