JPH0345578A - Glazing of multicolor design - Google Patents

Abstract

PURPOSE:To readily obtain multicolor design having alternately varied coloring design by applying glaze in which color is changed by melting with heating in specific gas atmosphere on the surface of substrate material and irradiating the applied glaze with laser light while alternately varying said atmosphere. CONSTITUTION:Glaze varying color by melting with heat in an atmosphere of gas selected from gas reactive with glaze component and inert gas is applied on the surface of substrate material to be glazed. Next, the glazed surface is irradiated with laser light while alternately varying at least two species of gas atmospheres covering said surface coated with glaze to afford the aimed multicolor design. As said substrate material, all of the substrate materials such as porcelain, ceramic article, metallic article or cement substance, etc., capable of glazing are able to be used. In a case of cement substance molded article, however, as thermal deterioration may be generated at glazing, at least the surface layer to be glazed is preferably hydraulic cement or cement substance composed of powder material vitrifying by melting in an effective amount for sintering.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a method for glazing multicolored patterns. Specifically, the surface of a base material coated with a glaze whose color changes depending on the atmosphere during melting is irradiated with laser light while alternating the gas atmosphere covering the surface to create a multicolored pattern whose color changes depending on the atmosphere. The present invention relates to a method of forming an oil layer. According to the present invention, the glaze layer, which has been difficult to form in the past, can be easily formed. 7. Conventional techniques and their problems In order to form a multicolored patterned oil layer on a substrate, conventional techniques such as screen printing or Very thin glaze layers in two or more different colors were printed on the base material using transfer paper, and then fired in a kiln to form an oil layer. However, in the printing or transfer methods, the oil layer is very thin, so it is impossible to form an oil layer with a colored or three-dimensional effect. Also,
Misalignment of printed patterns was also a major problem.

The present invention has unexpectedly solved the above problems.
An easy method of applying the glaze is provided.

Means for Solving the Problems Therefore, according to the invention: A glaze is to be applied which changes color by heating and melting 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. A glaze with a multicolored pattern of alternating colored patterns, which is applied to the surface of a base material and is characterized by irradiating laser light while alternating at least two types of gas atmospheres that cover the glazed surface. A 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, whose color is maintained 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, cementitious materials, and the like. However, in the case of cementitious molded products, thermal deterioration may occur during glazing, so that at least the surface layer of the molded product to be glazed is essentially made of hydraulic cement and an effective amount of sintering vitrification material powder. Preferably, the material is a cementitious material.

At least the surface layer to be glazed of the cementitious molded product is made of hydraulic cement, a sintering effective amount of melting vitrification material powder, magnesium silicate mineral powder, activated silicate mineral powder, aluminum silicate mineral powder, or two or more of these. Desirably, the cementitious layer consists essentially of a mineral powder selected from the group consisting of a mixture of the following, thereby providing a glazing method that further improves the efflorescence of the surface layer.

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 entire molded and cured cementitious material contains hydraulic cement, melt-vitrifying material powder, magnesium silicate mineral powder,
Molding and firing (e.g., at 1000°C or higher) 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.
It is advantageous from the viewpoint of material strength to use a cementitious ceramic material made of

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 an oil layer with a desired thickness and a multicolored pattern, the color of which changes as planned. In this manner, effects that were difficult to achieve with the prior art can be easily achieved by the action different from the prior art.

DETAILED DESCRIPTION OF THE INVENTION As noted 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 particular cementitious base material mentioned above,
Laser light irradiation and color-changing glaze will be described below.

(1) Raw materials for cementitious material As the hydraulic cement, any hydraulic binding material powder such as Portland cement, alumina cement, blast furnace cement, mixed Borland cement, etc. can be used.

The optional aggregate is preferably a stable material that does not undergo rapid expansion or contraction during the heating process (for example, ceramic chamotte), 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 vitrifiable igneous blue 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 viewpoint of its sinterability or high temperature reactivity, and generally has an average particle size of about 50 microns or less. The thickness is usually about 5 to 30 microns. The mineral powder is distinguished from aggregate for cement, and includes (a) one that is activated and sintered during heating and/or
or (b) reacts with the carunium component in cement at high temperature to form a sintered 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) Loading amount of raw materials The table below shows the preferred weight range of the heat deterioration resistant cementitious material containing the vitrifying material powder. To this is added an amount of water necessary for molding and hydration of the cement (for example, 0.1 to 0.5 parts by weight of water per 1 part of cement), and the mixture is mixed and molded. These compounding amounts indicate preferred effective amounts of each raw material to achieve the effects of the present invention.

Typical amounts of raw materials (parts by weight) Hydraulic cement 100 parts Vitrifying material powder Approximately 50-300 parts Mineral powder or mixture of the above (desirable ingredients) Approximately 20-400 parts (preferably approximately 50-300 parts) Aggregate: Approximately 500 to 0 parts Typical raw material content (parts by weight) Hydraulic cement (e.g. Portland cement) 100 parts Vitrifiable material powder (e.g. glass powder) Approximately 50 to 200 parts (e.g. around 100 parts) Silicic acid Magnesium mineral (e.g. serpentine) about 50 to 200 parts (e.g. around 100 parts) Silicate mineral and/or aluminum silicate mineral (e.g. waxite) about 5 to 150 parts (usually about 10 parts)
~100 parts) (For example, around 50 parts) Aggregate: Approximately 300 to 0 parts (For example, around 150 parts) The total amount of other components is generally 600 parts or less with respect to 100 parts of cement.

(3) Irradiation of laser light The laser light used in the present invention is caused by stimulated emission by the energy level system of bound electrons in atoms and molecules.
It refers to a coherent light beam that is made by oscillating and amplifying light waves. Typically, gas lasers such as CO lasers and solid state lasers such as YAG lasers can be effectively used.

The output of the laser device used in the present invention is not particularly limited, but it is usually preferably about 2kw or more, and about 5kw.
It is desirable that it is equal to or greater than w. The distance between the condensing lens of the irradiation device and the surface of the substrate is usually about 100 mm to 300 mm. However, since laser light is difficult to attenuate, there are no particular limitations.

The irradiation area of the laser beam on the substrate is generally about 1 in diameter.
It has a circular shape of about 0 to 50 mm.

When the output of the laser beam is approximately 5 KW, the laser beam is irradiated by scanning the laser gun or the substrate in the left-right direction at a constant scanning speed (usually several cm to several tens of cm/second) at constant scanning intervals (
Depending on the irradiation area of the laser beam, it is usually several mm to several tens of mm)
This is done by moving the

The method of the invention is usually advantageously applied to substrates having a substantially planar surface to be oiled, but can also be applied to substrates having a curved surface.

In addition, when applying oil to the surface of a rod-shaped base material such as a cylindrical or columnar shape, for example, the rod-shaped base material to be oiled can be rotated and relatively moved and irradiated with laser light.

The apparatus used in 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 oiled. Furthermore,
Means are provided for moving the gun support and/or the substrate support in order to apply laser light uniformly over the surface to be oiled. The above-mentioned movement means can be automatically controlled by electronics, if desired. These control means can be easily implemented, for example, based on common technical knowledge of automatic machine tools and the like.

Note that laser light irradiation can be performed using two methods: (a) Since laser light does not substantially attenuate, it can be guided to any location using mirrors, laser fibers, etc.; (b)
Since it is light, there is no influence from constituent materials such as plasma flame; (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) Install a light-transmission-blocking patterned mask immediately before or upstream of the surface to be irradiated, so that the patterned pattern of the mask can be easily irradiated. It has the advantage that it is possible to irradiate

(4) Color-changeable glaze The color-changeable glaze that forms the multicolor pattern used in the present invention is a gas that is reactive with the constituent components of the glaze [e.g., oxidizing gas (oxygen, air, etc.), reducing gases (hydrogen, methane,
A glaze whose color changes when heated and melted in an atmosphere of at least two gases selected from gases such as carbon dioxide (CO, etc.), other reactive gases, and inert gases (nitrogen, rare gases, etc.). 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 when melted under an air atmosphere (oxidizing). That is, it is a homogeneous mixture of 2 parts by weight of CuO as a pigment component and 100 parts by weight of the glaze matrix component described below. The glaze matrix component has the following composition according to the Seegel formula (molar ratio).

Example 1: By weight, 30 parts of glass powder, 30 parts of cement (ordinary Portland cement), 40 parts of porcelain nyamot (particle size 11III11 or less) as aggregate, 16 parts of water, and 1.2 parts of methyl cellulose were added. After mixing and kneading, the mixture was extruded to a size of 50 mm in width, 100 mm in length, and 10 ni in thickness, cured by hydration, and air-dried at 105° C. to obtain a test specimen.

A glaze slurry consisting essentially of 100 parts by weight of the color-changing glaze powder, 150 parts by weight of water and 50 parts by weight of ethanol was spray applied to the upper surface of the test specimen 2 to a thickness of about 0.15 mm.

Using a laser (Cow) gun manufactured by Shimada Rika Kogyo Co., Ltd., two gas jet nozzles are installed below the condenser lens 5.
8 was installed, and while nitrogen gas 6 and air were alternately sprayed onto the glaze-coated surface 3 at 4-second intervals, laser light 4 was irradiated under the following conditions, and the glaze was allowed to cool. (Although a low-output laser was used in this example, a laser with an output of 5 KW or more is desirable industrially.) Laser light energy density: approximately 200 W/cm2
Distance between condensing lens/citron surface: Approx. 30C+N Gun scanning speed (left/right direction): Approx. 8 cm 1 minute Gun scanning interval (width direction): Approx. 81 In this way, the coloring is subtly colored in red and blue-green. Beautiful two-color oiling layer 3 (thickness approximately 0゜1 mm)
) was obtained. Note that no deterioration in strength of the cementitious surface layer due to laser light irradiation was observed.

Example 2: Using the test specimens (1), (2), and (3) below, oil was applied in the same manner as in Example 1 while alternately blowing nitrogen and air.

(1) Waxite 2 as aluminum silicate mineral in parts by weight
0 parts, 20 parts of glass powder, 20 parts of ordinary Portland cement as cement, porcelain Nyamot (particle size 1
g+m or less), 17N of water (and 1 part of methyl cellulose), kneaded, and extruded to a width of 50.
It was molded into a size of 1 Goms in length and 1 hffi in thickness, hydrated and cured, and dried to obtain a test specimen.

(2) By weight, 20 parts of serpentine as magnenium silicate mineral, 20 parts of glass powder, 20 parts of ordinary Portland cement as cement, 40 parts of porcelain chamotte (particle size 1.mm or less) as aggregate, 17 parts of water, and methylcellulose. After mixing 1 part and kneading this, it was extruded into a width of 5 mm.
The sample was molded to a size between 0 mm+, length 100+ni, and thickness 10, hydrated, cured, and dried to give a test specimen.

(3) The following mixture (parts by weight) was used as a raw material.

Ordinary Portland cement 100 parts Serpentine (1
(50 mesh or less) 50 parts Glass powder (100 mesh or less) I25 parts Waxite (20
0 mesh or less) 25 parts Colored chamotte aggregate (particle size 1n++n or less) 200 parts Water and methyl cellulose were added to the above mixture, kneaded, extruded to a width of 50I11 and a thickness of 10nffi, and cut into lengths of 100+u+ to prepare samples. And so. The samples were hydrated and air dried at 105°C to prepare test specimens.

In this way, a cementitious board having a dichromatic oiling layer similar to that of Example 1 was obtained. The oil-applied 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 specimens were prepared as follows. That is, 63 weight S of a mixture of raw talc and pottery stone and 30 weight S of a mixture of feldspar and petalite are mixed, and a cotton layer is formed in a ball mill until the particle size of feldspar becomes about 2 microns or more to form a slurry. After mixing slurry clay 7S with this, it is dehydrated and milled to make clay. Press this clay at a pressure of 300
The molded body (1
00x 100x 5mm).

This molded body was fired in a tunnel kiln at a maximum temperature of 1150° C. for 36 hours to obtain a tile with a quality of 4.

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. An oil plate having a beautiful two-color glaze layer similar to that of Example 1 was obtained.

[Brief explanation of drawings]

FIG. 1 is an explanatory diagram of forming a multicolored patterned glaze layer by irradiating a laser beam in a gas atmosphere. ■... Oiled base material: 2... Base material plate; 3... Glaze layer; 4... Laser light beam: 5... Condensing lens; 6... Atmospheric gas 7. 8. Gas jet nozzle.

Claims (4)

[Claims] (1) A glaze that changes color by heating and melting 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 the substrate to be glazed, and the glaze is applied. A method of glazing a multicolored pattern with alternating colored patterns, characterized by irradiating laser light while alternating at least two types of gas atmospheres that cover the 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. The glazing method according to claim 1, wherein: the glaze layer, the surface layer of the cementitious material, and the bonding strength inside the surface layer are improved. (3) At least the surface layer of the molded article is made of hydraulic cement,
a cementitious layer consisting essentially of a sintering effective amount of meltable vitrifiable material powder and a 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 thereof; The glazing method according to claim 2, wherein the efflorescence of the surface layer is further improved. (4) The entire molded and cured cementitious material is selected from the group consisting of hydraulic cement, melt-vitrifying material powder, magnesium silicate mineral powder, activated silicate mineral powder, aluminum silicate powder, and mixtures of two or more of these. 3. The glazing method of claim 2, wherein the glazing is a cementitious ceramic material formed and fired, consisting essentially of selected mineral powders.