JPH08337042A - Sheet for forming pattern as well as forming and fixing method of pattern - Google Patents

Abstract

PURPOSE: To obtain a pattern forming sheet, capable of transferring ink on the surface of a substance easily and fixing the formed transfer pattern surely on the substance by baking the substance, by retaining the ink, containing inorganic compound and glass frit, on a substrate or in the substrate uniformly. CONSTITUTION: A sheet for forming pattern, which is employed for decorating and the like on a pottery, is constituted of a substrate provided uniformly with ink containing inorganic compound and glass frit, while a pattern, transferred on the surface of a substrate, is fixed onto the substance rigidly by melting the glass frit through baking. Upon actual. operation, black pigment, glass frit and the like are kneaded and dispersed to make paste while the paste is applied on a very thin polyethylene terephthalate film 1 and dried to manufacture a stamp transferring ribbon. Then, the obtained ribbon is employed to print the pattern 5 on a ceramics substrate 7 by a stamp transferring printer, then, the substrate 7 is baked at 650 deg.C to form the pattern 5'.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a pattern forming sheet, a printing ribbon and an ink ribbon cartridge using the pattern forming sheet, an ink receiving type flexible sheet for firing, a firing label material using the same, and a holder for these. Also, the present invention relates to a pattern formation fixing method using these.

[0002]

2. Description of the Related Art A technique for fixing a pattern by baking on a ceramic, forming a circuit pattern on a hybrid thick film IC substrate, forming patterns of electrodes, resistors, dielectrics, etc. of various electronic parts. In the field, in the conventional pattern formation, pigment, conductive material, resistance material, dielectric material, etc. are mixed with glass frit and a binder to form a paste-like ink, and the paste-like ink is formed by a screen printing method or the like. Printing and firing methods have been adopted. However, although the screen printing method is suitable for mass production of a single product, it takes a lot of time and money from the production of the plate to the production of the screen, resulting in a significant decrease in production efficiency. Therefore, it is not suitable for small-lot production of many kinds and product testing.

As a method of transferring the pattern to the base material, there are a direct printing method, a method of once printing on a transfer paper and a transfer method such as a water transfer method. However, even in this case, there is a problem in printing on a curved surface and automation of printing. In order to solve the above-mentioned problems, the present inventor first, as a pattern forming method, a method of drawing a pattern from the upper side of carbon paper by an XY plotter or the like, which is remarkably popular recently, and overlaps dots arbitrarily. Attempts were made to use various printers capable of forming the pattern. However, the carbon paper used in these plotters or the printing ribbon used in printers have the following basic drawbacks.

That is, as a conventional pattern forming sheet such as a carbon paper or a printing ribbon, for example, each color pigment such as carbon is kneaded and dispersed with a wax, a binder or the like to form a paste, and the paste is polyethylene terephthalate or the like. The film may be coated on the film, or the cloth may be impregnated with cloth, but since these are originally intended only for printing or transferring patterns, a step of baking at about 300 to 1400 ° C. When it is used for the above-mentioned required applications, the formed pattern is burnt or deteriorated, and a satisfactory pattern, printing, etc. cannot be obtained. Therefore, it can be said that there has not been a technical means suitable for the production of a large number of kinds in a small amount in the formation of a pattern that requires fixing the pattern by firing. The formation of such a pattern that requires firing is not only applied to the production means of the product itself as described at the beginning. In other words, in recent high-mix low-volume production processes, there are those that require heat treatment, chemical treatment with acid or alkali, various surface treatments, etc., but in production control of such products, raw materials or semi-finished products are required. There is an increasing need to attach a management label to each and to individually change the conditions of each process based on the information displayed on the label.

In such a management label, it is necessary to form a different recognition pattern for each sheet, that is, it is necessary to form a small number of patterns of a wide variety of products, and further, heat resistance, chemical resistance, and durability. It is required to have excellent properties. Conventionally, as a management label for glass products, metal products, sintered ceramics products, etc., which have excellent heat resistance, chemical resistance, durability, etc., those based on plate materials such as fired ceramics, enamel, stainless steel, etc. Is used.
However, these labels have various problems as described below.

(A) Since the substrate is generally flat and lacks flexibility, it cannot be attached to a curved surface, and it is also difficult to attach it directly to a product or automatically. is there. Therefore, it has to be fixed with screws or to be inserted into a pocket. (B) Since the flexibility of the substrate is low, it is difficult to perform automatic printing by a printer or the like, and thus it is difficult to issue a label on the spot in a factory production line. For this reason, it is impossible to issue a management label having a different pattern for each sheet in response to changes in the production items often performed in an automated production line that performs high-mix low-volume production. (C) Due to the high cost of materials, it is difficult to dispose of labels for each individual product.

[0007]

DISCLOSURE OF THE INVENTION In the technical field in which it is necessary to fix the pattern by firing as described above, the present inventor is lagging behind in dealing with small-lot production of a wide variety of products and automation and the firing. The subsequent pattern is generally excellent in heat resistance, chemical resistance, and durability, but since the material of the substrate to which the pattern is usually fixed is extremely poor in flexibility,
In view of various problems such as the management label illustrated above, it is intended to provide a technical means capable of fundamentally solving these problems.

The present invention provides (1) fundamental pattern formation,
A member for fixing, that is, a pattern forming sheet applicable to small-lot production of various kinds of printing ribbons or carbon paper, (2) An ink receiving type with flexibility as a substrate on which the pattern is to be fixed Flexible sheet for firing, holder for ensuring ease of handling of the flexible sheet, further, label material for firing having a pattern formed on the surface of the flexible sheet, and holder for ensuring handleability thereof The development of
(3) An effective pattern forming and fixing method using these members is provided.

[0009]

In the pattern forming sheet, the substrate uniformly has the ink containing the inorganic compound and the glass frit on the surface and / or the inside thereof.
The pattern transferred to the surface of the object is firmly fixed to the object including the inorganic compound because the glass frit is melted by firing. If the ink further contains an organic binder and / or wax, the pattern can be temporarily fixed to the object before firing. The inorganic compounds include inorganic pigments, metal powders, metal oxide powders and the like. It is convenient to handle if the substrate is coated or impregnated with the ink. If this is cut into a certain width and used as a printing ribbon to form an ink ribbon cartridge housed in a box, it becomes easy to use in various printers and is particularly convenient.

If the pattern forming sheet is placed on the surface of the object, the ink can be easily transferred to the surface of the object. The transfer pattern thus formed is then burned on the object to form the object. Can be securely fixed. In such a pattern forming and fixing method, using the above-mentioned ink ribbon or the like, using a thermal transfer type printer, an impact type printer, or a wire dot type printer of a format in which dots are printed as a transfer means,
In addition to directly transferring to a target object, it is transferred to a conventionally used transfer paper and then transferred to an object, or a special flexible sheet as described later or stainless steel or other metallic materials instead of it. A foil / sheet or the like can be used. This makes it possible to fix the pattern to a curved object without difficulty.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION A flexible sheet for ink-receptive firing for fixing a flexible sheet pattern is provided on one side of an adhesive layer such as an organic polymer resin with or without other flexible supporting members. If the ink receiving layer containing the inorganic compound and the glass frit is provided, the sheet can be temporarily fixed until the pressure-sensitive adhesive layer is attached to the object and fired.
At the time of firing, the pressure-sensitive adhesive layer is burned off, the glass frit is melted, and the ink and the inorganic compound are welded while being wrapped, so that the ink and the inorganic compound do not change even by firing, and a good pattern can be fixed. To be achieved.

Since the ink receiving layer inherently contains an inorganic compound and glass frit which lack flexibility, an organic binder may be further added to the ink receiving layer so that the ink receiving layer is more flexible and has heat resistance for firing. Flexible sheet. The inorganic compound may be an inorganic pigment described later, or may be an inorganic compound fiber when more flexibility is desired.

Usually, it has a self-supporting property due to a certain degree of rigidity of the ink receiving layer.
The strength may be improved by providing an ink receiving layer on one surface of the pressure-sensitive adhesive layer via another supporting member. In order to protect the pressure-sensitive adhesive layer and ensure the handleability even when the flexibility and strength are imparted in this way, the ink receiving type in which the other surface of the pressure-sensitive adhesive layer is coated with a releasable substrate is used. The flexible sheet holder for firing is more preferable from the viewpoint of handling and storage.

Pattern Forming and Fixing Method In the ink receiving type flexible sheet for baking, if a pattern is formed with an ink containing an inorganic compound different from the inorganic compound in the ink receiving layer and a glass frit, a good contrast baking is achieved. It can be used as a label material.
Also for this label material for firing, it is convenient to handle the label material holder for firing in which the pressure-sensitive adhesive layer is coated with the releasable substrate. On the ink receiving layer of such an ink receiving type flexible sheet for baking, a pattern is formed with an ink containing an inorganic compound different from the inorganic compound in the ink receiving layer and a glass frit, and then the pattern is formed by baking. Can be reliably formed and fixed.

When the formation and fixation of the pattern is performed by transferring the ink from the pattern forming sheet of the present invention to the ink receiving type flexible sheet for firing, automatic attachment by a robot becomes possible, and efficient and high-mix low-volume production is possible. Conforms to. When the printing ribbon of the present invention is used for pattern formation and the transfer is performed by a thermal transfer printer, an impact printer or a wire dot printer, it is possible to immediately form an arbitrary pattern with higher efficiency by a computer instruction. You can With such a pattern forming method, efficient pattern forming means for producing a variety of products in small quantities, for example, painting on ceramics, forming circuit patterns of thick film IC substrates, production of products, etc. Product or product management label material used in process, distribution process, production process,
It is possible to provide an effective method of forming a management pattern on a product or a product in a distribution process or the like.

Pattern Forming Sheet (Ink) In a preferred embodiment, the ink used in the pattern forming sheet and the printing ribbon made of the pattern forming sheet includes glass frit, an inorganic pigment, a metal powder and a metal oxide powder. Including. Any known glass frit can be used. Any known inorganic pigment can be used, and for example, red pigments, blue pigments, black pigments, natural mineral pigments and the like can be used.

Examples of red pigments include iron, chromium, copper,
Any known one containing at least one kind of metal ion such as gold or selenium can be used. For example, MnO—Al ₂ O ₃ , C
The _{r 2 O 3 -SnO 2, Fe} 2 O 3, CdS-SeS , etc. can be used. As the blue pigment, any known pigment containing at least one kind of metal ion such as copper, manganese, iron and cobalt can be used, and examples thereof include CoO, ZrO ₂ —V ₂ O ₃ ,
The Cr ₂ O ₃ -V ₂ O ₅ or the like can be used. As the black pigment, any known pigment containing at least one kind of metal ion such as iron, manganese, copper, chromium and cobalt can be used.
For example, it can be used _{Cr 2 O 3 -CoO-Fe 2} O 3 -MnO 2 , and the like.

As the metal powder, any of those used for printing by a screen printing method, forming a pattern or the like can be used. For example, powder of silver, gold, platinum, palladium, copper, nickel, tungsten or the like can be used. Further, it is possible to use a conductor forming material for electronic circuits such as and alloys. The metal oxide powder is one other than the metal oxide used in the above pigment, and specific examples thereof include resistors such as ruthenium oxide and dielectrics such as barium titanate. The particle size of the metal powder and the metal oxide powder is not particularly limited and may be appropriately selected, but is usually 0.1 to 2
Use the thing of about 0 μm.

The blending amount of each of the above components is not particularly limited and may be appropriately selected according to the purpose of pattern formation.
Usually, about 1.0 to 60% by weight of glass frit and about 10 to 80% by weight of at least one selected from inorganic pigments, metal powders and metal oxide powders may be contained. The ink used for the pattern forming sheet and the printing ribbon preferably contains an organic binder and / or wax. As the organic binder and wax, any known ones can be used, and for example, polyamide resin, petroleum resin, styrene resin, paraffin wax, carnauba wax and the like can be used. The blending amount of the organic binder and / or wax is not particularly limited and may be appropriately selected, but is usually 10 to 50% by weight in the ink.
It may be included to some extent.

In addition to the above components, at least one kind of dispersant, softening agent, solvent, foaming agent or the like may be added to the ink, depending on the purpose of pattern formation. Any of various commercially available dispersants can be used. Any known softening agent can be used, and for example, fats and oils, mineral oil, rapeseed oil, petrolatum, xylene resin and the like can be used. Any known solvent can be used, and for example, toluene, isopropanol, solvent naphtha and the like can be used. The blending amount of these is not particularly limited and may be appropriately selected depending on the application.

After the pattern formation, the ink is mixed with a material that foams at a high temperature, such as sodium silicate (water glass) in which silicon dioxide and sodium oxide are bonded together.
It is also possible to swell the pattern portion immediately after putting it in the firing furnace, and then to fix the swelled pattern after reaching the firing temperature. This ink can be produced by kneading the above components according to a usual method. At that time, as the kneading device, any known device can be used, and for example, a roll mill, a pot mill, a three roll mill, or the like can be used.

Pattern Forming Sheet (Substrate) As the film used for the pattern forming sheet and the printing ribbon, any of those conventionally used for printing ribbons and the like can be used. Examples thereof include polyethylene terephthalate and Teflon. , Synthetic resin film such as polyimide , fiber cloth such as nylon and polyester can be used.
It

Production of Pattern Forming Sheet In coating or impregnating the above-mentioned ink on a film, any known coating and impregnating method can be adopted.

Pattern Forming and Fixing Method The pattern forming sheet and the printing ribbon can be used by applying them to various printers having partial pressure or dots by manual operation, and the desired pattern, printing, etc. can be formed on the substrate itself or the transfer paper. Can be formed. For example, when using a printer to paint ceramics, form a circuit pattern on a mixed thick film IC substrate, and form patterns of electrodes, resistors, derivatives, etc. of various electronic components, 1) A method of directly printing a pattern on a substrate and baking it. 2) Once printing on a transfer paper or the like used for painting ceramics, etc., and then transferring this onto a target substrate to form a pattern. Any method such as a method of firing, 3) a method of temporarily transferring and printing it on an ink-receptive flexible sheet for firing, then pasting it onto a target substrate by a robot or the like to form a pattern and firing it can be adopted. .

The printing ribbon can be used as various printing ribbons such as a thermal transfer ribbon, an imprint transfer ribbon, and an imprint printing ribbon, depending on the type of the substrate to be patterned and the printer. Pattern forming sheets and printing ribbons are used, for example, to make picture plates for painting ceramics, glassware, enamel, etc., make circuit patterns such as mixed thick film ICs, and bar code labels using heat resistant substrates such as ceramics. It can be used for creating patterns.

Flexible Sheet (Ink Receiving Layer) As an inorganic compound constituting the ink receiving layer of the ink-receptive heat-resistant flexible sheet for baking, when used as a recognition label, it is clearly defined between the recognition pattern and the baking pattern. It is preferable that the ink receiving layer has a white contrast or a color close to white.
Carbonate, nitrate, and the like, which are oxidized at the sintering temperature of the powder of metal oxide ceramics such as SiO ₂ , ZrO ₂ , TiO ₂ , Al ₂ O ₃ , and CaO and the label to become these metal oxides,
Metal compounds such as sulfates can be used. These metal oxides and metal compounds may be used alone or in combination as needed.
Used as a mixture of two or more species. The flexibility can be increased by including inorganic compound fibers such as various ceramic fibers (alumina fibers, glass fibers, carbon fibers, etc.).

As the glass frit which is another material constituting the ink receiving layer, the glass frit also plays a role as a shape-retaining material for keeping the above metal oxide in a sheet form after firing at about 400 to 1700 ° C., Although not particularly limited,
400 to 1700 ° C, depending on the type of object to be fixed
What softens or melts within a certain range may be appropriately selected and used.

For example, when firing in a low temperature range of about 400 to 600 ° C., a lead glass system is used, and
When firing in a medium temperature range of about 1000 ° C., lead borosilicate glass type, soda glass type, etc. are used.
When firing is performed in a high temperature range of about 0 ° C. or higher, it is preferable to use a silicate glass type or a quartz glass type. As this glass frit, it is preferable that the glass frit also exhibits a color close to that of the ceramic in the coexistence state with the ceramic after firing and exhibits a clear contrast with the pattern.

When the ink-receptive flexible sheet for firing is used for printing and transferring a pattern, it is desirable that the glass be melted so as to sufficiently wrap the pigment in the ink after firing, and the glass in the ink-receptive layer The inorganic compound may be selected from those exhibiting a color that is well balanced with the pattern. When a circuit pattern is printed and attached to a substrate, it is desirable to select glass or an inorganic compound in consideration of sufficient adhesiveness after firing and preventing pinholes or cracks from entering.

As an organic binder which can be mixed to form an inorganic compound and a glass frit into a sheet, there is sufficient strength and flexibility as a label for a sheet without leaving ash content by sufficiently decomposing and burning during firing. It is required to be able to add such as. When the firing temperature is low, decomposition and combustion of the organic binder is insufficient, and incombustibles tend to remain, so it is necessary to pay attention to the selection, and materials such as nitrocellulose type and acrylic resin type are suitable. There is. When the firing temperature is high, the above-mentioned restrictions are relatively small, and urethane type, ethyl cellulose type, polyvinyl butyral type and the like can be used in addition to the above materials.

When the firing temperature is low and the decomposition and combustion of the binder are not sufficiently performed, known peroxides (eg sodium peroxide, calcium peroxide,
5% to 15% of binder weight by weight such as magnesium peroxide)
It is preferable to add to some extent. The organic binder is usually used as an organic solvent solution of about 5 to 40% by weight. The organic solvent is not particularly limited, and butyl carbitol, ethyl acetate, butyl cellosolve acetate, methyl ethyl ketone, methyl isobutyl ketone, toluene and the like can be used.

The inorganic compound different from the above used in the ink for forming the ink recognition pattern is excellent in heat resistance, corrosion resistance, durability and the like, and has a clear contrast with the sheet-like substrate after firing. Is not particularly limited as long as it indicates. When the sheet-shaped base material exhibits white or a color close to white,
Specifically, for example, oxides of single metals such as Fe, Cr, Co, and Mn, complex metal oxides composed of two or more of these metals, mixtures composed of two or more single metal oxides,
It is possible to use various black pigments or the like which are usually used for painting ceramics.

The glass frit used in the ink may be the same as that used in the ink receiving layer, but it is preferable that it does not affect the color of the pattern formed after firing. As the organic binder and the organic solvent used for preparing the ink, the same ones as used above can be used. As long as there is a clear contrast between the ink receiving layer and the pattern, the inorganic material used in the ink receiving layer and the inorganic material used in the ink may be used interchangeably. Even when there is a clear color difference between the ink receiving layer and the recognition pattern, accurate product management is performed, and therefore, each inorganic material that can form such a color difference is selected and used. May be.

Manufacture of Flexible Sheet The ink-receptive flexible sheet for firing can be usually manufactured as follows. First, the first inorganic compound 3 to 90
To 100 parts by weight of a mixture consisting of 100% by weight and glass frit of 97 to 10% by weight, a solution of an organic binder corresponding to about 20 to 80 parts by weight as a solid content is added and kneaded to prepare a paste, which is processed into a sheet. To do. When processing into a sheet, it may be applied onto a separate substrate film.

The mixing ratio of the inorganic compound and the glass frit is determined mainly depending on the baking temperature of the sheet to the article, the smoothness of the sheet, etc. When the baking temperature is low, the sheet surface requires a high degree of smoothness. In such cases, glass frit having a low melting point is often used. Inorganic compounds are often used when the baking temperature is high or when the smoothness of the sheet surface is not so required. In this way, an ink receiving type flexible sheet for firing is obtained.

Production of label material for firing (pattern formation
(Constant method) In order to manufacture a label material for firing, usually, in parallel with this, another inorganic compound (5 to 90% by weight) and a glass frit (9) are used.
To 100 parts by weight of a mixture composed of 5 to 10% by weight, a solution of an organic binder corresponding to about 5 to 50 parts by weight as a solid content is added and kneaded to obtain an ink. This ink is applied to a flexible sheet in a predetermined pattern to form a label material for firing.

The form of the pattern is any pattern or circuit pattern, and in the case of a pattern to be recognized by it, an arbitrary identification symbol such as a bar code, a company name, a lot number, a product name, a delivery destination name, an export country name, etc. Is also good. The pattern may be formed in a plurality of colors. When forming the pattern, screen printing may be directly performed on the sheet, or transfer printing using a thermal transfer ribbon or a dot impact ribbon may be performed.

Flexible Sheet (Adhesive Layer) The ink-receiving type flexible sheet for firing and the label material for firing are coated with an adhesive on the surface opposite to the surface on which the pattern is formed. It is preferable that a release substrate such as a release film or a release paper is coated on it in a bonded state.
It is advantageous in handling. As the pressure-sensitive adhesive, one that decomposes and burns out during baking may be selected.

Use of Flexible Sheet A flexible sheet (a label material for firing) is used in a predetermined range of 400 to 1700 ° C. after the release film or release paper is removed, and the adhesive sheet is fixed to an object with an adhesive. It suffices to bake at the temperature. Alternatively, it may be baked after being attached to an object by a water slide transfer method. The object referred to here may be anything that does not lose its shape by firing, and includes ceramics, ceramic substrates, products to be managed, and pallets therefor.

[0040]

EFFECT OF THE INVENTION When the pattern forming sheet and the printing ribbon of the present invention are used, it has been difficult to form an arbitrary pattern, printing, etc., in the pattern forming step which requires a firing step. The desired pattern, printing, etc. can be easily obtained, and more remarkable labor saving and efficiency can be achieved compared with the screen printing method which has been conventionally adopted. Mass production of a single kind and small quantity production of many kinds. Suitable for both.

The ink-receiving type flexible sheet for firing and the label material for firing of the present invention are low in cost and have a high degree of flexibility, so that they can be easily pasted and used directly on products of any shape. be able to. Further, since the pattern can be easily formed and fixed on site, it is possible to immediately respond to the change of the production line which is often carried out in the automated factory which carries out the production of a wide variety of products in small quantities. Further, after firing, the sintered body is excellent in heat resistance, corrosion resistance, water resistance, durability, etc., so that it is possible to perform highly reliable pattern fixing.

[0042]

【Example】

Example 1 (Ribbon for thermal transfer) Each component shown in Table 1 was kneaded and dispersed in a roll mill heated to 80 ° C. to form a paste, and this paste was applied to an ultrathin polyethylene terephthalate film having a thickness of 5 μm by a coating machine. The coated film was dried so that the thickness of the coating film after drying was about 10 μm and dried to obtain a pattern-forming flexible sheet, which was cut into a predetermined width to manufacture the thermal transfer ribbon of the present invention.

The obtained ribbon was wound on a roll and housed in a predetermined box to form an ink ribbon cartridge, which was set in a usual thermal transfer printer to print a pattern on a transfer paper. An overcoat is applied and dried on this in the same manner as in the usual case, and then the transfer pattern is peeled off from the transfer paper together with the overcoat in water and transferred onto a ceramic (dish), and then at 650 ° C. Upon firing, the desired pattern could be formed on the dish.

[0044]

[Table 1] Ink Black pigment 50% by weight Glass frit (lead silicate silica) 20% by weight Carnauba wax 13% by weight Paraffin wax 12% by weight Vaseline (softener) 5% by weight .

Example 2 (Ribbon for imprint transfer) The components shown in Table 2 were kneaded and dispersed with a stirrer to form a paste, and this paste was coated with an ultrathin polyethylene terephthalate film (1) having a thickness of 5 μm. Then, the coated film (3) was dried so that the thickness of the coated film (3) was about 15 μm and dried to manufacture an imprint transfer ribbon (see FIG. 1). Using the obtained ribbon, an ink cartridge produced in the same manner as in Example 1 was used to directly print a predetermined pattern (5) on a ceramics substrate (7) with an ordinary imprinting transfer printer, followed by firing at 650 ° C. The target circuit pattern (5 ′) could be formed on the ceramic substrate (see FIG. 2).

[0046]

[Table 2] Ink silver powder 80% by weight Glass frit (lead lead silicate type) 5% by weight Polyamide type resin 10% by weight Toluene 5% by weight .

Example 3 (Printing ribbon for imprinting) Each component shown in Table 3 was kneaded and dispersed by a three-roll mill to form a paste, and this paste was impregnated into a cloth by a coating machine to obtain a printing ribbon for imprinting. Manufactured. Using the obtained ribbon, an ink ribbon cartridge was obtained in the same manner as in Example 1, a bar code pattern was printed on a ceramic substrate by an ordinary dot printer, and fired at 650 ° C. to obtain heat resistance, weather resistance and chemical resistance. I was able to obtain an excellent barcode label.

[0048]

[Table 3] Ink Black pigment 60% by weight Glass frit (lead silicate silica) 15% by weight Rapeseed oil 10% by weight Polyamide resin 10% by weight Toluene isopropanol 5% by weight .

Example 4 The composition shown in Table 4 was uniformly kneaded with a roll mill to form a paste, which was then first coated with a doctor blade type coating machine.
Apply to the release surface of the release film, and dry it to a thickness of about 1
A coating film of 00 μm was formed. Then, the coating film is wound together with the first release film on a roll, an acrylic resin-based pressure-sensitive adhesive is applied to the coating film by a gravure coating machine, and dried to form a pressure-sensitive adhesive layer having a thickness of about 20 μm. After the second
The release film of 1 was laminated on the pressure-sensitive adhesive layer to obtain a flexible sheet holder for firing ink. Next, the first release film is peeled off, and a material for joining with the flexible sheet for ink-receptive firing comprising the second release film (13), the pressure-sensitive adhesive layer (11) and the receiving layer (9) is prepared. Obtained (see FIG. 3).

Using the inks having the compositions shown in Table 5, a bar code pattern (5) was formed on the receiving layer side of the above laminated material by a screen printing method to obtain a label material holder for firing (Fig. 4). Then, the second release film attached to the obtained label material holder for firing was peeled off, adhered to a glass product with an adhesive, and the glass product was annealed at 450 ° C. for 30 minutes and held in a furnace,
Prior to the melting of the glass frit, the pressure-sensitive adhesive and the organic binder in the receiving layer were completely decomposed and burned down, and a black bar code pattern was formed on the white base material with a high contrast and firmly fixed.

[0051]

[Table 4] Flexible sheet (ink receiving layer) ZrO ₂ 15 parts by weight Lead borosilicate glass frit 85 parts by weight Acrylic resin binder 10 parts by weight Butyl cellosolve acetate 40 parts by weight

[0052]

[Table 5] Ink Black pigment (1) 20 parts by weight Lead borosilicate type glass frit 80 parts by weight Ethylcellulose type binder 15 parts by weight Terpineol 50 parts by weight Note: (1) Consists of Cr ₂ O ₃ , Fe ₂ O ₃ and CoO Mixed pigments.

Example 5 The composition shown in Table 6 was processed into a sheet in the same manner as in Example 4, and then a bar code pattern was screen-printed using the ink having the composition shown in Table 7. The thus obtained label material for firing was attached to MnZn ferrite, and the ferrite was fired at 1000 ° C. for 1 hour, and the adhesive and the organic binder in the label were completely decomposed and burned off before melting the glass frit. A black barcode pattern was formed on the white base material with a strong contrast and was securely fixed.

[0054]

[Table 6] Flexible sheet (ink receiving layer) 20 parts by weight SiO ₂ 80 parts by weight quartz glass frit 80 parts by weight acrylic resin binder 10 parts by weight butyl cellosolve acetate 40 parts by weight

[0055]

[Table 7] Ink Black Pigment (2) 15 parts by weight Quartz glass frit 85 parts by weight Ethylcellulose based binder 15 parts by weight Terpineol 50 parts by weight Note: (2) Consists of Cr ₂ O ₃ , Fe ₂ O ₃ , MnO and CoO Mixed pigments.

Example 6 The composition shown in Table 8 was processed into a sheet in the same manner as in Example 4, and then a bar code pattern was screen-printed using the ink having the composition shown in Table 9. 600 in advance
The baking label material obtained as described above was attached to the surface of a stainless steel product having a thin oxide film formed on its surface by heat treatment at 600 ° C.
When baked for 0 minutes, the adhesive and the organic binder in the label were completely decomposed and burned off before the glass frit was melted, and a black barcode pattern was formed on the white base material with a strong contrast, and it was ensured. fixed. or,
The preformed oxide film and the glass frit were fused on the surface of the stainless steel product, and the label and the product adhered extremely strongly.

[0057]

[Table 8] Flexible sheet (ink receiving layer) Al ₂ O ₃ 15 parts by weight Lead borosilicate glass frit 85 parts by weight Acrylic resin binder 10 parts by weight Butyl cellosolve acetate 40 parts by weight

[0058]

[Table 9] Ink Black Pigment (3) 15 parts by weight Lead borosilicate glass frit 85 parts by weight Ethylcellulose based binder 15 parts by weight Terpineol 50 parts by weight Note: (3) Cr ₂ O ₃ , Fe ₂ O ₃ , MnO and CoO A mixed pigment consisting of.

Example 7 Using the ink ribbon cartridge obtained in Example 1,
A bar code pattern was formed on the ink receiving layer side of the laminated material obtained in Example 4 with a thermal transfer printer to obtain a label material holder for firing. Then, it was attached to a glass product with an adhesive in the same manner as in Example 4 and baked under the same conditions as in Example 4. As a result, a black barcode pattern was similarly formed on a white substrate with strong contrast, Fixed to.

Example 8 (Circuit pattern) Each component described in Table 10 was processed into a ribbon for thermal transfer in the same manner as in Example 1, and then each component described in Table 11 was processed in the same manner as in Example 4 into a sheet form. After processing into a sheet, a gold conductor circuit pattern was printed on the sheet with a thermal transfer printer, the sheet was carefully attached to the alumina substrate so as not to leave bubbles, and then baked at 800 ° C. A circuit pattern which was formed on the substrate and had sufficient conductivity without cracks or pinholes and without breakage was formed.

[0061]

[Table 10] Ink gold powder 70 parts by weight Glass frit (lead borosilicate) 5 parts by weight Garnabeu wax 10 parts by weight Paraffin wax 12 parts by weight Vaseline 3 parts by weight

[0062]

[Table 11] Flexible sheet (ink receiving layer) Al ₂ O ₃ powder 5 parts by weight Lead borosilicate glass frit 95 parts by weight Acrylic resin binder 10 parts by weight Acetate 40 parts by weight

[Brief description of drawings]

FIG. 1 is a sectional view of an imprint transfer ribbon obtained in Example 2.

FIG. 2 is a sectional view showing a process of forming a circuit pattern on a ceramic substrate using the imprint transfer ribbon obtained in Example 2.

FIG. 3 is a cross-sectional view showing a material to be combined with an ink receiving type flexible sheet for baking obtained in Example 4.

FIG. 4 is a cross-sectional view of a label material holder for firing, which is produced by using the laminating material shown in FIG.

Claims (7)

[Claims] 1. A pattern forming sheet for uniformly holding an ink containing an inorganic compound and a glass frit on or in a substrate. 2. The pattern forming sheet according to claim 1, wherein the ink containing the inorganic compound and the glass frit further contains an organic binder or a wax. 3. The pattern forming sheet according to claim 1, wherein the substrate is coated or impregnated with an ink containing an inorganic compound and a glass frit. 4. A printing ribbon obtained by cutting the pattern forming sheet according to claim 1 into a predetermined width. 5. An ink ribbon cartridge containing the printing ribbon according to claim 4 in a box. 6. The pattern forming sheet according to claim 1 is placed on the surface of an object, and an ink containing an inorganic compound and glass frit is transferred to the surface of the object, or the ink is transferred to the surface of the object. A method for fixing and forming a pattern, comprising the steps of transferring to a transfer paper, transferring to the object to form a pattern, and then baking the object to fix the pattern. 7. The flexible sheet is used as an object on which the pattern forming sheet is placed, and the ink containing the inorganic compound and the glass frit is transferred by a thermal transfer printer, an impact printer or a wire dot printer. The method for fixing pattern formation according to [4].