JP5901537B2 - Manufacturing method of glass substrate with pattern - Google Patents

Description

The present invention relates to a method of manufacturing a patterned glass substrate, for example, a conductive pattern layer, such as an antenna related to automobile window glass manufacturing method comprising the surface.

  A material obtained by sintering a conductive pattern layer such as an antenna wire or a defogger on the surface of a window glass of an automobile or the like is known. Such a conductive pattern layer is a method in which a conductive paste containing silver and glass frit is screen-printed on the surface of the window glass, and the conductive pattern layer is sintered on the window glass surface by heat treatment (for example, Patent Documents). 1) and a transfer film having a conductive pattern layer in which a conductive pattern layer containing silver and glass frit is formed in advance, and an adhesive layer provided on one surface of the conductive pattern layer is pasted on the window glass surface, It forms by the method (for example, patent document 2) etc. which decompose | disassemble the adhesion layer of a transfer film by heat processing, and sinter a conductive pattern layer on the window glass surface.

JP 2008-44800 A JP 2008-311356 A

  By the way, in the window glass for motor vehicles, there exists what sintered the light shielding layer (what is called black ceramics) which consists of a black ceramic layer in a peripheral part from a viewpoint of improving the appearance on an external appearance. The light shielding layer is formed by applying a black ceramic paste containing a pigment such as black or gray and glass frit to the surface of the window glass by screen printing and sintering the window glass surface by heat treatment. Since the conductive pattern layer may be provided on the peripheral edge of the window glass so as not to be noticeable, when the light-shielding layer is provided, the arrangement positions of both may overlap.

  However, in the case where the conductive pattern layer is disposed so as to overlap the light shielding layer, the conductive pattern layer containing silver is white, so that there is a problem that it is conspicuous on the black light shielding layer and has a poor appearance. . Also, as a manufacturing problem, the surface of the light-shielding layer before sintering is rougher than that of the glass substrate. Therefore, in the method using a transfer film, the adhesion between the adhesive layer and the light-shielding layer is poor, and the conductive layer Sintering failure and poor conductivity due to bubbles remaining between the conductive pattern layer and the light shielding layer, and traces of the transfer film remain on the light shielding layer even after the conductive pattern layer is formed. Therefore, a method for forming a conductive pattern layer on a light-shielding layer using a transfer film has not been implemented so far.

  In addition, the following problems have been confirmed when the conductive pattern layer is formed on the light-shielding layer by using the transfer film by the examination by the applicants. Since the edge portion of the light shielding layer forms a stepped portion on the glass substrate, when the conductive pattern layer has a portion that crosses the edge portion of the light shielding layer, the conductive pattern layer is the edge of the light shielding layer. The shape cannot be followed, the adhesion between the conductive pattern layer, the light shielding layer and the glass substrate is lowered, and the conductivity may be lowered due to poor sintering. When both the transfer film and the light shielding layer are heated to sinter the conductive pattern layer and the light shielding layer, the adhesive layer prevents diffusion of gas generated from the light shielding layer, and bubbles are formed on the surface of the light shielding layer after sintering. It remains and the appearance looks worse.

  Also, there are various problems with the transfer film used to form the conductive pattern layer. The transfer film may be stored in a state in which a plurality of transfer films are laminated to each other. For example, a laminate including a conductive pattern layer and an adhesive layer is supported on a support film that can be peeled off from the laminate, and is adhered. Some layers are laminated together such that the layers are releasably in contact with the back of another support film. Also, the support film that supports the laminate is strip-shaped, the adhesive layer is continuous with the support film, a plurality of conductive pattern layers are intermittently arranged in the longitudinal direction of the support film, and the transfer film is wound on a reel. In some cases, each layer is laminated in the radial direction of the reel. In the transfer film stored in such a laminated state, the conductive pattern layer is often harder than the adhesive layer, so that the portion of the adhesive layer sandwiched between the conductive pattern layers in the stacking direction is the conductive pattern. Compressed between layers, the film thickness may be reduced. When the thickness of the adhesive layer is reduced, the followability (adhesiveness) to the surface to be attached is lowered, and there is a problem that the conductive pattern layer cannot be appropriately attached at a predetermined position. In particular, since the light-shielding layer has a rougher surface than the glass substrate, there is a problem that the adhesive layer cannot be properly adhered. In addition, since the film thickness of only the portion sandwiched between the conductive pattern layers becomes thin, the surface of the adhesive layer becomes uneven, and it becomes easy to bite bubbles when attaching the adhesive layer to the glass substrate surface or the like There is. In order to avoid such thinning of the adhesive layer, it is conceivable to form the adhesive layer from a relatively hard material that does not become thin even when subjected to compression. There is a problem that the adhesion of the resin is lowered.

  When the outside glass substrate and the inside glass substrate constituting the laminated glass are thermoformed, it is generally performed in a state in which both glass substrates are overlapped, so that the light shielding layer is on the contact surface of both glass substrates. In some cases, both glass substrates are fused via the light shielding layer. Therefore, in conventional laminated glass for automobiles, a light shielding layer is formed on the inner surface of the vehicle outside glass substrate, a conductive pattern layer is formed on the inner surface of the vehicle inner glass substrate, and the light shielding layer and the conductive pattern layer are overlapped. Measures were taken to prevent them from forming. However, in this case, the heating process for sintering the light shielding layer and the heating process for forming the vehicle outer glass substrate and the vehicle inner glass substrate must be performed separately, and productivity is poor. There was a problem.

  The present invention has been made in view of the above problems, and provides a method for producing a patterned glass substrate, which can satisfactorily form a conductive pattern layer on a light shielding layer using a transfer film. Another object of the present invention is to provide a patterned glass substrate having a conductive pattern layer that is not conspicuous on the light shielding layer and is well bonded to the light shielding layer by using this production method. Moreover, let it be a subject to provide the transfer film used for said manufacturing method and a glass substrate with a pattern.

  In order to solve the above-mentioned problems, the present invention provides a method for producing a patterned glass substrate (1) having a conductive pattern layer (8) containing a glass component on the surface, the glass substrate (3). A first step of applying a light-shielding paste containing a pigment and a glass component to a part of the glass substrate and forming a light-shielding layer (6) on the glass substrate; and a conductive pattern layer (8) and an adhesive layer (28). A transfer film (20) having a laminate (30) and a support film (21) releasably laminated on a surface of the laminate opposite to the adhesive layer is provided on the outer surface of the light shielding layer. A second step of affixing the transfer film to the glass substrate so that the layers come into contact with each other, subsequently peeling the support film from the laminate, and transferring the laminate to the glass substrate; A light shielding layer, and the laminate. And a third step of removing the adhesive layer, sintering the light shielding layer on the glass substrate, and sintering the conductive pattern layer on the light shielding layer. To do.

  According to this structure, a conductive pattern layer can be favorably formed on a light shielding layer using a transfer film.

  In another aspect of the present invention, in the second step, the conductive pattern layer includes a portion that crosses an edge of the light shielding layer on the glass substrate. In the third step, the conductive pattern layer A part of is sintered on the glass substrate.

  According to this structure, the freedom degree in arrangement | positioning of an electroconductive pattern layer can be raised.

  According to another aspect of the present invention, in the first step, the edge portion of the light shielding layer on the glass substrate forms an inclined surface that forms an angle of 10 ° or less with the surface of the glass substrate. A light shielding layer is formed.

  According to this configuration, the conductive pattern layer easily follows the surface of the light shielding layer at the edge of the light shielding layer, suppresses poor sintering of the conductive layer to the light shielding layer and the glass substrate, and suppresses poor conductivity. be able to. Even when the thickness of the conductive pattern layer is thinner than that of the light shielding layer, the conductive layer can be satisfactorily disposed on the edge portion of the light shielding layer. In other words, the thickness of the conductive pattern layer can be made thinner than that of the light shielding layer.

  Another aspect of the present invention is characterized in that a thermal decomposition temperature of the laminate excluding the conductive pattern layer is lower than a melting temperature of a glass component contained in the light shielding layer. That is, in the heating process of the light shielding layer and the laminate in the third step, the thermal decomposition (weight reduction) of the laminate excluding the conductive pattern layer is completed before the glass component contained in the light shielding layer starts to melt. It is characterized by.

  According to this configuration, since the laminate excluding the conductive pattern layer decomposes faster than the glass component of the light shielding layer melts, the conductive pattern is generated when the glass component of the light shielding layer melts and generates gas. The laminate excluding the layers does not already exist, and the gas generated from the light shielding layer can diffuse from the light shielding layer to the outside. Therefore, bubbles do not remain inside and on the surface of the light shielding layer, and the appearance of the light shielding layer is improved.

  In another aspect of the present invention, the maximum height in the surface roughness of the light shielding layer formed on the glass substrate in the first step is less than the film thickness of the adhesive layer of the transfer film. It is characterized by that. Here, the maximum height (Rmax) means that only the reference length is extracted from the roughness curve in the direction of the average line, and the distance between the peak line and the valley line of the extracted part is the direction of the vertical magnification of the roughness curve. And the value is expressed in micrometers (μm).

  According to this configuration, the adhesive layer is easily adhered to the surface of the light shielding layer.

  Another aspect of the present invention is characterized in that the method further includes a step of pressing the laminated body onto the glass substrate between the second step and the third step.

  According to this configuration, the pressure-sensitive adhesive layer is more easily adhered to the light shielding layer and the glass substrate, and the conductive pattern is reliably sintered to the light shielding layer and the glass substrate.

  Another aspect of the present invention is characterized in that the method further includes a step of heating the stacked body between the second step and the third step.

  According to this configuration, since the adhesive layer is generally softened after removing the support film that is harder than the laminate, the adhesive layer easily follows the surface shape of the light shielding layer and the glass substrate.

  Another aspect of the present invention further includes a step of heating the light shielding layer and pre-sintering the light shielding layer on the glass substrate after the first step and before the third step. .

  According to this configuration, since the unevenness of the surface of the light shielding layer and the inclination of the edge portion are alleviated by the preliminary sintering, the adhesive layer is easily adhered, and the conductive pattern is sintered to the light shielding layer and the glass substrate. It will surely be done. In addition, before the transfer film is applied onto the light shielding layer, the light shielding layer is heated in advance to dissipate the gas that accompanies the firing, so that gas is generated from the light shielding layer during heating when firing the conductive pattern layer. No gas remains inside and on the surface of the light shielding layer. Therefore, the appearance of the light shielding layer can be formed satisfactorily.

  Another aspect of the present invention is characterized in that the adhesive layer of the transfer film is made of a material having a glass transition temperature of −60 ° C. or higher and −20 ° C. or lower.

  According to this configuration, the pressure-sensitive adhesive layer is formed to be relatively soft and can reliably adhere to the surface of the light shielding layer.

  Another aspect of the present invention is characterized in that the thickness of the adhesive layer of the transfer film is 3 μm or more and 15 μm or less, more preferably 3 μm or more and 7 μm or less.

  According to this configuration, the pressure-sensitive adhesive layer can surely adhere to the surface of the light shielding layer whose surface irregularities are generally larger than those of the glass substrate. Moreover, by setting the film thickness to 7 μm or less, the pressure-sensitive adhesive layer can be made as thin as possible within a range where the adhesiveness can be secured, and the pressure-sensitive adhesive layer can disappear at an early stage during heating.

  In another aspect of the present invention, the adhesive layer of the transfer film prepared in the second step includes a hard inner layer (36) having a relatively high glass transition temperature and a soft material having a relatively low glass transition temperature. And an outer layer (37).

  According to this structure, even if it laminates | stacks at the time of storage and an adhesion layer is compressed between electroconductive pattern layers, since a hard inner layer resists compression, an adhesion layer can maintain predetermined | prescribed film thickness. Moreover, since the soft outer layer ensures the flexibility of the adhesive layer surface, the adhesion to the glass substrate or the like can be improved.

  In another aspect of the present invention, the glass transition temperature of the hard inner layer is −30 ° C. or higher and 0 ° C. or lower, the glass transition temperature of the soft outer layer is −20 ° C. or lower, and the glass of the hard inner layer is The temperature is 10 ° C. or more lower than the transition temperature. The soft outer layer has a weight average molecular weight of 70,000 to 200,000, and the hard inner layer has a weight average molecular weight of 300,000 to 1,500,000.

  According to this configuration, the hard inner layer and the soft outer layer can be suitably formed.

  In another aspect of the present invention, the thickness of the hard inner layer is 2 μm or more and 7 μm or less.

  According to this structure, the film thickness required for adhesion of the adhesive layer to the glass substrate or the like can be ensured.

  Another aspect of the present invention is characterized in that the thickness of the soft outer layer is 3 μm or more and 10 μm or less.

  According to this configuration, even when the transfer film is stored in a laminated state and the adhesive layer is compressed, the soft outer layer can remain on the outer surface of the adhesive layer.

  Another aspect of the present invention is a patterned glass substrate (1) comprising a glass substrate (3), a pigment and a glass component, and a light shielding layer (6) sintered on the surface of the glass substrate, A conductive pattern layer (8) sintered on the light shielding layer, and the conductive pattern layer includes a conductive layer (11) including a glass component, a pigment and a glass component, and surrounds the conductive layer. And a covering layer (15, 16).

  According to this configuration, since the conductive layer is surrounded by the coating layer, it can be made inconspicuous even on the light shielding layer.

  Another aspect of the present invention is characterized in that the conductive pattern layer includes a portion crossing an edge of the light shielding layer on the glass substrate.

  According to this structure, the freedom degree in arrangement | positioning of an electroconductive pattern layer can be raised.

  In another aspect of the present invention, the conductive pattern layer has a thickness of 20 μm or less, and the edge portion forms an inclined surface having an angle of 10 ° or less with the surface of the glass substrate. To do.

  According to this configuration, the conductive pattern layer can be satisfactorily formed even when the conductive pattern layer crosses the edge portion of the light shielding layer.

  Another aspect of the present invention is characterized in that the glass substrate is a window glass for an automobile, and the light shielding layer and the conductive pattern layer are provided on an inner surface of the glass substrate.

  According to this configuration, the appearance of the patterned glass substrate can be improved.

  In another aspect of the present invention, the glass substrate is a glass substrate constituting the inside of a laminated window glass for an automobile, and the light shielding layer and the conductive pattern layer are on the inside surface of the glass substrate. It is provided.

  According to this configuration, the light shielding layer and the conductive pattern layer are disposed so as to avoid the mating surfaces of the glass substrates constituting the laminated window glass. The conductive pattern layer can be baked.

  According to another aspect of the present invention, a laminate (30) including a conductive pattern layer (8) and an adhesive layer (28) is detachably laminated on a surface of the laminate opposite to the adhesive layer. A transfer film used to sinter the conductive pattern layer onto the substrate by transferring the laminate to the surface of the substrate and heating the laminate. Includes a hard inner layer (36) having a relatively high glass transition temperature and a soft outer layer (37) having a relatively low glass transition temperature.

  According to this structure, even if it laminates | stacks at the time of storage and an adhesion layer is compressed between electroconductive pattern layers, since a hard inner layer resists compression, an adhesion layer can maintain predetermined | prescribed film thickness. Moreover, since the soft outer layer ensures the flexibility of the adhesive layer surface, the adhesion to the glass substrate or the like can be improved.

  Another aspect of the present invention is characterized in that the transfer film is wound in a belt shape, and a plurality of the conductive pattern layers are arranged along the longitudinal direction of the support film. To do.

  According to this configuration, since the adhesive layer can maintain a predetermined film thickness even when the transfer film is stored in a laminated state, the transfer film can be stored in a form wound on a reel. In this storage mode, the transfer film can be easily taken out and the workability is good.

  Another aspect of the present invention is characterized in that the thickness of the hard inner layer of the adhesive layer is 2 μm or more and 7 μm or less.

  According to this structure, the film thickness required for adhesion of the adhesive layer to the glass substrate or the like can be ensured.

  Another aspect of the present invention is characterized in that the thickness of the soft outer layer of the adhesive layer is 3 μm or more and 10 μm or less.

  According to this configuration, even when the transfer film is stored in a laminated state and the adhesive layer is compressed, the soft outer layer can remain on the outer surface of the adhesive layer.

  In another aspect of the present invention, the glass transition temperature of the hard inner layer is −30 to 0 ° C., the glass transition temperature of the soft outer layer is −20 ° C. or less, and the glass transition of the hard inner layer. It is 10 ° C. or more lower than the temperature. The soft outer layer has a weight average molecular weight of 70,000 to 200,000, and the hard inner layer has a weight average molecular weight of 300,000 to 1,500,000.

  According to this configuration, the hard inner layer and the soft outer layer can be suitably formed.

  According to the above configuration, the conductive pattern layer can be formed at a position overlapping the light shielding layer without impairing the appearance.

Schematic side view of the windshield of an automobile viewed from the inside II-II sectional view of FIG. III-III sectional view of FIG. Schematic showing the cross section of the transfer film and the storage form of the transfer film Explanatory drawing which shows the process in which a light shielding layer and a conductive pattern layer are formed on a glass substrate Schematic showing the state where the transfer film is stuck on the glass substrate and the light shielding layer Graph showing surface shape of shading layer

  Hereinafter, an embodiment in which the present invention is applied to an automobile windshield (windshield glass) will be described in detail with reference to the drawings.

(Glass substrate with conductive pattern layer)
As shown in FIG.1 and FIG.2, the glass substrate 1 with a conductive pattern layer which concerns on embodiment is applied to the vehicle inside board | substrate of the windshield 10 for motor vehicles which is a laminated glass. The windshield 10 is interposed between the outside glass substrate 2 constituting the outside surface of the vehicle, the inside glass substrate 3 constituting the inside surface of the vehicle, and both the glass substrates 2 and 3, and the both glass substrates 2 and 3 are bonded to each other. And an intermediate film 4 made of resin. A light-shielding layer (so-called black ceramic) 6 made of a black ceramic layer is sintered at the peripheral edge of the vehicle inner surface 5 of the vehicle interior glass substrate 3. On the surface of the glass substrate 3 and the light shielding layer 6, the conductive pattern layer 8 is sintered with a portion that crosses the edge 7 of the light shielding layer 6 on the glass substrate 3.

  The light shielding layer 6 in the present invention is a layer made of a glass component containing a pigment, and is bonded onto the glass substrate 3 by fusing the glass component to the surface of the glass substrate 3. The pigment preferably contains at least one of copper oxide, chromium oxide, iron oxide and manganese oxide, and these may be used alone, in combination of plural types, or in combination with other pigments. . The light shielding layer 6 is not particularly limited as long as it has a light shielding function, but preferably exhibits a dark color such as black or gray. The glass component includes crystallized glass and amorphous glass such as bismuth borosilicate and zinc borosilicate as essential components, and transition metal oxidation including at least one oxide of vanadium, manganese, iron, and cobalt as necessary. And additives such as alumina.

  As shown in FIG. 3, the conductive pattern layer 8 includes a conductive layer 11 made of a glass component containing a conductive material and a coating layer 15, 16 made of a glass component containing a pigment and surrounding (covering) the conductive layer 11. And have. The conductive layer 11 includes a linear portion 13 that forms an antenna pattern, and a feed portion 14 that is wider than the linear portion 13 provided at one end of the linear portion 13. The conductive material may be gold, silver, copper, or an alloy thereof. In the present embodiment, the conductive material includes silver. The conductive layer 11 has conductivity by including a conductive material. The pigment contained in the coating layers 15 and 16 can include a pigment applicable to the light shielding layer 6 described above, and preferably exhibits a dark color such as black or gray, and is composed of the same pigment as the light shielding layer 6. Is preferred. The glass component contained in the conductive layer 11 and the coating layers 15 and 16 includes crystallized glass and amorphous glass such as bismuth borosilicate and zinc borosilicate as essential components, and vanadium, manganese, iron, and An additive such as transition metal oxide containing at least one oxide of cobalt or alumina is included.

  The covering layers 15 and 16 in this embodiment are formed by laminating two layers of the first covering layer 15 and the second covering layer 16 so as to sandwich the conductive layer 11. The linear portion 13 is covered in all directions while the power feeding portion 14 is covered so that the outer surface facing the vehicle interior is exposed. In the conductive layer 11 and the coating layers 15 and 16, the glass components are fused to each other, and are fused to the surface of the light shielding layer 6 and the surface of the glass substrate 3.

  The patterned glass substrate 1 configured as described above is applied to the vehicle interior glass substrate 3 constituting the laminated glass, and since both the light shielding layer 6 and the conductive pattern layer 8 are provided on the vehicle interior surface 5, the vehicle exterior glass substrate. When the 2 and the vehicle interior glass substrate 3 are stacked and thermoformed, the light shielding layer 6 and the conductive pattern layer 8 can be fired simultaneously, and the productivity is good. Further, the linear portion 13 of the conductive layer 11 containing silver and being baked to be white is covered with the covering layers 15 and 16 having the same color as or similar to the light shielding layer 6, so that it can be seen from the inside of the vehicle. In addition, the conductive pattern layer 8 can be made inconspicuous on the light shielding layer 6 and the appearance of the windshield 10 can be enhanced.

(Transfer film)
The structure of the transfer film 20 used in the manufacturing process of the window glass with an electroconductive pattern layer mentioned later is demonstrated. The transfer film 20 includes the conductive pattern layer 8 before the heat treatment, which becomes the conductive pattern layer 8 by being heated (baked), and is attached to the surfaces of the glass substrate 3 and the light shielding layer 6. By being attached, the conductive pattern layer 8 can be easily formed on the surfaces of the glass substrate 3 and the light shielding layer 6.

  As shown in FIG. 4, the laminated body 30 containing the electroconductive pattern layer 8 is laminated | stacked on one surface of the support film 21 which has peelability. On both surfaces of the conductive pattern layer 8, a resin layer made of an organic material that can be removed by baking is laminated in order to improve transferability. Specifically, the transfer film 20 according to this embodiment includes a protective layer 23, a second coating layer 16, a conductive layer 11, a first coating layer 15, an intermediate layer 27, an adhesive layer 28 (hard layer) on a support film 21. The inner layer 36 and the soft outer layer 37) are laminated in this order.

  In order to form such a laminated structure, for example, first, a coating solution for the intermediate layer 27 is applied on the temporary support to form the intermediate layer 27, and then the first coating layer 15 is formed thereon. The conductive layer 11 is printed using a pattern by screen printing, and then the conductive layer 11 paste is printed on the first coating layer 15 by screen printing using a pattern plate to form the conductive layer 11. Next, the paste for the second coating layer 16 is printed using a pattern by screen printing to form the second coating layer 16 so as to cover the conductive layer 11, and a protective layer is further formed thereon. A protective layer 23 is formed by applying a coating solution for the layer 23, and a support film 21 having peelability is bonded thereto to obtain a first laminate. On the other hand, an adhesive for the soft outer layer 37 and an adhesive for the hard inner layer 36 constituting the adhesive layer 28 are sequentially applied to another temporary support, and an adhesive layer comprising the soft outer layer 37 and the hard inner layer 36 is applied. 28 is formed to obtain a second laminate. Finally, the temporary support is peeled off from the first laminate, and the intermediate layer 27 of the first laminate is bonded to the adhesive layer 28 (hard inner layer 36) of the second laminate. 20 can be made. In other embodiments, the adhesive layer 28 may be a single layer.

  The support film 21 is peelable from the laminate 30 including the conductive pattern layer 8. In the present embodiment, the support film 21 has a release layer 31 made of silicone or alkyd resin on the surface opposite to the laminate 30 side, and a re-peeling slightly adhesive layer 32 on the surface of the laminate 30 side. Have The support film 21 may be subjected to roughening treatment such as embossing or sandblasting for improving workability. The support film 21 is preferably made of a flexible material so as not to impair the adhesion of the laminate 30 to the light shielding layer 6 and the surface of the glass substrate 3, for example, polyethylene, polyimide, polyethylene terephthalate. Plastics such as acrylic and paper can be used. When various materials are used, it is desirable that the support film 21 be thinned in order to further increase the flexibility. For example, when polyethylene is used as the material, it is preferably 25 μm or less.

  The conductive layer 11 contains a conductive material for developing conductivity after firing, a glass frit for thermally fusing with a substrate to express mechanical strength, and an organic binder that can be removed by firing, It is comprised in the shape which has a shape part and an electric power feeding part. As the conductive material, a powder of gold, silver, copper, or the like, or an alloy powder containing these can be used, and a material corresponding to a desired function after firing may be appropriately selected and used. From the viewpoint of forming a sintered body of the conductive layer 11, it is desirable to select a material that is excellent in conductivity, can be fired in the atmosphere, and is inexpensive, and silver, silver-palladium, silver-platinum For example, a conductive material containing silver as a main component can be preferably used.

  The glass frit is included for the purpose of providing the conductive pattern layer 8 with mechanical strength and chemical resistance against sulfuric acid, salt water, and the like, and fusing the conductive layer 11 and the coating layers 15 and 16 by heat melting. Yes. A glass frit having a suitable composition can be appropriately selected and used in consideration of a balance such as a firing temperature and a heat shrinkage rate. The glass frit includes, for example, crystallized glass and amorphous glass such as bismuth borosilicate and zinc borosilicate as an essential component, and a transition containing at least one oxide of vanadium, manganese, iron, and cobalt as necessary. It contains additives such as metal oxide and alumina.

  The organic binder contained in the conductive layer 11 of the present invention is not particularly limited as long as it is a material that can be removed by firing. Examples of materials that can be easily removed by thermal decomposition by firing include resins such as acrylic, methylcellulose, nitrocellulose, ethylcellulose, vinyl acetate, polyvinyl petital, polyvinyl acetal, polyvinyl alcohol, polyethylene oxide, and polyester. Or it can be mixed and used. Moreover, you may add a plasticizer as an organic component in order to provide flexibility to the coating film before baking. The plasticizer can be appropriately selected and used from fatty acid esters and phosphate esters.

  The coating layers 15 and 16 contain a glass frit and the organic binder which can be removed by baking other than a black pigment. The black pigment contains at least one kind of chromium oxide, cobalt oxide, copper oxide, or a combination thereof for expressing the concealability after firing and making the appearance black. The glass frit is thermally melted to give the coating layers 15 and 16 mechanical strength and chemical resistance against sulfuric acid, salt water, etc., and the coating layers 15 and 16, the conductive layer 11, the light shielding layer 6, and the glass substrate 3. Is included for the purpose of fusing. As the glass frit and the organic binder, those similar to those used for the conductive layer 11 can be appropriately selected and used.

  The conductive pattern layer 8 is formed by laminating two black layers of the first coating layer 15 and the second coating layer 16 so as to sandwich the conductive layer 11. According to this aspect, since the conductive layer 11 is surrounded by the two coating layers 15 and 16, it can be reliably concealed and the appearance can be improved. In addition, the part corresponding to the electric power feeding part 14 of the conductive layer 11 is not provided with the 2nd coating layer 16 in order to expose the vehicle inner surface of the electric power feeding part 14 after sintering. The line widths of the covering layers 15 and 16 are preferably wider than the line width of the conductive layer 11. Preferably, the pattern width of the second covering layer 16 is 0.2 mm or more wider than the pattern width of the conductive layer 11.

  The adhesive layer 28 includes a hard inner layer 36 laminated on the intermediate layer 27 side, and a soft outer layer 37 laminated on a side different from the intermediate layer 27 side of the hard inner layer 36 and serving as a contact surface of the glass substrate 3 or the like. Have. The hard inner layer 36 and the soft outer layer 37 are not particularly limited as long as they are organic materials that can be removed by baking and have appropriate tackiness when bonded to the light-shielding layer 6 and the glass substrate 3, but are acrylic having tackiness at room temperature. System, rubber, and methacrylic and acrylic monomers can be copolymerized to use a pressure sensitive adhesive such as a resin set at a desired glass transition temperature. As acrylic monomers, methyl acrylate, ethyl acrylate, butyl acrylate, stearyl acrylate and 2-ethylhexyl acrylate can be applied. As methacrylic monomers, ethyl methacrylate, butyl methacrylate, methacrylic acid are applicable. Isobutyl, stearyl methacrylate and the like can be applied. Moreover, when constructing by heat lamination etc., you may use the organic substance which softens at the lamination temperature. For example, in the case of a resin obtained by copolymerizing methacrylic and acrylic monomers, the glass transition temperature can be adjusted by changing the mixing ratio of each monomer.

  The hard inner layer 36 is formed of a polymer material having a glass transition temperature of −30 ° C. or higher and 0 ° C. or lower. When defined using other parameters, the hard inner layer 36 is a polymer material having a weight average molecular weight of 300,000 to 1,500,000.

  The soft outer layer 37 is made of a polymer material having a glass transition temperature of −20 ° C. or lower and lower by 10 ° C. or more than the hard inner layer 36. When defined using other parameters, the hard inner layer 36 is a polymer material having a weight average molecular weight of 70,000 to 200,000.

  The thickness of the hard inner layer 36 is 2 μm or more and 7 μm, preferably 4 μm or more and 7 μm or less. The thickness of the soft outer layer 37 is 3 μm or more and 10 μm or less, preferably 7 μm or more and 10 μm or less. If the combined thickness of the hard inner layer 36 and the soft outer layer 37 is less than 2 μm, the adhesive force is insufficient and the transferability is lowered, and if it is thicker than 10 μm, the generation amount of pyrolysis gas increases and the decomposition is completed. Therefore, the conductive pattern layer 8 and the light shielding layer 6 are likely to be defective, and are likely to be defective in firing.

  The pressure-sensitive adhesive layer 28 is formed so as to have a larger film thickness of the hard inner layer 36 and the soft outer layer 37 than the maximum height Rmax in the surface roughness of the light shielding layer 6 so that the adhesive layer 28 can be securely adhered to the surface of the light shielding layer 6. It is preferable that The film thickness of the soft outer layer 37 may be larger than the maximum height Rmax in the surface roughness of the light shielding layer 6. The thickness of the adhesive layer 28 is, for example, 2 μm to 10 μm. From the viewpoint of adhesion, the thickness of the adhesive layer 28 is preferably 7 μm to 10 μm. If the film thickness is less than 2 μm, the adhesive strength is insufficient and transferability is lowered. If the film thickness is greater than 10 μm, the amount of pyrolysis gas increases, and the time required for the completion of the decomposition increases. 8 and the light-shielding layer 6 are likely to be defective, and are likely to be defective in firing.

  The organic matter constituting the adhesive layer 28 (the hard inner layer 36 and the soft outer layer 37) has a thermal decomposition temperature lower than the glass transition point of the glass frit contained in the light shielding layer 6, and constitutes the adhesive layer 28. The thermal decomposition temperature of the organic substance is preferably 30 ° C. or more, more preferably 50 ° C. or more lower than the glass transition point of the glass frit contained in the light shielding layer 6. For example, when the glass transition point of the glass frit contained in the light shielding layer 6 is 550 ° C., the thermal decomposition temperature of the adhesive layer 28 is preferably 500 ° C. or less.

  The pressure-sensitive adhesive layer 28 has a thickness of 10 μm or less so that the conductive pattern layer 8 and the light-shielding layer 6 are heated (fired) relatively quickly and thermally decomposed. From the viewpoint of thermal decomposition, the thickness of the adhesive layer 28 is preferably 7 μm or less. As described above, when the adhesiveness to the surface of the light shielding layer 6 is taken into consideration, the thickness of the adhesive layer 28 is 2 μm or more and 10 μm or less, more preferably 2 μm or more and 7 μm or less.

  The adhesive layer 28 may be formed on the entire surface of the support film 21 having peelability so as to cover the conductive pattern layer 8, or a pattern similar to that of the conductive pattern layer 8 may be formed. In the present embodiment, the adhesive layer 28 is formed on the entire surface of the support film 21.

  The intermediate layer 27 and the protective layer 23 are layers that can be selectively added, and are not essential to the present invention. The intermediate layer 27 is provided between the conductive pattern layer 8 and the adhesive layer 28 in order to prevent the solvent or organic matter contained in the adhesive of the adhesive layer 28 from entering the conductive pattern layer 8. The material used for the intermediate layer 27 is not particularly limited as long as it is an organic substance that can be removed by firing, and may be the same as the organic binder used for the conductive layer 11 and the coating layers 15 and 16, and particularly has a glass transition temperature. A polymer resin having a temperature of 50 ° C. or higher can be preferably used. For example, the intermediate layer 27 may be formed by copolymerizing methacrylic and acrylic monomers and setting a desired glass transition temperature. Methacrylic and acrylic monomers can be applied by changing the blending ratios of those exemplified for the adhesive layer 28. Similarly to the adhesive layer 28, the organic matter constituting the intermediate layer 27 has a thermal decomposition temperature lower than the glass transition point of the glass frit contained in the light shielding layer 6, and the organic matter constituting the intermediate layer 27 is thermally decomposed. The temperature is preferably 30 ° C. or more, more preferably 50 ° C. or more lower than the glass transition point of the glass frit contained in the light shielding layer 6. For example, when the glass transition point of the glass frit contained in the intermediate layer 27 is 550 ° C., the thermal decomposition temperature of the organic matter constituting the intermediate layer 27 is preferably 500 ° C.

  The intermediate layer 27 is preferably made as thin as possible so that the conductive pattern layer 8 and the light shielding layer 6 are heated (fired) relatively quickly, and the thickness is preferably 10 μm or less, more preferably 7 μm or less. More preferably, it is 5 μm or less. On the other hand, the intermediate layer 27 is 0.5 μm or more, more preferably 1 μm or more in order to stabilize the barrier effect. Therefore, the thickness of the adhesive layer 28 is 1 μm or more and 10 μm or less, more preferably 1 μm or more and 7 μm or less, and further preferably 1 μm or more and 5 μm or less.

  The intermediate layer 27 may be formed on the entire surface of the support film 21 having peelability so as to cover the conductive pattern layer 8, or a pattern similar to that of the conductive pattern layer 8 may be formed. In the present embodiment, the intermediate layer 27 is formed on the entire surface of the support film 21.

  The protective layer 23 is provided so as to cover the conductive pattern layer 8 for the purpose of preventing foreign matters from attaching to the conductive pattern layer 8 before firing transferred to the substrate or causing scratches. The material used for the protective layer 23 is not particularly limited as long as it is an organic substance that can be removed by firing, and may be the same as the organic substance used for the conductive layer 11 and the coating layers 15 and 16. For example, the protective layer 23 may be formed by copolymerizing methacrylic and acrylic monomers and setting a desired glass transition temperature. Methacrylic monomers and acrylic monomers can be applied to those exemplified for the adhesive layer 28 by changing the blending ratio. The organic material constituting the protective layer 23 is formed of a material having a thermal decomposition temperature lower than the glass transition point of the glass frit contained in the light shielding layer 6, similarly to the adhesive layer 28, and constitutes the protective layer 23. The thermal decomposition temperature of the organic substance is preferably 30 ° C. or more, more preferably 50 ° C. or more lower than the glass transition point of the glass frit contained in the light shielding layer 6. For example, when the glass transition point of the glass frit contained in the protective layer 23 is 550 ° C., the thermal decomposition temperature of the intermediate layer 27 may be 500 ° C.

  The protective layer 23 is preferably made as thin as possible so that the conductive pattern layer 8 and the light shielding layer 6 are heated (fired) relatively quickly, and the thickness is preferably 10 μm or less, more preferably 7 μm or less. It is. The protective layer 23 is preferably 3 μm or more so that the conductive pattern layer 8 can be covered. Therefore, the thickness of the protective layer 23 is 3 μm or more and 10 μm or less, more preferably 3 μm or more and 6 μm or less. The protective layer 23 may be formed on the entire surface of the support film 21 having peelability so as to cover the conductive pattern layer 8, or a pattern similar to that of the conductive pattern layer 8 may be formed.

  As shown in FIG. 4, the storage form of the transfer film 20 can take a reel form 41, a stack form 42, and a single layer form 43. In the reel form 41, the support film 21 is formed in a band shape, and the laminate 30 including the conductive pattern layer 8, the protective layer 23, the intermediate layer 27, and the adhesive layer 28 is intermittently formed along the longitudinal direction of the support film 21. It is supported on the support film 21. The laminate 30 may be supported on either the outer surface or the inner surface of the support film 21. In other embodiments, the protective layer 23, the intermediate layer 27, and the adhesive layer 28 may be continuous along the support film 21, and only the conductive pattern layer 8 may be intermittently disposed in the longitudinal direction of the support film 21. Good. A plurality of conductive pattern layers 8 are arranged along the longitudinal direction of the support film 21. The transfer film 20 is wound around a reel 44 such that the adhesive layer 28 contacts the back surface of the support film 21 (side different from the protective layer 23 side). In use, the end of the continuous transfer film 20 is pulled out and the adhesive layer 28 is exposed for use. In addition, you may process perforation etc. to the support film 21 so that it can be set as the independent transfer film 20 containing the electroconductive pattern layer 8. FIG.

  In the stack form 42, each transfer film 20 is cut in advance so as to include one conductive pattern layer 8, and the adhesive layer 28 of each transfer film 20 is in contact with the back surface of the support film 21 of the other transfer film 20. Are stacked. A separator film 46 having a silicone layer that can be peeled off from the adhesive layer 28 is attached to the adhesive layer 28 located at the lowermost layer. At the time of use, the transfer film 20 located in the uppermost layer is peeled off from the other lower transfer film 20, and the adhesive layer 28 is exposed for use.

  In the single layer form 43, each transfer film 20 is cut in advance so as to include one conductive pattern layer 8, and the adhesive layer 28 of each transfer film 20 is provided with a silicone layer that can be peeled off from the adhesive layer 28. The provided separator film 46 is affixed. In use, the separator film 46 is peeled off from the adhesive layer 28 of the transfer film 20 to expose the adhesive layer 28.

  The reel form 41 and the stack form 42 are advantageous in that it is not necessary to provide the separator film 46 on each transfer film 20 as compared with the single layer form 43, but the adhesive layer 28 is interposed between the overlapping conductive pattern layers 8. Has the disadvantage of receiving compressive force.

  In the transfer film 20 configured as described above, since the adhesive layer 28 is composed of the hard inner layer 36 and the soft outer layer 37, the hard inner layer 36 resists the compressive force, and the adhesive layer 28 is It can be maintained above the thickness. Therefore, even if the transfer film 20 is stored in the reel form 41 or the stack form 42, the film thickness is maintained against the pressure applied from the conductive pattern layer 8 between the conductive pattern layers 8 with which the hard inner layer 36 overlaps. Can do. Thereby, the thickness of the adhesive layer 28 can be maintained at 2 μm or more necessary for exhibiting adhesiveness. In addition to the hard inner layer 36, the soft outer layer 37, which is softer than the hard inner layer 36, is provided as a contact surface for the bonding target such as the glass substrate 3, so that the surface of the surface of the bonding target is followed. It can be further bonded.

  Further, since the film thickness is made thicker than the maximum height Rmax in the surface roughness of the light shielding layer 6, the adhesive layer 28 can be brought into close contact with the surface irregularities of the light shielding layer 6 and can be reliably adhered. Further, by increasing the flexibility of the support film 21, the flexibility of the laminate 30 is maintained even when supported by the support film 21, and the pressure-sensitive adhesive layer 28 has unevenness on the surface of the light shielding layer 6 and the light shielding layer. 6 can follow and adhere to the edge 7.

(Method for producing window glass with conductive pattern layer)
With reference to FIG.5 and FIG.6, the 1st procedure which forms the light shielding layer 6 and the electroconductive pattern layer 8 on the glass substrate 3 using the transfer film 20 mentioned above is demonstrated.

  First, as shown in FIG. 5A, a glass substrate 3 is prepared. As the glass substrate 3, a general float plate glass can be applied, and the softening point thereof may be 650 to 700 ° C.

  In the next step, as shown in FIG. 5B, a colored ceramic paste (light-shielding paste) is printed in a predetermined pattern on the surface of the glass substrate 3 by screen printing and dried to form the light-shielding layer 6. . The colored ceramic paste contains pigments and glass frit as main components, and contains a resin such as ethyl cellulose and an organic solvent such as pine oil as necessary.

  The pigment preferably contains at least one of copper oxide, chromium oxide, iron oxide and manganese oxide, and these may be used alone, in combination of plural kinds, or in combination with other pigments. Glass frit contains transitional metal oxidation containing crystallized glass and amorphous glass such as bismuth borosilicate and zinc borosilicate as essential components, and optionally containing at least one oxide of vanadium, manganese, iron, and cobalt. And additives such as alumina.

  The content of each component in the colored ceramic paste is, for example, 10 to 35% by mass of pigment, 50 to 70% by mass of glass frit, 5 to 20% by mass of resin, and 5 to 30% by mass of organic solvent. The content of each component in the colored ceramic paste is such that the angle θ formed between the inclined surface 9 formed on the edge 7 on the glass substrate 3 of the light shielding layer 6 after drying and the surface of the glass substrate 3 is 0 °. It is desirable that the angle is set to be greater than 10 °, more preferably greater than 0 ° and less than 5 °. Since the angle θ formed between the inclined surface 9 and the surface of the glass substrate 3 is smaller as the viscosity of the colored ceramic paste is lower, the mass% of the resin is reduced within a range in which the form of the light shielding layer 6 can be maintained, The mass% may be increased. A resin having a low viscosity may be selected.

  Further, the content of each component in the colored ceramic paste is preferably set so that the maximum height Rmax of the surface roughness of the light-shielding layer 6 after drying is 10 μm or less, more preferably 5 μm or less. The maximum height Rmax decreases as the viscosity of the colored ceramic paste decreases.

  Screen printing may be performed using a polyester screen of about 100 to 300 mesh, and drying may be performed at 150 ° C. for about 10 minutes. By drying, the organic solvent in the light shielding layer 6 is evaporated, and the light shielding layer 6 is evaporated to dryness.

  In the next step, a transfer film 20 having the above-described configuration is prepared. Then, in the subsequent step, as shown in FIGS. 5C and 6, the transfer film 20 is attached to the glass substrate 3 on which the light shielding layer 6 is formed by the adhesive layer 28. The transfer film 20 is disposed so that the conductive pattern layer 8 crosses over the edge 7 on the surface of the glass substrate 3 of the light shielding layer 6, and the adhesive layer 28 is disposed on the surfaces of the light shielding layer 6 and the glass substrate 3. Stick. In other embodiments, the transfer film 20 may be attached so as to be located only on the surface of the light shielding layer 6.

  In the next step, as shown in FIG. 5D, in order to improve the adhesion between the adhesive layer 28, the light shielding layer 6 and the surface of the glass substrate 3, the back surface of the support film 21 of the transfer film 20 is covered with a roller 50. Press toward the glass substrate 3 side. The material of the surface of the roller 50 is not particularly limited, but is preferably a flexible rubber, silicone material, or resin material. The pressure applied to the transfer film 20 by the roller 50 is preferably as large as possible so long as the laminate 30 is not crushed (buckled). The pressure by the roller 50 is such that pressure is applied particularly to the portion corresponding to the edge 7 of the light shielding layer 6 so that the adhesive layer 28 wraps around the corner of the edge 7 of the light shielding layer 6. Is preferred.

  In the next step, the support film 21 of the transfer film 20 is peeled from the protective layer 23 as shown in FIG.

  In the next step, as shown in FIG. 5 (F), the back surface of the protective layer 23 of the transfer film 20 is pressed to the glass substrate 3 side with a heated roller 51, and the adhesive layer 28, the light shielding layer 6, and the glass substrate 3 are pressed. An aging treatment is performed to increase the adhesion with the surface of the material. In the aging process, the temperature of the roller 51 is heated to 100 ° C. or more and pressed for about 10 minutes. The pressing may be performed by setting the pressure to 0.5 MPa and moving the roller 51 along the protective layer 23 at 10 mm / second. By this aging treatment, the protective layer 23, the intermediate layer 27, and the adhesive layer 28 constituting the laminate 30 are softened, and the adhesive layer 28 is further adhered to the light shielding layer 6, and the corner portion of the edge portion 7 of the light shielding layer 6 is formed. To get around.

  The material of the surface of the roller 51 is not particularly limited, but is preferably a silicone material that does not adhere to the protective layer 23 and has flexibility. The pressure applied to the transfer film 20 by the roller 51 is preferably as large as possible so that the laminate 30 is not crushed (buckled) in order to enhance the adhesion between the adhesive layer 28, the light shielding layer 6 and the surface of the glass substrate 3. The pressing by the roller 51 is to apply pressure particularly to the portion corresponding to the edge 7 of the light shielding layer 6 so that the adhesive layer 28 goes around the corner of the edge 7 of the light shielding layer 6. Is preferred. The step of pressing the back surface of the protective layer 23 has a higher effect of bringing the adhesive layer 28 into close contact with the light shielding layer 6 than the step of pressing the back surface of the support film 21. This is because the support film 21 is harder than the laminated body 30, and thus the followability of the laminated body 30 to the light shielding layer 6 can be improved by removing the support film 21.

  Since the above-described aging treatment process after peeling of the support film 21 is an additional process, it may not be performed in other embodiments.

  In the next step, heat treatment (firing) is performed on the glass substrate 3 on which the light shielding layer 6 and the laminate 30 are laminated, and as shown in FIG. 5G, the conductive pattern layer 8 is replaced with the light shielding layer 6 and the glass substrate. Then, the conductive pattern layer 8 after sintering is formed. The heat treatment is performed at a firing temperature of 550 to 700 ° C. for 1 to 20 minutes. More preferably, the heat treatment is performed at a firing temperature of 550 to 650 ° C. for 1 to 10 minutes. This baking may be performed simultaneously with the bending process of the glass plate and, if necessary, the strengthening treatment. After the heat treatment, the glass substrate 3 is gradually cooled (an operation for relaxing the cooling rate) so that distortion (perspective and reflection) is not generated or remains in the glass substrate 3.

  During this heat treatment, organic substances contained in the light shielding layer 6, the protective layer 23, the conductive layer 11, the coating layers 15 and 16, the intermediate layer 27 and the adhesive layer 28 are volatilized or burned and decomposed. As the decomposition of the protective layer 23, the intermediate layer 27, and the adhesive layer 28 proceeds, the conductive pattern layer 8 approaches the surface of the light shielding layer 6 and the glass substrate 3, and finally the light shielding layer 6 in the first covering layer 15. And it contacts the surface of the glass substrate 3. Subsequently, the glass frit contained in the light shielding layer 6, the conductive layer 11, and the coating layers 15 and 16 is melted and fused to each other. The pour point of the glass frit is 300 to 700 ° C. Further, the glass substrate 3 has a pour point of 850 ° C. or higher and does not flow in firing, but is softened to the extent that it can be bent. Therefore, the glass substrate 3 and the light shielding layer 6, the conductive layer 11, the coating layer 15, 16 is firmly bonded to each other, and the mutual adhesion is improved.

  First, the temperature in this heat treatment is a predetermined temperature that is equal to or higher than the thermal decomposition temperature of the organic matter contained in the adhesive layer 28, the intermediate layer 27, and the protective layer 23 and less than or equal to the glass point transfer of the glass frit contained in the light shielding layer 6. After the temperature is raised, the temperature may be maintained for a predetermined period of time, for example, 1 to 5 minutes, and then raised to a temperature higher than the glass point transfer of the glass frit contained in the light shielding layer 6. By raising the temperature in this way, the adhesive layer 28, the intermediate layer 27, and the protective layer 23 can be reliably decomposed before the glass frit contained in the light shielding layer 6 starts to melt.

  According to the manufacturing method described above, the laminate 30 is attached to the light shielding layer 6 and the glass substrate 3, and the support film 21 is peeled off, and then the heat treatment is performed to soften the adhesive layer 28. Can follow and adhere more closely to the surface of the light shielding layer 6 and the shape of the edge 7. Since the support film 21 is less flexible than the laminated body 30 and there is a possibility that the bending of the laminated body 30 may be suppressed, the adhesive layer 28 follows the light shielding layer 6 and the like further when the support film 21 is removed. This is because it can be bent. Similarly, the adhesion between the pressure-sensitive adhesive layer 28, the light shielding layer 6, and the glass substrate 3 can be enhanced also by the step of pressing the laminated body 30 against the glass substrate 3 after peeling the support film 21. By increasing the adhesion between the adhesive layer 28 and the light shielding layer 6 and the glass substrate 3, sintering failure between the conductive pattern layer 8, the light shielding layer 6 and the glass substrate 3 after firing the laminate 30, The bubble entrainment between the conductive pattern layer 8 and the light shielding layer 6 and the glass substrate 3 is suppressed.

  Further, since the thermal decomposition temperature of the organic matter contained in the adhesive layer 28, the intermediate layer 27 and the protective layer 23 is set lower than the melting temperature of the glass frit in the light shielding layer 6, when the conductive pattern layer 8 and the light shielding layer 6 are baked, The adhesive layer 28, the intermediate layer 27, and the protective layer 23 are decomposed faster than the glass frit in the light shielding layer 6 is melted. Therefore, the gas generated when the glass frit of the light shielding layer 6 is melted can diffuse to the outside, and the light shielding layer 6 is fired satisfactorily. In particular, the temperature in the heat treatment is initially a predetermined temperature that is equal to or higher than the thermal decomposition temperature of the organic matter contained in the adhesive layer 28, the intermediate layer 27, and the protective layer 23 and lower than the glass point transfer of the glass frit contained in the light shielding layer 6. Before the glass frit of the light shielding layer 6 is melted, the temperature is raised to a temperature, and this temperature is maintained for a predetermined period, and then the temperature is raised to a temperature higher than the glass point transfer of the glass frit contained in the light shielding layer 6. The adhesive layer 28, the intermediate layer 27, and the protective layer 23 can be reliably decomposed.

  Next, a second procedure in which some processes are different from the first procedure described above will be described. In the second procedure, after the step of printing and drying the light shielding layer 6 in the first procedure shown in FIG. 5B and before the step of attaching the transfer film 20, the light shielding layer 6 is subjected to the firing temperature 580. It includes a pre-baking step of performing heat treatment at ˜700 ° C. for 1 to 20 minutes to sinter the light shielding layer 6. Thereby, the organic matter in the light shielding layer 6 is volatilized or burned and decomposed, and the glass frit is melted and fused to each other. After this step, it is the same as the first procedure.

  According to the second procedure, the unevenness of the surface of the light shielding layer 6 and the inclination of the shape of the edge portion 7 are alleviated by melting the glass frit by temporary firing, and the adhesive layer 28 and the light shielding layer 6 of the transfer film 20 are reduced. Adhesion (adhesiveness) can be improved. Further, when the light shielding layer 6 is baked, there is no laminated body 30 covering the light shielding layer 6, so that the gas generated from the light shielding layer 6 by the diffusion diffuses without being held inside or on the surface of the light shielding layer 6, The light shielding layer 6 is formed satisfactorily.

(Transfer film)
Example 1 which is one example of the transfer film 20 was configured as follows. As a temporary support, a PET film “A70” provided with a silicone release layer (manufactured by Teijin DuPont Films Ltd., film size 20 cm × 30 cm thickness 50 μm) was prepared. As a coating solution for the intermediate layer 27, a polymer (thermal decomposition temperature 450 ° C.) prepared by copolymerizing methyl acrylate and methyl methacrylate at a predetermined blending ratio and adjusting the glass transition temperature Tg to 55 ° C. A solution dissolved in toluene was prepared. As a coating solution for the protective layer 23, a polymer (thermal decomposition temperature 400 ° C.) prepared by copolymerizing methyl acrylate and isobutyl methacrylate at a predetermined blending ratio and adjusting the glass transition temperature Tg to 50 ° C. An aqueous solution was prepared. Moreover, the conductive layer paste containing glass frit, silver powder, and an organic binder was prepared as a paste for conductive layers. Components of the conductive layer paste are: silver: 70-80%, terpineol, dibutycarbitol: 10-20%, ethyl cellulose, rosin resin: 1-10%, glass made of bismuth, zinc, boron, silica, barium, and the like, and Metal oxide: 1 to 10%, additive 1 to 10%. The coating layer paste was prepared by dispersing a composite pigment of chromium oxide and copper oxide, glass frit, and organic binder with a three-roll mill. As an organic binder, acrylic resin BR102 (manufactured by Mitsubishi Rayon Co., Ltd.) is dissolved in bis (2-butoxyethyl) ether (manufactured by Wako Pure Chemical Industries, Ltd.), and P / R = 80/20 The thing adjusted to was prepared.

  First, the intermediate layer 27 was formed by applying the intermediate layer coating solution on the entire surface of the temporary support having the peelability to a thickness of 1.5 μm using a Mayer bar. On top of that, the size of the portion corresponding to the linear portion 13 of the conductive pattern layer 8 is 0.4 mm wide × 500 mm long and the size corresponding to the power feeding portion 14 is screen-printed with paste for the coating layer. Was printed to be 5.4 mm × 5.4 mm and a thickness of 5 μm to form the first coating layer 15. Next, the conductive layer paste is screen-printed on the first coating layer 15 so that the size of the portion corresponding to the linear portion 13 of the conductive pattern layer 8 is 0.2 mm wide × 500 mm long. The conductive layer 11 was formed by printing so that the size of the portion corresponding to the portion 14 was 5 mm × 5 mm and the thickness was 10 μm. Next, a portion of the conductive pattern layer 8 excluding a portion corresponding to the power feeding portion 14, that is, a portion corresponding to the linear portion 13, is formed on the conductive layer 11 by screen printing with a coating layer paste. The second coating layer 16 was formed so as to cover the conductive layer 11 by printing so that the size was 0.4 mm wide × 500 mm long and 5 μm thick. On the second coating layer 16 and the intermediate layer 27, the coating liquid for the protective layer is applied to a thickness of 5 μm using a Mayer bar so as to cover the entire surface of the intermediate layer 27. A protective layer 23 was formed.

  Next, a PET film “SRL-0504” (manufactured by Lintec Corporation) having a film thickness of 25 μm to which the slightly adhesive layer 32 was applied to be the support film 21 was prepared. The fine adhesive surface of this PET film is bonded to the protective layer 23 formed on the temporary support, and pressure is applied from above the temporary support using a rubber roller at a pressure of 0.5 kg / cm. A laminate was made.

  On the other hand, as another temporary support, a PET film “A31” provided with a silicone release layer (manufactured by Teijin DuPont Films, film size 20 cm × 30 cm, thickness 50 μm) was prepared. A pressure-sensitive adhesive material was applied to the entire surface of the other temporary support having peelability so as to have various thicknesses using a Mayer bar to prepare a second laminate. For the adhesive, a polymer prepared by copolymerizing methyl acrylate and n-butyl acrylate at a predetermined blending ratio and adjusting the glass transition temperature Tg to −36 ° C. was dissolved in toluene and used. The thickness of the adhesive layer 28 was 7 μm. Finally, the temporary support was peeled off from the first laminate, and the intermediate layer 27 of the first laminate was bonded to the adhesive layer 28 of the second laminate to produce a transfer film 20.

  For the purpose of comparison with Example 1 of the transfer film 20 described above, only the thickness of the adhesive layer 28 was changed from Example 1, and Example 2 (12 μm), Example 3 (22 μm), and comparison Example 1 (3 μm) was prepared. Moreover, only the material and thickness of the adhesion layer 28 were changed with respect to Example 1, and the comparative example 2 (glass transition temperature Tg: -19 degreeC, 6 micrometers) was produced. The glass transition temperature Tg-19 ° C. of the adhesive layer 28 in Comparative Example 2 was adjusted by changing the blending ratio of methyl acrylate and n-butyl acrylate.

(Glass substrate with pattern)
Example 10 which is one example of the patterned glass substrate 1 was configured as follows. For the glass substrate 3, a 2.0 mm thick glass plate (float glass, manufactured by Nippon Sheet Glass Co., Ltd.) was prepared. The colored ceramic paste is mainly composed of 20% by mass of pigment mainly composed of copper oxide, chromium oxide, iron oxide or manganese oxide, 10% by mass of cellulose resin, 10% by mass of pine oil, bismuth borosilicate or zinc borosilicate. The composition contained 65% by mass of glass frit (melting temperature of about 500 ° C.) as a component, and the viscosity was 200 dPa · s. A colored ceramic paste was screen-printed on the peripheral edge of one surface of the glass substrate 3 to form the light shielding layer 6. The conditions for screen printing are polyester screen: 200 mesh, coat thickness: 6 μm, tension: 20 Nm, squeegee hardness: 65 degrees, attachment angle: 75 degrees, and printing speed: 300 mm / s. After printing, the glass substrate 3 was dried at 150 ° C. for 10 minutes in a drying furnace. The dried light shielding layer 6 had a film thickness of 25 μm, a maximum surface roughness height Rmax of 5 μm, and an angle θ between the inclined surface 9 of the edge 7 and the surface of the glass substrate 3 was 5 °.

  Subsequently, the adhesive layer 28 side of the transfer film 20 according to Example 1 described above is placed on the surface of the light shielding layer 6 and the glass substrate 3 so that the conductive pattern layer 8 crosses the edge portion 7 of the light shielding layer 6. Pasted. The back side of the support film 21 was pressed against the glass substrate 3 with a pressure of 0.5 MPa by a rubber roller 50. Subsequently, the support film 21 was peeled off from the protective layer 23, and the back side of the protective layer 23 was pressed against the glass substrate 3 side with a silicone roller 51 heated to 200 ° C. to perform an aging treatment. The pressure of the roller 51 against the protective layer 23 was 0.5 MPa, and the roller 51 was moved along the protective layer 23 at 10 mm / second.

  The glass substrate 3 onto which the laminate 30 including the conductive pattern layer 8 was transferred was baked using an electric furnace. Firing is performed in an air atmosphere at a rate of temperature increase of 95 ° C./minute from room temperature to 600 ° C., and after maintaining that temperature for 3 minutes, heating is stopped and the mixture is allowed to cool naturally to 100 ° C. or less. (Slow cooling). The cooled glass plate was taken out from the electric furnace to obtain a patterned glass substrate 1 on which a fired body of the conductive pattern layer 8 was formed. The patterned glass substrate 1 thus obtained is referred to as Example 10.

  For the purpose of comparison with Example 10 described above, with the pattern obtained by performing only the pressing process at room temperature without heating the roller 51 in the aging process after peeling the support film 21 with respect to Example 10 The glass substrate 1 with the pattern 10 obtained by omitting only the pressing process by the roller 51 of the protective layer 23 after removing the support film 21 from the comparative example 10 and the laminated film 30 was heated to 200 ° C. for 10 minutes instead. The glass substrate 1 with a pattern obtained by omitting the heat treatment after peeling of the comparative example 11 and the support film 21 and the pressing treatment of the protective layer 23 is referred to as comparative example 12. Further, the light shielding layer 6 is heated and fired between the printing / drying process and the transfer film 20 attaching process on the glass substrate 3, and the transfer film is formed on the fired light shielding layer 6 and the glass substrate 3. Example 11 was pasted. The conditions for firing the light shielding layer 6 are the same as the conditions for firing the light shielding layer 6 and the conductive pattern layer 8 in the process of producing Example 10. Moreover, in Example 13, the glass substrate 1 with a pattern obtained by omitting the heat treatment after peeling the support film 21 and the pressing treatment of the protective layer 23 is referred to as Example 12.

(Evaluation of adhesion of transfer film)
The adhesiveness to the light shielding layer 6 of the transfer films 20 of Examples 1 to 3 and Comparative Examples 1 to 2 was evaluated. Evaluation is made in the process of producing the patterned glass substrate 1 described above, by sticking the adhesive layer 28 side of the transfer film 20 to the surface of the light shielding layer 6 and the glass substrate 3, and peeling the support film 21 after pressing with the roller 50 When doing, it was performed by whether the laminated body 30 followed the support film 21 and the adhesion layer 28 peeled from the light shielding layer 6. FIG. The evaluation was performed by visual inspection, and the case where peeling of the pressure-sensitive adhesive layer 28 from the light-shielding layer 6 was not confirmed was ○, the case where peeling was confirmed in part was △, and the case where peeling was confirmed in most was × It was. The results are shown in Table 1 below.

  As shown in Table 1, from the comparison between Example 1 and Comparative Example 2, the adhesive layer 28 made of a material having a low glass transition temperature, that is, a soft material, has higher adhesion to the light shielding layer 6. confirmed. Moreover, it was confirmed from the comparison with Examples 1-3 and the comparative example 1 that the one where the adhesion layer 28 is thick has high adhesiveness to the light shielding layer 6. FIG. This is because the adhesive layer 28 is softer, and the thicker the adhesive layer 28 is, the deeper the unevenness on the surface of the light shielding layer 6 is, and the contact area increases, and bubbles are formed between the adhesive layer 28 and the light shielding layer 6. This is thought to be due to not being bitten.

(Evaluation of manufacturing method)
About the glass substrate 1 with a pattern of Examples 10-12 and Comparative Examples 10-12, the form of the electroconductive pattern layer 8 was evaluated. Evaluation was performed by visually confirming the appearance of the conductive pattern layer 8 after firing. In the evaluation, the conductive pattern layer 8 is surely fused to the light shielding layer 6 and there is no entrapment of bubbles, and in some cases, the conductive pattern layer 8 is lifted from the light shielding layer 6 or bubbles are entrained. What was confirmed was indicated by Δ, and most of the conductive pattern layer 8 was confirmed to be lifted from the light-shielding layer 6 or bubbled x. In this evaluation, attention was paid particularly to the form of the conductive pattern layer 8 at the edge 7 of the light shielding layer 6. The results are shown in Table 2 below.

  As shown in Table 2, from the comparison between Example 10 and Comparative Examples 10-12, after the support film 21 was peeled off, the one subjected to the pressing treatment with the heated roller 51 was the conductive pattern layer 8 after firing. Has been confirmed to be fused well to the light shielding layer 6. This is considered to be due to the fact that the laminate 30 is softened and the followability to the surface of the light-shielding layer 6 is increased by performing the heating and pressing treatment in a state where the support film 21 that is harder than the laminate 30 is removed. It is done. In addition, it was confirmed that the thing which performed only one of heating or pressing still has insufficient tracking of the laminated body 30 to the light shielding layer 6.

  Further, from the comparison between Examples 11 and 12 and Comparative Example 12, the conductive pattern layer 8 after sintering is obtained by temporarily firing the light shielding layer 6 before the step of attaching the transfer film 20 to the light shielding layer 6. Has been confirmed to be fused well to the light shielding layer 6. In FIG. 7, the result of having measured the surface shape of the edge part vicinity of the light shielding layer 6 just before sticking the transfer film 20 of Example 10 and Example 11 is shown. As shown in FIG. 7, the light-shielding layer 6 that has been pre-sintered has a smaller film thickness and a smaller surface roughness than those that have not been pre-fired, and the rising angle at the edge 7. (An angle formed with the surface of the glass substrate 3) is small. This is because the organic matter in the light shielding layer 6 is volatilized or burned and decomposed by pre-baking the light shielding layer 6, and the glass frit in the light shielding layer 6 is melted, and the surface shape of the light shielding layer 6 is blunted. This is because. Therefore, in Example 13, compared with Comparative Example 10, it is considered that the adhesive layer 28 is easily adhered to the light shielding layer 6, and the conductive pattern layer 8 is well fused to the light shielding layer 6. Therefore, when temporary baking was performed, after peeling off the support film 21, it was confirmed that the favorable electroconductive pattern layer 8 is obtained even if neither a heat processing nor a press process is implemented. In each of Examples 10-12 and Comparative Examples 10-12, the thickness of the light-shielding layer 6 after firing was 13-18 μm, and the thickness of the conductive pattern layer 8 after firing was 16-17 μm. It was. Moreover, the angle θ formed by the inclined surface 9 of the edge 7 after firing and the surface of the glass substrate 3 was 9 °.

  As another example, when the pressure-sensitive adhesive layer 28 is composed of two layers, a hard inner layer 36 and a soft outer layer 37, a soft pressure-sensitive adhesive material is formed on the entire surface having the peelability of the PET film “A31” as a temporary support. Was applied using a Meyer bar to a thickness of 5 μm to produce a soft outer layer 37. As the soft adhesive material, a polymer prepared by copolymerizing methyl acrylate and n-butyl acrylate at a predetermined blending ratio and adjusting the glass transition temperature Tg to −36 ° C. was dissolved in toluene and used. Next, a hard adhesive material was applied on the soft outer layer 37 so as to have a thickness of 5 μm using a Mayer bar, and the hard inner layer 36 was produced. For the hard adhesive material, a polymer prepared by copolymerizing methyl acrylate and n-butyl acrylate at a predetermined blending ratio and adjusting the glass transition temperature Tg to −29 ° C. was dissolved in toluene and used. Finally, the temporary support was peeled from the first laminate, and the intermediate layer of the first laminate was bonded to the hard inner layer 36 of the second laminate, thereby producing the transfer film 20.

  Although the description of the specific embodiment is finished as described above, the present invention is not limited to the above embodiment and can be widely modified. For example, the present invention can be applied to tempered glass constituting rear window glass and side door glass.

  DESCRIPTION OF SYMBOLS 1 ... Patterned glass substrate, 2 ... Car outside glass substrate, 3 ... Car inside glass substrate, 6 ... Light-shielding layer, 7 ... Edge edge part, 8 ... Conductive pattern layer, 9 ... Inclined surface, 10 ... Car windshield , 11 ... conductive layer, 13 ... linear part, 14 ... power feeding part, 15 ... first covering layer, 16 ... second covering layer, 20 ... transfer film, 21 ... support film, 23 ... protective layer, 27 ... Intermediate layer 28 ... Adhesive layer 30 ... Laminate 31 ... Peeling layer 32 ... Slightly adhesive layer 36 ... Hard inner layer 37 ... Soft outer layer 41 ... Reel form 42 ... Stack form 43 ... Single layer Form, 44 ... reel, 46 ... separator film, 50, 51 ... roller

Claims (14)

On the surface, a method for producing a patterned glass substrate in which a conductive pattern layer containing a glass component is sintered,
A first step of applying a light-shielding paste containing a pigment and a glass component to a part of the glass substrate, and forming a light-shielding layer on the glass substrate;
A transfer film having a laminate including a conductive pattern layer and an adhesive layer, and a support film that is detachably laminated on a surface of the laminate opposite to the adhesive layer is provided on the outer surface of the light shielding layer. A second step of affixing the transfer film to the glass substrate so that the layers come into contact with each other, subsequently peeling the support film from the laminate, and transferring the laminate to the glass substrate;
The glass substrate, the light shielding layer and the laminate are heated together, the adhesive layer is removed, the light shielding layer is sintered on the glass substrate, and the conductive pattern layer is baked on the light shielding layer. A third step of ligating,
In the first step, the viscosity of the light-shielding paste is set so that an edge portion of the light-shielding layer on the glass substrate forms an inclined surface having an angle of 10 ° or less with the surface of the glass substrate,
In the second step, the conductive pattern layer includes a portion crossing the edge of the light shielding layer on the glass substrate,
In the third step, a part of the conductive pattern layer is sintered on the glass substrate.   The light-shielding paste contains 10 to 35% by mass of pigment, 50 to 70% by mass of glass frit, 5 to 20% by mass of resin, and 5 to 30% by mass of an organic solvent. Item 2. A method for producing a patterned glass substrate according to Item 1.   The thermal decomposition temperature of the said laminated body except the said electroconductive pattern layer is lower than the melting temperature of the glass component contained in the said light shielding layer, The manufacture of the glass substrate with a pattern of Claim 1 or Claim 2 characterized by the above-mentioned. Method.   2. The film is formed so that a maximum height in surface roughness of the light shielding layer formed on the glass substrate in the first step is less than a film thickness of the adhesive layer of the transfer film. The manufacturing method of the glass substrate with a pattern as described in any one of Claims 3-4.   The pattern according to any one of claims 1 to 4, further comprising a step of pressing the laminated body onto the glass substrate between the second step and the third step. A manufacturing method of a glass substrate.   The manufacturing of the glass substrate with a pattern according to any one of claims 1 to 5, further comprising a step of heating the laminated body between the second step and the third step. Method.   2. The method of claim 1, further comprising a step of heating the light-shielding layer and pre-sintering the light-shielding layer on the glass substrate between after the first step and before the third step. The manufacturing method of the glass substrate with a pattern as described in any one of Claims 6.   The said adhesion layer of the said transfer film is comprised with the material whose glass transition temperature is -60 degreeC or more and -20 degrees C or less, With a pattern in any one of Claims 1-7 characterized by the above-mentioned. A method for producing a glass substrate. Wherein the thickness of the adhesive layer, the patterned glass substrate manufacturing method according to any one of claims 1 to claim 8, characterized in that a 15μm hereinafter more 3μm of the transfer film.   The adhesive layer of the transfer film prepared in the second step includes a hard inner layer having a relatively high glass transition temperature and a soft outer layer having a relatively low glass transition temperature. The manufacturing method of the glass substrate with a pattern of any one of Claims 1-7.   The glass transition temperature of the hard inner layer is −30 ° C. or more and 0 ° C. or less, the glass transition temperature of the soft outer layer is −20 ° C. or less, and 10 ° C. or more lower than the glass transition temperature of the hard inner layer. The method for producing a patterned glass substrate according to claim 10.   The weight average molecular weight of the soft outer layer is from 70,000 to 200,000, and the weight average molecular weight of the hard inner layer is from 300,000 to 1,500,000. A method for producing a patterned glass substrate.   The thickness of the said hard inner layer is 2 micrometers or more and 7 micrometers or less, The manufacturing method of the glass substrate with a pattern as described in any one of Claims 10-12 characterized by the above-mentioned.   The thickness of the said soft outer layer is 3 micrometers or more and 10 micrometers or less, The manufacturing method of the glass substrate with a pattern as described in any one of Claims 10-13 characterized by the above-mentioned.

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