JP2843918B2 - Patterning sheet for firing, method for producing the same, and method for forming firing pattern - Google Patents

Description

The present invention relates to a firing pattern sheet comprising a non-glass ceramic sheet provided with a metal pattern and an adhesive layer containing a non-glass ceramic powder, and a method for producing the same. Further, the present invention relates to a method for forming a fired pattern formed of a fired body of such a sheet and having excellent sharpness and the like.

Conventional technologies and issues As the production system changes to small-lot, high-mix production, products such as metal or fired ceramic, or semi-finished products, parts, etc. have been used as identification labels for management. In the case of using a substrate type body consisting of a body, etc., it takes a lot of time to fix a curved surface due to rigidity, to lack the possibility of forming an identification label due to patterning in the field, etc., and to fix it with screws. Since there is a problem of lack of easy fixability, a pattern sheet for firing is proposed in which a pattern made of ink using glass powder is applied by a screen printing method to a sheet in which glass powder is preserved with a wax-based binder. Have been. This is such that the fired body is fixed to the adherend by firing, and has flexibility and a special label-forming property, and the fired body has excellent scratch resistance, heat resistance, and chemical resistance.

However, in a production system with a large variety of small quantities, the screens to be prepared in advance are enormous, and the preparation requires a lot of time and labor. There is a problem that a pattern in the fired body formed by the treatment is blurred and a sharp pattern is not formed. Such bleeding may cause illegibility or misidentification in the case of an identification label such as a barcode pattern in addition to poor appearance. Even if an adhesive layer is provided so that it can be temporarily temporarily attached to an adherend, the adhesion between the adherend and the formed fired body after firing may be poor, and the stability of the fired adhesive force is poor. There were also problems.

Means for Solving the Problems The present inventors overcame the above-mentioned problems, and as a result of intensive research to develop a firing pattern sheet capable of forming a sharp firing pattern, as a result, a non-glass ceramic The present inventors have found that the object can be achieved by combining a sheet, a metal-based pattern that changes to an oxide upon firing, and an adhesive layer containing a non-glass-based ceramic powder, and have accomplished the present invention.

That is, the present invention has a pattern made of a powder of a metal or a metal compound which can be an oxide when fired, and has a non-glass based ceramic powder on one surface of a ceramic sheet formed by preserving a non-glass ceramic powder with a resin binder. A baking pattern sheet comprising a pressure-sensitive adhesive layer containing ceramic powder, and a heat-fixable ink comprising a powder of a metal or a metal compound which can become an oxide during baking and a heat-fusible binder. Through a thermal transfer printer using an ink sheet held by a material, a step of forming a pattern on one side of the ceramic sheet, and before or after forming the pattern, a non-glass ceramic powder on the other side of the ceramic sheet A method for producing the pattern sheet for firing, comprising a step of attaching a pressure-sensitive adhesive layer to be contained, and The pattern sheet for firing is temporarily attached to the heat-resistant adherend via the adhesive layer, or the ceramic sheet is temporarily attached to the heat-resistant adherend via the adhesive layer, and then a pattern is provided thereon. After forming the above-mentioned pattern sheet for firing, this is heated in an oxidizing atmosphere to fix the ceramic sheet to the heat-resistant adherend while firing, and the powder of the metal or metal compound forming the pattern is formed of metal oxide. And fixing to a fired body of a ceramic sheet while changing the firing pattern.

Action The above-described ceramic sheet has flexibility and curved surface adhesion, and can be provided with a pattern by an appropriate printing method such as a thermal transfer printer or screen printing.
In addition, temporary attachment can be easily performed on the adherend via the adhesive layer.

On the other hand, the baking pattern sheet is formed into a baking body while preserving the pattern applied thereto, and is fixed to the heat-resistant adherend. At this time, the powder of the metal or metal compound forming the pattern changes into a metal oxide and reacts with the ceramic sheet to form a composite oxide, etc., and exhibits a color peculiar to the oxide to exhibit heat resistance, abrasion resistance, A baking pattern with excellent chemical properties and excellent sharpness is formed. Further, it is stably baked and fixed to the heat-resistant adherend via the non-glass ceramic powder contained in the adhesive layer, and is excellent in its fixing force.

Illustrative Components of the Invention The ceramic sheet used in the present invention is obtained by preserving non-glass ceramic powder with a resin binder.

As the non-glass-based ceramic powder, a powder that adheres to the heat-resistant adherend by reacting during firing or the like is used.
Therefore, an appropriate type of ceramic powder may be used according to the heat-resistant adherend to be fixed. Generally, alumina, zirconia, alumina / silica, calcium oxide, magnesia and the like are used. The particle size of the powder is 0.1-100 μm, especially 0.1.
5 to 20 μm is appropriate.

As the resin binder, one that is thermally decomposed and disappears during firing is used, and the type thereof is not particularly limited. Generally, hydrocarbon resins, vinyl or styrene resins, acetal resins, butyral resins, acrylic resins, polyester resins, urethane resins, cellulose resins and the like are used. The amount of the resin binder used may be appropriately determined according to the specific gravity and particle size of the ceramic powder used in combination. Generally 5 to 1 per 100 parts by weight of ceramic powder
00 parts by weight, especially 15 to 50 parts by weight, are used.

The formation of the ceramic sheet can be performed by, for example, a method in which components to be formed are mixed by a ball mill or the like using a solvent or the like, and the mixed solution is spread on a supporting substrate such as a separator by an appropriate method and dried. As the spreading method, the doctor blade method is preferable from the viewpoint of the control accuracy of the layer thickness. It is preferable to perform a sufficient defoaming treatment by using an antifoaming agent or the like so that no air bubbles remain in the spread layer. When forming the ceramic sheet, appropriate additives such as a plasticizer, a dispersant, and a sintering aid may be added as necessary. The thickness of the ceramic sheet may be appropriately determined according to the purpose of use. Generally
10 μm to 5 mm.

The firing pattern sheet of the present invention has a metal pattern on one side of a ceramic sheet and an adhesive layer containing a non-glass type ceramic powder on the other side.

The metal-based pattern is formed using one or more kinds of powders of a metal or a metal compound that can become an oxide when fired. Examples of usable metal or metal compound powders include metals such as iron, chromium, nickel, cobalt, molybdenum, manganese, titanium, copper, and aluminum, and silicides, nitrides, carbides, borides, and carbonates thereof. Examples include nitrates and sulfates. The particle size of the powder is suitably from 0.1 to 50 μm, preferably from 0.2 to 20 μm.

The pattern to be provided is arbitrary such as a print pattern, a transfer pattern, a picture pattern, a barcode pattern, and the like. The pattern formation method is also arbitrary. Appropriate methods such as a direct application method using a pattern forming mask such as a handwriting method and a screen printing method, a method of transferring a pattern provided on transfer paper, and a forming method by a printer may be applied.

The ink liquid that can be used in the handwriting method, the coating method, and the like can be prepared as a liquid in which metal powder or the like is simply dispersed in a solvent, a paste liquid using a binder together, or the like. Thermal fixing ink using a heat-fusible binder made of wax, polymer, etc., is an XY plotter, wire dot type,
It can be advantageously used for forming an ink sheet for forming a pattern using an appropriate printer such as a thermal transfer type or an impact type. The pattern forming method using a printer has an advantage that an appropriate pattern can be formed efficiently and accurately.

The composition ratio of the metal or metal compound powder and the heat-fusible binder in the heat-fixable ink may be appropriately determined. Generally, 3 to 1000 parts by weight of a heat-fusible binder, 3 to 500 parts by weight of a wax, and 0 to 500 parts by weight of a polymer are used per 100 parts by weight of the metal or metal compound powder in total. The heat-fixable ink can be prepared by appropriately mixing them using a solvent or the like. At that time, an appropriate additive such as a softener may be added.

An ink sheet to be applied to a printer or the like can be formed by applying a heat-fixable ink to a supporting base material or by impregnating the supporting base material and holding it. Papers, resin films or paper / film composites, metal sheets, cloths and the like are generally used as the support base material. In an ink sheet to be applied to a thermal transfer printer, it does not soften or plasticize at the heating temperature of a heat source such as a thermal head, and has heat resistance or dimensional stability that maintains toughness as a support, A support base material having a surface smoothness that does not inhibit the transfer of the heat fixing ink can be preferably used.

A method of forming a pattern on a ceramic sheet via a thermal transfer type ink sheet and a printer, and assuming a pattern under the melting of a heat-fusible binder to obtain a firing pattern sheet, is a method of manufacturing efficiency and forming a firing pattern. It is excellent in handling properties of the sheet at the time and is preferable.

In the present invention, the step of applying the pattern to the ceramic sheet may be before or after the ceramic sheet is temporarily attached to the heat-resistant adherend via the adhesive layer. In the former case of applying a pattern before temporary attachment, there is an advantage that a fine pattern can be applied using an appropriate device. In the latter case of applying a pattern after temporary attachment, the ceramic sheet temporarily attached to the adherend is processed to form a firing pattern sheet. In this case, although not limited, a pattern sheet formed by providing a pattern made of a heat-fixable ink on transfer paper so that the pattern can be applied by a transfer method is preferably used for applying the pattern.

For the formation of the adhesive layer provided on one side of the ceramic sheet,
An adhesive is used which has an adhesive strength capable of temporarily adhering to an adherend and disappears due to thermal decomposition at a firing temperature or lower. Generally, a rubber-based adhesive, an acrylic-based adhesive, a vinyl alkyl ether-based adhesive, or the like is used. Above all, from polymers such as natural rubber (synthetic natural rubber), butyl rubber, polyisoprene rubber, styrene / butadiene rubber, styrene / isoprene / styrene block copolymer rubber, styrene / butadiene / styrene block copolymer rubber Rubber-based pressure-sensitive adhesive or 100 parts by weight of such a polymer, a petroleum-based resin, a terpene-based resin, a rosin-based resin, a xylene-based resin, and a tackifier resin such as a coumarone-indene-based resin.
~ 300 parts by weight, rubber-based pressure-sensitive adhesive with addition of other softeners, anti-aging agents, coloring agents, fillers and other compounding agents, acrylic pressure-sensitive adhesives based on polymers of alkyl esters of acrylic acid or methacrylic acid Are used.

The pressure-sensitive adhesive layer contains a non-glass-based ceramic powder in order to enhance the stability of the sintering adhesion to the heat-resistant adherend or the adhesion. Examples of the non-glass ceramic powder include those exemplified above for the ceramic sheet. In particular, when alumina powder is used for the ceramic sheet, a non-glass ceramic powder of the same type as that used for the ceramic sheet is preferably used so that the adhesive layer also contains the alumina powder.

The formation of the adhesive layer containing the non-glass ceramic powder can be performed, for example, by using a pressure-sensitive adhesive mixed with the non-glass ceramic powder in a ball mill or the like with the use of a solvent or the like as necessary. The content of the non-glass ceramic powder in the adhesive layer is appropriately determined depending on the specific gravity, particle size, and the like of the ceramic powder. Generally, the content is 10 to 90% by weight, preferably 35 to 80% by weight. The adhesive layer can be attached by, for example, a method of transferring the adhesive layer provided on the separator, or a method of applying an adhesive on a ceramic sheet or the like. The step of attaching the adhesive layer to the ceramic sheet may be before or after the pattern is provided on the other surface of the ceramic sheet. If the applied pattern is likely to fall off, it is preferable to attach an adhesive layer before applying the pattern. In this case, the exposed surface of the adhesive layer is usually used for pattern formation under protection by a separator or the like. The thickness of the adhesive layer may be appropriately determined according to the purpose of use. Generally, it is 1 to 200 μm. For the temporary attachment of the ceramic sheet or the firing pattern sheet to the heat-resistant adherend via the adhesive layer, an automatic adhesion method by a robot or the like may be employed.

The firing of the firing pattern sheet temporarily attached to the heat-resistant adherend via the adhesive layer is performed in an oxidizing atmosphere. Thus, when the ceramic sheet is fired and fixed to the heat-resistant adherend, the metal forming the pattern or the powder of the metal compound can be fixed to the fired body of the ceramic sheet while changing the powder to the metal oxide. . The sintering may be performed at an appropriate heating temperature depending on the temperature at which an oxide of a non-glass-based ceramic powder or a metal powder for forming a pattern or the like is formed.

The above-described method for forming a fired pattern can be preferably applied to the application of an identification label made of a barcode or the like to a heat-resistant adherend made of heat-resistant brick or other fired ceramics, fired table, metal, or the like. When the heat-resistant adherend is made of an unfired ceramic molded body or the like, the firing of the firing pattern sheet and the firing or heat treatment of the adherend can be combined.

Effect of the Invention Since the firing pattern sheet of the present invention is composed of a non-glass ceramic sheet, a metal pattern that changes to an oxide during firing, and an adhesive layer containing a non-glass ceramic powder, the firing pattern is less likely to bleed. A fine pattern can be formed with high precision. In addition, it can be easily temporarily attached to a curved surface and fixed by firing, and an arbitrary pattern can be easily and flexibly provided. Furthermore, the pattern has excellent preservation during firing, and the fired body has excellent scratch resistance, heat resistance, and chemical resistance. In addition, due to the adhesive action of the non-glass ceramic powder contained in the pressure-sensitive adhesive layer, the fired body is solidified with respect to the adherend. Excellent in adhesion and stability of its fixation.

Example 1 Alumina powder having an average particle size of 2 μm (parts by weight, the same applies hereinafter)
80 parts, 20 parts of talc powder having an average particle diameter of 3 μm, 30 parts of polyisobutyl methacrylate, 3 parts of dibutyl phthalate and 1 part of stearic acid were uniformly mixed by a ball mill using 55 parts of toluene, and a doctor blade was used. A 15 μm thick adhesive layer made of an acrylic adhesive mixed with the same amount of alumina powder having an average particle size of 2 μm on the surface after being spread on a separator by a method and dried to form a 60 μm thick ceramic sheet. And protected by coating with a separator.

Next, 20 parts of nickel powder having an average particle size of 2 μm and 10 parts of polyisobutyl methacrylate were added to toluene with a roll mill.
A slurry-like ink liquid prepared by uniformly mixing 20 parts was applied and printed on an exposed surface of the ceramic sheet through a pattern mask, dried to form a barcode pattern, and a firing pattern sheet was formed. .

Next, the separator was peeled off from the firing pattern sheet, and temporarily attached to an alumina-based refractory plate (alumina 80% by weight, silica 20% by weight) via the adhesive layer, and heated at a rate of 10 ° C./min. It was calcined (in air) at 1550 ° C. for 1 hour.

As described above, a fired pattern firmly fixed to the alumina-based refractory plate was obtained. The barcode pattern is greenish,
It was clear without bleeding.

Example 2 A coating solution of a heat fixing ink prepared by uniformly mixing 20 parts of nickel powder having an average particle diameter of 1 μm, 5 parts of paraffin wax, and 5 parts of polyisobutyl methacrylate with 20 parts of toluene using a roll mill was applied to a 5 μm-thick film. It is applied on a polyester film by a coating machine so that the thickness after drying is about 20 μm, dried to produce an ink sheet, and the ink sheet is cut into a predetermined width, and a ribbon obtained is stored in a case. The ink ribbon cartridge was used to print a barcode pattern on the exposed surface of the ceramic sheet obtained in Example 1 through a normal thermal transfer printer to obtain a firing pattern sheet. Temporarily attached to a system refractory plate and fired.

As described above, a fired pattern firmly fixed to the alumina-based refractory plate was obtained. The barcode pattern is greenish,
It was clear without bleeding.

Example 3 A barcode pattern made of a heat-fixable ink was printed on transfer paper in the same manner as in Example 2 to obtain a pattern sheet.

Next, after the same ceramic sheet as in Example 1 was temporarily attached to the alumina-based refractory plate via the adhesive layer, the bar code pattern in the pattern sheet was transferred to the ceramic sheet via a hot roll, and the firing pattern sheet was fired. This was fired according to Example 1.

As described above, a fired pattern firmly fixed to the alumina-based refractory plate was obtained. The barcode pattern is greenish,
It was clear without bleeding.

Claims (4)

(57) [Claims] 1. A ceramic sheet obtained by preserving a non-glass ceramic powder with a resin binder has a pattern made of a powder of a metal or a metal compound which can be an oxide when fired, and a non-glass ceramic powder on the other face. A pattern sheet for firing, comprising an adhesive layer containing ceramic powder. 2. A ceramic sheet through a thermal transfer printer using an ink sheet in which a supporting material is used to hold a powder of a metal or a metal compound which can become an oxide during firing and a heat-fixable ink comprising a heat-fusible binder. Step of forming a pattern on one side of, and before forming the pattern,
The method according to claim 1, further comprising a step of attaching an adhesive layer containing a non-glass-based ceramic powder to the other surface of the ceramic sheet later. 3. The pattern sheet for firing according to claim 1 is temporarily attached to the heat-resistant adherend via the adhesive layer, and is heated in an oxidizing atmosphere to fire the ceramic sheet while firing the ceramic sheet. A method for forming a fired pattern, comprising: fixing a metal or metal compound forming a pattern to a metal oxide while fixing the powder to a fired body of a ceramic sheet, while fixing the powder to a body. 4. The firing pattern according to claim 1, wherein the ceramic sheet is temporarily attached to a heat-resistant adherend via an adhesive layer containing non-glass ceramic powder attached thereto, and a pattern is provided thereon. After the sheet is formed, it is heated in an oxidizing atmosphere to fix the ceramic sheet to the heat-resistant adherend while firing, and to change the powder of the metal or metal compound forming the pattern into a metal oxide while forming the ceramic. A method for forming a fired pattern, comprising fixing to a fired body of a sheet.