JP2007219709A - Security glass, its manufacturing method, and security glass system using it - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide security glass which can easily be wired in a uniform fashion even with a metallic wiring pattern of a very fine wire so fine as to be invisible, and which is excellent in productivity, while ensuring detection of damage; its manufacturing method; and a security glass system using it. <P>SOLUTION: In the security glass 1 having a resistor 4 disposed thereon, the resistor 4 comprising a wiring pattern 7 of a conductive metal and metal plating layers 8a, 8b deposited thereon is stuck by transfer to one side of a first glass sheet 2 forming the security glass 1. The resistor 4 is sandwiched between the first glass sheet 2 and a second glass sheet 6. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a crime prevention glass attached to a building or a structure, for example, attached to a window glass, a door glass, a showcase, a show window, etc., and capable of detecting breakage of the glass. The present invention relates to a security glass, a method of manufacturing the same, and a security glass system using the security glass, which are excellent in performance and capable of reliably detecting breakage.

In recent years, there has also been a remarkable increase in crime cases that cause bandits to enter buildings due to worsening security, resulting in theft and burglary cases. Individual houses, companies, public facilities and buildings, etc. Entrusting security to a security company is becoming widespread in order to ensure security.
Specialized security companies provide various detection / alarm facilities for the target properties that have been entrusted with security, and are alerted by alarm devices. Security companies are competing for how to reliably detect the intrusion of a bandit, issue a warning more quickly and dismiss the bandit, and how quickly the guard can be dispatched to the scene.

  A commonly used intrusion technique for bandits is to break a part of the window glass near the doorknob and then enter the door by unlocking the door lock. However, in a quiet residential area with a distance from the neighbor, if the inhabitants invading the bandits are away, the neighbors will not notice the sound of the window glass breaking down, and a situation in which the bandits can easily be allowed to enter. For this reason, crime prevention glasses and crime prevention glass systems using the crime prevention glasses are becoming more and more important in security devices that detect the intrusion of bandits regardless of day or night and issue warnings.

  Conventionally, as a method of directly detecting that a bandit breaks the window glass and invades, a method of analyzing ultrasonic waves generated when the window glass is broken by a detector or a vibration detector attached to the window glass Methods are used to detect window glass breakage. However, any of these detection methods has a disadvantage that certainty is not guaranteed to detect the true breakage of the window glass as distinguished from other noises. For example, in the case of using ultrasonic detection, it is necessary to analyze and discriminate a short-time ultrasonic wave generated when the window glass is broken from ultrasonic noise caused by other causes, which is technically difficult. In the case of using a vibration detector, for example, the vibration of a window glass caused by the passage of an automobile or the vibration generated when another object collides with the window glass during a storm, etc. It is technically difficult to distinguish from

  Compared to these detection methods, which have technical problems that are difficult to solve and are relatively likely to cause false alarms, a resistor is placed on the window glass, and the resistor breaks when the window glass is broken. A simple detection method of detecting breakage of the window glass by utilizing the change in the resistance value is effective as a method for reliably detecting breakage of the window glass.

By the way, as crime prevention glass using the method which arrange | positions a resistor to this window glass, it describes in patent documents 1-4, etc., for example.
In Patent Document 1, a conductive paint is applied to the surface of tempered glass, a lead wire is connected to the paint and a current of a predetermined value is passed, and it is detected that the current value has fallen below a certain value. And detecting glass damage.
Patent Document 2 discloses the existence of a conductive wire in which a plurality of extremely thin conductive wires having a thickness that is difficult to be visually recognized by a viewer are arranged inside a base made of a transparent electrical insulating material, and a terminal portion is connected to an electric circuit. An unknown security glass is disclosed.
In Patent Document 3, a conductor such as copper or aluminum, which is made of a fine wire having a thickness that is difficult to be visually recognized by a viewer, is embedded in the adhesive layer provided on one side of the resin film, and the resin film is arranged. Is attached on a transparent body such as glass or transparent plastic, and the destruction of the transparent body is detected by disconnection of the conductor.
Patent Document 4 discloses a configuration of a detection device in which a resistor is disposed on the surface of a glass to detect breakage of the glass.
In addition, as a method for producing an electromagnetic shielding material using a conductive metal mesh, after forming a fine line pattern with developed silver produced by a photographic method, a conductive metal pattern is formed by plating on this developed silver thin film. A photographic silver-plating method is known (see, for example, Patent Document 5 and Patent Document 6).
JP-A-55-162194 Japanese Patent Laid-Open No. 3-141497 JP 9-007076 A JP-A-3-34094 JP 2004-221564 A International Publication No. 2004/007810 Pamphlet

The method of detecting breakage of glass by a wiring made of a conductive paint disclosed in Patent Document 1 has a technical limit in a method of applying a conductive paint, and a thin wiring cannot be applied so as not to be visually recognized. Therefore, there was a fault that it would be visually recognized by the viewer.
Further, the technique disclosed in Patent Document 2 uniformly distributes a plurality of fine wires having a diameter or width of 100 μm or less, preferably 40 μm or less, in order to eliminate the disadvantage of being visually recognized by this viewer. Wiring is technically difficult and has the disadvantage of poor productivity.
Furthermore, the technique disclosed in Patent Document 3 performs wiring of ultrafine wires made of a conductor (copper, aluminum, etc.) having an outer diameter of 50 μm or less in an adhesive layer formed on one side of a resin film. As in the technique of Patent Document 2, it is technically difficult to distribute the fine wires having a thickness that cannot be visually recognized evenly, and the productivity is inferior.

  The present invention has been made in view of the above circumstances, and even a very thin metal wiring pattern with a thickness that cannot be visually recognized can be easily and uniformly wired, is excellent in productivity, and reliably. It is an object of the present invention to provide a crime prevention glass, a method for manufacturing the crime prevention glass, and a crime prevention glass system using the same, in which breakage can be detected.

In order to solve the above-described problems, the present invention provides a crime prevention glass in which a resistor comprising a conductive metal wiring pattern and a metal plating layer laminated thereon is provided in the crime prevention glass provided with a resistor. Provided is a security glass which is attached to one side of a first plate glass 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.
It is preferable that a detector for detecting a breakage of the glass by measuring a change in the resistance of the resistor is connected to electrodes disposed at both ends of the resistor of the security glass.
The conductive metal plating layer is preferably a copper plating layer and / or a nickel plating layer.
The resistor is a regular resistor having a line width of 20 to 60 μm that is not visible to the viewer (used for detection of destruction) and a dummy having a width of 61 to 500 μm that is visible to the viewer. It is preferable to dispose a resistor (not used for detecting breakage).

Further, the present invention is a method of manufacturing a crime prevention glass in which a resistor is provided, a wiring pattern generation step of generating a developed silver wiring pattern on a support substrate by a photographic method, and the development silver wiring pattern A security process comprising: a plating step of forming a resistor with a conductive metal plating layer thereon; and a transfer step of transferring and pasting the resistor to one side of a plate glass constituting the security glass. A method for producing glass is provided.
By immersing the resistor formed on the support substrate in a strong alkaline solution having a pH of 11 to 13 between the plating step and the transfer step, the adhesion between the resistor and the support substrate is reduced. It is preferable to have an alkali treatment step.
The developed silver wiring pattern is preferably produced by a positive photographic process or a negative photographic process.
In the transfer step, the resistor formed on the support substrate is pressure-bonded to one side of a plate glass constituting the crime prevention glass through an adhesive layer, and then the resistor is bonded to the adhesive layer from the resistor. It is preferable to peel off the material.

  According to the present invention, a fine and regular resistor of 20 to 60 μm that is invisible to the viewer is disposed, and a line width of 61 to 500 μm that is visible to the viewer, By intentionally disposing a dummy resistor, the crime prevention effect can be enhanced by recognizing that the bandit is provided with security glass.

In the present invention, since the resistor is surely broken together with the breakage of the plate glass by using the ultrafine resistor transferred and fixed to the plate glass, there is no possibility of generating a false alarm. Moreover, since the resistor is sandwiched between the two plate glasses constituting the security glass, the durability of the security glass and the resistor can be enhanced.
Furthermore, of the resistors, by checking the presence / absence of the breakage of the dummy resistor disposed in the vicinity of the regular resistor, whether or not the security glass system is malfunctioning, Since it can be judged intuitively on the spot, psychological anxiety about malfunction can be resolved.

In the present invention, by laminating a copper plating layer by electroless plating and / or electrolytic plating in contact with a developed silver wiring pattern generated by a photographic method, metal silver diffuses and migrates to the copper plating layer, The adhesion between the developed silver wiring pattern and the support substrate is reduced, and the resistor can be lifted from the support substrate, and the resistor is easily peeled from the support substrate.
Moreover, since this invention is reducing the contact | adhesion power of a resistor and a support base material by immersing the resistor formed on the support base material in the strong alkaline liquid of pH 11-13, a resistor Is easily peeled off from the support substrate.
For this reason, in the present invention, in the step of peeling the resistor from the support substrate and transferring it to the plate glass, the resistor formed on the support substrate is pressure-bonded toward the plate glass, and then is bonded to the adhesive layer. The transfer work performed by peeling the supporting base material from the formed resistor can be performed smoothly.

The present invention will be described below with reference to the drawings based on the best mode.
FIG. 1 is a schematic cross-sectional view showing a configuration example of the security glass of the present invention. FIG. 2: is a front view which shows the outline of the 1st example of a crime prevention glass and crime prevention glass system of this invention. FIG. 3: is a front view which shows the outline of the 2nd example of the crime prevention glass and crime prevention glass system of this invention. FIG. 4 is a schematic cross-sectional view showing an example of a laminate in which a resistor is provided on a support base material. FIG. 5A is a schematic cross-sectional view illustrating a state in which a resistor 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 resistor. It is typical sectional drawing to do.

As shown in FIG. 1, the security glass according to the present embodiment includes a conductive metal wiring pattern 7 and a metal plating layer 8a laminated thereon in a security glass 1 in which a resistor 4 is disposed inside a laminated glass. , 8b are attached to the adhesive layer 3 provided on one side of the first glass plate 2 constituting the crime prevention glass 1 by transfer, and the resistor 4 is a transparent resin layer. The resistor 4 is sandwiched between two sheet glasses 2 and 6 that are bonded to the second glass sheet 6 via the second glass sheet 6 and bonded to the entire surface.
As the plate glasses 2 and 6, inorganic glass such as tempered glass is widely used, but organic glass made of acrylic resin or the like may be used.

  2 and 3 are front views showing a security glass system of this embodiment including the security glass having the cross-sectional structure shown in FIG. In these security glass systems 10 and 20, the security glasses 11 and 21 have resistors 13 and 23 sandwiched between two plate glasses 12 and 22 on an adhesive layer provided on one side of one plate glass. On the other hand, it has a structure in which the resistors 13 and 23 are bonded to the other plate glass through a transparent resin layer while being bonded by transfer.

A plurality of resistors 13, 23 arranged in parallel are connected in parallel by collector electrodes 14, 24 at both ends thereof, and are further connected via conductors 16, 26 connected to end portions 15, 25 of collector electrodes 14, 24. By being connected to the detectors 17 and 27, a circuit for detecting breakage is formed. The detectors 17 and 27 are parts for measuring a change in resistance of the resistor and detecting breakage of the glass.
The dummy resistors 18 and 28 are wiring having a thickness that can be visually recognized, and it is not necessary to form a circuit. It is arranged in the vicinity of the regular resistors 13 and 23 so that it can be visually observed intentionally.
In the security glass 11 and 21 of this embodiment, a plurality of resistors 13 and 23 are arranged in parallel and connected in parallel. However, the resistors 13 and 23 are connected to electrodes at both ends. Furthermore, it is possible to adopt a configuration in which the electrodes are connected to the detectors 17 and 27.

(Metal wiring pattern manufacturing method)
In the crime prevention glasses 11 and 21 of the present embodiment, the regular resistors 13 and 23, the electrodes (collector electrodes) 14 and 24, and the dummy resistors 18 and 28 are two different silver salt photographic development methods (positive type photographs). A wiring pattern composed of a developed silver thin film produced by a photographic method on a supporting substrate using any one of a manufacturing method-plating method, a negative photographic method-plating method, and this wiring pattern A metal wiring pattern in which a conductive metal layer is laminated by plating is formed on the substrate, and the metal wiring pattern is transferred onto a plate glass.

  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 method of silver salt photographic development (positive photographic process) is a method described in Patent Document 6, that is, a silver salt photographic development method, in which silver halide is dissolved with a soluble silver complex salt forming agent. In this method, a soluble silver complex salt is formed and simultaneously reduced with a reducing agent (developing agent) such as hydroquinone to deposit metallic 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 support base S (see FIG. 4) on which the developed silver wiring pattern is formed is preferably provided with a physical development nucleus layer in advance. The support substrate S 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. , 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 support substrate S by vacuum deposition, cathode sputtering, coating, 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.

  The support substrate S can be provided with an adhesive layer of a polymer latex layer such as vinylidene chloride or polyurethane, 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 silver metal 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 the support substrate S, or separately. 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 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. The silver halide emulsion layer is exposed in the form of a wiring pattern in order to form a wiring pattern that becomes a resistor of the security glass of the present invention. As an exposure method, the transparent original of the wiring pattern and the silver halide emulsion layer are closely attached. Then, there are a method of exposing with ultraviolet light, a method of scanning exposure using various laser beams, and the like. 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 support substrate S 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 the support interposed therebetween. May contain a dye or pigment for preventing halation or irradiation.

(Positive photographic process-plating method: exposure and development)
When a wiring pattern is prepared 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 wiring pattern and the photosensitive material Is exposed to light, or a digital image of an arbitrary wiring pattern is scanned and exposed to the photosensitive material with various laser beam output machines, and then processed in an alkaline solution in the presence of a soluble silver complex salt forming agent and a reducing agent. As a result, 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, and metal silver is precipitated to form a physically developed silver thin film having a wiring pattern. Can be obtained. The exposed portion is chemically developed in the silver halide emulsion layer to become blackened silver. After the development, the silver halide emulsion layer and the intermediate layer, or the protective layer provided as necessary, are removed by washing to expose the physically developed silver thin film of the wiring pattern 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 support substrate S coated with the physical development nucleus layer, the silver halide emulsion layer is exposed as described above. Then, the support substrate S coated with the physical development nucleus layer and another photosensitive material coated with the silver halide emulsion layer are mixed in an alkaline solution in the presence of a soluble silver complex salt forming agent and a reducing agent. After overlapping and adhering and taking out from the alkaline solution, after several tens of seconds to several minutes have passed, both are peeled off to obtain a physically developed silver thin film having a wiring 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-described soluble silver complex salt forming agent and reducing agent may be applied to the supporting substrate S together with the physical development nucleus layer, may be added to the silver halide emulsion layer, or in the alkaline solution. It may be contained, and may be further contained at 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. In the dipping method, for example, the supporting substrate S provided with the physical development nucleus layer and the silver halide emulsion layer is conveyed while being immersed in an alkaline liquid 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 crime prevention glasses using conductive wires are provided with conductive wires having a thickness of about 40 to 100 μm, for example. 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 line width of the thin line is reduced. In particular, if the line width is about 60 μm or less, visual observation becomes difficult, but the conductivity becomes low. Conversely, when the line width is increased, the viewer can easily see the line width, but the conductivity is increased.
In the crime prevention glass of the present invention, the line width of the regular resistors 13 and 23 is set to a line width of 20 to 60 μm, which is a thickness that cannot be visually recognized by the viewer, and the line width of the dummy resistors 18 and 28 is set to the viewer. It is preferable that the line width is 61 to 500 μm, which is a thickness that can be visually recognized. By deliberately arranging dummy resistors with a line width of 61-500 μm, which is a thickness that can be visually recognized by the viewer, the crime prevention effect can be enhanced by recognizing that the bandits are provided with security glass. it can.

(Plating of metal wiring pattern on metallic silver)
After a metal wiring pattern made of the developed silver layer 7 is formed on the support substrate S by a photographic method, the thickness of the metal plating layer provided on the developed silver layer 7 can be arbitrarily changed according to desired characteristics. However, it is in the range of 0.5 to 15 μm, preferably 2 to 12 μm.

  The conductive silver can be plated on the developed silver layer 7 by any of electroless plating, electrolytic plating, or a combination of both. The viewpoint that a roll-shaped long web provided with a physical development nucleus layer and a silver halide emulsion layer on the support substrate S can be subjected to at least a series of treatments of exposure, development treatment and plating treatment of a metal wiring pattern. Therefore, a method in which electrolytic plating or a combination of electroless plating is preferable.

In the present invention, the method of plating the metals 8a and 8b on the developed silver layer 7 is as follows.
A developed silver wiring pattern 7 generated by a photographic method is formed on one side of the supporting substrate S, and one or more conductive metals are plated on the developed silver layer 7.
The metal plating on the developed silver layer 7 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”.

It is preferable to use copper (Cu) and / or (Ni) nickel for reasons such as easy plating, excellent conductivity, and capable of plating a thick film, and low cost.
In particular, the first plating layer 8a laminated on the developed silver layer 7 is a copper plating layer formed by electroless copper plating and / or electrolytic copper plating, and the second plating laminated on the first plating layer 8a. A combination in which the layer 8b is a nickel plating layer is preferable. It is preferable to apply a blackening treatment to the surface of the second plating layer 8b.
In this embodiment, since the resistor 4 is attached to one side of the first glass plate 2 by transfer on the metal plating layer 8b side, the blackened plating layer 8b is arranged on the visual side (for example, the outdoor side). be able to.

(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 metal plating layer 8b is preferably blackened to prevent reflection of light due to the gloss of the plated metal. For example, as a method of blackening treatment of the surface of the nickel plating layer 8b, there is no particular limitation on the type of blackening treatment film and the composition of the blackening treatment liquid to be used. As a preferred example, when black nickel is used, the blackening treatment is performed. The concentration of nickel sulfate in the treatment liquid is preferably 10 to 50 g / liter, 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 substrate)
After the step of producing a metal wiring pattern by the developed silver layer 7 generated by the photographic method on the support substrate S, conductive metal plating layers 8a and 8b are formed on the developed silver layer 7 forming the metal wiring pattern. By laminating, the thickness of the metal wiring pattern is increased, and the conductivity as the detection resistor 4 is improved. In the process of transferring the obtained metal wiring pattern 4 to one side of the first glass sheet 2, the support substrate S on which the metal wiring pattern 4 is formed is formed so that the metal wiring pattern 4 can be easily peeled off from the support substrate S. Is treated with alkali.

  The alkali treatment is performed by immersing the support base S on which the metal wiring pattern 4 is formed in a strong alkaline solution (aqueous sodium hydroxide solution or aqueous potassium hydroxide solution) having a pH of 11 to 13. By this alkali treatment, the adhesion between the metal wiring pattern 4 and the support base material S is reduced, and the metal wiring pattern 4 is easily peeled from the support base material S. After the support substrate S on which the metal wiring pattern 4 is formed is alkali-treated, the excess chemical solution adhering to the metal wiring pattern 4 and the support substrate S is sufficiently washed and removed by neutralization treatment, water washing, etc. Then, drain and dry.

(Method of manufacturing crime prevention glass)
In this invention, it produces | generates on the support base material S by the photographic manufacturing method using either of two different silver salt photographic development methods (positive type photographic manufacturing method-plating method, negative type photographic manufacturing method-plating method). A metal wiring pattern composed of the developed silver layer 7 is formed, and metal plating layers 8 a and 8 b are laminated on the developed silver layer 7 to form the resistor 4. Furthermore, after transferring the resistor 4 formed on the supporting substrate S by the photolithography method-plating method to one surface of the first plate glass 2, the second plate glass 6 is further bonded to form two resistors 4 The glass 1 is formed by being sandwiched between the glass plates 2 and 6.
In addition, in the manufacturing method of the crime prevention glass of this invention, a metal wiring pattern is manufactured on a roll-shaped support base film, and a resistor is added to this plate glass from this roll-shaped support base film according to demand. It is also possible to produce crime prevention glass by transcription.

  Although the manufacturing method of the crime prevention glass 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 7 formed on a supporting substrate S and produced by a photographic method and plated layers 8a and 8b laminated thereon, preferably copper A metal wiring pattern 4 is prepared by a metal wiring pattern composed of a plating layer 8a (by electroless copper plating and / or electrolytic copper plating) and / or a nickel plating layer 8b.
The metal wiring pattern 4 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 metal wiring pattern 4 and the support substrate S. It is preferable to make it easy to peel from the support substrate S.
(2) The adhesive layer 3 is provided on one side of the first plate glass 2. On the adhesive layer 3, the metal wiring pattern 4 on the support base material S is bonded and pressure-bonded as shown in FIG. 5 (a), and then the support base material S is attached as shown in FIG. 5 (b). The metal wiring pattern 4 is peeled off and transferred onto the adhesive layer 3, and the resistor 4 of the security glass 1 is formed by the metal wiring pattern 4.
(3) The transparent resin layer 5 is formed by embedding and smoothing a transparent resin in the depression of the metal wiring pattern 4 transferred onto the first plate glass 12.
(4) A second plate glass 6 is further laminated on the transparent resin layer 5 to obtain the crime prevention glass 1 of this embodiment (see FIG. 1).

  In the above-described method, the adhesive layer 3 is provided on one surface of the plate glass 2 in order to transfer the metal wiring pattern 4 to the plate glass 2 with certainty. Or a curable adhesive that is cured by light, ionizing radiation, heat, or the like. In the present invention, an acrylic-based thermosetting adhesive is particularly preferable because it is cured after bonding and the shape is stabilized.

  Moreover, as transparent resin which comprises the transparent resin layer 5, as the 2nd plate glass 6 is bonded together, the adhesive which has a suitable adhesive force, or the curable adhesive hardened | cured with a light ray, ionizing radiation, a heat | fever, etc. 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.

In the security glass 1, 11 and 21 of the present embodiment, the use of the ultra-fine resistors 4, 13, and 23 that are transferred and fixed to the plate glass ensures that the resistor breaks along with the breakage of the plate glass. There is no fear of emitting. The resistors 4, 13, and 23 are peeled off from the support base material S, and the support base material S is not included in the structure of the security glass 1, 11, and 21. It is possible to avoid uncertain disconnection of the body.
Moreover, since the resistor 4 is sandwiched between the two glass plates 2 and 6 constituting the crime prevention glass, the durability of the crime prevention glass and the resistor can be enhanced.

20 and 60 μm thick and regular resistors 13 and 23 (used for detection of destruction) that are invisible to the viewer are disposed, and 61 to 500 μm in thickness that are visible to the viewer. By deliberately providing dummy resistors (not used for detection of destruction) 18 and 28 with a line width, it is possible to recognize that the crime band has been provided with a crime prevention glass and to enhance the crime prevention effect.
Furthermore, the security glass system malfunctions by visually confirming whether or not the dummy resistors 18 and 28 arranged near the regular resistors 13 and 23 are disconnected. It is possible to intuitively determine whether or not there is, so that psychological anxiety about malfunction can be resolved.

  Since the copper plating layer 8a is laminated by electroless plating and / or electrolytic plating in contact with the developed silver layer 7 formed by the photographic method formed on the supporting substrate S, the surface of the supporting substrate S is Due to the phenomenon in which metallic silver diffuses and migrates from the developed silver layer 7 into the copper plating layer 8a, the adhesive force between the resistor 4 and the support substrate S decreases, and the resistor 4 floats from the support substrate S, causing resistance. It becomes easy to peel the body 4 from the support base material S.

In the present invention, since the resistor 4 formed on the support substrate S is immersed in a strong alkaline solution having a pH of 11 to 13, the adhesion between the resistor 4 and the support substrate S is reduced. It becomes easy to peel the resistor 4 from the support base material S.
For this reason, in the present invention, the resistor 4 formed on the support substrate S is included in the constituent layer of the security glass 1 in the step of peeling the resistor 4 from the support substrate S and transferring it to the plate glass 2. After the pressure bonding to the plate glass 2 via the adhesive layer 3, the operation of peeling off and transferring the resistor 4 whose adhesion with the supporting substrate S is lowered can be smoothly performed.

  The present invention relates to a security glass attached to a building or a structure, for example, a window glass, a door glass, a showcase, a show window, etc., which can detect the breakage of the glass, and a security glass system using the same. Can be used.

It is typical sectional drawing which shows the structural example of the crime prevention glass of this invention. It is a front view showing the outline of the 1st example of a crime prevention glass and a crime prevention glass system of the present invention. It is a front view which shows the outline of the 2nd example of the crime prevention glass and crime prevention glass system of this invention. It is typical sectional drawing which shows an example of the laminated body in which the resistor was provided on the support base material. (A) is typical sectional drawing explaining a mode that the resistor provided on the support base material is transcribe | transferred to plate glass, (b) is a typical cross section explaining a mode that a support base material is peeled from a resistor. FIG.

Explanation of symbols

DESCRIPTION OF SYMBOLS S ... Support base material, 1 ... Security glass, 2 ... 1st plate glass, 3 ... Adhesive layer, 4 ... Resistor (metal wiring pattern), 5 ... Transparent resin layer, 6 ... 2nd plate glass, 7 ... Development Silver layer (development silver wiring pattern), 8a ... 1st metal plating layer (copper plating layer), 8b ... 2nd metal plating layer (nickel plating layer), 10, 20 ... Security glass system, 11, 21 ... Security glass, 12, 22 ... Plate glass, 13, 23 ... Resistor, 14, 24 ... Collector, 15, 25 ... End, 16, 26 ... Conductor, 17, 27 ... Detector, 18, 28 ... Dummy resistance body.

Claims (8)

  In the crime prevention glass provided with a resistor, a resistor composed of a conductive metal wiring pattern and a metal plating layer laminated thereon is attached to one side of the first plate glass constituting the crime prevention glass by transfer. And the security glass characterized by being clamped between said 1st plate glass and 2nd plate glass.   The security glass according to claim 1, wherein the conductive metal wiring pattern is a developed silver wiring pattern produced by a photographic method.   The crime prevention 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.   The security glass according to claim 2 or 3, wherein the developed silver wiring pattern is produced by a positive photographic method or a negative photographic method.   A detector that detects a breakage of the glass by measuring a change in resistance of the resistor is connected to the electrodes disposed at both ends of the resistor of the security glass according to any one of claims 1 to 4. Security glass system characterized by   A method of manufacturing a crime prevention glass provided with a resistor, comprising: 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. A security glass manufacturing method comprising: a plating step of forming a resistor with a metal plating layer; and a transfer step of transferring and pasting the resistor onto one side of a plate glass constituting the security glass.   By immersing the resistor formed on the support substrate in a strong alkaline solution having a pH of 11 to 13 between the plating step and the transfer step, the adhesion between the resistor and the support substrate is reduced. It has the alkali treatment process to make, The manufacturing method of the crime prevention glass of Claim 6 characterized by the above-mentioned.   The method for producing a crime prevention glass according to claim 6 or 7, wherein the developed silver wiring pattern is generated by a positive photographic method or a negative photographic method.

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