JPH02104679A - Formation of calcined pattern and pattern sheet used therefor - Google Patents

Abstract

PURPOSE:To easily form a calcined pattern on a body to be patterned by carving a hole or rugged pattern in a sheet contg. glass frit to form an uncalcined pattern sheet, which is then adhered to the body and calcined by heating. CONSTITUTION:A hole or rugged pattern is carved in a sheet contg. glass frit such as lead glass, soda glass or silicate glass frit to form a pattern sheet. This sheet consists of about 1-100wt.% glass frit and about 99-0wt.% other components remaining after calcining such as zirconia, alumina and black pigment. A compounding agent may properly be incorporated into the sheet. The sheet is then adhered to a body to be patterned and calcining is carried out. A calcined pattern functioning as an identifying mark, etc., is easily formed.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a fired pattern forming method in which a fired pattern that functions as an identification mark is formed on an adherend via a glass frit-containing sheet, and a pattern sheet used therein. Regarding.

Background of the Invention As production systems shift to high-mix, low-volume production, identification labels are frequently used to manage products, semi-finished products, parts, and the like. If simply attaching an identification label is likely to cause problems of loss or confusion due to the wide variety of production processes, a measure is taken to attach the identification label directly to the quantity to be controlled. In addition, “wear and tear due to numerous processes,
If there is a risk that the identification label may be lost due to burning through a heat treatment process or melting away through a chemical treatment process using acids, alkalis, etc., the necessary resistance such as durability, heat resistance, and chemical resistance should be applied. An identification label is required. Identification labels for controlling glass products, metal products, sintered ceramic products, etc. are often required to have such resistance.

Conventional technologies and issues Traditionally, identification labels that have durability, heat resistance, chemical resistance, etc. and are directly attached to adherends are made of substrates such as fired ceramics, stainless steel, and wax bodies. was known.

However, there are problems in that it takes time and effort to fix it with screws, etc., it lacks flexibility and is difficult to fix on curved surfaces, and it is difficult to add patterns with excellent heat resistance etc. on site. There was a problem in that it was difficult to add patterns and create identification labels on an ad hoc basis.

On the other hand, a paste-like ink made by mixing glass frit and optional components such as pigments with a binder is applied directly to an adherend using a screen printing method, or it is first applied to a transfer paper and then transferred. to form a pattern,
A method of firing this was known.

However, in addition to the difficulty of applying it to curved surfaces,
Under a high-mix, low-volume production system, a huge amount of screens must be prepared in advance, and the preparation requires a lot of time and effort from multiple sources.

Means for Solving the Problems The present invention solves the above problems by a method of firing an unfired pattern sheet made of a glass frit-containing sheet and fixing the formed fired body to an adherend via the glass frit. It is something that has been overcome.

That is, in the present invention, an unfired pattern sheet made by carving a pattern consisting of holes or irregularities on a glass frit-containing sheet is adhered to an adherend, heat-treated to bake the pattern sheet, and the adherend is baked. A firing pattern forming method characterized by forming a pattern, an unfired pattern sheet formed by engraving a pattern consisting of holes or irregularities on a glass frit-containing sheet, and bonding the glass frit-containing sheet to an adherend. Baked pattern formation, characterized by engraving a pattern consisting of holes or irregularities on the glass frit-containing sheet, and heating and firing the formed unfired pattern sheet to form a fired pattern on an adherend. The method is characterized in that after a glass frit-containing sheet is adhered to an adherend, a pattern made of firing ink is provided on the sheet and fired together with the sheet to form a fired pattern on the adherend. A firing pattern forming method is provided.

By the action firing, the unfired glass frit-containing sheet is turned 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 a firing residual component other than the glass frit, the firing residual component is also incorporated into the fired body to form a fired pattern.

The unfired glass frit-containing sheet is soft or flexible and can be easily engraved with a pattern consisting of holes or irregularities. Furthermore, by forming a pattern on the sheet using firing ink, the pattern can be preserved and the sheet can be used as a fired body.

Exemplification of Constituent Elements of the Invention The glass frit-containing sheet used in the present invention contains glass frit and is formed so that its residue adheres to an adherend upon firing.

As the glass frit, one that softens or melts at a predetermined firing temperature and adheres to the adherend is used. Therefore, known glass frits can be used. The firing temperature may be determined as appropriate depending on the heat resistance of the adherend. in general,
When the firing temperature is 400 to 600°C, a lead glass frit is preferably used, and when the firing temperature is 500 to 1000°C, a borosilicate lead glass or soda glass frit is preferably used. Moreover, when the temperature exceeds 900°C, especially when the temperature is from 1000 to 1200°C, a silicate glass-based or quartz glass-based frit is preferably used.

In forming the glass frit-containing sheet, the residual component after firing may be only the glass frit, or other components may be blended. As other components remaining after firing, for example, inorganic powders and fibers made of ceramics, metals, alloys, oxides thereof, etc. are generally used. When the sheet is fired, the components remaining after firing other than the glass frit are retained by the molten glass frit and incorporated into the fired body, forming a fired pattern. The types and combinations of ingredients may be determined as appropriate. For example, when used as an identification label, it is desirable that the label has good contrast with the adherend, and pigments or fillers are suitable for coloring.

Examples of commonly used pigments or fillers include whitening products such as silica, calcium carbonate, titanium oxide, zinc white, zirconia, calcium oxide, alumina, carbonates and nitrates that become oxides when oxidized at the firing temperature. , white substances such as metal compounds such as sulfates, iron, chromium, copper, gold,
Red materials containing metal ions such as selenium such as manganese oxide-alumina, chromium oxide-tin oxide, iron oxide, cadmium sulfide-selenium sulfide, etc. Cobalt oxide and zirconia containing metal ions such as copper, manganese, cobalt, and iron. - Vanadium oxide, chromium oxide - Blue substances such as vanadium pentoxide, black substances such as chromium oxide - cobalt oxide - iron oxide - manganese oxide, etc. containing metal ions such as iron, manganese, copper, chromium and cobalt. It will be done.

The blending ratio of the components remaining after firing may be determined as appropriate.

When the firing temperature is low or when a fired product with a smooth surface is desired, it is preferable to use a glass frit with a low melting point. When the firing temperature is high or when the surface smoothness of the fired body is not required, a large amount of firing residual components other than glass frit may be used. Generally, glass frit is 1 to 100% by weight.
, especially 1 to 97% by weight, preferably 10 to 80% by weight,
Other residual components after firing are 99 to 0% by weight, particularly 99 to 3% by weight, preferably 90 to 20% by weight. Each firing residual component used may be one type, or may be 2ffI or more. The size of the firing residual component to be used is usually 0.1 to 2 Qu+s in the case of powder, and 1100 u or less in length with the above diameter in the case of fiber, but is not limited to this.

The glass frit-containing sheet can be formed by mixing the residual components after sintering with other compounding agents such as an organic binder and wax as necessary in an appropriate kneading machine such as a roll mill or bot mill, and forming the mixture into a sheet. This may be carried out by any suitable method, such as by applying the mixture onto a support such as a film. The product coated on the support may be used as it is as a support-attached sheet, or the coated layer may be peeled off from the support and used as a single layer sheet consisting of a layer containing a component remaining after firing.

Like wax, the organic binder is added as necessary for the purpose of adjusting the strength, flexibility, etc. of the glass frit-containing sheet to be formed. Further, the organic binder is more useful in that it imparts adhesive strength to the adherend to the formed sheet. The organic binder used is preferably one that is burnt out by firing. For example, 300-600℃
Examples of binders for low-temperature firing include nitrocellulose-based and acrylic resin-based binders; examples of binders for medium-to-high temperature firing exceeding 500°C include urethane-based,
Examples include binders such as ethyl cellulose and polyvinyl butyral. In addition, known organic binders such as polyamide resin, petroleum resin, and styrene resin may also be used. In order to reduce the burnout temperature and improve the burnout property, it is effective to add a combustion improver made of peroxides such as sodium peroxide, calcium peroxide, and magnesium peroxide. The amount added is suitably 5 to 15% by weight of the organic binder.

The organic binder is usually formulated as a 5-40% by weight solution in an organic solvent. There are no particular limitations on the organic solvent used. Generally, pentanol, ethyl acetate, butyl cellosolve acetate, methyl ethyl ketone, methyl isobutyl ketone, toluene, etc. are used.

As the wax, known waxes such as paraffin wax and carnauba wax may be used.

The amount of the organic binder and wax to be blended is appropriately determined depending on the properties of the sheet to be formed or the layer containing the firing residual components, and the total amount thereof generally accounts for 10 to 10% of the firing residual components.
0% by weight, especially 20-80% by weight.

When forming a glass frit-containing sheet, appropriate compounding agents such as a dispersant, a softener, a solvent, a foaming agent, etc. may be added as necessary depending on the purpose of use.

As the compounding agents, known ones are used in usual amounts. High-temperature foaming agents such as sodium silicate (water glass) made of silicon oxide and sodium oxide can thicken the firing pattern,
Useful for smoothing surfaces.

In addition, fats and oils, mineral oil, rapeseed oil, vaseline, xylene resin, etc. are generally used as softeners, and toluene, isopropanol, solvent naphtha, etc. are generally used as solvents.

The glass frit-containing sheet used in the present invention may be in the form of a sheet having an adhesive layer to increase adhesive strength to an adherend. The formation is carried out, for example, by applying a sheet-forming mixture to the other side of a support having an adhesive layer on one side, or by applying the mixture onto an adhesive layer provided on a separator. be able to.

It is appropriate that the adhesive used be one that is burnt off during firing. Note that it is desirable to attach a separator to the exposed surface of the adhesive layer to improve handling properties.

The separator is peeled off when a sheet or a pattern sheet with a pattern engraved thereon is adhered to an adherend.

The thickness of the firing residual component-containing layer in the glass frit-containing sheet is 1 gm to 5μIIl to 1m in 5I+l111
Although n+ is generally used, it is not limited to this and may be determined as appropriate depending on the purpose of use.

In the present invention, a glass frit-containing sheet is used to form a patterned sheet by engraving a pattern consisting of holes or unevenness therein. It is also used as a pedestal sheet when a pattern is formed on it using baking ink.

The step of engraving a pattern consisting of holes or irregularities on the glass frit-containing sheet to form an unfired patterned sheet may be performed after the sheet and the adherend are bonded,
It may be done before the adhesion.

Therefore, in the former case, a pattern consisting of holes or irregularities is engraved on the glass frit-containing sheet that is adhered to the adherend. This method is preferably applied when the adherend is a substrate or sheet-like object. On the other hand, in the latter case, an unfired pattern sheet is formed in advance by carving a pattern of holes or irregularities on a glass frit-containing sheet, and then the pattern sheet is adhered to the adherend. This method has the advantage that fine patterns can be easily formed using an appropriate engraving device. In addition, we have adopted a transfer method, such as a method in which a layer containing firing residual components is prepared in advance on an appropriate transfer paper such as release-treated paper, film, or metal foil, and a pattern is formed on this layer and transferred to the adherend. There are some advantages to doing so.

The pattern of holes or irregularities engraved on the glass frit-containing sheet is arbitrary. Moreover, the engraving method is also arbitrary. Regarding the hole pattern, in addition to the method where the hole portion 2 of the sheet 1 represents the display content as shown in Fig. 1, there are also methods such as the method where the portion 3 of the sheet 1 other than the hole represents the display content as shown in Fig. 2. Can be adopted. Furthermore, as shown in Fig. 3, in the transfer method, etc., a perforation pattern 4 is punched out on the sheet 1, and in the end, only the inner part of the perforation pattern 4 (the shaded area) remains on the adherend. You may also adopt a method that allows This method can be preferably applied to, for example, forming barcode patterns, picture patterns, etc., and is particularly useful for applying barcode patterns to appropriate adherends. Incidentally, a pattern made of unevenness can also be used to form a barcode pattern applied to a recognition device that detects the amount of reflected light.

When adhering a glass frit-containing sheet or a patterned sheet to an adherend, if the adhesion strength is insufficient (for example, because it does not have an adhesive layer and falls easily), use an adhesive or adhesive as appropriate. It may be adhesively treated. In this case, it is preferable that the adhesive or pressure-sensitive adhesive used be one that is burnt out during firing. Note that an automatic adhesion method using a robot may also be used for the adhesion process.

Firing the unfired pattern sheet adhered to the adherend is as follows:
The heating may be carried out at an appropriate heating temperature depending on the glass frit used. As a result, the pattern sheet is fired, and the molten glass frit functions like an adhesive, so that the formed fired pattern is fixed to the adherend, thereby forming the fired pattern.

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

Another firing pattern forming method in the present invention is to bond a glass frit-containing sheet to an adherend, then provide a pattern made of firing ink on the sheet and fire it together with the sheet, so that the fired pattern is formed on the adherend. It forms the

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 patterned sheet.

Of course, the glass frit-containing sheet 1 may be formed into a patterned sheet by forming a pattern consisting of holes or irregularities.

The firing ink has traditionally been used in direct application methods such as screen printing, or in transfer methods of the coated material onto transfer paper, for example, by mixing glass frit with optional components such as pigments together with a binder. Paste-like ink may be used.

Also, a formulation for forming the glass frit-containing sheet described above for use in the present invention, which contains glass frit and other optional firing residual components, may also be used. In that case, the blending ratio of each component is glass 797810-9.
5% by weight, other firing residual components 90-5% by weight, organic binder used as necessary: 5-5% of the total firing residual components
A suitable amount is 50% by weight.

There are no particular limitations on the shape and formation method of the pattern on the glass frit-containing sheet using the baking ink. Any suitable method may be used, such as handwriting, application via a pattern-forming mask, or transfer of a pattern provided on transfer paper.

In addition, a layer of firing ink is provided on a support made of a film or the like, or an ink sheet is formed by impregnating a support made of cloth or the like with the firing ink, and this ink sheet is used to form a glass frit-containing sheet. A pattern may be formed thereon. In this case, the ink sheet can be used as a printing ribbon (by applying a pattern forming method using an XY block, wire dot type, thermal transfer type, or impact type printer, etc., to form a printed pattern, a transferred pattern, etc.). , the painting can efficiently create appropriate patterns such as patterns,
And precision (can be formed.

When the adherend consists of a substrate or the like, it is also easy to directly form a pattern on the glass frit-containing sheet adhered thereto. In addition, as a support for the baking ink used to form ink sheets used as thermal transfer ribbons, stamp transfer ribbons, stamp printing ribbons, etc., generally known plastic films such as polyester, polyimide, and fluororesin, nylon, and polyester are used. Examples include cloth made of fibers such as, but any suitable material may be selected and used. When the purpose is to form an identification label, a firing residual component such as a pigment different from that used to form the glass frit-containing sheet is used to ensure that the pattern consisting of the sheet base and firing ink is good in the fired body. It is preferable to combine them so that a contrast or difference in tone is created.

The firing pattern forming method of the present invention can be preferably applied to painting, circuit pattern formation, identification label formation, and the like. Examples of adherends that can be painted include ceramics, glass products, and floating objects. For example, the adherend may be attached with an identification label consisting of a company name, lot number, product name, delivery name, export country name, or any other identification symbol, color pattern, color pattern, bar code, etc. Made of ceramic, metal, etc.
Various products including pallets for transporting products, especially heat-resistant substrates such as ceramics, prototypes, etc. Of course, it is not limited to the above.

Effects of the Invention According to the forming method of the present invention, since an unfired sheet made of glass frit is adhered to an adherend, curved adhesion can be easily performed even on a curved surface, and The firing pattern can be formed on an adherend. The formed firing pattern is durable, heat resistant,
Excellent chemical resistance, etc.

In addition, it is possible to easily and flexibly form any pattern consisting of holes or unevenness or firing ink on an unfired sheet, and it is not only suitable for mass-produced products (identification labels for high-mix, low-volume products). Patterns such as or pictures can be easily obtained.

Further, by using an unfired pattern sheet on which a pattern consisting of holes or irregularities has been formed in advance, minute patterns can be easily formed.

Examples Reference Example 1 85 parts (by weight, same hereinafter) of lead borosilicate glass frit, 15 parts of zirconia, 10 parts of acrylic resin binder, and 40 parts of butyl cellosolve acetate were kneaded in a roll mill to make a uniform mixed paste, and this was mixed with a doctor. Using a blade type applicator, apply onto the separator that has been released.
A glass frit-containing sheet with a coating layer of about 100 μm in thickness is obtained by drying, and on the coating layer, a glass frit-containing sheet with a thickness of about 20 μm is obtained.
An acrylic adhesive layer of m was provided, and the adhesive layer was wrapped with a separator and wound up.

Reference Example 2 A glass frit-containing sheet with an adhesive layer was obtained according to Reference Example 1 using 80 parts of quartz glass frit, 20 parts of alumina, 10 parts of acrylic resin binder, and 40 parts of butyl cellosolve acetate.

Reference Example 3 85 parts of lead borosilicate glass frit, 15 parts of alumina,
A glass frit-containing sheet with an adhesive layer was obtained according to Reference Example 1 using 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 lead borosilicate glass frit, 5 parts of alumina, 10 parts of acrylic resin binder, and 40 parts of butyl cellosolve acetate.

Reference Example 5 15 parts of lead borosilicate glass frit, 60 parts of black pigment,
10 parts of polyamide resin, 10 parts of rapeseed oil, and 5 parts of toluene isopropanol were kneaded in a three-roll mill to obtain a firing ink consisting of a uniformly mixed paste, and this was impregnated into fabric using a coating machine to obtain a printing ribbon. .

Reference Example 6 80 parts of lead borosilicate glass frit, 20 parts of black pigment (chromium oxide-iron oxide-cobalt oxide), 15 parts of ethyl cellulose binder, and 50 parts of terpineol were kneaded in a roll mill to make a uniform mixed paste, and the resulting mixture was used to prepare an ink for firing. I got it.

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

Reference Example 8 85 parts of lead borosilicate glass frit, 15 parts of black pigment (chromium oxide-iron oxide-manganese oxide-cobalt oxide),
15 parts of ethylcellulose binder, 5 parts of terpineol
A baking ink was obtained according to Reference Example 6 using 0 parts.

Example 1 A mark having a predetermined pattern of unevenness was pressed on a cut piece of 30 mm x 50 mm obtained by cutting the glass frit-containing sheet obtained in Reference Example 1, and the surface was marked with a radius of curvature made of stainless steel whose surface had been heated and oxidized. After adhering to a 50 mm metal tube via the adhesive layer, it was baked at 450° C. for 30 minutes. The separator was peeled off in advance (the same applies below). Note that during firing, the adhesive and organic binder were completely burned out before the glass frit was melted.

As a result of the above, a metal cylinder was obtained, to which an identification label made of a white fired body with the pressing pattern well preserved was firmly attached.

Example 2 A cut piece of 30+a x 50m+ obtained by cutting the glass frit-containing sheet obtained in Reference Example 1 was adhered to a metal plate via the adhesive layer, and then the above-mentioned mark was pressed on the cut piece, A metal plate was obtained by firing in accordance with Example 1, to which an identification label was firmly attached, which was made of a fired body in which the white press pattern was well preserved.

Example 3 A cut piece of 30 + no +
It was baked at 0°C for 1 hour. During firing, the adhesive and organic binder were completely burned out before the glass frit melted.

As a result of the above process, a metal tube was obtained which had a strong identification label made of a fired body having a clear pattern of ground-colored numbers surrounded by a white frame.

Example 4 After adhering the glass frit-containing sheet obtained in Reference Example 4 to an aluminum plate via its adhesive layer, a roller having protruding lines of different widths provided at various intervals on the coating layer of the sheet was pressed and rotated. A pattern consisting of barcode-like unevenness was engraved on the substrate, and this was baked at 600° C. for 10 minutes. During firing, the adhesive and organic binder were completely burned out before the glass frit melted.

As a result of the above process, an aluminum plate was obtained, on which a white coating layer was firmly fixed, in which a pattern consisting of barcode-like irregularities was well preserved.

Example 5 After adhering the glass frit-containing sheet obtained in Reference Example 3 onto a ceramic substrate via its adhesive layer, a cartridge containing the printing ribbon of Reference Example 5 and a common dot printer were used to adhere the glass frit-containing sheet obtained in Reference Example 3 to the ceramic substrate. A predetermined barcode pattern was formed, and this was baked at 650° C. for 10 minutes.

As a result, 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 onto a glass plate via its adhesive layer, and then a barcode pattern was printed on it using the baking ink obtained in Reference Example 6. was screen printed and baked at 450°C for 30 minutes.

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

Example 7 A small piece of the glass frit-containing sheet obtained in Reference Example 2 was adhered onto a ceramic substrate via its adhesive layer, and then a barcode pattern was printed on it using the baking ink obtained in Reference Example 7. Screen print this at 1000°C.
Baked for an hour.

As a result, 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 Glass frit-containing sheet obtained in Reference Example 3 and Reference Example 8
The firing condition was set to 600℃.
℃ for 10 minutes, in accordance with Example 7, to obtain a ceramic substrate in which a fired body having a predetermined black barcode pattern was firmly adhered to a white background.

[Brief explanation of the drawing]

FIG. 1, FIG. 2, FIG. 3, and FIG. 4 are explanatory diagrams of examples of pattern formation. 1 Nigaras frit-containing sheet or patterned sheet 2: Hole portion 3: Portion other than holes 4: Hole line pattern 5: Pattern consisting of firing ink Patent applicant: Nitto Electric Industry Co., Ltd. Former Daiken Chemical Industry Co., Ltd. Representative: Mr. Fuji Book Tsutomu Figure 1 Figure S Figure Now Figure 2 Figure 4

Claims (1)

[Scope of Claims] 1. An unfired pattern sheet made by engraving a pattern consisting of holes or irregularities on a glass frit-containing sheet is adhered to an adherend, and the pattern sheet is fired by heat treatment. A method for forming a fired pattern, the method comprising: forming a fired pattern. 2. An unfired pattern sheet made by engraving a pattern consisting of holes or irregularities on a glass frit-containing sheet. 3. A glass frit-containing sheet is adhered to an adherend, a pattern consisting of holes or unevenness is engraved on the glass frit-containing sheet, and the formed unfired pattern sheet is heat-treated and fired, and the glass frit-containing sheet is engraved onto the adherend. A firing pattern forming method characterized by forming a firing pattern. 4. Firing characterized by adhering a glass frit-containing sheet to an adherend, and then providing a pattern made of firing ink on the sheet and firing it together with the sheet to form a fired pattern on the adherend. Pattern formation method.