JP3609852B2 - Method for producing drawing fired body - Google Patents

Description

[0001]
[Industrial application fields]
The present invention relates to a method for producing a drawing fired body capable of drawing an image having excellent durability on the surface of a drawing material such as ceramics.
[0002]
[Prior art]
Conventionally, Japanese Patent Publication No. 5-77474 discloses a method for accurately coloring on the surface of ceramics such as ceramics.
In this method, a chelate compound is used as a liquid pigment, and the liquid pigment is drawn by being jetted onto the ceramic surface by an ink jet printer, and the liquid pigment is permeated from the ceramic surface to a predetermined depth at a uniform concentration. Thereafter, firing is performed at a temperature at which the liquid pigment develops color, and then the surface of the ceramic is polished and finished.
Inkjet printers arrange and attach liquid pigments as independent droplets one by one to the surface of the ceramic, and the size of the droplets is made uniform, so there is little variation in the liquid pigment adhering to the ceramic surface, and high In addition to enabling accurate drawing, since the chelate compound is electrically neutral, there is an advantage that a fine image can be drawn because the pigment does not spread when penetrating into a negatively charged ceramic.
[0003]
[Problems to be solved by the invention]
However, in the case of a chelate compound, since the absolute amount of metal pigment contained in a unit volume is small, the concentration of the chelate compound penetrating into ceramics is insufficient and the density of the image of the droplets by inkjet is low, and the clearness is clear. There is a drawback that an accurate image cannot be obtained.
On the other hand, when an aqueous solution of a soluble metal salt (hereinafter referred to as a metal ion aqueous solution) is used instead of the chelate compound, the absolute amount of the metal pigment contained in the unit volume is larger than that of the chelate compound, and the image density is increased. be able to. However, since the dissolved metal salt is a cation, when it is attached as a droplet to a negatively charged ceramic, there is a drawback in that it diffuses inside the ceramic and blurs the image.
Accordingly, an object of the present invention is to provide a method for producing a drawing fired body capable of forming a clear and precise image on the surface of a drawing material using a liquid pigment made of an aqueous metal ion solution.
[0004]
[Means for Solving the Problems]
According to a first production method of the present invention, as in claim 1 , the step of electrically neutralizing an unfired glaze with an antistatic agent and the surface of the drawing material are electrically A step of forming a glaze layer with neutralized unfired glaze, a step of injecting a liquid pigment made of an aqueous metal ion solution onto the glaze layer with an ink jet nozzle, and allowing the liquid pigment to penetrate into the glaze layer; And baking the drawing material at a temperature at which the liquid pigment develops color and the glaze layer is fused to the surface of the drawing material, and the antistatic agent disappears by baking .
According to a second manufacturing method, as in claim 2, a step of forming an unfired glaze layer on the surface of the drawing material and an antistatic agent is applied to the unfired glaze layer to electrically apply the glaze layer. A step of neutralizing, a step of injecting a liquid pigment made of an aqueous metal ion solution onto the glaze layer by an ink jet nozzle and infiltrating the liquid pigment into the glaze layer, and the liquid pigment coloring the drawing material, And a step of firing at a temperature at which the glaze layer is fused to the surface of the drawing material, and causing the antistatic agent to disappear by firing .
In the third production method, as in claim 3 , the step of electrically neutralizing the unfired glaze with an antistatic agent and the formation of the first fired surface on the surface are formed. Forming a second glaze layer of the electrically neutralized unfired glaze on the first glaze surface of the drawing material, and applying a liquid pigment comprising an aqueous metal ion solution to the second glaze Injecting the liquid pigment into the second glaze layer by spraying onto the layer with the ink jet nozzle, the liquid pigment develops color on the drawing material, and the second glaze layer is fused to the first glaze surface. Firing at a temperature and eliminating the antistatic agent by firing.
According to a fourth manufacturing method, as in claim 4 , an unfired second glaze layer is formed on the first flange surface of the drawing material in which the fired first flange surface is formed on the surface. A step of electrically neutralizing the second glaze layer by applying an antistatic agent to the unfired second glaze layer, and a liquid pigment comprising an aqueous metal ion solution as the second glaze Injecting the liquid pigment into the second glaze layer by spraying onto the layer with the ink jet nozzle, the liquid pigment develops color on the drawing material, and the second glaze layer is fused to the first glaze surface. Firing at a temperature and eliminating the antistatic agent by firing.
[0005]
In the case of the first method, first, a glaze layer suitable for the fusion of the pigment is formed on the surface of the drawing material, and the liquid pigment is infiltrated into the glaze layer by spraying the liquid pigment on the surface with an ink jet nozzle. Then, the glaze layer and the pigment are fired simultaneously. Since unfired glaze is negatively charged, it is necessary to previously electrically neutral the glaze layer by mixing the antistatic agent (a cationic surfactant). Since the glaze layer is electrically neutralized, the aqueous metal ion solution penetrates without diffusing. Since the metal pigment reacts with the glaze and develops color, it has good color developability and fixability. In addition, since the glaze is not limited to transparent Yu, the firing temperature can be lowered compared to the sketch system, and pigments of various colors can be used. The drawing material in this case is not limited to ceramics, and non-permeable materials (iron, stainless steel, glass, etc.) can be used.
[0006]
Inkjet nozzles are used to inject droplets of liquid pigment sucked up by capillary action, etc. in the form of drops using electrical vibration, etc., such as paint jet printers (trade name, manufactured by Hewlett Packard) and bubble jet printers (trade name, manufactured by Canon). And other known printers. Since the ink jet nozzle can have a drawing point diameter of, for example, about 60 to 240 microns, a finer image can be drawn as compared with other types of nozzles (for example, air spray nozzles). On the other hand, since the injection pressure is small, if the metal particles are contained in the pigment like an inorganic metal pigment, the metal particles are precipitated and the nozzle is likely to be clogged. On the other hand, in the case of a liquid pigment made of an aqueous metal ion solution, there is no risk of precipitation of metal particles, so that it can be easily drawn with a known ink jet printer. Further, in the case of an ink jet nozzle, since the injected drip is small, a concentration suitable for the color development of the metal pigment is required to be at least about 2 mol / liter, but in the case of an aqueous metal ion solution, the above concentration can be easily obtained. This makes it possible to draw a clear drawing.
[0007]
In the second method, the antistatic agent is not mixed with the glaze in advance as in the first method , but after forming an unfired glaze layer on the surface of the drawing material, the antistatic agent is applied to the unfired glaze layer. Is applied to neutralize the glaze layer. As a neutralization method, for example, an antistatic agent (cationic surfactant) is applied to the surface portion of the glaze layer by spraying or the like and penetrated to a predetermined depth, or a synthetic paste, an acrylic resin, or the like is applied. A method may be used. Thereby, the surface layer part of the glaze layer charged negatively is electrically neutralized. The subsequent steps are the same as in the first method.
[0008]
When a liquid pigment composed of an aqueous metal ion solution is directly drawn on ceramics, if the ceramic itself has a small amount of glass (glass) component, it may be difficult to obtain sufficient fixability and color developability of the pigment. In the present invention, a glaze layer is formed on the surface of the drawing material, and after the liquid pigment is sprayed onto the glaze layer with an inkjet nozzle , the liquid pigment and the glaze are fired at the same time, so the metal pigment reacts with the glaze layer. Color development and fixing properties are improved.
Here, the antistatic agent includes a synthetic surfactant, an acrylic resin, etc. in addition to the cationic surfactant as described above, and has a function of electrically neutralizing a negatively charged material. The thing which has.
[0009]
Third, in the fourth method, is formed in advance Baked first釉面(glassy layer) on the surface of the drawing pixel material. Therefore, there is an advantage that the fusion with the second glaze is good and there is no risk of bubbles or the like being generated from the surface of the material at the time of firing, and the sharpness of drawing increases. As a drawing material in this case, glass or metal materials (iron, stainless steel, etc.) can be used in addition to ceramics. In the case of glass, since the surface already constitutes the first flange surface, it is not necessary to separately form the first flange surface.
[0010]
In addition to a flat plate, the shape of the drawing material may be, for example, a simple curved body (for example, a cylindrical basket, a cylindrical vase, a coffee cup, etc.).
In the present invention, the term “drawing” includes not only patterns and paintings but also all kinds of images such as characters and figures.
As a method of forming an unfired glaze layer, for example, a method of spraying a glaze with a spray or the like, or a method of pasting a sheet provided with a glaze layer called glaze on a drawing material in advance is used. it can. The use of glaze paper has the advantage that a glaze layer with a certain thickness can be formed on the drawing material.
[0011]
The ink jet printer can draw various shades and shades freely by computer processing. For example, when an enlarged image of a color original image is drawn, an original image such as a color photograph or painting is read in advance by an image scanner, and the position and color of each pixel of the original image are stored by computer processing. Next, a nozzle head having a plurality of nozzles for ejecting liquid pigments, each of which produces a different color, is arranged facing the drawing material creation screen. While the nozzle head is intermittently moved by a constant pitch by computer control, a small amount of liquid pigment that develops a color corresponding to the color of the pixel is applied to the portion of the screen corresponding to the pixel of the original image in synchronization with the nozzle head. A precise enlarged image can be easily drawn by spraying in a shape. Needless to say, if the pixels are subdivided, a more precise drawing image can be drawn.
[0012]
FIG. 1 shows a method for producing a drawing fired body as a first reference example . This example is an example of a sketch scheme.
In (I), the drawing material 1 was made of an unglazed ceramic plate, and an antistatic agent 2 was applied to the surface thereof and allowed to penetrate to a certain depth (for example, 1-2 mm). In this reference example , a commercially available unglazed ceramic plate (for example, manufactured by Shibata Pottery) was used as the ceramic plate. Further, as the antistatic agent 2, a commercially available cationic surfactant was used.
[0013]
Next, as shown in (II), a known ink jet printer 3 having ink jet nozzles 3a is arranged on the surface of the ceramic plate 1 infiltrated with the antistatic agent 2, and a liquid pigment 4 made of an aqueous metal ion solution is applied from each nozzle 3a. Sprayed in a drip and drawn. In the ink jet printer 3 of this reference example , a plurality of (for example, 4 to 8) ink jet nozzles 3a are arranged in the direction perpendicular to the paper surface, and each nozzle ejects an individual color. Then, while the inkjet printer 3 is moved intermittently by a constant pitch in the direction of the arrow, drawing is performed by ejecting the liquid pigment 4 from a desired nozzle 3a each time it is stopped. The diameter of the dot on the ceramic plate 1 was about 240 μm, for example. Examples of the aqueous metal ion solution include a mixture of cobalt chloride and aluminum chloride in a 1: 1 molar ratio (blue), and a molar ratio of tin chloride, calcium chloride, and chromium chloride in a 1.2: 1 to 0.1 molar ratio. And a mixture of zinc chloride, aluminum chloride and chromium chloride in a molar ratio of 1: 5 to 2 (yellow), etc., and these were adjusted to a concentration of at least 2 mol / liter.
[0014]
Next, as shown in (III), the liquid pigment 4 was allowed to permeate into the surface layer of the ceramic plate 1 by leaving it for a predetermined time. This penetration depth is about 1 mm, which is equal to or shallower than the penetration depth of the antistatic agent 2. Since the ceramic plate 1 is electrically neutralized by the antistatic agent 2, the droplets of the liquid pigment 4 do not diffuse.
Next, as shown in (IV), the ceramic plate 1 was primarily fired under predetermined conditions. This baking temperature is a temperature suitable for color development and fixing of the liquid pigment 4, for example, about 800 ° C., and the maximum temperature holding time is about 30 minutes to 1 hour. By the primary firing, the antistatic agent 2 was evaporated and disappeared, and the liquid pigment 4 was also colored by the oxidation reaction, and a vivid drawing emerged.
[0015]
Thereafter, as shown in (V), the glaze 5 was applied to the surface of the ceramic 1 plate 1 by spraying, followed by secondary firing. This glaze 5 is a mixture of fine powder of 18% silica sand, 26% borax, 10% fluorite, 38% feldspar, 5% soda ash, 3% potassium nitrate, and a viscosity suitable for spraying. It is a clarified transparent Yu and does not need to contain an antistatic agent. The secondary firing is a temperature suitable for fusion of the glaze 5, for example, 950 to 1150 ° C. Since the drawing surface of the ceramic plate 1 after the secondary firing was covered with the ridges 5, it became a drawing fired body excellent in terms of glazing and durability.
In the above example , the glaze 5 is applied to the surface of the ceramic plate 1 after the primary firing and the secondary firing is performed. However, by polishing the surface of the ceramic plate 1 after the primary firing, The next firing step may be omitted. Since the metal pigment remaining on the surface of the ceramic plate 1 is removed by polishing, a smooth and clear drawing fired plate can be obtained.
[0016]
FIG. 2 shows a method for producing a drawing fired body as a second reference example . This example is also an example of a sketch scheme.
First, as shown in (I), the antistatic agent 2 was applied to the surface of the unglazed ceramic plate 1 and allowed to penetrate to a certain depth. The ceramic plate 1 and the antistatic agent 2 used here are the same as in FIG.
Next, as shown in (II), a liquid pigment 4 made of an aqueous metal ion solution was sprayed onto the surface of the ceramic plate 1 by an ink jet printer 3 in a drip manner for drawing. The inkjet printer 3 and the liquid pigment 4 are the same as in FIG.
Next, as shown in (III), the liquid pigment 4 was allowed to permeate into the surface layer of the ceramic plate 1 by leaving it for a predetermined time. This penetration depth is about 1 mm, which is equal to or shallower than the penetration depth of the antistatic agent 2. Since the ceramic plate 1 is electrically neutralized by the antistatic agent 2, the droplets of the liquid pigment 4 do not diffuse.
Next, glaze 6 was applied to the surface of ceramic plate 1 as in (IV). The components of the glaze 6 are the same as those of the glaze 5 in FIG. 1 except that an antistatic agent is mixed. Therefore, the liquid pigment 4 remaining on the surface layer portion of the ceramic plate 1 is prevented from diffusing into the glaze 6.
Thereafter, the ceramic board 1 was fired at a predetermined temperature as in (V) to obtain a drawn fired body. The firing temperature is a temperature suitable for color development and fixing of the liquid pigment 4 and suitable for fusion of the glaze 6 and is the same as in FIG. By firing, the antistatic agent 2 that has penetrated into the ceramic plate 1 evaporates, the glaze 6 changes to transparent, and the liquid pigment 4 also develops color due to the oxidation reaction. Therefore, a vivid drawing appears under the surface.
[0017]
FIG. 3 shows a first embodiment of a method for producing a drawn fired body according to the present invention. This embodiment is an example of the top picture method.
As in (I), a glaze 7 for dye fusion mixed with an antistatic agent was applied to the entire surface of the unglazed ceramic plate 1 as a drawing material, and dried to such an extent that the glaze 7 did not flow. The glaze 7 used here was prepared by mixing 21% silica sand, 43% boric acid, 10% soda ash, 12% potassium carbonate, 14% zinc white with water and adjusting it to a viscosity suitable for spraying. It is. The thickness of the glaze 7 was set to be equal to or thicker than the depth of penetration of the liquid pigment later. In this embodiment, the ceramic plate 1 is used as a drawing material. However, the present invention is not limited to this, and a heat-resistant metal plate or glass plate such as iron or stainless steel may be used.
Next, as shown in (II), the liquid pigment 4 of the metal ion aqueous solution was sprayed onto the surface of the glaze 7 applied to the surface of the ceramic plate 1 by the ink jet printer 3 in a drip form and drawn. The ink jet printer 3 and the liquid pigment 4 are the same as those in FIG.
Next, the liquid pigment 4 was allowed to permeate the glaze 7 by leaving it for a predetermined time as in (III). Since the glaze 7 is electrically neutralized by the antistatic agent, the droplets of the liquid pigment 4 do not diffuse in the glaze 7.
Thereafter, the ceramic plate 1 is fired at a predetermined temperature. This firing temperature is a temperature suitable for color development and fixing of the liquid pigment 4 and for fusing the glaze 7, and is preferably 900 to 1100 ° C., for example. By baking, the antistatic agent contained in the glaze 7 evaporates, the glaze 7 melts, and the liquid pigment 4 also develops color due to the oxidation reaction. Therefore, vivid drawing emerges.
[0018]
FIG. 4 shows a second embodiment of a method for producing a drawn fired body according to the present invention. This embodiment is also an example of the above picture method.
In (I), a vitreous layer (back surface) 8 that has been pre-glazed and fired is formed on the surface layer portion of the ceramic plate 1 that is a drawing material. This glassy layer 8 is obtained by applying glaze to the surface of the unglazed ceramic plate 1 and firing it at a temperature at which this glaze melts. As the ceramic plate 1 having the glassy layer 8, for example, commercially available tiles made by Mitsui tile, Shibata earthenware or Inax can be used.
Next, as shown in (II), a glaze 9 for dye fusion mixed with an antistatic agent was applied to a predetermined drawing position on the surface of the glassy layer 8 and dried until the glaze 9 did not flow. . The glaze 9 is made of the same material as that of the glaze 7 in the embodiment of FIG. 3, and its melting temperature is equal to or lower than the melting temperature of the glassy layer 8.
Next, as shown in (III), the liquid pigment 4 made of an aqueous metal ion solution was ejected in a drip form from the inkjet printer 3 and drawn. The ink jet printer 3 and the liquid pigment 4 are the same as those in FIG.
Next, as shown in (IV), the liquid pigment 4 was allowed to permeate the glaze 9 by leaving it for a predetermined time. Since the glaze 9 is electrically neutralized by the antistatic agent, the droplets of the liquid pigment 4 do not diffuse in the glaze 9.
Thereafter, as shown in (V), the ceramic plate 1 was fired at a temperature suitable for melting the glaze 9 (partially melting the vitreous layer 8) and coloring the liquid pigment 4. The firing temperature is desirably about 800 ° C. By the firing, the glaze 9 was melted and fused and integrated with the homogeneous glassy layer 8. Further, the liquid pigment 4 was oxidized and colored, and a vivid image appeared. In addition, the antistatic agent contained in the glaze 9 evaporated by baking. Further, since the surface of the ceramic plate 1 was previously covered with the vitreous layer 8, bubbles were not generated from the ceramic plate 1 during firing, and bubbles did not enter the glaze 8 to deteriorate the image.
As a drawing material, a metal plate or a glass plate can be used instead of the ceramic plate.
[0019]
【The invention's effect】
As apparent from the above description, according to the present invention , the liquid pigment made of the aqueous metal ion solution is jetted by the ink jet nozzle onto the electrically neutralized unfired glaze layer. In this way, the liquid pigment does not diffuse and a fine drawing can be drawn. In addition, since the aqueous metal ion solution has a larger absolute amount of the metal pigment contained in the unit volume than the chelate compound, the image density can be increased and a clear image can be drawn.
[Brief description of the drawings]
FIG. 1 is a process diagram showing a manufacturing method which is a first reference example ;
FIG. 2 is a process diagram showing a manufacturing method which is a second reference example ;
FIG. 3 is a process diagram showing a first embodiment of the present invention.
FIG. 4 is a process diagram showing a second embodiment of the present invention.
[Explanation of symbols]
DESCRIPTION OF SYMBOLS 1 Ceramics board 2 Antistatic agent 3 Inkjet printer 3a Inkjet nozzle 4 Liquid pigment 5-7, 9 Glaze 8 Glassy layer (surface)

Claims (4)

Electrically neutralizing by mixing an antistatic agent with the unbaked glaze,
Forming a glaze layer of the electrically neutralized unfired glaze on the surface of the drawing material;
A step of injecting a liquid pigment made of an aqueous metal ion solution onto the glaze layer with an inkjet nozzle, and allowing the liquid pigment to penetrate into the glaze layer;
Baking the drawing material at a temperature at which the liquid pigment develops color and the glaze layer is fused to the surface of the drawing material, and the step of eliminating the antistatic agent by baking. A method for producing a fired body. Forming an unfired glaze layer on the surface of the drawing material;
Electrically neutralizing the glaze layer by applying an antistatic agent to the unfired glaze layer;
A step of injecting a liquid pigment made of an aqueous metal ion solution onto the glaze layer with an ink jet nozzle and allowing the liquid pigment to penetrate into the glaze layer;
Baking the drawing material at a temperature at which the liquid pigment develops color and the glaze layer is fused to the surface of the drawing material, and the step of eliminating the antistatic agent by baking. A method for producing a fired body. Electrically neutralizing by mixing an antistatic agent with the unbaked glaze,
Forming a second glaze layer of the electrically neutralized unfired glaze on the first glaze surface of the drawing material having the first calcined face on the surface formed;
Spraying a liquid pigment made of an aqueous metal ion solution onto the second glaze layer with an ink jet nozzle, and infiltrating the liquid pigment into the second glaze layer;
Firing the drawing material at a temperature at which the liquid pigment develops color and the second glaze layer is fused to the first glaze surface, and the antistatic agent disappears by firing. A method for producing a drawn fired body. A step of forming an unfired second glaze layer on the first flange surface of the drawing material on which a first fired flange surface is formed;
Electrically neutralizing the second glaze layer by applying an antistatic agent to the unfired second glaze layer;
Spraying a liquid pigment made of an aqueous metal ion solution onto the second glaze layer with an ink jet nozzle, and infiltrating the liquid pigment into the second glaze layer;
Firing the drawing material at a temperature at which the liquid pigment develops color and the second glaze layer is fused to the first glaze surface, and the antistatic agent disappears by firing. A method for producing a drawn fired body.

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