JPS6015598B2 - Manufacturing method of sintered body - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing aggregates for ceramics, tile products, etc., and particularly to a method for producing aggregates with a sketch.

Conventionally, various methods have been used for painting ceramics or tiles, such as hand-painting, screen printing, and transfer.

However, the hand-drawing method is time-consuming because it is done manually, and the same pattern cannot be reproduced, making it impractical for industrial production.
In addition, although the screen printing method and the transfer method have good reproducibility of the image, when the yuzu is applied directly onto the image, the polymer contained as an ink binder in the transferred pattern layer generally has a small surface energy and poor absorption, so it is difficult to absorb water. The mixed liquid consisting of yuzu and yuzu medicine is repelled by the pattern surface, making it difficult to hang the pongee evenly. If the firing is continued in this state, the yuzu layer will not be placed on the design and it will not be an underpainting. Therefore, conventionally,
Before pongee hanging, preliminary adhesion was performed to remove the polymer, removing excess components (particularly polymer components) in the pattern, and making sure that the yuzu slurry was placed on the pattern as well.

Conventionally, this meant that firing required two times, a preliminary firing and a main firing, which was a drawback when taking into account the time and cost involved. The present invention provides an underpainting technique that can omit the above-mentioned preliminary firing step after firing, and aims to obtain a underpainted competitive twilled body with only one firing.

In other words, the surface of the transferred pattern is made to have a finely uneven or porous shape, which makes it easier for the mixture of water and pure medicine to adhere to the pattern. A transfer pattern layer is formed on the rough surface of a base material having a paper surface, and the pattern is then transferred to the late-set material surface. By doing this, the transferred pattern layer has a shape that is a copy of the rough surface of the transfer paper base material, and has a finely uneven surface, so it has water retention properties.Another convenient method is: The composition of the transfer paper is:
It can be broadly divided into a base material and a transfer pattern layer, and among the transfer pattern layer, there is an adhesive layer that adheres to the base surface of ceramics, tiles, etc. by heating and pressure, a pattern ink layer containing pigments for painting ceramics and tiles, and a foaming agent is contained in at least one layer of the peeling layer that separates the base layer and the transfer pattern supply layer.

A pattern is transferred to the base surface of the sintered body using a transfer paper for underpainting having such a transfer pattern layer, and then the transferred pattern is subjected to a foaming treatment. By doing this, the surface is made finely porous or uneven, giving it water-retaining properties for post-hanging, and it becomes possible to hang the citron evenly as with the above-mentioned means. These two means are effective even when used alone, but are even more effective when used together. Also, a mixture of pongee medicine and water is sufficient for hanging yuzu, but it is better to add a surfactant to increase the affinity for the base surface and pattern surface. . Although the explanation has been complicated, the transfer painting method adopted in the present invention is a dry heat transfer method, and compared to the conventional wet transfer method, this method eliminates the complexity of the transfer process and the post-transfer washing and drying process. It can be easily mechanized and suitable for mass production. Further, when it is necessary to improve the suitability for printing on a cold material having a rough surface, a sealing layer may be provided on the base material, and then the transfer pattern layer described above may be formed.

To explain the present invention in more detail below, cellophane, polyester film, etc. are generally used as base materials for dry heat transfer methods, and the transfer layer obtained by transfer reproduces the smoothness of the base material and is relatively smooth. Become something.

As mentioned before, when using this method to apply yuzu to a sintered body such as ceramics or tiles that have transfer paintings, the wetting of the pure medicine is poor and a so-called repelling phenomenon occurs, making it difficult to apply the pongee medicine uniformly. Another major drawback is that it takes a long time for the water from the citron to permeate into the tiles. For this reason, preliminary firing is required to decompose and eliminate the resin content. In the present invention, we have discovered a method that eliminates these drawbacks and can omit firing to one step. The structure of the transfer paper will be explained.

A major feature of this transfer paper is that it uses a base material with a lees-like surface as the base material for the transfer paper.

Specifically, the base materials include high-quality paper, matte art paper, pseudo-art paper, and matte polyester film. When such paper is used, the surface of the transferred layer is uneven and more porous than art paper, polyester film, etc., which have good smoothness. For this reason, when the surface is sprinkled with citron, the pure chemical penetrates into the pores, improving wettability and water absorption. When paper is used, a basis weight of 30 to 60 m/m is appropriate in consideration of heat conduction efficiency during transfer or tensile strength during printing.

In addition, it is appropriate that the paper surface has a roughness of 7 degrees or more in the stylus method.

The adhesive layer is a resin that can impart adhesive properties to the base of Akatsuki compacts such as ceramics and tiles by pressurizing and heating.
Thermoplastic resins such as polyamides and acrylic maleic resins are suitable. The ink layer uses a resin binder that holds pigments for ceramics and tiles that have excellent high-temperature resistance and does not cause cracks or pinholes during firing.

The release layer is between the base material or the base material/blocking layer and the release layer,
It can be peeled off by pressure and heating, and the resin content can be completely eliminated by firing. Furthermore, when a sealing layer is provided, the sealing layer should be one that improves printability without impairing the wettability and water absorption of the yuzu medicine, and that peels off between the release layer and the sealing layer during transfer and peeling. It is.

When a foaming agent is added to the entire transfer layer, air bubbles are generated by foaming treatment such as heating, and fine pores are generated throughout the transfer layer, resulting in uniform stagnation of the pure chemical during pongee making.
This makes the water absorption even more effective, and also makes it possible to shorten the application time.

Foaming agents include inorganic foaming agents such as sodium bicarbonate and ammonium bicarbonate, azodicarbonamide, azobisisobutyronitrile, diazoaminobenzene, N,N'-methyl N
, N'-dinitrosoterephthalamide, benzenesulfonylhydrazide, P-toluenesulfonylhydrazide, and the like. Among the above-mentioned foaming agents, inorganic foaming agents such as ammonium carbonate, ammonium bicarbonate, and sodium bicarbonate, which generate carbon dioxide gas and easily generate open cells throughout the transfer paper layer, are more effective. Note that the effect is recognized when the amount of the foaming agent added to each of the release layer, ink layer, and adhesive layer constituting the transfer layer is within 100% by weight based on the resin content constituting each layer. To transfer the transfer paper with the above-mentioned structure to a solid base material such as ceramics or tiles using the dry heat transfer method, apply the adhesive layer of the transfer paper to the sintered base material such as ceramics or tiles, and heat it from the base material side. Pressure is applied using a rubber roll, and the transfer painting is applied. Next, for painted tiles to which a foaming agent has been added, the added foaming agent is foamed by heating, etc. to improve the wetting of the pongee agent during application, improve water absorption, and shorten the pongee application time, and the entire transfer layer is heated. This creates continuous fine pores in the material, making it porous. Next, the pongee making process will be explained.

The tiles with the transferred paintings as described above are hung with yuzu using a mixture of water and pongee medicine, or a mixture prepared by adding a surfactant to yuzu and water and dispersing the solution.

The surfactants used here include anionic surfactants such as sulfonates, sulfates, phosphate salts, soaps, etc.
Aliphatic amine salts and ammonium salts, long-chain thiuronium compounds, cationic surfactants such as alkylpyridium salts, polyethylene oxide type, polyhydric alcohol type,
These include nonionic surfactants such as glyceride type and alkylolamide type, and zwitterionic surfactants such as carboxylic acid type, sulfuric acid type, and sulfonic acid type. Among these, the addition of anionic and nonionic surfactants was particularly effective. The effect is observed when the amount added is within 1% by weight relative to the amount of water added. When pongee hanging is carried out using a mixture of sode medicine and water, the above-mentioned action will result in uniform wetting of the pongee medicine,
Water absorption is improved, and this effect is even more enhanced when using a mixed solution of water and yuzu medicine containing a surfactant, and this is sufficient for transfer tiles that have been foamed by adding a foaming agent. It is effective, and the pure chemical is evenly applied to the painted surface of the tile base, improving water absorption and water absorption, making it possible to shorten the pongee application time.

To fire a mass of ceramics, tiles, etc. that has been treated in this way, the firing time is 10 to 24 hours, and the maximum temperature is 1.
It is best to carry out the test under the conditions of 00:00 to 1,300:00. According to this method, the resin content of the transfer layer is decomposed and removed at around 300 to 60,000, and as the temperature rises further, the pongee is fired.
In this method, the step of decomposing and removing the resin component and the step of firing the yuzu medicine are performed in the same process, and there is no need to separate the step of decomposing and removing the resin component and the step of firing the pure chemical as in the conventional method, thereby improving work efficiency. Example 1 Transfer paper composition Motomura High quality paper 35 sheets/
Force release layer Ink layer Adhesive layer After a self-locking treatment consisting of three layers of polyethylene glycol/polyamidonopolyethylene glycol was performed on the high-quality paper, the above composition was further printed in the order of release layer, ink layer, and adhesive layer. Transfer paper was obtained.

The adhesive layer was applied to the tile base using this transfer paper, and pressure was applied from the base material side with a rubber roller heated to 23,030°C to perform painting by dry heat transfer. Next, when the transferred tile was hung with a mixed solution of water and yuzu, the yuzu was uniformly wetted and had good water absorption. Furthermore 70qo/H
When the temperature was raised to a maximum of 1,090° C. and fired at a heating rate of r, a tile product with good pattern reproducibility was obtained. Example 2 In Example 1, when applying yuzu using a mixed solution of pure medicine and water to which 5% by weight of nonionic surfactant was added, good wetting and water absorption of pongee medicine were obtained. It was done.

Furthermore, the tiles obtained by firing under the same conditions as in Example 1 had good pattern reproducibility. Example 3 Transfer layer configuration Release layer Ink layer Ink layer Sodium bicarbonate 10 Adhesive layer After performing sealing treatment consisting of three layers of polyethylene glycol/bolyamide/polyethylene glycol on high-quality paper (35 sheets/force), The above composition was printed in the order of a release layer, an ink layer, and an adhesive layer to obtain a transfer paper.

The adhesive layer was applied to the tile base using this transfer paper, and the rubber was heated to 240°C from the base material side. The transfer painting was applied using a dry heat method. Thereafter, the film was kept in a gear oven maintained at 200° C. for 2 minutes to carry out a foaming treatment to obtain a porous transfer layer. Next, when I sprinkled yuzu on the painted surface of the transfer tile that had been foamed with a mixture of water and coffin, not only was the pure medicinal substance filled, but the water absorption was also in good condition, and the cuff-hanging time was shortened, resulting in foaming. The effect of adding the agent was observed. When this pongee tile was heated to a maximum temperature of 1,090° C. at a heating rate of 70 qo/hr and fired, a tile product with good pattern reproducibility was obtained.

Example 4 In Example 3, when making pongee, a combination of water to which 5% by weight of the nonionic surfactant polyoxyethylene nonyl phenyl ether or polyoxyethylene octylphenyl ether was added and citrus When pongee was applied to the surface of a foam-treated painted tile using the mixed solution, the pongee medicine was well wetted and had good water absorption, and the pongee application time was also shortened.

As a result, the effects of adding the foaming agent to the transfer layer and the addition of the surfactant to the mixed solution of pongee and water were observed. When firing was carried out under the same conditions as in Example 3, a tile product with good pattern reproducibility was obtained.

Claims (1)

[Claims] 1. A pattern is transferred onto the base surface of a sintered body using a transfer paper for underpainting, which has a transfer pattern layer on the rough surface of a base material having a rough surface, and then a glaze and water are applied. A method for producing a sintered body having a pattern, which comprises glazing with a mixture of the above and then firing it. 2. The method for producing a sintered body according to claim 1, wherein glazing is performed using a liquid mixture of glaze and water to which a surfactant is further added. 3 Transfer the pattern onto the base surface of the sintered body using a transfer paper for underpainting, which has a transfer pattern layer containing a foaming agent on the rough surface of the base material having a rough surface, and then transfer the transferred pattern. A method for manufacturing a sintered body having a pattern, which comprises performing foaming treatment, glazing with a mixture of glaze and water, and then firing. 4. The method for producing a sintered body according to claim 3, wherein glazing is performed using a liquid mixture of glaze and water to which a surfactant is further added.