JP2974679B2 - Method for forming fired pattern and pattern sheet used therefor - Google Patents

Description

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for forming a fired pattern in which a fired pattern that functions as an identification mark or the like is formed on an adherend via a glass frit-containing sheet, and a pattern sheet used therefor. About.

BACKGROUND OF THE INVENTION With the transition of production systems to high-mix low-volume production, identification labels are frequently used for managing products, semi-finished products, parts, and the like. If the identification label is simply attached and the problem of loss or confusion is likely to occur due to a wide variety of production processes, a measure is taken to fix the identification label directly to the managed product. In addition, if the identification label may be lost due to abrasion due to a number of steps, burnout due to a heat treatment step, loss due to a chemical treatment step with an acid, an alkali, etc., durability, An identification label having required resistance such as heat resistance and chemical resistance is required. Such labels are often required for identification labels for managing glass products, metal products, sintered ceramic products, and the like.

2. Description of the Related Art Conventionally, as an identification label of a type having durability, heat resistance, chemical resistance, etc. and directly adhered to an adherend, a label made of a substrate such as fired ceramic, stainless steel, enameled body, etc. is known. Had been.

However, the problem that it takes time to fix by screwing and the like, the problem that it is difficult to fix to a curved surface due to lack of flexibility,
There is a problem that it is difficult to add a pattern having excellent heat resistance or the like in the field, and thus it is difficult to give a pattern on the spot and make an identification label.

On the other hand, a paste-like ink obtained by mixing a glass frit and an optional component such as a pigment with a binder can be directly applied to an adherend by a screen printing method or the like, or once applied to transfer paper and then transferred. A method of forming a pattern and firing the pattern has been known.

However, in addition to the difficulty of coating on a curved surface, there is a problem that the number of screens to be prepared in advance becomes large under a multi-product small-quantity production system, and the preparation requires a lot of time and labor.

Means for Solving the Problems The present invention is, through firing the unsintered pattern sheet made of a glass frit containing sheet, through the glass frit,
The above object has been overcome by a method of fixing the formed fired body to an adherend.

That is, the present invention comprises an organic binder or wax that is burned off during firing and contains 10 to 100% by weight of the remaining fired component, and has an adhesive force to an adherend itself or adheres to the adherend. An unfired pattern sheet obtained by engraving a pattern made of holes or irregularities on a glass frit-containing sheet provided with an adhesive layer is adhered to an adherend via the above-described adhesive force, and is heated to bake the pattern sheet. A baking pattern forming method characterized by forming a baking pattern on the adherend, and an organic binder or wax that is burned off during baking is blended in an amount of 10 to 100% by weight of a baking residual component. A glass frit-containing sheet having an adhesive force to the body or provided with an adhesive layer for bonding to an adherend is formed by engraving a pattern composed of holes or irregularities. A baked pattern sheet, and a glass frit-containing sheet containing 10 to 100% by weight of an organic binder or wax that is burned off during firing is adhered to an adherend, and the glass frit-containing sheet has holes or irregularities. The pattern is engraved, the formed unbaked pattern sheet is heated and baked, and a baked pattern forming method characterized by forming a baked pattern on an adherend, and an organic binder or wax that is burned off during baking. After adhering a glass frit-containing sheet containing 10 to 100% by weight of the firing residual component to an adherend, a pattern made of firing ink is provided on the sheet, and baked together with the sheet. And forming a firing pattern.

Action By firing, the unfired glass frit-containing sheet is formed into a fired body while preserving the pattern formed thereon, and the molten glass frit functions as an adhesive to fix the fired body to the adherend. When the sheet contains fired residual components other than the glass frit, the fired residual components are also taken into the fired body to form a fired pattern.

The unfired glass frit-containing sheet is flexible or flexible, and can easily engrave a pattern composed of holes or irregularities. Also, by a method in which a pattern is formed on a sheet using a firing ink, the pattern can be preserved to form a fired body together with the sheet.

Illustrative components of the invention The glass frit-containing sheet used in the present invention,
A glass frit is contained, and the residue is fixed to the adherend by firing.

As the glass frit, one that is softened or melted at a predetermined firing temperature and fixed to an adherend is used. Therefore, a known glass frit can be used. The firing temperature may be appropriately determined according to the heat resistance of the adherend. Generally, when the firing temperature is 400 to 600 ° C., a frit such as a lead glass frit is preferably used, and when the firing temperature is 500 to 1000 ° C., a frit such as a lead borosilicate glass or a soda glass is preferably used. If the temperature exceeds 900 ℃, 100
In the case of 0 to 1200 ° C., silicate glass-based or quartz glass-based frit is preferably used.

In forming the glass frit-containing sheet, only the glass frit may be used as the fired residual component, or another component may be blended. Other firing residual components to be blended, for example, ceramic, metal or alloy,
Powders, fibers, and the like are generally used as the inorganic substance composed of the oxide or the like. When the sheet is fired, the fired residual components other than the glass frit are retained in the molten glass frit and taken into the fired body to form a fired pattern. The types and combinations of the components may be determined as appropriate. For example, when used as an identification label, it is desirable that the contrast with the adherend be good, and a pigment or filler is appropriate in terms of coloring.

Examples of commonly used pigments or fillers include:
White substances such as silica, white substances such as calcium carbonate, titanium oxide, zinc oxide, zirconia, calcium oxide, alumina, and metal compounds such as carbonates, nitrates, and sulfates which are oxidized at the firing temperature to form such oxides, iron , Chrome, copper,
For example, manganese oxide containing metal ions such as gold and selenium
Red materials such as alumina, chromium oxide-tin oxide, iron oxide, cadmium sulfide-selenium sulfide, etc., including metal ions such as copper, manganese, cobalt, and iron, for example, cobalt oxide, zirconia-vanadium oxide, chromium oxide-divanadium pentoxide And black materials such as chromium oxide-cobalt oxide-iron oxide-manganese oxide containing metal ions such as iron, manganese, copper, chromium, and cobalt.

The mixing ratio of the firing residual component may be appropriately determined. When the firing temperature is low or when a fired body with a smooth surface is desired, it is preferable to use a glass frit having a low melting point. When the firing temperature is high or when the surface of the fired body is not required to be smooth, a firing residual component other than the glass frit may be frequently used. In general, the glass frit is 1 to 100% by weight, preferably 1 to 97% by weight, preferably 10 to 80% by weight, and other fired residual components 99 to 0% by weight, especially 99 to 3% by weight, preferably 90 to 20% by weight. Each of the calcined residual components used may be one type, or two or more types. Incidentally, the size of the calcined residual component used is usually 0.1 to 20 in the case of powder.
μm particle size, in the case of fibers, a length 10
The thickness is 0 μm or less, but is not limited thereto.

The formation of the glass frit-containing sheet is carried out by mixing the remaining fired component with an organic binder, other compounding agents such as wax, if necessary, using a suitable kneader such as a roll mill or a pot mill, and forming the mixture into a sheet. Such as a method of applying the mixture on a support such as a film,
It may be performed by an appropriate method. What is coated on the support may be used as it is as a sheet with a support, or the coated layer may be peeled off from the support and used as a single-layer sheet composed of a layer containing a fired residual component.

Like the wax, the organic binder is blended as needed for the purpose of adjusting the strength and flexibility of the formed glass frit-containing sheet. Further, the organic binder is more useful than providing the sheet to be formed with an adhesive force to the adherend, and therefore, the sheet itself can be provided with an adhesive force to the adherend. The organic binder used is one that is burned off by firing. For example,
Nitrocellulose-based and acrylic resin-based binders are used for low-temperature firing at 300 to 600 ° C, and 500 ° C
In addition to the above, binders of urethane type, ethylcellulose type, polyvinyl butyral type, etc. may be mentioned as those for medium-high temperature sintering. In addition, a known organic binder such as a polyamide resin, a petroleum resin, and a styrene resin may be used. To reduce the burning temperature and improve the burning property,
It is effective to add a heating aid composed of a peroxide such as sodium peroxide, calcium peroxide, and magnesium peroxide. The addition amount is suitably 5 to 15% by weight of the organic binder. The organic binder is usually formulated as a 5 to 40% by weight organic solvent solution. There is no particular limitation on the organic solvent used. Generally, pentanol, ethyl acetate, butyl cellosolve acetate, methyl ethyl ketone, methyl isobutyl ketone, toluene and the like are used.

Known waxes such as paraffin wax and carnauba wax may be used as the wax.

The compounding amount of the organic binder and the wax is 10 to 100% by weight, preferably 20 to 80% by weight of the total amount of the fired residual components, depending on the properties of the formed sheet or the layer containing the fired residual components.
It is.

In forming the glass frit-containing sheet, an appropriate compounding agent such as a dispersant, a softener, a solvent, and a foaming agent may be added as necessary depending on the purpose of use. As the compounding agent, a known compound is used in a usual amount. A high-temperature blowing agent such as sodium silicate (water glass) composed of silicon oxide and sodium oxide is useful for increasing the thickness of the firing pattern and smoothing the surface. In addition, as a softener, fats and oils, mineral oil, rapeseed oil,
Vaseline, xylene resin and the like are generally used, and solvents such as toluene, isopropanol and solvent naphtha are generally used.

The glass frit-containing sheet used in the present invention may be a sheet having a pressure-sensitive adhesive layer to enhance the adhesive strength to an adherend. The formation is performed by, for example, a method of applying a mixture for sheet formation on the other surface of a support having an adhesive layer on one side, or a method of applying the mixture on an adhesive layer provided on a separator. be able to. It is appropriate that the pressure-sensitive adhesive used burns off during firing. Note that it is desirable to improve the handleability by attaching a separator to the exposed surface of the pressure-sensitive adhesive layer. The separator is peeled off when a sheet or a pattern sheet having a pattern engraved thereon is adhered to an adherend.

The thickness of the fired residual component-containing layer in the glass frit-containing sheet is generally from 1 μm to 5 mm, especially from 5 μm to 1 mm, but is not limited to this and may be appropriately determined according to the intended use.

In the present invention, the glass frit-containing sheet is used for forming a pattern sheet by engraving a pattern comprising holes or irregularities on the sheet. Further, it is also used as a pedestal sheet when a pattern is formed thereon with firing ink.

The step of forming an unfired pattern sheet by engraving a pattern formed of holes or irregularities on the glass frit-containing sheet may be after the sheet and the adherend are bonded, or may be before the bonding. . Therefore, in the former case, a pattern consisting of holes or irregularities is engraved on the glass frit-containing sheet adhered to the adherend.
This method is preferably applied when the adherend is a substrate or a sheet. On the other hand, in the latter case, after an unfired pattern sheet formed by engraving a pattern composed of holes or irregularities on a glass frit-containing sheet is formed in advance, the pattern sheet is bonded to an adherend. This method has an advantage that a fine pattern can be easily formed using an appropriate engraving device. In addition, a transfer method such as a method in which a layer containing a fired residual component is provided in advance on an appropriate transfer paper such as a release paper or a film or a metal foil, and a pattern is formed on the layer and transferred to an adherend. There are also benefits that you can do.

The pattern of the holes or irregularities formed by engraving on the glass frit-containing sheet is arbitrary. The engraving method is also arbitrary. In the hole pattern, the hole portion 2 of the sheet 1 represents the display content as shown in FIG.
As shown in the figure, a method in which the portion 3 other than the hole of the sheet 1 represents the display content can be adopted. Further, as shown in FIG. 3, in the transfer method or the like, a punching type hole line pattern 4 is formed on the sheet 1, and finally only the inner part (hatched portion) of the hole line pattern 4 remains on the adherend. Alternatively, a method of causing such a situation may be adopted. This method can be preferably applied to, for example, formation of a barcode pattern, a picture pattern, and the like, and is particularly useful for applying a barcode pattern to an appropriate adherend. It should be noted that a pattern composed of irregularities can also be used for forming a bar code pattern applied to a reflected light amount detection type recognition device or the like.

When bonding the glass frit-containing sheet or the pattern sheet to the adherend, it easily falls because it does not have an adhesive layer, and if the adhesive strength is insufficient, use an adhesive or an adhesive as appropriate. May be bonded. At this time, it is preferable that the adhesive and the pressure-sensitive adhesive to be used are burned off during firing. Note that an automatic bonding method using a robot may be used for the bonding processing.

The firing of the unfired pattern sheet adhered to the adherend may be performed at an appropriate heating temperature according to the glass frit used. Thus, the pattern sheet is fired, and the molten glass frit functions as an adhesive, and the formed fired pattern is fixed to the adherend to form the fired pattern.

The adherend may be a completed product made of glass, fired ceramic, metal, or the like, or may be an unfinished product such as an unfired ceramic molded product. In the case of an unfinished product, the baking of the adherend may be combined with that of the pattern sheet.

Another method of forming a fired pattern in the present invention is that, after bonding a glass frit-containing sheet to an adherend, a pattern made of firing ink is provided on the sheet and fired together with the sheet, and the fired pattern is formed on the adherend. Is formed.

As shown in FIG. 4, the forming method is the same as that described above, except that a pattern 5 made of firing ink is formed on the glass frit-containing sheet 1 and fired together with the sheet 1 to form a fired pattern-attached sheet. Of course, the glass frit-containing sheet 1 may be a pattern sheet formed by forming a pattern composed of holes or irregularities.

As the firing ink, conventionally, for example, a glass frit and an optional component such as a pigment, which have been used in a direct application method by screen printing or the like, or a method of transferring an applied body to transfer paper, are mixed together with a binder. A paste-like ink may be used. Further, a composition for forming the above-mentioned glass frit-containing sheet used in the present invention, which contains glass frit and other optional fired residual components, may be used. In this case, the mixing ratio of each component is 10 to 95% by weight of glass frit, 90 to 5% by weight of other fired residual components, and an organic binder used as needed:
A suitable amount is 5 to 50% by weight of the total calcined residual components.

There is no particular limitation on the method of forming the pattern on the glass frit-containing sheet using the firing ink. An appropriate method such as handwriting, application through a pattern forming mask, and transfer of a pattern provided on a transfer sheet may be adopted.

Further, a baking ink layer is provided on a support made of a film or the like, or a baking ink is impregnated in a support made of a cloth or the like to form an ink sheet, and a glass frit-containing sheet is formed using this ink sheet. A pattern may be formed thereon. In this case, the ink sheet is applied like a print ribbon, and a pattern forming method using an XY plotter, a printer of a wire dot type, a thermal transfer type or an impact type, or the like can be adopted, and a print pattern, a transfer pattern , Efficient patterns such as painting patterns,
And it can form accurately. When the adherend is made of a substrate or the like, it is easy to directly form a pattern on the glass frit-containing sheet adhered to the substrate.
In addition, as a support of the firing ink used for forming the ink sheet used as a thermal transfer ribbon, an imprint transfer ribbon, an imprint print ribbon, and the like, generally, a known plastic film such as polyester, polyimide, and fluororesin,
A cloth made of fibers such as nylon and polyester can be used, but an appropriate cloth may be selected and used. When the purpose is to form an identification label, using a fired residual component such as a pigment different from that forming the glass frit-containing sheet, the sheet base and the pattern composed of the firing ink have a good quality in the fired body. It is preferable to combine them so that a difference in contrast or color tone is formed.

The method of forming a fired pattern according to the present invention can be preferably applied to painting, circuit patterns, formation of identification labels, and the like. The adherends to be painted include, for example, ceramics, glassware, enamel bodies, and the like. Company name,
For example, glass or ceramic may be used for the adherends to which identification labels consisting of lot numbers, product names, destination names, exporting countries, and any other identification signals, coloring patterns, color-specific patterns, barcodes, etc. are attached. And various products including metal and other pallets for transporting products, especially heat-resistant substrates such as ceramics and prototypes. Of course, it is not limited to the above.

Effects of the Invention According to the forming method of the present invention, the glass frit-containing sheet is formed of holes or irregularities by a printing method such as an engraving device such as an engraving roller or a printer or a screen method such as a thermal transfer method, or a firing ink. It is possible to easily and arbitrarily apply an arbitrary fine pattern such as a pattern before and after adhesion to the adherend, and it is easy to form identification labels for not only high-volume products but also high-mix low-volume products, It can be easily curved and adhered to the curved surface of the adherend without any damage to the curved surface of the adherend by an automatic adhesion method by a robot, and in particular, a pattern is applied before adhesion to the adherend to make a pattern sheet and adhere it to the adherend In this case, the glass frit-containing sheet itself or the pressure-sensitive adhesive layer provided thereon can be easily curved and adhered to the curved surface of the adherend without damage to the curved surface of the adherend, and the adhesive under the adhesive The baking pattern preserving the applied pattern can be formed on the adherend, the sheet thickness can be easily controlled to 1 μm to 5 mm, etc., and the baking pattern with excellent thickness can be efficiently formed by simple and efficient work. The firing pattern is excellent in durability, heat resistance, chemical resistance and the like.

Example Reference Example 1 85 parts of lead borosilicate glass frit (parts by weight, the same applies hereinafter), 15 parts of zirconia, 10 parts of acrylic resin binder,
40 parts of butyl cellosolve acetate is kneaded with a roll mill to form a uniform mixed paste, which is applied to a separator subjected to a release treatment by a doctor blade type coater, dried, and dried to form a glass frit-containing sheet having a coating layer having a thickness of about 100 μm. And an acrylic pressure-sensitive adhesive layer having a thickness of about 20 μm was provided on the coating layer, and the pressure-sensitive adhesive layer was wound while being covered with ceramic.

Reference Example 2 A glass frit-containing sheet with an adhesive layer was obtained in the same manner as in Reference Example 1 using 80 parts of a quartz glass-based frit, 20 parts of alumina, 10 parts of an acrylic resin-based binder, and 40 parts of butyl cellosolve acetate.

Reference Example 3 A glass frit-containing sheet with an adhesive layer was obtained according to Reference Example 1 using 85 parts of a lead borosilicate glass frit, 15 parts of alumina, 10 parts of an acrylic resin binder, and 40 parts of butyl cellosolve acetate.

Reference Example 4 A glass frit-containing sheet with an adhesive layer was obtained according to Reference Example 1 using 95 parts of a lead borosilicate glass frit, 5 parts of alumina, 10 parts of an acrylic resin binder, and 40 parts of butyl cellosolve acetate.

Reference Example 5 Lead borosilicate glass frit 15 parts, black pigment 60 parts, polyamide resin 10 parts, rapeseed oil 10 parts, toluene isopropanol 5 parts were kneaded with a three-roll mill to obtain a firing ink composed of a uniform mixed paste, The fabric was impregnated with the coating machine to obtain a printing ribbon.

Reference Example 6 80 parts of a lead borosilicate glass frit, 20 parts of a black pigment (chromium oxide-iron oxide-cobalt oxide), 15 parts of an ethylcellulose binder and 50 parts of terpineol were kneaded with a roll mill to form a uniform mixed paste, and a firing ink. I got

Reference Example 7 85 parts of quartz glass frit, black pigment (chromium oxide
A firing ink was obtained according to Reference Example 6 using 15 parts of iron oxide-manganese oxide-cobalt oxide), 15 parts of an ethylcellulose binder, and 50 parts of terpineol.

Reference Example 8 An ink for firing according to Reference Example 6, using 85 parts of a lead borosilicate glass frit, 15 parts of a black pigment (chromium oxide-iron oxide-manganese oxide-cobalt oxide), 15 parts of an ethylcellulose binder, and 50 parts of terpineol. I got

Example 1 A 30 mm × 50 mm cut piece obtained by cutting the glass frit-containing sheet obtained in Reference Example 1 was pressed with a mark having a predetermined pattern of irregularities, and this was made of stainless steel whose surface was heated and oxidized. After bonding to a metal cylinder having a radius of curvature of 50 mm via the pressure-sensitive adhesive layer, it was baked at 450 ° C. for 30 minutes. The separator was peeled off in advance (the same applies hereinafter). At the time of firing, the adhesive and the organic binder were completely burned off before melting the glass frit.

As described above, a metal cylinder to which an identification label made of a white fired body with a good preservation of the pressing pattern was firmly fixed was obtained.

Example 2 A 30 mm × 50 mm cut piece obtained by cutting the glass frit-containing sheet obtained in Reference Example 1 was adhered to a metal plate via the adhesive layer, and the above-mentioned mark was pressed on the cut piece. And
By firing according to Example 1, a metal plate to which an identification label made of a fired body in which a white pressing pattern was well preserved was firmly fixed was obtained.

Example 3 A 30 mm × 50 mm cut piece obtained by hollowing out figures from the glass frit-containing sheet obtained in Reference Example 2 was adhered to the above-mentioned metal cylinder via its adhesive layer, and then fired at 1000 ° C. for 1 hour. did. At the time of firing, the adhesive and the organic binder were completely burned off before melting the glass frit.

As described above, a metal cylinder having a strong identification label made of a fired body having a clear pattern in which a white frame surrounds a ground color number was obtained.

Example 4 After bonding the glass frit-containing sheet obtained in Reference Example 4 to an aluminum plate via the pressure-sensitive adhesive layer, the rollers having protruding lines having different widths provided at various intervals on the coating layer of the sheet were pressed and rotated. A pattern consisting of bar code-like irregularities was engraved and baked at 600 ° C. for 10 minutes.
At the time of firing, the adhesive and the organic binder were completely burned off before melting the glass frit.

As described above, an aluminum plate was firmly fixed with a white coating layer in which a pattern composed of bar-code-like irregularities was well preserved.

Example 5 After the glass frit-containing sheet obtained in Reference Example 3 was adhered on a ceramic substrate via the adhesive layer, a cartridge containing the printing ribbon of Reference Example 5 and a conventional dot printer were placed thereon. A predetermined barcode pattern was formed by using this and baked at 650 ° C. for 10 minutes.

As described above, a ceramic substrate was obtained in which a fired body having a predetermined black barcode pattern was firmly fixed on a white background.

Example 6 A small piece of the glass frit-containing sheet obtained in Reference Example 1 was adhered on a glass plate via its pressure-sensitive adhesive layer, and then a bar code pattern was formed thereon using the firing ink obtained in Reference Example 6. Was screen printed and baked at 450 ° C. for 30 minutes.

As described above, a glass plate was obtained in which a fired body having a predetermined black barcode pattern was firmly fixed on a white background.

Example 7 After bonding a small piece of the glass frit-containing sheet obtained in Reference Example 2 on a ceramic substrate via the adhesive layer,
A barcode pattern was screen-printed thereon using the firing ink obtained in Reference Example 7 and fired at 1000 ° C. for 1 hour.

As described above, a ceramic substrate was obtained in which a fired body having a predetermined black barcode pattern was firmly fixed on a white background.

Example 8 A combination of the glass frit-containing sheet obtained in Reference Example 3 and the firing ink obtained in Reference Example 8 was used, and the firing conditions were set to 600.
According to Example 7, a ceramic substrate in which a fired body having a predetermined black barcode pattern was firmly fixed on a white background at 10 ° C. for 10 minutes was obtained.

[Brief description of the drawings]

FIG. 1, FIG. 2, FIG. 3, and FIG. 4 are explanatory diagrams of examples of pattern formation. 1: Sheet containing glass frit or pattern sheet 2: Hole part 3: Part other than hole 4: Hole pattern 5: Pattern composed of firing ink

────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Minoru Yamano 1-4-7 Yamatedai, Ibaraki-shi, Osaka (72) Inventor Masaaki Shimada 4-1-1 Kiyomidai, Kawachinagano-shi, Osaka Examiner Osamu Kawabata ( 58) Field surveyed (Int.Cl. ⁶ , DB name) C23D 5/06

Claims (4)

(57) [Claims] An organic binder or wax, which is burned off during firing, is blended in an amount of 10 to 100% by weight of a residual component of the firing, and has an adhesive force to an adherend itself or an adhesive for adhering to the adherend. An unfired pattern sheet obtained by engraving a pattern comprising holes or irregularities on a glass frit-containing sheet provided with an agent layer is adhered to the adherend through the above-described adhesive force, and the pattern sheet is fired by heat treatment. ,
A method for forming a fired pattern, comprising forming a fired pattern on an adherend. 2. An organic binder or wax, which is burned off during firing, is blended in an amount of 10 to 100% by weight of a residual component of firing, and has an adhesive force to an adherend itself or an adhesive to adhere to the adherend. An unfired pattern sheet obtained by engraving a pattern comprising holes or irregularities on a glass frit-containing sheet provided with an agent layer. 3. A glass frit-containing sheet containing 10 to 100% by weight of a residual component of a fired organic binder or wax which is burned off during firing is adhered to an adherend, and a pattern comprising holes or irregularities is formed on the glass frit-containing sheet. Sculpture and
A fired pattern forming method, wherein the formed unfired pattern sheet is heated and fired to form a fired pattern on an adherend. 4. A glass frit-containing sheet containing 10 to 100% by weight of an organic binder or wax which is burned off during firing is adhered to an adherend, and a pattern made of firing ink is formed on the sheet. And firing the sheet together with the sheet to form a firing pattern on the adherend.