JPH0567594B2 - - Google Patents

Description

[Detailed description of the invention]

FIELD OF INDUSTRIAL APPLICATION The present invention relates to a method for glazing with multicolored patterns. Specifically, the surface of the base material coated with a glaze whose color changes depending on the atmosphere during melting was irradiated with laser light while alternating the gas atmosphere covering the surface, and the color changed depending on the atmosphere. This invention relates to a method for forming a glaze layer with a multicolored pattern. According to the present invention, the glaze layer, which has conventionally been difficult to form, can be easily formed. Conventional techniques and their problems In order to form a multicolored patterned glaze layer on a substrate, conventionally, very thin layers of two or more different colors are printed on the substrate by screen printing or transfer paper. The glaze layer was printed and fired using a kiln to form the glaze layer. However, with printing or transfer methods, it has been impossible to form a glaze layer with a sense of color or three-dimensionality because the glaze layer is very thin. In addition, misalignment of printed patterns was also a major problem. The present invention unexpectedly provides a simple glazing method that overcomes the above problems. Means for Solving the Problems According to the present invention: A glaze whose color changes when heated and melted in an atmosphere of a gas selected from the group consisting of a gas reactive with the components of the glaze and an inert gas. is applied to the surface of the substrate to be glazed, and the glazed surface is irradiated with laser light while alternating at least two types of gas atmospheres covering the glazed surface. A color pattern glazing method is provided. The above-mentioned method of "covering the glaze-applied surface with a gas atmosphere" can be easily achieved by spraying the atmospheric gas onto the application surface. In the case of an air atmosphere, it is possible to create an air atmosphere to some extent even without blowing air because the laser beam has no exhaust property. The pigment component of the glaze, which is colored by heating under a specific atmosphere, is substantially covered by the vitrification component of the glaze, so that the color is stably maintained. As the above-mentioned base material, all base materials that can be glazed by conventional methods can be used, such as ceramics, ceramic products, metal products, and cementitious materials. However, in the case of a cementitious molded product, it may be thermally degraded during glazing, so at least the surface layer to be glazed of the molded product is essentially made of hydraulic cement and a sintering effective amount of meltable vitrifying material powder. Preferably, it is a cementitious material. At least the surface layer to be glazed of the cementitious molded product comprises hydraulic cement, a sintering effective amount of melting vitrifying material powder, and magnesium silicate mineral powder,
The cementitious layer is preferably made essentially of mineral powder selected from the group consisting of activated silicate mineral powder, aluminum silicate mineral powder, and mixtures of two or more of these, thereby further improving the efflorescence of the surface layer. A glazing method is provided. In addition, since the above-mentioned mineral powders, glass powders, etc. are relatively inexpensive, the entire molded and cured cementitious material contains hydraulic cement, a sintering effective amount of melting vitrifying material powder, magnesium silicate mineral powder, It can be a cementitious material formed by molding and hydrating a mixture consisting essentially of mineral powder selected from the group consisting of activated silicate mineral powder, aluminum silicate mineral powder, and mixtures of two or more of these. . The cementitious molded and cured product as a whole is made of hydraulic cement, melt-vitrifying material powder, and mineral powder selected from the group consisting of magnesium silicate mineral powder, activated silicate mineral powder, aluminum silicate mineral powder, and mixtures of two or more of these. From the viewpoint of material strength, it is advantageous to use a cementitious ceramic material formed by molding and firing (for example, at 1000° C. or higher). Functions and Effects According to the present invention, one type of glaze is applied to the required surface of the base material by spraying or the like, so the glaze can be easily applied to the required thickness. It is possible to arbitrarily change the gas atmosphere during laser beam irradiation.
Therefore, it is easy to obtain a glaze layer with a desired thickness and a multicolored pattern in which the colors change as planned. In this manner, effects that were difficult to achieve with the prior art can be easily achieved due to the effect that is different from that of the prior art. DETAILED DESCRIPTION OF THE INVENTION As mentioned above, any substrate that can be glazed by conventional methods can be used in the present invention. Since laser light is a high-temperature beam, there are no particular limitations on the melting temperature of the glaze used. Therefore, the above-mentioned specific cementitious base material, irradiation with laser light,
and color-changing glazes are described below. (1) Raw materials for cementitious materials As hydraulic cement, any hydraulic binding material powder such as Portland cement, alumina cement, blast furnace cement, mixed Portland cement, etc. can be used. As for the optional aggregate, it is preferable to use a stable material that does not undergo rapid expansion or contraction during the heating process (for example, ceramic shamotzu), and river sand, sea sand, silica sand, andesite, basalt, hard sandstone, etc. can also be used. . The vitrifying material powder described above forms a flux such as a glassy melt when heated and penetrates between particles of other materials to achieve a sintering effect. Specific examples include various glass powders, commercially available frits, feldspar, shirasu, volcanic ash, and other vitrifying igneous rock powders. Usually glass powder, feldspar powder or a mixture thereof is used. The mineral powder selected from the above group (the preferred ingredient) needs to be finely granular from the point of view of its sinterability or high temperature reactivity, and generally has an average particle size of about 50 microns or less. And usually it is about 5 to 30 microns. The mineral powder is distinguished from aggregate for cement, and is (a) activated and sintered during heating and/or (b) sintered by high-temperature reaction with calcium components in cement. It forms a high-strength material. Examples of the magnesium silicate mineral powder containing a silicic acid component and a magnesium oxide component include powders of talc, serpentine, chlorite, and the like. Usually serpentine powder, talcum powder or mixtures thereof are advantageously employed. Active silicate mineral powders or aluminum silicate mineral powders containing silicic acid components and aluminum oxide components include amorphous silica, finely powdered silica sand (coarse silica sand for aggregate is ineffective), pyrophyllite powder, kaolin or Clay mineral powders such as sericite are exemplified. Typically, waxite, finely divided silica sand, amorphous silica or mixtures thereof are advantageously used. (2) Amounts of raw materials blended The table below shows the preferred range of blended weights of heat deterioration resistant cementitious materials containing vitrifying material powder. Add to this the amount of water required for shaping and hydration of the cement (e.g.
Add 0.1 to 0.5 parts by weight of water), mix, and shape. These compounding amounts indicate preferred effective amounts of each raw material to achieve the effects of the present invention. Amounts of general raw materials (parts by weight) Hydraulic cement 100 parts Vitrifying material powder Approximately 50 to 300 parts Mineral powder or mixture mentioned above (desirable ingredients)
Approximately 20-400 parts (preferably approximately 50-300 parts) Aggregate Approximately 500-0 parts Typical raw material content (parts by weight) Hydraulic cement (e.g. Portland cement)
100 copies. Vitrifiable material powder (e.g. glass powder)
Approximately 50 to 200 parts (e.g. around 100 parts) Magnesium silicate mineral (e.g. serpentine)
Approximately 50 to 200 parts (e.g. around 100 parts) Silicate mineral and/or aluminum silicate mineral (e.g. waxite) Approximately 50 to 150 parts (usually approximately 10 to 100 parts) (For example around 50 parts) Aggregate Approximately 300 to 0 parts (for example, around 150 parts) In addition, the total amount of other ingredients is generally 600 parts or less per 100 parts of cement. (3) Irradiation of laser light The laser light used in the present invention means a coherent light beam obtained by oscillating and amplifying light waves by stimulated emission by an energy level system of bound electrons in atoms and molecules. Typically,
Gas lasers such as CO ₂ lasers and solid state lasers such as YAG lasers can be used effectively. Although the output of the laser device used in the present invention is not particularly limited, it is usually preferably about 2 kW or more, and desirably about 5 kW or more. The distance between the condensing lens of the irradiation device and the surface of the substrate is usually about 100 mm to 30 mm. However, since laser light is difficult to attenuate, there are no particular limitations. The area irradiated with the laser beam on the base material is generally circular with a diameter of about 10 to 50 mm. The output of laser light irradiation is approximately 5KW, for example.
In the case of
The laser beam is moved at fixed scanning intervals (usually several mm to several tens of mm, depending on the area irradiated with the laser beam). The method of the invention is usually advantageously applied to substrates having a substantially planar surface to be glazed, but can also be applied to substrates having a curved surface. In addition, when applying a glaze to the surface of a rod-shaped base material such as a cylinder or a cylinder, the rod-shaped base material to be glazed can be relatively moved while rotating, and the laser beam can be irradiated, for example. The apparatus used according to the invention essentially consists of at least one laser gun and a support respectively holding the laser gun and, if necessary, the substrate to be glazed. Furthermore, means are provided for moving the gun support and/or the substrate support in order to uniformly apply the laser light over the entire surface to be glazed. The movement means described above can be automatically controlled by electronics if required. These control means can be easily implemented, for example, based on common technical knowledge of automatic machine tools and the like. Laser light irradiation is: (a) Laser light does not substantially attenuate, so it can be guided to any location using mirrors, laser fibers, etc., and (b) Since it is light, plasma flame can be (c) The shape and energy distribution of the irradiation beam can be changed freely by using an optical system; (d) There is little influence from wind, etc.; (e) The surface to be irradiated. By installing a light-transmitting pattern mask immediately before or upstream of the mask, it is possible to easily irradiate the mask pattern. There are advantages such as (4) Color-changeable glaze The color-changeable glaze that forms the multicolored pattern used in the present invention refers to gases that are reactive with the constituent components of the glaze [e.g., oxidizing gases (oxygen, air, etc.),
The color changes when heated and melted in an atmosphere of at least two gases selected from reducing gases (hydrogen, methane, CO, etc.), other reactive gases, and inert gases (nitrogen, rare gases, etc.) It means glaze. Typical examples of glaze components that change color upon heating and melting include compounds (eg, oxides) of metals such as copper and iron. In the examples of the present invention, a glaze having the following composition was used, which changes color from red when melted under a nitrogen atmosphere (inert) to blue-green under an air atmosphere (oxidizing). That is, CuO2 as a pigment component
parts by weight and 100 parts by weight of the following glaze matrix components. The glaze matrix component has the following composition according to the Seegel formula (molar ratio).

[Table] Specific example 1 By weight, 30 parts of glass powder, 30 parts of cement (ordinary Portland cement), 40 parts of porcelain shimotsu (particle size 1 mm or less) as aggregate, 16 parts of water, and 1.2 parts of methylcellulose were mixed. After kneading, the mixture was extruded into a size of 50 mm in width, 100 mm in length, and 10 mm in thickness, cured by hydration, and air-dried at 105°C to prepare a test specimen. 100 parts by weight of the above color-changing glaze powder, 150 parts by weight of water
About 0.15 parts by weight of a glaze slurry consisting essentially of 50 parts by weight of ethanol and 50 parts by weight of
Spray coated to a thickness of mm. Using a laser (CO ₂ ) gun manufactured by Shimada Rika Kogyo Co., Ltd., two gas jetting nozzles 7 and 8 were installed below the condenser lens 5, and nitrogen gas 6 and air were injected at intervals of 4 seconds. While spraying the glaze on the surface 3 alternately, the laser beam 4 was irradiated under the following conditions, and the glaze was allowed to cool. (Although a low-power laser was used in this example, a laser with an output of 5KW or higher is desirable for industrial purposes.) Laser light energy density: Approx. 200W/parallel cm Distance between condenser lens/glaze surface: Approx. 30cm Gun Scanning speed (horizontal direction): approx. 8 cm/min Gun scanning interval (width direction): approx. 8 cm In this way, the beautiful two-tone glazed layer 3 (thick agreement
A glazed plate 1 having a diameter of 0.1 mm) was obtained. Note that no deterioration in strength of the cementum surface layer due to laser light irradiation was observed. Example 2 Using the following test specimens (1), (2), and (3), glazing was carried out in the same manner as in Example 1 while alternately blowing out nitrogen and air. (1) By weight: 20 parts of waxite as aluminum silicate mineral, 20 parts of glass powder, 20 parts of ordinary Portland cement as cement, 40 parts of porcelain shamotzu (particle size 1 mm or less) as aggregate, 17 parts of water, and 1 part of methylcellulose. After mixing and kneading, it was extrusion molded into a size of 50 mm in width, 100 mm in length, and 10 mm in thickness, hydrated, cured, and dried to obtain a test specimen. (2) By weight, 20 parts of serpentine as magnesium silicate mineral, 20 parts of glass powder, 20 parts of ordinary Portland cement as cement, 40 parts of porcelain shamotzu (particle size 1 mm or less) as aggregate, 17 parts of water, and 1 part of methylcellulose. After mixing and kneading, extrusion molding is performed to make a product with a width of 50 mm, a length of 100 mm, and a thickness of 10 mm.
It was molded to a size of mm, hydrated and cured, and dried to obtain a test specimen. (3) The following mixture (parts by weight) was used as a raw material. Ordinary Portland cement 100 parts serpentine (150 mesh or less) 50 parts glass powder (100 mesh or less) 125 parts waxite (200 mesh or less) 25 parts colored syamoto aggregate (particle size 1 mm or less) 200 parts Water and Methyl cellulose was added and kneaded, extrusion molded to a width of 50 mm and a thickness of 10 mm, and the sample was cut to a length of 100 mm. The samples were hydrated and air dried at 105°C to form test specimens. In this way, a cementitious board having a dichromatic glazed layer similar to that of Example 1 was obtained. The glazed plate of this example is further characterized in that there is substantially no risk of efflorescence on its unglazed surface and side surfaces. Example 3 Ceramic tile test specimens were prepared as follows. That is, 63% by weight of a mixture of raw talc and pottery stone and 30% by weight of a mixture of feldspar and petalite are mixed and ground into a slurry using a ball mill until the particle size of the feldspar becomes approximately 2 microns or more.
After mixing 7% slurry clay with this, it is dehydrated and milled to make clay. This clay was pressed at a press pressure of 300 kg/cm2 to form a molded product (100 x 100 x 5 mm) with a filling rate of 0.7.
Form into. This molded body was fired in a tunnel kiln at a maximum temperature of 1150° C. for 36 hours to obtain a tile made of brick. A glaze was applied to the surface of this tile base material in the same manner as in Example 1, and the glaze was applied by irradiating laser light while alternately jetting nitrogen and air. A glazed plate having a beautiful two-color glaze layer similar to that in Example 1 was obtained.

[Brief explanation of the drawing]

FIG. 1 is an explanatory diagram of forming a multicolored patterned glaze layer by irradiating a laser beam in a gas atmosphere. 1... Glazed base material; 2... Base material plate; 3... Glazed layer; 4... Laser beam; 5... Condensing lens; 6... Atmosphere gas; 7, 8... Gas jetting nozzle.

Claims (1)

[Claims] 1. A glaze whose color changes when heated and melted in an atmosphere of a gas selected from the group consisting of a gas that is reactive with the components of the glaze and an inert gas is applied to the surface of a substrate to be glazed. A method for applying a multicolor pattern with alternating colored patterns, characterized by irradiating laser light while alternating at least two types of gas atmospheres covering the glazed surface. 2. The base material is made of a cementitious molded and cured product, and at least the surface layer to be glazed of the molded product is characterized in that it consists essentially of hydraulic cement and a sintering effective amount of meltable vitrifying material powder; 2. The glazing method according to claim 1, wherein the glaze layer, the surface layer of the cementitious material, and the bonding strength within the surface layer are improved. 3. At least the surface layer of the molded product contains hydraulic cement, a sintering effective amount of melting vitrification material powder, magnesium silicate mineral powder, activated silicate mineral powder,
The glazing method according to claim 2, wherein the efflorescence of the surface layer is further improved, the cement mass consisting essentially of mineral powder selected from the group consisting of aluminum silicate mineral powder and mixtures of two or more thereof. 4. The cementitious molded cured product as a whole is made of hydraulic cement, molten vitrifiable material powder, and minerals selected from the group consisting of magnesium silicate mineral powder, activated silicate mineral powder, aluminum silicate mineral powder, and mixtures of two or more of these. 3. The glazing method according to claim 2, wherein the glazing material is a cementitious ceramic material formed essentially from powder and formed and fired.