JPH02283676A - Production of metal substrate having baked pattern - Google Patents

Abstract

PURPOSE:To produce the subject substrate having improved durability by attaching a baking sheet having baking pattern to a surface of a ceramic sheet containing ceramic powder and a resin binder, temporarily attaching a metal substrate to the other surface via a tacky adhesive layer and baking the laminate. CONSTITUTION:A ceramic sheet having a thickness of 10-500mum is produced by mixing 100 pts.wt. of ceramic powder such as lead borate glass powder with about 20 pts.wt. of TiO2, about 1 pt.wt. of a melt accelerator such as Al2O3, about 20 pts.wt. of polyisobutyl methacrylate and about 48 pts.wt. of a solvent, etc. A tacky adhesive layer having a thickness of 5-50mum and containing acrylic tacky adhesive is formed on one surface of the ceramic sheet and a bar-code pattern is printed to the other surface with a baking ink containing an inorganic colorant, a binder and a solvent through a pattern mask and the printed layer is dried to obtain a sheet for baking. The sheet is temporarily attached via a tacky adhesive layer to a metal substrate made of stainless steel containing Al and Cr and baked at about 600 deg.C for 20min to burn the organic components such as tacky adhesive and obtain the objective metal substrate having a baked pattern fixed to the surface.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a method for manufacturing a metal substrate with a fired pattern, which is suitable for identification labels and the like, and has a fired pattern formed through layers of ceramic.

Conventional technology As the production system shifts to high-mix, low-volume production, products made of metal, glass, fired ceramics, etc., as well as semi-finished products and parts, are required to have heat resistance, durability, chemical resistance, etc. used to manage them. Providing superior identification labels has become an important issue.

Conventionally, methods for manufacturing metal substrates with firing patterns that can be used for identification labels, etc. include directly applying a pattern made of firing ink containing glass powder to a metal substrate made of aluminum or the like using a screen printing method, or - A method is known in which a pattern is formed by first coating it on a transfer paper, transferring it, and then firing it to form a fired pattern.

Problems to be Solved by the Invention However, the conventional method has problems such as poor manufacturing efficiency as it requires multiple steps to apply the fired pattern, difficulty in applying it to curved substrates, and difficulty in applying the fired pattern to metal. There was a problem in that it was necessary to perform surface treatment such as oxidizing the substrate in advance in order to adhere it closely to the substrate. Another problem was that it was difficult to provide chemical resistance by covering the entire surface of the metal substrate with a fired layer. Chemical resistance can be imparted by using a waxy substrate, but in this case, it becomes more difficult to adhere the fired pattern, and a waxing process is also required, resulting in lower manufacturing efficiency.

The present invention first aims at overcoming the above-mentioned problems. This objective is achieved by a sheet-mediated method in which a pattern is applied through a ceramic sheet and then fired.

Another object of the present invention is to improve pattern discrimination in the sheet-mediated method. In other words, in the sheet-mediated method described above, the reflectance of the fired sheet layer is low (and the reflection density ratio (PC3 value) with respect to the fired pattern is poor, and the pattern This is especially true for sheets based on glass powder.Identification labels require a high degree of pattern identification, so
Such discrimination problems are particularly important. Extensive use of colorants is PC
Although it is effective in improving the 8-value, it is necessary to overcome the problem of poor printability on metal substrates. The present invention overcomes this problem by using a melting accelerator, and makes it possible to incorporate a high amount of colorant.

Means for Solving the Problems The present invention involves firing a ceramic sheet made of ceramic powder and a resin binder, which has a firing pattern on one side, and a temporary bonded body with a metal substrate through an adhesive layer. The present invention provides a method for manufacturing a metal substrate with a fired pattern, which is characterized by the following.

Another object of the present invention is to provide a method for manufacturing a ceramic sheet with excellent firing pattern discrimination by using the ceramic sheet containing a melt accelerator and an inorganic colorant.

By applying a pattern through a ceramic sheet and firing it, the sheet firmly adheres to the metal substrate through the process of forming a fired body through the firing process, and also fuses with the fired body of the applied pattern. As a result, the fired pattern firmly adheres to the metal substrate through the ceramic layer.

In addition, by blending a melting accelerator into the ceramic sheet, the melting temperature or melt viscosity of the sheet can be lowered. It can be printed with good adhesion.As a result, a high reflectance of the fired layer of the sheet and a high PC8 value with the fired pattern are achieved.

Examples of Components of the Invention In the present invention, a ceramic sheet made of ceramic powder and a resin binder is used.

The ceramic powder used is one that softens or melts at a temperature below the melting temperature of the metal substrate and adheres to the metal substrate. Glass powder is generally used. Among them, 400~ such as lead glass type, lead borosilicate glass type, and soda glass type.
Those that soften or melt at 1000°C are preferably used.

The ceramic sheet may contain a fired body forming component other than the ceramic powder. The fired body forming components other than the ceramic powder are incorporated into the softened or melted ceramic powder during firing of the ceramic sheet to form the fired body.

As the components for forming the fired body other than the ceramic powder, for example, inorganic powders and fibers made of different types of ceramics, metals, alloys, oxides thereof, etc. having a melting point higher than the firing temperature are generally used.

Powder with a particle size of 0.1~20μ, the same diameter and length 10ha
The following fibers are suitable for use, but are not limited thereto: The types and combinations of ingredients may be determined as appropriate. From the viewpoint of coloring, it is appropriate to use an inorganic coloring agent consisting of a pigment or a filler. Examples include silica, calcium carbonate, titanium oxide. White materials such as metal compounds such as carbonates, nitrates, and sulfates that oxidize below the firing temperature to become oxidized oxides, iron, and steel. , containing metal ions such as gold, selenium, and chromium, such as red substances such as manganese oxide, alumina, chromium oxide, tin oxide, iron oxide, cadmium sulfide, and selenium sulfide, and metal ions such as manganese, cobalt, copper, and iron. Contains, e.g. cobalt oxide, zirconia.
Blue substances such as vanadium oxide, chromium oxide, divanadium pentoxide, black substances such as chromium oxide, cobalt oxide, iron oxide, manganese oxide, vanadium, Contains metal ions such as tin, zirconium, chromium, titanium, and antimony, including yellow substances such as zirconium, silicon, praseodymium, vanadium, tin, chromium, titanium, and antimony, and metal ions such as chromium, aluminum, cobalt, and calcium. , including green substances such as chromium oxide, cobalt chromium, and alumina chromium, and metal ions such as iron, silicon, zirconium, aluminum, and manganese.
Examples include pink materials such as aluminum, manganese, iron, silicon, and zirconium.

The amount of the fired body forming components other than the ceramic powder is 150 parts by weight per 100 parts by weight of the ceramic powder, considering the scratch resistance, durability, chemical resistance, and adhesion to the metal substrate of the fired layer to be formed. Below, 2 to 45 parts by weight is particularly suitable.

In preparing a ceramic sheet that forms a fired layer with high reflectance, it is effective to use a melting accelerator in combination. What is a melt accelerator?
For example, it is a substance that can lower the melting temperature or melt viscosity of a ceramic sheet by adding it, such as alumina powder to a ceramic sheet based on glass powder. By lowering the melting temperature of the ceramic sheet by using a melting accelerator, it is possible to improve the adhesion of the fired layer to the metal substrate. The reflectance is increased, and it becomes possible to create a high PC 8-value with the fired pattern. The reflectance of the fired layer may be set as appropriate depending on the purpose of use, but when used as an identification label,
From the viewpoint of pattern discrimination, it is preferable to mix an inorganic coloring agent so that the reflectance is 50% or more.

The amount of the melt accelerator may be determined as appropriate. Usually, 10 parts by weight or less, especially 0 parts by weight per 100 parts by weight of ceramic powder.
．． A blending amount of 5 to 5 parts by weight is sufficient. In the case of a melt accelerator that can also be used as an inorganic coloring agent, such as alumina, the amount to be blended may be determined depending on the purpose of use as an inorganic colorant or melt accelerator. In addition, when using a melt accelerator and forming a dark color pattern such as black, the inorganic coloring agent used in conjunction with the above-mentioned white, red, yellow, etc.
Green, pink, etc. are suitable in terms of reflectance, contrast, etc.

As the resin binder, one that is burnt off during firing is used. Examples include hydrocarbon resins, vinyl or styrene resins, acetal resins, butyral resins, acrylic resins, polyester resins, urethane resins, and cellulose resins. It is preferable to use materials that have good burnout properties during firing, and from this point of view, hydrocarbon resins, acetal resins, acrylic resins, cellulose resins, and especially acrylic resins are preferred.

The ceramic sheet can be formed, for example, by mixing one or more fired body forming components and a resin binder with an organic solvent and spreading the mixed liquid. Additives such as plasticizers may also be added. The thickness of the sheet may be determined as appropriate. Generally, 30 to 1 in lO to 500-1
It is assumed to be 00u■. If it is too thin, it will be difficult to handle, and if it is too thick, it will likely cause firing defects such as foaming in the fired layer.

In the present invention, the ceramic sheet is temporarily attached to a metal substrate via an adhesive layer as it is or as a sheet for firing.

The firing sheet is a ceramic sheet with a firing pattern provided on one side.

The adhesive layer is formed so as to be burned away during firing.

Adhesives that can be preferably used for the formation include rubber adhesives, acrylic adhesives, vinyl alkyl ether adhesives, and the like. Among these, natural rubber and similar synthetic rubbers, butyl rubber, polyisoprene rubber, styrene rubber, etc.
A rubber adhesive consisting of a single polymer such as butadiene rubber, styrene/isoprene/styrene block copolymer rubber, or styrene/butadiene/styrene block copolymer rubber, or 100 parts by weight of such polymer, petroleum-based resin, terpene-based 10 tackifiers such as resins, rosin resins, xylene resins, coumaron indene resins.
~300 parts by weight, other softeners, anti-aging agents, colorants,
Preferred are rubber-based adhesives containing additives such as fillers, and acrylic adhesives based on polymers consisting of alkyl esters of acrylic acid or methacrylic acid.

The adhesive layer may be provided on a ceramic sheet, a sheet for firing, or a metal substrate at an appropriate stage. From the viewpoint of simple temporary attachment to the metal substrate and attachment efficiency, it is preferable to attach it to one side of the ceramic sheet in advance. The adhesive layer can be attached to the ceramic sheet using an appropriate method similar to the method used to form adhesive tapes, such as applying the adhesive using an appropriate coating machine or transferring the adhesive layer provided on the separator. You can go there. The thickness of the adhesive layer is usually 5 to 50 nm, especially 8 to 20 nm.
It is assumed that u+m. If it is too thin, sufficient adhesive strength will not be developed,
If it is too thick, it may fall off during firing or cause poor firing. Note that when the adhesive layer is provided on the ceramic sheet in advance, it is preferable to protect it by pasting a separator or the like until it is temporarily attached to the metal substrate.

An example of a firing sheet formed by providing a firing pattern on one side of a ceramic sheet is shown in FIG.

1 is a firing pattern, 2 is a ceramic sheet, and 3 is an adhesive layer.

The firing pattern may be applied using firing ink, or a punched pattern forming sheet having a structure similar to the ceramic sheet described above, or a pattern consisting of holes or unevenness may be formed on such a pattern forming sheet. It may also be applied by engraving and temporarily adhering it to a ceramic sheet via an adhesive layer or the like. Alternatively, a pattern consisting of holes or irregularities may be carved into the ceramic sheet itself. In this case, the ceramic sheet itself undergoes formation of the engraved pattern and is transformed into a sheet for firing. Therefore, in the present invention, the meaning of having a firing pattern on one side of the ceramic sheet includes the case where the ceramic sheet has a pattern consisting of through holes.

In the case of a ceramic sheet containing a melt accelerator, it is advantageous to apply a pattern using a firing ink that can efficiently form even minute patterns.

The above-mentioned firing ink is prepared so that the fired product adheres to the ceramic sheet through a firing process.

Such firing inks are usually prepared by using one or more inorganic colorants in a solvent and, if necessary, in combination with appropriate additives such as ceramic powder, a binder, a plasticizer, a dispersant, etc., using a ball mill or the like. It is mixed to form a fluid such as a paste.

Optional ingredients such as glass powder and inorganic pigments, which were used in conventional direct coating methods such as screen printing methods and transfer methods of coating patterns formed on transfer paper,
A typical example is a paste-like ink made by mixing a colored glass pigment alone with a binder.

The composition of the firing ink may be determined as appropriate depending on the contrast with the ceramic sheet, adhesion, etc. The composition of the components that remain after firing and form the fired pattern is usually as follows:
The content is 1 to 100% by weight of an inorganic coloring agent and 99 to 0% by weight of a ceramic powder, especially a glass powder. Examples of the inorganic colorant and ceramic powder that can be used to prepare the firing ink include those used for the ceramic sheet.

As the binder in the firing ink, a binder such as wax or resin that is thermally decomposed and burned out at a temperature below the firing temperature is used. Waxes that can be preferably used include:
Examples include paraffin waxes, natural waxes, ester waxes, higher alcohol waxes, and higher amide waxes. Examples of the resin include the resin binder exemplified in the case of the ceramic sheet. If the properties such as thermal decomposition temperature of the binder in the firing ink and the resin binder of the ceramic sheet are significantly different, the fired product is likely to suffer from poor appearance such as foaming or deformation. From this point of view, it is preferable to use the same kind of resin binder as the resin binder used for the ceramic sheet as the binder for the firing ink.

The appropriate amount of the binder used as needed is 5 to 80% by weight of the components forming the fired body.

The method of forming the firing pattern on the ceramic sheet using the firing ink is arbitrary. Any suitable pattern forming method may be employed, such as a handwriting method, a coating method using a pattern forming mask, a method of transferring a pattern provided on transfer paper, or a forming method using a printer such as an inkjet type.

The firing pattern to be formed is also arbitrary. printing pattern,
Any pattern such as a transfer pattern, picture pattern, barcode pattern, circuit pattern, etc. may be applied.

Ink sheets such as printing ribbons, which are necessary when forming patterns using printers such as XY block, wire dot type, thermal transfer type, or impact type, are made by applying firing ink from film, cloth, etc. by coating method, impregnation method, etc. It can be formed by holding it on a supporting base material.

As the supporting base material, usual materials such as plastic films made of polyester, polyimide, fluororesin, etc., and cloth made of fibers such as nylon, polyester, etc. may be used. Pattern forming methods using printers have the advantage of being able to form appropriate patterns with high accuracy and efficiency.

The step of applying the firing pattern to the ceramic sheet using the firing ink may be performed before or after the ceramic sheet is temporarily attached to the metal substrate via the adhesive layer. When applying a firing pattern using a printer, it is customary to apply the pattern to a ceramic sheet in advance and temporarily attach it to a metal substrate as a firing sheet.

In addition, when a pattern is provided to the ceramic sheet in advance, the surface on which the pattern for firing is formed may be protected by pasting a separator or the like, if necessary, before the firing process.

In the case of a transfer method, the transfer paper can be attached as is and used as a separator.

When applying a pattern for firing by punching out the above-mentioned pattern forming sheet or by carving a pattern consisting of holes or unevenness on the pattern forming sheet or ceramic sheet itself, the applied pattern, punching method, or engraving The method and application step are arbitrary as in the case of the baking ink. The method of providing an engraved pattern in advance and temporarily attaching it to a metal substrate as a sheet for firing has the advantage that a minute pattern can be easily provided using an appropriate engraving device.

In the present invention, metal substrates made of various materials can be used. Among these, iron-based alloys containing aluminum, chromium, etc. are preferably used. By containing the aluminum component, it reacts with the ceramic components in the ceramic sheet, especially the glass component, especially the lead glass component, and firmly adheres to the ceramic component. The form of the substrate is generally a foil or a plate, but is not limited thereto.

The firing process of the temporary bonded body via the adhesive layer between the firing sheet and the metal substrate is performed under appropriate heating conditions depending on the firing temperature of the ceramic sheet and the like.・During the firing process, the binder, adhesive layer, etc. are burned out, and the components forming the fired body in the firing sheet are converted into a fired body while preserving the pattern, and the ceramic sheet and the firing pattern are fused and integrated as shown in Figure 2. A fixed body of the fired pattern 4 and the metal substrate 5 is obtained.

Note that the ceramic sheet or firing sheet may be temporarily attached so as to surround the entire metal substrate.

The obtained fired patterned metal substrate is preferably used as an identification label, other display material, decorative board, etc. The attachment to the adherend may be carried out by an appropriate method such as adhesion with an adhesive or an adhesive, or caulking. In the case of metallic adherends, welding methods and brazing methods can also be applied.

Effects of the Invention According to the present invention, since the firing pattern is applied through the ceramic sheet and subjected to firing treatment, the firing pattern can be easily fixed to the metal substrate. In addition, since it is a temporary attachment method using the adhesive layer of the sheet, it can be easily applied to curved parts and has excellent manufacturing efficiency. Furthermore, it is easy to enclose the entire surface, and it is also easy to provide chemical resistance in addition to durability and heat resistance. In addition, it has the advantage that any pattern can be easily and flexibly applied.

In addition, even when a large amount of inorganic colorant is blended by using a melting accelerator, the fired layer can be firmly adhered to the metal substrate. As a result, it is possible to improve the reflectance of the fired layer and achieve a high PO2 value with the fired pattern.

Examples Example 1 100 parts (parts by weight, same below) of lead borosilicate glass powder
, 10 parts of titanium oxide, 2 parts of polyisobutyl methacrylate
0 parts, stearic acid 1 part, dibutyl phthalate 2 parts, and toluene 45 parts were mixed in a ball mill, the mixture was developed using a doctor blade method, and dried to obtain a thickness of 60 μs.
A 15μ-thick adhesive layer made of acrylic adhesive is formed on one side of the ceramic sheet, and a barcode pattern made of baking ink is printed on the other side through a pattern mask, and dried to form the baking sheet. I got it. The baking ink used was a mixture of 20 parts of a chromium oxide/iron oxide/cobalt oxide black pigment, 10 parts of polyisobutyl methacrylate, and 20 parts of toluene.

Next, the above-mentioned baking sheet was attached to stainless steel foil (thickness 50 μI) containing 5% AI and 20% C through the adhesive layer.
Temporarily attach to
Baked (in air) for minutes. Organic components such as polyisobutyl methacrylate and acrylic adhesive were burned out by baking.

As a result of the above process, a stainless steel foil having a clear black barcode formed of a fired pattern firmly adhered thereto was obtained. The firing pattern was a barcode pattern fused onto the surface of the fired layer of the ceramic sheet.

Example 2 A sheet for firing was obtained according to Example 1, except that the amount of titanium oxide used was 20 parts, and a ceramic sheet containing 1 part of alumina powder was used, and this was temporarily attached to stainless steel foil. and fired.

As a result of the above process, a stainless steel foil was obtained in which a fired pattern in which a clear black barcode pattern was fused and integrated on the surface of a fired glass layer was fixed.

Comparative Example A stainless steel foil with a firing pattern was obtained in the same manner as in Example 2, except that a ceramic sheet containing no alumina powder was used. However, the fusion state of the fired pattern was poor.

The following tests were conducted on the stainless steel foils with firing patterns obtained in the evaluation test examples and comparative examples.

[Adhesion strength 1] A dolly is adhesively fixed to the fired pattern layer via an epoxy adhesive, and the dolly is pulled in a direction perpendicular to the plane of the fired pattern layer (at a speed of 10017 minutes), and the fired glass layer and stainless steel foil The adhesion force was measured.

[Reflectance] The reflectance in the fired glass layer part of the fired pattern layer is
Measurement was performed using light with a wavelength of 800 nm (normal barcode league reading range).

The results are shown in the table.

[Brief explanation of drawings]

FIG. 1 is a perspective view of an example of a sheet for firing, and FIG. 2 is a perspective view of an example of a metal substrate with a firing pattern. 1: Firing pattern 2; Ceramic sheet 3: Adhesive layer 4: Firing pattern 5: Metal substrate Patent applicant Nitto Denko Corporation

Claims (1)

[Claims] 1. A ceramic sheet made of ceramic powder and a resin binder, which has a firing pattern on one side, and a temporary bonded body formed by a metal substrate through an adhesive layer are fired. A method for manufacturing a metal substrate with a fired pattern. 2. The method according to claim 1, wherein the firing sheet used has a firing pattern made of firing ink on one side of a ceramic sheet containing a melt accelerator and an inorganic colorant. 3. The method according to claim 1 or 2, wherein the ceramic sheet uses glass powder as its ceramic powder. 4. The method according to claim 2 or 3, wherein the ceramic sheet contains alumina powder as a melting accelerator.