JP4862586B2 - Color toner for electronic printing and method for producing glass plate with ceramic color print - Google Patents

Description

  The present invention relates to a method for producing a color toner for electronic printing and a glass plate with a ceramic color print, and in particular, can form a ceramic color print excellent in adhesion to a glass plate surface used for a window of an automobile or the like. The present invention relates to a color toner for electronic printing and a method for producing a glass plate with a ceramic color print.

  A glass plate used for a window of an automobile is provided with a ceramic color print so as to be interposed between the window glass and a urethane sealant that holds the window glass at the periphery from the inside of the vehicle. Such a ceramic color print is mainly provided in the inner peripheral area of the fixed window of the automobile, prevents the urethane sealant from being deteriorated by ultraviolet rays, and is also used as a heating wire provided in the inner peripheral part of the window glass. It has a function of preventing the terminal from being seen from the outside of the vehicle. Further, in recent years, ceramic color prints in which minute dot patterns are formed in gradation are widely used for improving the design.

  The ceramic color print is mainly composed of a fired body of a paste containing inorganic pigment fine particles (hereinafter referred to as inorganic pigment paste). Specifically, a paste containing heat-resistant inorganic pigment fine particles and glass frit in a resin solution is printed on a glass plate surface in a predetermined pattern by screen printing, and the resin is decomposed by heating the glass plate. Then, the inorganic pigment fine particles are fixed on the glass plate surface with a glass frit to provide a ceramic color print on the glass plate surface (see, for example, Patent Document 1). As the heat-resistant inorganic pigment fine particles, black ones are usually used.

  Since automobiles are mass-produced products, glass plates for windows used in automobiles are also mass-produced products. Therefore, once the ceramic color print is determined, it is required to sequentially print the inorganic pigment paste on a large number of glass plates according to the determined pattern. For such mass production, screen printing of an inorganic pigment paste using a screen plate is suitable. However, when a glass plate is used for an automobile window, the shape of the glass plate, the shape of the ceramic color print, and the like differ depending on the type of the automobile. Therefore, screen plates must be prepared according to the type of automobile, and many screen plates must be stocked. For this reason, development of the manufacturing method of the glass plate with a ceramic color print which does not require correction of a screen plate, and the ceramic color composition for it is calculated | required.

  On the other hand, in recent years, color toner (ink) containing inorganic pigment fine particles and thermoplastic resin has been printed on a ceramic transfer sheet by an electronic printing method, and the transfer sheet is adhered to the surface of an inorganic substrate and baked to produce a color print. And color toners have been proposed. As a typical example of this, for example, in Patent Document 2, a thermoplastic resin is used for a colorant obtained by mixing inorganic pigment fine particles such as carbon black and glaze frit, melting, cooling, and pulverizing. A method using an added color toner has been proposed. However, in Patent Document 2, a process of transferring a toner image to a film made of a water-soluble polymer on the surface of a transfer sheet, peeling the toner image held on the film from the transfer sheet, and retransferring it to the substrate is essential. Therefore, there is a problem that the process becomes complicated and the transfer rate itself is lowered. Further, in this color toner, since a large amount of thermoplastic resins such as polyester, polystyrene and styrene acrylic resins are used, the resin is likely to remain as a carbide in the ceramic color print after firing. There was also a problem that it was difficult to obtain a ceramic color print excellent in adhesion to the surface of the inorganic substrate.

JP-A-62-72545 (Claims) JP 2000-214624 A (Claims, Examples)

  The present invention relates to a method for producing a color toner for electronic printing and a glass plate with a ceramic color print, and in particular, can form a ceramic color print excellent in adhesion to a glass plate surface used for a window of an automobile or the like. It is an object of the present invention to provide a method for producing a color toner and a glass plate with a ceramic color print.

  The present invention provides a color toner for electronic printing described in (1) to (7) below and a method for producing a glass plate with a ceramic color print described in (8) to (10) below.

  (1) 10 to 50 parts by mass of inorganic pigment fine particles, 5 to 40 parts by mass of thermally decomposable binder resin having an acid value of 5 or more, and 40 to 85 parts by mass of glass frit in 100 parts by mass of the total solid content of the toner A color toner for electronic printing (hereinafter referred to as a first embodiment).

  (2) Color toner for electronic printing containing inorganic pigment fine particles, a heat-decomposable binder resin having an acid value of 5 or more, and a glass frit, wherein the mass ratio of the glass frit and the heat-decomposable binder resin in the toner [Glass frit] / [Pyrolytic binder resin] ≧ 1.5. Color toner for electronic printing (hereinafter referred to as second embodiment).

  (3) The color toner for electronic printing according to (1) or (2), wherein the mass ratio of the inorganic pigment fine particles to the glass frit in the toner is [glass frit] / [inorganic pigment fine particles] ≧ 1.

  (4) The heat-decomposable binder resin having an acid value of 5 or more is an acid-modified thermoplastic resin obtained by reacting an unsaturated carboxylic acid or an unsaturated carboxylic acid anhydride with a thermoplastic resin (1) to (3 The color toner for electronic printing according to any one of the above.

  (5) The color toner for electronic printing according to (4), wherein the acid-modified thermoplastic resin is a maleic anhydride-modified thermoplastic resin.

  (6) The color toner for electronic printing according to (4) or (5), wherein the acid-modified thermoplastic resin is maleic anhydride-modified polyolefin.

(7) an acid value of from 5 or more thermally decomposable binder _{resin, T 100} is thermally decomposable resin of 350 to 550 ° C., (1) The color toner for electro printing according to any one of the - (6).

Here, T ₁₀₀ indicates a temperature at which the weight change disappears when the temperature is increased from room temperature at a temperature increase rate of 10 ° C./min using a thermogravimetric analyzer (TG).

  (8) Using the color toner according to any one of (1) to (7) above, forming the color toner pattern on a glass plate surface by an electronic printing method, and forming the color toner pattern A method for producing a glass plate with a ceramic color print, the method comprising: heating the glass plate to produce a glass plate having a ceramic color print pattern by ceramicizing the color toner.

  (9) The manufacturing method of the glass plate with a ceramic color print as described in (8) whose temperature which heats the said glass plate is 600-740 degreeC.

  (10) A ceramic color print according to (8) or (9), wherein the glass plate on which the color toner pattern is formed is heated to ceramicize the color toner, and the heated glass plate is thermally processed. Manufacturing method of glass plate.

  According to the present invention, the color toner for electronic printing is printed in a predetermined pattern by electronic printing on the glass plate surface, and fired to provide the ceramic color layer of the predetermined pattern on the glass plate surface. Without preparing a plate, a ceramic color print having excellent adhesion to the glass plate surface can be formed. In particular, when changing the pattern and the screen plate, it is possible to cope with only replacement of the electronic information, and therefore, it is possible to cope with a small amount and a variety of production in a short time.

  In the present invention, electronic printing refers to xerographic printing. In the xerographic method, an electrostatic latent image is exposed to form an electrostatic latent image, and the latent image is developed with toner to form a toner pattern on the surface of the photosensitive drum. Basically, it is transferred to the surface of the substrate (in the case of the present invention, the surface of the glass plate is a representative example). The present invention is an invention of a color toner suitable for electronic printing. This color toner is used for an application in which a pattern of an electronically printed toner is baked to form a ceramic color print (print pattern formed from a molten glass frit containing inorganic pigment fine particles). In particular, with this color toner, the glass plate surface is electronically printed to form a print pattern comprising this color toner, and then the color toner print pattern on the glass plate surface is baked to convert it into a ceramic color print. It is a color toner suitable for use in producing a glass plate. The present invention is also a method for producing a glass plate with a ceramic color print using the color toner.

Hereinafter, embodiments of the present invention will be described with reference to the drawings.
FIG. 1 is a side conceptual view showing an example of a series of steps for producing a glass plate with a ceramic color print of the present invention. The glass plate G is conveyed to a printing process through steps (ST1) such as cutting, chamfering, and washing into a predetermined shape. In the printing step ST <b> 2, color toner containing inorganic pigment fine particles is printed in a predetermined pattern on the glass plate G surface by the electronic printing apparatus 10. The glass plate G on which toner is printed in a predetermined pattern is conveyed into the heating furnace 30. In the heating furnace 30, the glass plate G is heated to a predetermined temperature, and the toner is baked onto the surface of the glass plate G to produce a glass plate with a ceramic color print having a predetermined pattern. The formed ceramic color print is conveyed to an inspection process (ST4; not shown), and the concealment performance is inspected. The inspection result in the inspection step ST4 is transmitted to the computer C, and after it is determined whether or not the desired concealment performance is obtained, it is converted into adjustment information such as a predetermined pattern and a toner supply amount, and the printing pattern in the printing step ST2 Used for control.

  In the step ST1, a rectangular glass plate is cut into a predetermined shape, and the cut surface is chamfered. Thereafter, the glass plate is washed, preheated as necessary, and conveyed to the printing process ST2 by the conveying roll 20.

  In the printing process ST2, after the photosensitive drum 13 is neutralized by the static eliminator 14 while rotating the photosensitive drum 13, the photosensitive drum 13 is charged by the charger 12, and exposed to exposure light from the light source 15 to be exposed in a predetermined pattern. The drum 13 is exposed. Next, the exposure surface of the photosensitive drum 13 is rotated to the toner supply unit 11, and toner is given to the photosensitive drum 13, whereby a toner layer having a predetermined pattern is formed on the surface of the photosensitive drum 13. The toner layer having a predetermined pattern on the surface of the photosensitive drum 13 is transferred to the surface of the glass plate G that has been conveyed along with the rotation of the photosensitive drum 13. Thus, a toner layer having a predetermined pattern is formed on the glass plate G surface. At this time, a secondary transfer plate such as an intermediate transfer belt may be interposed between the photosensitive drum 13 and the glass plate G surface.

  The computer C stores pattern information for exposing with a predetermined pattern by irradiating exposure light. Therefore, the exposure light is emitted from the light source 15 in a predetermined pattern according to a command from the computer C. When the glass plate G is used for an automobile window, the shape of the glass plate, the pattern shape of the ceramic color print, and the like differ depending on the model of the automobile. Therefore, by changing the command signal based on these data corresponding to the model of the automobile, it is possible to easily change from the production of one type of glass plate to the production of another type of glass plate.

  The glass plate G having a toner layer of a predetermined pattern is conveyed into the heating furnace 30 and heated to a predetermined temperature, usually about 600 to 740 ° C. Thus, the toner is baked on the glass plate G surface, and a ceramic color print having a predetermined pattern is provided on the glass plate. Since glass plates for automobile windows are usually curved, when a glass plate with a ceramic color print manufactured as described above is used for an automobile window, it is heated in the firing step ST3 and subjected to a strengthening process after bending. Is done. In some cases, not the tempering treatment but the slow cooling treatment is performed (bending of a glass plate for laminated glass). The thermal processing of the glass plate means that the glass plate is heated to bend or strengthen.

  The color toner for electronic printing of the present invention (hereinafter referred to as “the toner”) that can be used in the above-described process includes inorganic pigment fine particles, a thermally decomposable binder resin having an acid value of 5 or more (hereinafter referred to as “the present binder resin”), and glass frit. It consists of particles containing. In this case, the toner is fixed on the glass plate surface before heating due to the adhesiveness of the binder resin. Thereafter, in the heating process, the binder resin is first decomposed. The decomposed binder resin is volatilized from the glass plate by heating. After most of the binder resin volatilizes, the glass frit begins to melt and the toner is fixed to the glass plate surface mainly by the adhesiveness of the glass frit. In these processes, by completely decomposing and volatilizing the binder resin until the glass frit is completely melted, the remaining carbide in the ceramic color print after firing can be suppressed. Finally, when the glass plate is heated to a temperature exceeding 600 ° C., the molten glass frit frit in which the inorganic pigment fine particles are dispersed forms a layer on the glass plate surface.

  The inorganic pigment fine particles are an essential component for shielding ultraviolet rays or visible light, and it is preferable to use heat-resistant pigments. When obtaining a black pattern, one or more oxides selected from the group consisting of Co, Cr, Mn, Fe and Cu, or two or more complex oxides are preferable. Specifically, Cu—Cr—Mn composite oxide, Cr—Co composite oxide, Fe—Mn composite oxide, Cr—Fe—Ni composite oxide, Cr— It is particularly preferable to use one or more heat-resistant pigments selected from the group consisting of Cu-based composite oxides and magnetites.

  The inorganic pigment fine particles preferably have an average particle size of 0.2 to 5 μm. When the average particle size is 0.2 μm or more, the concealability inside the obtained ceramic color print can be maintained, and the glass can be prevented from being seen through from the printed surface. On the other hand, when the average particle size is 5 μm or less, the print quality of the obtained ceramic color print can be improved. The inorganic pigment fine particles particularly preferably have an average particle size of 0.5 to 3 μm.

  Next, in the present toner, the present binder resin is employed as a binder resin that has good adhesion to a glass plate and has good decomposability during heat treatment. The reason why the fixability is improved by the use of this binder resin has not been clarified yet, but it is considered that the carboxy group in the binder resin interacts with the silanol group on the surface of the glass plate. Here, when the acid value of the binder resin is 5 or more, the above-described interaction is sufficiently caused, so that the fixability of the print is stabilized when the toner is electronically printed on the glass plate surface. As a result, after firing, it is considered that poor adhesion of the ceramic color print does not easily occur and a print having good adhesion can be formed. On the other hand, the toner value is preferably 100 or less because the toner can be sufficiently fixed on the glass plate surface when electronic printing is performed, and defects such as offset are less likely to occur on the transfer roll. The acid value is particularly preferably 20-80. In addition, an acid value means the mg number of potassium hydroxide required in order to neutralize the acidic group which exists in 1g of resin.

  The binder resin is preferably a thermally decomposable resin mainly composed of an acid-modified thermoplastic resin having an acid value of 5 or more. The binder resin may be composed of an acid-modified thermoplastic resin alone, and is composed of a combination of an acid-modified thermoplastic resin and other thermally decomposable resin (for example, a thermoplastic resin having no acidic group). Also good. In the latter case, the proportion of the thermally decomposable resin other than the acid-modified thermoplastic resin is preferably a relatively small amount relative to the acid-modified thermoplastic resin, and the proportion is 30 with respect to the total resin amount of the binder resin. It is preferably not more than 10% by weight, particularly not more than 10% by weight. The polymer of the main chain of the acid-modified thermoplastic resin and the polymer of the main chain of another thermally decomposable resin are preferably polymers obtained by vinyl polymerization. Both main chain skeletons may be the same or different. Even when other thermally decomposable resins are contained, the acid value of this binder resin is 5 or more, and the acid value of all resins including other thermally decomposable resins having no acidic group is 5 or more. is there. Moreover, a commercially available thing can be used as an acid-modified thermoplastic resin and other thermally decomposable resin in this binder resin.

  The acid-modified thermoplastic resin is a polymer having an acidic group, and the acidic group in the present invention refers to a carboxy group and a carboxylic anhydride group. The acid-modified thermoplastic resin is a thermoplastic resin having one or both of a carboxy group and a carboxylic anhydride group. The acid-modified thermoplastic resin is preferably a polymer obtained by copolymerizing a monomer having an acidic group or a polymer obtained by reacting a compound having an acidic group with a thermoplastic resin. Moreover, an acidic group containing polymer can also be obtained by hydrolyzing a polymer obtained by copolymerizing an unsaturated carboxylic acid ester monomer. The acid-modified thermoplastic resin in the present invention is particularly preferably an acid-modified thermoplastic resin obtained by reacting a pre-manufactured thermoplastic resin with a compound having an acidic group.

  The main monomers constituting the acid-modified thermoplastic resin include aromatic vinyl monomers such as olefins and styrene, (meth) acrylate monomers such as acrylic esters and methacrylic esters, and unsaturated alcohol ester monomers such as vinyl acetate. And diene monomers such as butadiene. In particular, a thermoplastic resin obtained using an olefin having 6 or less carbon atoms such as ethylene or propylene as a main monomer is preferable.

  As the compound having an acidic group (hereinafter referred to as an acid modifier), an unsaturated carboxylic acid or an unsaturated polycarboxylic acid anhydride is preferable. In particular, unsaturated dicarboxylic acid and unsaturated dicarboxylic acid anhydride are preferable. Specific examples include acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, maleic anhydride, itaconic anhydride, and citraconic anhydride. In particular, maleic anhydride is preferred as the acid modifier. Accordingly, the acid-modified thermoplastic resin is preferably an acid-modified thermoplastic resin obtained by reacting an unsaturated carboxylic acid or an unsaturated carboxylic acid anhydride with a thermoplastic resin, and particularly preferably a maleic anhydride-modified thermoplastic resin.

  As the acid-modified thermoplastic resin, an acid-modified polyolefin obtained by reacting a polyolefin-containing compound with an acidic group is preferable. Examples of the polyolefin include polyethylene, polypropylene, and ethylene-propylene copolymer. Among them, polypropylene is preferable because it is easy to ensure a stable charge amount as a toner. As a method of reacting an acid modifier with a polyolefin, a method in which an acid modifier and a radical generator (peroxide, etc.) are mixed in the polyolefin and heated, a low molecular weight obtained by partial thermal decomposition of the polyolefin in advance. A method in which an acid modifier is mixed and reacted with polyolefin (having a reactive site such as an unsaturated group) can be employed. As the acid-modified polyolefin, maleic anhydride-modified polyolefin obtained by these methods using maleic anhydride as an acid-modifying agent, particularly maleic anhydride-modified polypropylene, has a large charge amount, a rapid charge rise, and stable charge. From the viewpoint of sex. The weight average molecular weight of the acid-modified polyolefin is not particularly limited, but is preferably 3000 to 150,000, and particularly preferably 5000 to 80,000.

  Any glass frit can be used regardless of whether it is lead-based or lead-free, but lead-free bismuth-silica glass frit is preferable from the viewpoint of the environment. The glass frit is preferably a powder having an average particle size of 0.1 to 5 μm. When the glass frit has an average particle size of 0.1 μm or more, sufficient adhesion to the glass plate surface can be secured, while when the average particle size is 5 μm or less, the glass frit is formed on the surface of the toner particles. It is possible to prevent exposure, and the fixability is unlikely to deteriorate when printed on a glass plate surface by an electronic printing method. The glass frit particularly preferably has an average particle size of 0.5 to 3 μm. The glass transition temperature Tg of the glass frit is preferably 350 to 500 ° C. When Tg is 350 ° C. or higher, melting of the glass frit can be prevented before the resin is decomposed, so that the ceramic color print is not properly baked, that is, the inorganic pigment fine particles are not well integrated or the ceramic color print is poorly adhered. Can be reduced. On the other hand, since the Tg is 500 ° C. or lower, it is possible to prevent the resin from decomposing and volatilizing before the glass frit is melted. The adhesion to the glass plate surface can be ensured.

  The color toner for electronic printing according to the first aspect of the present invention comprises 10 to 50 parts by mass of inorganic pigment fine particles, 5 to 40 parts by mass of the binder resin, and 100% by mass of 100 parts by mass of the total solid content of the toner. It contains 40 to 85 parts by mass of frit. The color toner for electronic printing according to the second aspect of the present invention also contains 10 to 50 parts by mass of inorganic pigment fine particles, 5 to 40 parts by mass of the binder resin, and 40 to 85 parts by mass of glass frit. preferable.

  By setting the content of the inorganic pigment fine particles to 10 parts by mass or more, sufficient concealability can be exhibited when viewed from the printing surface. On the other hand, the adhesiveness of a ceramic color print and a glass plate surface is securable by making content of inorganic pigment microparticles into 50 mass parts or less. The content of the inorganic pigment fine particles is particularly preferably 15 to 40 parts by mass. Moreover, when the content of the binder resin is 5 parts by mass or more, the ceramic color print can be fixed to the glass plate surface by the adhesiveness of both the resin and the glass frit, and the adhesion between the glass plate surface and the ceramic color print can be improved. Enhanced. On the other hand, when the content of the binder resin is 40 parts by mass or less, carbides are less likely to remain in the fired ceramic color print, and sufficient adhesion between the ceramic color print and the glass plate surface is ensured over a long period of time. it can. Further, it is possible to prevent the occurrence of defects such as cracks and voids in the ceramic color print due to the decomposition of the resin. The content of the binder resin is particularly preferably 10 to 30 parts by mass. Furthermore, when the content of the glass frit is 40 parts by mass or more, the adhesiveness between the ceramic color print and the glass plate surface can be sufficiently ensured over a long period, while the content is 85 parts by mass or less, The inorganic pigment fine particles can be dispersed at a high concentration in the ceramic color print, and the concealability as a pattern is easily obtained. The content of the glass frit is preferably 45 to 80 parts by mass with respect to 100 parts by mass of the total solid content of the toner.

  Furthermore, in the color toner for electronic printing according to the second aspect of the present invention, the content ratio of the glass frit and the present binder resin is [glass frit] / [the present binder resin] ≧ 1.5 in mass ratio. In the color toner for electronic printing according to the first aspect of the present invention, the content ratio of the glass frit and the present binder resin is [glass frit] / [the present binder resin] ≧ 1.5 in terms of mass ratio. preferable. In the first and second aspects of the present invention, the content ratio of the glass frit and the binder resin is more preferably 2 or more. With this configuration, carbides are less likely to remain in the fired ceramic color print, and sufficient adhesion between the ceramic color print and the glass plate surface can be ensured over a long period of time. Further, it is possible to prevent the occurrence of defects such as cracks and voids in the ceramic color print due to the decomposition of the resin. In the first and second aspects of the present invention, the upper limit of the content ratio of the glass frit and the present binder resin is 10 or less, that is, [glass frit] / [the present binder resin] ≦ 10 in mass ratio. Is preferred. More preferably, it is 8 or less. With this configuration, since a small amount of the binder resin remains even when the glass frit starts to melt, the ceramic color print can be fixed to the glass plate surface by the adhesiveness of both the resin and the glass frit. Adhesion of ceramic color print can be improved. The content ratio of the glass frit and the present binder resin is particularly preferably in the range of [glass frit] / [the present binder resin] = 2 to 8 by mass ratio.

  On the other hand, in the first and second aspects of the present invention, the content ratio of the glass frit and the inorganic pigment fine particles is preferably [glass frit] / [inorganic pigment fine particles] ≧ 1 by mass ratio. With such a configuration, the inorganic pigment fine particles can be highly dispersed in the ceramic color print and can be firmly fixed on the glass plate surface, so that the adhesion between the ceramic color print and the glass plate surface can be sufficiently secured over a long period of time. Further, it is possible to prevent the occurrence of defects such as cracks and voids in the ceramic color print due to the decomposition of the resin. Further, the upper limit is preferably 5 or less, that is, [glass frit] / [inorganic pigment fine particles] ≦ 5. With this configuration, it is possible to obtain a ceramic color print having a desired color tone and excellent in concealment. The content ratio of the glass frit and the inorganic pigment fine particles is particularly preferably [glass frit] / [inorganic pigment fine particles] = 1.5 to 4 in terms of mass ratio.

The binder resin _is preferably _{T 100} is at 350 to 550 ° C.. In the present invention, T ₁₀₀ is a point at which the temperature change from the room temperature using a thermogravimetric analyzer (TG) is performed at a rate of temperature increase of 10 ° C./min, and the change in the weight of the resin is measured to eliminate the change in weight. The temperature at is shown. By T ₁₀₀ is 350 ° C. or higher, prior to decomposition of the resin can prevent the molten glass frit occurs, it is possible to sufficiently secure the ceramic color print to the glass plate surface. On the other hand, when T ₁₀₀ is 550 ° C. or lower, on the contrary, when the toner is baked, the resin quickly decomposes and volatilizes, so that there is almost no residual carbon remaining in the ceramic color print. It is possible to obtain a ceramic color print that is excellent in adhesion and easily develops the target color tone. T ₁₀₀ is particularly preferably 400 to 450 ° C.

Further, the binder resin _is preferably is _{0.1~15 ℃ (T 100 -T 90)} . Here, T ₉₀ is the temperature at which the decrease amount of the resin becomes 90% by weight when the temperature is raised from room temperature at a heating rate of 10 ° C./min using a thermogravimetric analyzer (TG). Show. Since (T ₁₀₀ -T ₉₀ ) is 0.1 ° C. or higher, a small amount of the binder resin remains even when the glass frit starts to melt, so that the ceramic color is around the glass transition temperature Tg of the glass frit. The print can be fixed to the glass plate surface by the adhesiveness of both the resin and the glass frit, and the adhesion between the glass plate surface and the ceramic color print can be improved. On the other hand, when (T ₁₀₀ -T ₉₀ ) is 15 ° C. or less, the binder resin can be sufficiently decomposed until the glass frit is completely melted. As a result, it is possible to obtain a ceramic color print that is less likely to remain, easily develops the target color tone, and has excellent adhesion to the glass plate surface. In particular, (T ₁₀₀ -T ₉₀ ) is preferably 5 to 15 ° C.

  In addition, the present toner may be used in order to suppress a decrease in strength of the ceramic color print or to prevent the ceramic color print from adhering to a press mold used during press bending of a glass plate, that is, to improve mold release properties. An inorganic filler may be added inside. At this time, it is preferable to use a heat-resistant inorganic filler as the inorganic filler, from aluminum borate, α-alumina, potassium titanate, zinc oxide, magnesium oxide, magnesium borate, basic magnesium sulfate and titanium diboride. It is more preferable to use a filler made of one or more inorganic substances selected from the group consisting of: The shape of the inorganic filler is not particularly limited, but it is preferable to use a plate-like filler because the concealability inside the ceramic color print can be increased. The amount of the inorganic filler is preferably such that the total amount of the inorganic pigment fine particles and the inorganic filler is in a quantitative range that satisfies the preferable conditions of the inorganic pigment fine particles for the glass frit described above. That is, when an inorganic filler is contained, it is preferable that 1 ≦ [glass frit] / [inorganic pigment fine particles + inorganic filler] ≦ 5 by mass ratio.

  In addition to the inorganic filler, other blending components can be blended as necessary. For example, a charge control agent such as an azo metal-containing dye, a salicylic acid metal-containing dye, or a quaternary ammonium salt may be contained in the toner. The blending amounts of these blending components including the inorganic filler can be used within a range that satisfies the quantitative conditions of the three essential components.

  The toner is manufactured by, for example, mixing the binder resin, inorganic pigment fine particles, glass frit, and the like, kneading and cooling to produce pellets, and then pulverizing and classifying. The heating temperature during kneading is preferably 150 to 200 ° C. By setting the heating temperature to 150 ° C. or higher, the resin, inorganic pigment fine particles, glass frit, and the like can be mixed uniformly. On the other hand, when the heating temperature is 200 ° C. or lower, it is possible to prevent the binder resin from being decomposed in the toner preparation stage. The toner preferably has an average particle size of 5 to 50 μm. When the average particle size is 5 μm or more, the inorganic pigment fine particles and glass frit in the toner are not exposed on the surface, and the charge amount of the toner can be secured. Therefore, the charge amount of the toner is insufficient when performing electronic printing. The occurrence of printing defects such as ground fogging can be suppressed. On the other hand, when the average particle size is 50 μm or less, high-definition print quality can be easily obtained.

  After the obtained toner is printed on the glass plate surface by an electronic printing method, the glass plate on which the toner is printed is heated to a predetermined temperature, and the toner is baked to form a ceramic color print. At this time, the heating temperature is preferably 600 to 740 ° C. When the heating temperature is 600 ° C. or higher, the glass frit is completely melted, so that the adhesion between the ceramic color print and the glass plate surface can be sufficiently ensured over a long period of time. On the other hand, when the heating temperature is 740 ° C. or lower, the deformation of the glass plate can be prevented. In the present invention, soda lime glass, non-alkali glass, quartz glass and the like can be used as the glass plate.

  The film thickness of the ceramic color print formed according to the present invention is preferably 5 to 30 μm. When the film thickness is 5 μm or more, a stable concealing property can be easily obtained, and when the film thickness is 30 μm or less, a desired film thickness can be easily obtained even by one-time electronic printing, and the handling is excellent. The film thickness is particularly preferably 10 to 20 μm.

  FIG. 2 is a conceptual diagram illustrating a control process according to a preferred embodiment of the present invention. The glass plate pretreated in ST1 is printed with a toner in a predetermined pattern in the printing step ST2, heated in the firing step ST3, and the toner is baked to produce a glass plate with a ceramic color print. After the firing step ST3, the concealment performance of the ceramic color print formed in the inspection step ST4 is measured. The measured concealment performance data is sent to a computer C that controls the toner pattern in the printing process. If necessary, temperature data in the firing step ST3 is also sent to the computer C. The data sent to the computer C is used as data for determining whether a desired concealment performance can be obtained. When it is determined that the desired performance is not obtained, the printing pattern and supply amount of the toner printed so as to obtain the desired performance are adjusted by the calculation of the computer C. The adjusted printing pattern and supply amount of the toner are fed back to the printing process ST2, and a ceramic color print is provided on the next glass plate.

  When the desired concealment performance is obtained by such feedback, the control data is fixed, and a large number of glass plates with ceramic color prints can be manufactured continuously.

  Further, when the glass plate G is used for an automobile window, the computer C can store and accumulate glass plate shape data, ceramic color print pattern shape data, etc. according to the type of the vehicle. This makes it easy to change from one model to another by sending a command to the electronic printer based on the data related to the pattern shape of the ceramic color print corresponding to that model when manufacturing a glass plate for that model. The printing according to each model can be performed. Furthermore, by sending a command based on the shape data of the glass plate among the data relating to the model to the cutting and chamfering step (ST1) of the glass plate, it is possible to easily change from one type to another type according to each type. Cutting and chamfering can be performed.

  In the printing step ST2, not only the color toner but also toner containing conductive fine particles (hereinafter referred to as conductive toner) can be printed on the glass plate surface. For example, the rear window of the automobile illustrated in FIG. 3 is provided with a conductive printed wire (defogger 1, antenna wire 2, bus bar 3) in the central region of the glass plate G, and a dark ceramic print 4 in the peripheral region. By printing conductive toner in a predetermined pattern on the photosensitive drum shown in FIG. 1, the conductive toner can be printed on the glass plate surface together with the color toner. Similarly to the color toner, the conductive toner has been conventionally printed by screen printing. Thus, by performing electronic printing of the conductive toner together with the color toner, a manufacturing method suitable for mass production can be obtained.

Examples 1 to 8 (Examples) and Examples 9 to 13 (Comparative Examples) are shown below. In this example, the decomposition temperature was measured from room temperature to 700 ° C. at a temperature rising rate of 10 ° C./min using a thermogravimetric analyzer (manufactured by Shimadzu Corporation, model: DTG-50). conducted, and the temperature T ₁₀₀ of weight change of the resin is eliminated, reducing the amount of the resin was determined and the temperature T ₉₀ at the time point when 90%.

  Moreover, the average molecular weight of the resin used in Examples 1 to 10, 12, and 13 is a weight average molecular weight, and the average molecular weight of the resin used in Example 11 is a number average molecular weight.

[Example 1]
In a container made of stainless steel (SUS304) having a capacity of 200 mL, maleic anhydride-modified polypropylene (manufactured by Sanyo Kasei Co., Ltd., trade name: Umex 110TS, average molecular weight 12000, acid value 7, T ₁₀₀ = 450 ° C., T ₉₀ = 435 ° C.) 20 Part by mass, 18 parts by mass of black heat-resistant pigment fine particles (made by Toago Material Technology, trade name: 42-302A, average particle size 0.6 μm) made of Cu—Cr—Mn composite oxide, glass frit (bismuth- Silica-based lead-free frit, glass transition temperature Tg = 461 ° C., melting temperature = 565 ° C., average particle size 2 μm) 62 parts by mass are mixed and heated to 180 ° C. Obtained. This solid was pulverized with a jet mill and classified to obtain a toner having an average particle diameter of 20 μm.

  Using this toner, a rectangular pattern with a line width of 10 mm and a length of 80 mm was printed on a 30 cm × 30 cm plate glass with an electronic printer, and then baked at 700 ° C. for 4 minutes to form a ceramic color print. did. This ceramic color print was evaluated as follows. The evaluation results are shown in Table 1. Hereinafter, evaluation was similarly performed in Examples 2 to 12, and the results are shown in Table 1. Further, when the same evaluation is made in Example 13, the results shown in Table 1 are obtained.

[Adhesion evaluation]
The adhesion part with a ceramic color print was observed from the back side of the glass plate with the optical microscope, and the presence or absence of peeling of a ceramic color print and adhesion defect was confirmed. The poor adhesion means that the ceramic color print is not in close contact with the glass plate surface and is in a floating state. As an evaluation, the case where there was no peeling at all was A, the case where there were 5 or less adhesion defects with a diameter of 0.5 mm or less at the interface between the glass plate and the ceramic color print, the diameter B present at the interface between the glass plate and the ceramic color print was 0. C, which has 6 to 10 adhesion defects of 5 mm or less, 11 or more adhesion defects of 0.5 mm or less in diameter, or an adhesion defect of more than 0.5 mm is observed, and a ceramic color print The product without peeling was evaluated as D, the ceramic color print partially peeled off as E, and all peeled off as F. As evaluation, what was judged as A, B, and C was set as the pass.

[Visible light transmittance evaluation]
The visible light transmittance of the ceramic color print was measured with a spectrophotometer (manufactured by MINOLTA, trade name: spectrocolorimeter CM-3600d), and the visible light transmittance of 0.3% or less was regarded as acceptable.

[Example 2]
A toner having an average particle diameter of 20 μm was obtained in the same manner as in Example 1 except that 32 parts by mass of pigment fine particles and 48 parts by mass of glass frit were used.

[Example 3]
A toner having an average particle diameter of 20 μm was obtained in the same manner as in Example 1 except that 15 parts by weight of maleic anhydride-modified polypropylene, 19 parts by weight of pigment fine particles, and 66 parts by weight of glass frit were used.

[Example 4]
A toner having an average particle diameter of 20 μm was obtained in the same manner as in Example 1 except that 10 parts by mass of maleic anhydride-modified polypropylene, 20 parts by mass of pigment fine particles, and 70 parts by mass of glass frit were used.

[Example 5]
In Example 1, maleic anhydride-modified polypropylene (manufactured by Sanyo Chemical Co., Ltd., trade name: Umex 1001, average molecular weight 40000, acid value 26, T ₁₀₀ = 450 ° C., T ₉₀ = 435 ° C.) was used in the same manner. The operation was performed to obtain a toner having an average particle diameter of 20 μm.

[Example 6]
In Example 1, maleic anhydride-modified polypropylene (manufactured by Sanyo Kasei Co., Ltd., trade name: Umex 1003, average molecular weight 20000, acid value 21, T ₁₀₀ = 440 ° C., T ₉₀ = 430 ° C.) was used in the same manner. The operation was performed to obtain a toner having an average particle diameter of 20 μm.

[Example 7]
In Example 1, the same operation was performed except that maleic anhydride-modified polypropylene (sample manufactured by Sanyo Kasei Co., Ltd., average molecular weight 43000, acid value 38, T ₁₀₀ = 430 ° C., T ₉₀ = 420 ° C.) was used. A toner having a particle size of 20 μm was obtained.

[Example 8]
In Example 1, maleic anhydride-modified polypropylene (manufactured by Sanyo Kasei Co., Ltd., trade name: Yumex 1010, average molecular weight 30000, acid value 52, T ₁₀₀ = 430 ° C., T ₉₀ = 420 ° C.) was used in the same manner. The operation was performed to obtain a toner having an average particle diameter of 20 μm.

[Example 9 (comparative example)]
A toner having an average particle diameter of 20 μm was obtained in the same manner as in Example 1 except that the pigment fine particles were 55 parts by mass and the glass frit was 25 parts by mass.

[Example 10 (comparative example)]
A toner having an average particle diameter of 20 μm was obtained in the same manner as in Example 1 except that 50 parts by mass of maleic anhydride-modified polypropylene, 11 parts by mass of pigment fine particles, and 39 parts by mass of glass frit were used.

[Example 11 (comparative example)]
The same as Example 1 except that polypropylene (manufactured by Sanyo Chemical Co., Ltd., trade name: Biscol 660-P, average molecular weight 7900, T ₁₀₀ = 380 ° C., T ₉₀ = 365 ° C.) was used instead of maleic anhydride-modified polypropylene. Then, a toner having an average particle diameter of 20 μm was obtained.

[Example 12 (comparative example)]
In Example 1, the same except that maleic anhydride-modified polypropylene (manufactured by Sanyo Kasei Co., Ltd., trade name: Umex 100TS, average molecular weight 10,000, acid value 3.5, T ₁₀₀ = 380 ° C., T ₉₀ = 370 ° C.) was used. Then, a toner having an average particle diameter of 20 μm was obtained.

[Example 13 (comparative example)]
The same as Example 1 except that polystyrene (manufactured by Sanyo Kasei Co., Ltd., trade name: Heimer ST-120, average molecular weight 10,000, T ₁₀₀ = 460 ° C., T ₉₀ = 445 ° C.) was used instead of maleic anhydride-modified polypropylene. Then, a toner having an average particle diameter of 20 μm was obtained.

  From the results in Table 1, it can be seen that in Examples (Examples 1 to 8) using the present toner, a glass plate with a ceramic color print having good adhesion and low visible light transmittance was obtained. .

  The present invention relates to a method for providing a ceramic color print on a glass plate surface and a color toner for electronic printing therefor, and is particularly applicable to a method for producing a glass plate with a ceramic color print for an automobile window.

It is a side surface conceptual diagram which shows an example of a series of processes which manufacture the glass plate with a ceramic color print of this invention. It is a conceptual diagram explaining the control process which concerns on the preferable form of this invention. It is a front view which shows an example of a motor vehicle rear window.

Explanation of symbols

1: Defogger 2: Antenna wire 3: Bus bar 4: Dark ceramic print 10: Electronic printing device 11: Toner feeder 12: Charging machine 13: Photoconductive drum 14: Electrification machine 15: Light source 20: Transport roll 30: Heating furnace G: Glass plate C: Computer ST1: Chamfering process ST2: Printing process ST3: Firing process ST4: Inspection process

Claims (10)

  Electronic printing containing 10 to 50 parts by weight of inorganic pigment fine particles, 5 to 40 parts by weight of thermally decomposable binder resin having an acid value of 5 or more, and 40 to 85 parts by weight of glass frit in 100 parts by weight of the total solid content of the toner. Color toner.   A color toner for electronic printing containing inorganic pigment fine particles, a thermally decomposable binder resin having an acid value of 5 or more, and a glass frit, wherein the mass ratio of the glass frit and the thermally decomposable binder resin in the toner is [ Glass frit] / [thermally decomposable binder resin] ≧ 1.5   The color toner for electronic printing according to claim 1 or 2, wherein a mass ratio of the inorganic pigment fine particles to the glass frit in the toner is [glass frit] / [inorganic pigment fine particles] ≧ 1.   The heat-decomposable binder resin having an acid value of 5 or more is an acid-modified thermoplastic resin obtained by reacting an unsaturated carboxylic acid or an unsaturated carboxylic acid anhydride with a thermoplastic resin. The color toner for electronic printing as described.   The color toner for electronic printing according to claim 4, wherein the acid-modified thermoplastic resin is a maleic anhydride-modified thermoplastic resin.   The color toner for electronic printing according to claim 4 or 5, wherein the acid-modified thermoplastic resin is a maleic anhydride-modified polyolefin. The acid value of 5 or more thermally decomposable binder resin, T ₁₀₀ is 350 to 550 ° C. thermally decomposable resin, the electronic printing for color toner according to any one of claims 1 to 6.
Here, T ₁₀₀ indicates a temperature at which the weight change disappears when the temperature is increased from room temperature at a temperature increase rate of 10 ° C./min using a thermogravimetric analyzer (TG).   A step of forming the color toner pattern on the glass plate surface by an electronic printing method using the color toner according to claim 1, and heating the glass plate on which the color toner pattern is formed And manufacturing a glass plate having a ceramic color print pattern by converting the color toner into a ceramic.   The manufacturing method of the glass plate with a ceramic color print of Claim 8 whose temperature which heats the said glass plate is 600-740 degreeC.   The method for producing a glass plate with a ceramic color print according to claim 8 or 9, wherein the glass plate on which the color toner pattern is formed is heated to ceramicize the color toner, and the heated glass plate is thermally processed. .

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