JP2001253763A - Thin film ceramic sheet, green sheet and their manufacturing methods - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thin film ceramic sheet whose manufacturing process history can be managed as a product and which has 0.5 mm or smaller thickness and to provide a green sheet for obtaining this thin film ceramic sheet and methods for manufacturing these sheets. SOLUTION: This thin film ceramic sheet has 0.5 mm or smaller thickness and has information printed by a laser marker for discriminating this sheet from others within the area which accounts for 20% or smaller of the whole sheet area. The green sheet has 0.7 mm or smaller thickness and has information printed by the laser marker for discriminating this sheet from others within the area which accounts for 20% or smaller of the whole sheet area. The methods for manufacturing the thin film ceramic sheet and the green sheet comprise a step to print the information on the green sheet by the laser marker.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thin-film ceramic sheet and a green sheet on which product information is printed, and a method for producing the same.

[0002]

2. Description of the Related Art It is common practice to provide ceramic products with information for identifying individual products such as a manufacturer, a processing history, a manufacturing date, and a product number. These pieces of information are used for managing the manufacturing process history of the product. 2. Description of the Related Art Conventionally, as a method of printing product information on a ceramic product, (1) a method of writing characters using ink, (2) a method of printing a concave shape on a green sheet using a marking device having a convex portion, or (3) A method of printing on a sintered body using a laser marker has been adopted.

However, for example, in the case of a ceramic product such as an electrolyte of a solid oxide fuel cell, the conventional printing method as described in the above (1) to (3) uses information for identifying each product. Was difficult to impart. That is, for example, as an electrolyte of a solid oxide fuel cell, a thin-film ceramic sheet containing zirconia as a main component and having a thickness of 0.5 mm or less is used, and this ceramic sheet is usually used as an electrode during the fuel cell manufacturing process. Is applied and fired in an electrode attaching process.
Exposure to high temperatures above ℃. Further, since the output of the fuel cell increases in proportion to the electrode area, it is desired that the electrode-coated portion be as large as possible. Therefore, in order to leave product information after electrode application, information must be printed on a portion other than the electrode portion, and it is necessary to write information in as small a character as possible within a limited small area.

For this reason, for example, when printing product information on the electrolyte of a solid oxide fuel cell, the printing with the ink of the above (1) may be erased due to the high temperature treatment, and the ink dots may not be printed. Due to the size limit, printing a small character in a small area may cause a problem that the character is crushed and cannot be recognized. Further, as described in (2) above, in a printing method using an engraving device having a convex portion, there is a limit in reducing the size of characters, and fine characters cannot be printed. Further, according to the method of (3) for printing on a sintered body using a laser marker, fine characters can be printed. However, when printing is performed on a thin-film ceramic sheet sintered body having a thickness of 0.5 mm or less, exposure to high temperatures may occur. In such a case, the printing portion may be undulated or may be broken from the printing portion. In addition,
In the case of printing using a laser marker, printing is generally performed on the sintered body because the sintered body is easier to handle.

As described above, it is necessary to print fine letters and numbers like the electrolyte of a solid oxide fuel cell.
Moreover, in the case of a ceramic product in an application that may be exposed to a high temperature in a later process or the like, it is difficult to attach product information by the conventional printing technology, and an effective printing method has been demanded.

[0006]

The problem to be solved by the present invention is to provide a thin-film ceramic sheet having a thickness of 0.5 mm or less and a method of manufacturing the thin-film ceramic sheet, which can manage the history of the manufacturing process of the product. It is an object of the present invention to provide a green sheet for obtaining a ceramic sheet and a method for manufacturing the same.

[0007]

Means for Solving the Problems The present inventor has made intensive studies to solve the above-mentioned problems. As a result, when using a laser marker that can print fine letters and numbers, if printing is performed on a sintered body as in the past, stress will occur in the printing part due to high heat, but in the state of the green sheet before firing When baked after printing, it was found that the stress in the printed portion was alleviated, and it was subsequently exposed to high temperature to prevent swelling and cracking, thereby completing the present invention. That is, the thin film ceramic sheet according to the present invention is a thin film ceramic sheet having a thickness of 0.5 mm or less, and has a total sheet area of 20 mm.
%, Information for identifying the sheet is written by printing with a laser marker in an area of not more than%.

In the method of manufacturing a thin film ceramic sheet according to the present invention, after printing is performed on a green sheet using a laser marker, the printed green sheet is fired. The green sheet according to the present invention has a thickness of 0.7 m.
m of green sheet of less than 20 m
%, Information for identifying the sheet is written by printing with a laser marker in an area of not more than%. The method for manufacturing a green sheet according to the present invention includes a step of printing a green sheet using a laser marker.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, an embodiment of the present invention will be described.
This will be described in detail. Thin film ceramic sheet of the present invention
Is a thin-film ceramic sheet with a thickness of 0.5 mm or less.
For example, a ceramic raw material powder, a binder,
A slurry consisting of a mixture containing a solvent and
Smooth bases can be obtained by methods such as
It is applied in a predetermined thickness on the material and dried to remove the solvent by volatilization.
By firing the obtained green sheet,
It is manufactured. Ceramic sheet in the present invention
Examples of ceramic raw materials that can be used for
Konia, alumina, titania, aluminum nitride, ho
Single or mixed silicate glass, cordierite, mullite, etc.
Compounds or composite oxides.
Solid electrolytes for solid electrolyte fuel cells that can be used effectively
Especially preferred as a constituent material such as membranes and electrode substrates
Is a zirconia ceramic. Specifically, Jill
Konia, Alka such as MgO, CaO, SrO, BaO
Lithium metal oxide, Y₂ O₃ , La₂ O₃ , Ce
₂ O₃ , Pr₂ O₃ , Nd₂ O₃ , Sm₂ O
₃ , Eu₂ O₃ , Gd₂ O₃ , Tb₂ O₃ , D
y ₂ O₃ , Ho₂ O₃ , Er₂ O₃ , Yb₂ O
₃ And rare earth metal oxides such as Sc₂ O₃ , Bi₂ O
₃ , In₂ O₃ Or two or more stabilizers
Zirconia-based ceramics containing the above are mentioned.
Contains SiO 2 as another additive.₂, Al₂ O₃ ,
Ge₂ O₃ , SnO₂ , Ta₂ O₅ , Nb₂ O₅
 Etc. may be included. In addition, CeO₂ Or
Bi₂ O₃In addition, CaO, SrO, BaO, Y₂ O
₃ , La₂ O₃ , Ce₂ O₃ , Pr ₂ O₃ , N
d₂ O₃ , Sm₂ O₃ , Eu₂ O₃ , Gd₂ O
₃ , Tb₂O₃ , Dr₂ O₃ , Ho₂ O₃ , Er
₂ O₃ , Yb₂ O₃ , PbO, WO₃ , MoO
₃ , V₂ O₅ , Ta₂ O₅ , Nb₂ O₅ Etc. 1
Ceria or bismuth added with one or more species
System and even LaGdO₃ Gallate solids such as
Electrolyte membranes are also exemplified as preferred.

The constituent materials of the anode electrode sheet include Ni, Co, Fe or oxides thereof.
A cermet with the zirconia and / or ceria,
Further, cermets to which alkaline earth metal oxides such as MgO, CaO, SrO, and BaO, MgAl ₂ O _{4, and the} like are added, and the like can be given. As a constituent material of the cathode electrode sheet, lanthanum manganate, lanthanum cobaltate having a perovskite-type crystal structure, or these lanthanums are partially substituted with Ca, Sr, or the like, or manganese is replaced with Co, Fe, Cr, or the like. Partially substituted, and further, part of lanthanum and cobalt was Ca, Sr, Co,
A composite oxide substituted with Fe or the like can be given.

The ceramic sheet used for the solid electrolyte membrane of the fuel cell requires higher thermal, mechanical, electrical and chemical properties. More preferably, zirconium oxide (tetragonal and / or cubic zirconia) stabilized with 2 to 12 mol%, more preferably 2.5 to 10 mol%, and still more preferably 3 to 8 mol% yttrium oxide. The binder is not particularly limited, and a conventionally known organic or inorganic binder may be appropriately selected and used. As the organic binder, for example, ethylene copolymer, styrene copolymer, acrylate or methacrylate copolymer,
Examples include vinyl acetate copolymers, maleic acid copolymers, vinyl butyral resins, vinyl acetal resins, vinyl formal resins, vinyl alcohol resins, waxes, and celluloses such as ethyl cellulose. Examples of the inorganic binder include, for example, zirconia sol, silica sol, alumina sol, titania sol, and the like. These may be used alone or in combination of two or more.

The use ratio of the ceramics raw material powder and the binder is based on 100 parts by mass of the raw material powder.
The binder is preferably 5 to 30 parts by mass, more preferably 10 to 20 parts by mass. When the amount of the binder used is small, the strength and flexibility of the green sheet become insufficient, so that cracks and cracks are easily generated when printing with a laser marker, and there is a tendency that handling becomes difficult, while if too much, Not only is it difficult to adjust the viscosity of the slurry, but also the amount of decomposition and release of the binder component during firing becomes large and intense, making it difficult to obtain a uniform sheet. The solvent is not particularly limited, but includes, for example, water; alcohols such as methanol, ethanol, 2-propanol, 1-butanol and 1-hexanol; ketones such as acetone and 2-butanone; pentane, hexane and heptane And the like; aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene; acetates such as methyl acetate, ethyl acetate and butyl acetate; and the like.
These may be used alone or in combination of two or more.

The amount of the solvent used may be appropriately adjusted in consideration of the viscosity of the slurry at the time of forming the green sheet, and is preferably in the range of 1 to 20 Pa · s, more preferably 1 to 5 Pa · s. It is better to adjust so that The slurry may include, if necessary, a polymer electrolyte such as polyacrylic acid and ammonium polyacrylate for promoting dusting and dispersion of the ceramic raw material powder; an organic acid such as citric acid and tartaric acid; isobutylene or styrene. A dispersant comprising a copolymer of styrene and maleic anhydride and its ammonium salt or amine salt, a copolymer of butadiene and maleic anhydride and its ammonium salt; dibutyl phthalate for imparting flexibility to the green sheet Plasticizers comprising phthalic acid esters such as dioctyl phthalate; glycols such as propylene glycol; and glycol ethers; further, a surfactant or an antifoaming agent may be added.

As the smooth substrate on which the slurry is applied, for example, a polyethylene terephthalate film or the like can be used. In the thin-film ceramic sheet of the present invention, information for identifying the sheet is provided by printing with a laser marker in an area of 20% or less, preferably 10% or less, more preferably 2% or less of the entire sheet area. Is what it is. This printing area is usually
It is provided on the outer peripheral portion of the seat, but is not limited to this. By using a laser marker, fine letters and numbers can be easily printed, and product information can be written in an extremely narrow printing area of 20% or less of the entire sheet area. When the printing area increases, for example,
In the use of an electrolyte for a flat solid electrolyte fuel cell, the area where the electrode can be applied is reduced, which not only causes a decrease in the output of the fuel cell, but also tends to decrease the strength of the sintered body. For example, if the printing area exceeds 20% of the total sheet area, the strength is reduced and the sintered body is easily broken. The printing area is calculated by multiplying the character height of a printed character or the like by the length of a printed character string.

In the present invention, when printing is performed on a green sheet using a laser marker, for example, the output is 0.5 to 8 W, preferably 1 to 5 W, and the scanning speed is 100 to 100 W.
It may be performed at 700 mm / sec, preferably 200 to 500 mm / sec. Further, as the laser marker, for example, a product name “ML-9110” manufactured by Keyence or the like can be used. As a firing method when firing the printed green sheet, the binder is decomposed and removed,
There is no particular limitation as long as the ceramic powder can be sintered, but preferably at 1000-1600 ° C.
It is preferable to bake for up to 5 hours. Specifically, the printed green sheet is cut into an appropriate size, placed on a setter or the like, and fired. In addition, in order to suppress the undulation and warpage of the entire green sheet, it is preferable that the green sheet is placed on a porous sheet or fired so as to be sandwiched between two porous sheets.

In the present invention, the depth of the concave portion of the printed portion formed by the laser marker is preferably 40% or less, more preferably 30% or less, and further preferably 20% or less of the thickness of the ceramic sheet. It is good. If the depth of the concave portion of the printed portion is deeper than the above range, cracks are likely to occur in the printed portion, but if it is 40% or less of the thickness of the ceramic sheet, the frequency of occurrence of cracks is significantly reduced. In order to make the depth of the concave portion of the printing portion in the thin film ceramic sheet 40% or less of the thickness of the ceramic sheet, at the stage of printing on the green sheet, the depth of the concave portion is 40% of the thickness of the green sheet.
What is necessary is just to make it as follows.

The thin film ceramic sheet of the present invention has a thickness of 130
The undulation height generated by heat treatment at 0 ° C for 2 hours is 10
It is preferably 0 μm or less. The undulation referred to here is a continuous uneven portion developed on the sheet.
If the undulation height exceeds 100 μm, for example, when subjected to high-temperature treatment in applications such as electrolytes of solid oxide fuel cells, it lacks smoothness and cannot be used as a defective product. The thin-film ceramic sheet obtained by the method does not lack smoothness even when exposed to high temperatures. Such a thin-film ceramic sheet can be easily obtained by the production method of the present invention, that is, by printing a green sheet using a laser marker and then firing the printed green sheet. By sintering after printing in the state of the green sheet before sintering, it is possible to prevent undulation at high temperatures.

The depth of the concave portion of the printed portion and the undulation height of the sheet are obtained by irradiating the sheet surface with laser light using a laser optical three-dimensional shape measuring device and analyzing the reflected light thereof in three-dimensional shape. be able to. Specifically, when a laser optical three-dimensional shape measuring device irradiates a ceramic sheet surface to be measured with laser light to focus on the sheet surface, and when the reflected light is uniformly imaged on the photodiode, Non-contact micro tertiary system with a function to control the lens so that the objective lens always focuses on the sheet surface by issuing a signal to immediately resolve the unevenness in the image due to the displacement of the sheet surface. This is an original shape analyzer, which can detect unevenness of a sheet surface to be measured in a non-contact manner by detecting the movement amount. The resolution is usually 1 μm or less, more preferably 0.1 μm or less. By using such an apparatus, the depth of the concave portion of the printing portion and the undulation height of the sheet surface can be accurately detected. As a laser optical three-dimensional shape measuring device, for example, UB
For example, Micro Focus Expert (trade name: UBC-14 type) manufactured by Company M can be used.

The green sheet of the present invention has a thickness of 0.7
mm or less, and 2% of the total sheet area
Within the area of 0% or less, information for identifying the sheet is written by printing with a laser marker, and as described above, a mixture containing a ceramic raw material powder, a binder, and a solvent is used. The resulting slurry, for example, doctor blade method, calendar method, applied to a predetermined thickness on a smooth substrate by extrusion method, etc., after drying to remove the solvent by volatilization, using a laser marker on the obtained sheet It is manufactured by applying printing. This printing area is usually provided in the outer peripheral portion of the sheet, but is not limited to this. The green sheet of the present invention may be in a form wound into a sheet, or may be cut into an appropriate size by cutting, punching, or the like. Preferably, printing is performed after cutting to an appropriate size. In addition, the shape at the time of cutting,
Squares, rectangles, circles, as well as triangles, polygons such as pentagons and ellipses, etc., if necessary,
Further, a shape having a hole, a notch, or the like in these shapes may be used.

The thin-film ceramic sheet of the present invention is very thin, does not cause cracking or undulation even when exposed to high temperatures, and has product information written in an extremely small area. It is useful for applications such as electrolyte membranes for fuel cells, circuit boards, heat-resistant / fire-resistant board outer materials, and sliding members. Particularly, it is suitably used as an electrolyte used in a flat solid electrolyte fuel cell. The electrolyte used in the flat solid electrolyte fuel cell is manufactured according to the process diagram shown in FIG.
When the thin film ceramic sheet or green sheet of the present invention is used as (A) or (B), (g) in FIG.
In the electrode attaching step (i), usually 800 to 1500
Even when heat-treated at a high temperature of not less than ℃, no cracks or undulations occur, and the thin-film ceramic sheet or green sheet of the present invention has product information written in an extremely small area. Like electrolyte with
The electrode 1 can be provided in a wide range, and a fuel cell capable of providing a large output can be obtained.

[0021]

EXAMPLES Examples and comparative examples according to the present invention will be described below, but the present invention is not limited by these examples. Example 1 3 mol% yttria-stabilized zirconia powder (trade name "HSY-3.0" manufactured by Daiichi Rare Element Co., Ltd.) 1
The binder composed of a methacrylate polymer (molecular weight: 30,000, glass transition temperature: −00 parts by mass)
(8 ° C., solid content concentration: 50% by mass) 30 parts by mass, 2 parts by mass of dibutyl phthalate as a plasticizer, and 50 parts by mass of a mixed solvent of toluene / isopropyl alcohol (mass ratio = 3/2) as a dispersion medium. Place in a nylon pot with a zirconia pole 10 mm in diameter
For 40 hours to prepare a slurry. This slurry was concentrated and defoamed to adjust the viscosity to 3 Pa · s, and then 2
This was passed through a 00 mesh filter, and was coated on a polyethylene terephthalate film by a doctor blade method to obtain a green sheet having a thickness of 200 μm. Next, a blade was attached to this green sheet on a continuous die-cutting machine (trade name “865B” manufactured by Sakamoto Zoki Co., Ltd.), and the press stroke was 40 mm and the press speed was 80 s.
At pm, it was punched into a circle with a diameter of 13 cm.

Next, using a laser marker (manufactured by KEYENCE, trade name "ML-9110"), an output of 3.6 was obtained.
W, at a scanning speed of 300 mm / sec, a portion of the green sheet punched in a circular shape from the edge of the outer peripheral portion to 4 mm from the edge of the green sheet within a range of height 4 mm and width 2.3 cm (0.7% of the total sheet area).
%) Was printed as "ABCD1234". The printed letters and numbers were readable with the naked eye. Subsequently, the printed green sheet was fired at 1400 ° C. to obtain a disc-shaped sintered body having a diameter of 10 cm and a thickness of 150 μm. The obtained disc-shaped sintered body was 3 mm from the end of the outer peripheral portion.
"ABCD1234" was printed in the area up to 3 mm in height and 1.8 cm in width (0.7% of the total sheet area), and the printed letters and numbers were readable to the naked eye. . Further, the depth of the concave portion of the printed portion is determined by a laser optical three-dimensional shape measuring device (trade name “UB” manufactured by UBM Corporation).
When measured at a measurement pitch of 10 points / mm using a “C-14 type” micro focus expert), it was 44
μm (29% of the thickness of the sintered body).

Next, an anode paste was prepared. That is, nickel oxide and 3 mol% yttria-stabilized zirconia powder (trade name “HSY-3.
0 ") at a mass ratio of 2: 1 to obtain an anode material. For 100 parts by mass of the anode material, 10 parts by mass of polyvinyl alcohol and 10 parts by mass of polyethylene glycol as binders, and ethanol 3 as a solvent.
0 parts by mass and wet mixing to prepare an anode paste. The obtained anode paste was applied onto the 20 disc-shaped sintered bodies obtained above in a circular shape having a diameter of 9 cm, and fired at 1350 ° C. to obtain an electrolyte with a cathode.

The obtained electrolyte with a cathode has no cracks or cracks in all of the 20 sheets, and is measured using a laser optical three-dimensional shape measuring device (Micro Focus Expert, trade name “UBC-14 type”, manufactured by UBM). When the swell height was measured at a pitch of 10 points / mm, it was 22 μm. Example 2 A green sheet punched out in a circular shape was obtained in the same manner as in Example 1, and then, using a laser marker (manufactured by KEYENCE, trade name “ML-9110”), an output of 3.6 W and a scanning speed of 300 mm / In seconds, "ABCD1" was obtained over the entire circumference (8% of the total sheet area) up to 2.6 mm from the outer edge of the green sheet punched in a circular shape.
234 "was repeatedly printed. The printed letters and numbers were readable with the naked eye.

Subsequently, the printed green sheet is
Fired at 1400 ° C, diameter 10cm, thickness 150μm
Was obtained. The obtained disc-shaped sintered body is repeatedly printed with “ABCD1234” on the entire circumferential area (8% of the entire sheet area) from the end of the outer peripheral part to 2 mm, and the printed letters and numbers are It was readable with the naked eye. When the depth of the concave portion of the printed portion was measured in the same manner as in Example 1, it was 45 μm (30% of the thickness of the sintered body). Next, the obtained disc-shaped sintered body 2
An anode paste was applied to 0 sheets and fired at 1350 ° C. in the same manner as in Example 1 to obtain an electrolyte with a cathode.

The resulting electrolyte with a cathode had no cracks or cracks in all 20 sheets, and the swell height was measured in the same manner as in Example 1. As a result, it was 25 μm. Example 3 A green sheet punched in a circular shape was obtained in the same manner as in Example 1, and then, using a laser marker (manufactured by KEYENCE, trade name "ML-9110"), an output of 3.6 W and a scanning speed of 300 mm / In seconds, “ABCD” was applied over the entire circumference (15% of the total sheet area) of 5.2 mm from the edge of the outer periphery of the green sheet punched in a circular shape.
1234 ". The printed letters and numbers were readable with the naked eye.

Subsequently, the printed green sheet is
Fired at 1400 ° C, diameter 10cm, thickness 150μm
Was obtained. The obtained disc-shaped sintered body is repeatedly printed with “ABCD1234” on the entire circumference (15% of the total sheet area) from the edge of the outer periphery to 4 mm, and the printed letters and numbers are It was readable with the naked eye. When the depth of the concave portion of the printed portion was measured in the same manner as in Example 1, it was 44 μm (29% of the thickness of the sintered body). Next, an anode paste was applied to the obtained 20 disc-shaped sintered bodies in the same manner as in Example 1 and then fired at 1350 ° C. to obtain an electrolyte with a cathode.

The obtained electrolyte with a cathode had no cracks or cracks in all 20 sheets, and the swell height was measured in the same manner as in Example 1. As a result, it was 28 μm. Example 4 A green sheet punched in a circular shape was obtained in the same manner as in Example 1, and the green sheet was
By firing at 00 ° C., a disk-shaped sintered body having a diameter of 10 cm and a thickness of 150 μm was obtained. Subsequently, using a laser marker (manufactured by KEYENCE, trade name "ML-9110"), at an output of 3.6 W and a scanning speed of 300 mm / sec, from the end of the outer peripheral portion of the obtained disk-shaped sintered body to 3 mm. Was printed with "ABCD1234" within the range of 3 mm in height and 1.8 cm in width (0.7% of the total sheet area). The printed letters and numbers were readable with the naked eye. When the depth of the concave portion of the printed portion was measured in the same manner as in Example 1, it was 3 μm (2% of the thickness of the sintered body).

Next, an anode paste was applied to the obtained 20 disc-shaped sintered bodies and fired at 1350 ° C. in the same manner as in Example 1 to obtain an electrolyte with a cathode. The obtained cathode-equipped electrolyte had no cracks or cracks in all 20 sheets, and the swell height was measured in the same manner as in Example 1.
It was 75 μm. Example 5 A green sheet punched out in a circular shape was obtained in the same manner as in Example 1, and this green sheet was
By firing at 00 ° C., a disk-shaped sintered body having a diameter of 10 cm and a thickness of 150 μm was obtained.

Subsequently, using a laser marker (manufactured by KEYENCE, trade name "ML-9110"), an output of 3.6 was obtained.
W, at a scanning speed of 300 mm / sec, "ABCD1234" was repeatedly printed on the entire circumference (8% of the total sheet area) from the end of the outer peripheral portion to 2 mm of the obtained disk-shaped sintered body. The printed letters and numbers were readable with the naked eye. When the depth of the concave portion of the printed portion was measured in the same manner as in Example 1, the depth was 3 μm (2% of the thickness of the sintered body).
Met. Next, an anode paste was applied to the obtained 20 disc-shaped sintered bodies in the same manner as in Example 1 and then fired at 1350 ° C. to obtain an electrolyte with a cathode.

The obtained electrolyte with a cathode had no cracks or cracks in all 20 sheets, and the swell height was measured in the same manner as in Example 1. As a result, it was 82 μm. Example 6 A green sheet punched out in a circular shape was obtained in the same manner as in Example 1, and the green sheet was
By firing at 00 ° C., a disk-shaped sintered body having a diameter of 10 cm and a thickness of 150 μm was obtained. Subsequently, using a laser marker (manufactured by KEYENCE, trade name "ML-9110"), at an output of 3.6 W and a scanning speed of 300 mm / sec, from the end of the outer peripheral portion of the obtained disk-shaped sintered body to 4 mm. "ABCD123" is added to the entire circumference (15% of the total sheet area).
"4" was repeatedly printed. The printed letters and numbers were readable with the naked eye. When the depth of the concave portion of the printed portion was measured in the same manner as in Example 1, it was 3 μm (2% of the thickness of the sintered body).

Next, the anode paste was applied to 20 disc-shaped sintered bodies in the same manner as in Example 1 and fired at 1350 ° C. to obtain an electrolyte with a cathode. The obtained cathode-equipped electrolyte had no cracks or cracks in all 20 sheets, and the swell height was measured in the same manner as in Example 1.
It was 88 μm. [Comparative Example 1] A green sheet punched into a circle was obtained in the same manner as in Example 1, and then, using a laser marker (manufactured by KEYENCE, trade name "ML-9110"), an output of 3.6 W and a scanning speed of 300 mm / In seconds, "ABCD" was applied over the entire circumference (23% of the total sheet area) up to 7.8 mm from the edge of the outer periphery of the green sheet punched in a circular shape.
1234 ". The printed letters and numbers were readable with the naked eye.

Subsequently, the printed green sheet is
Fired at 1400 ° C, diameter 10cm, thickness 150μm
Was obtained. The obtained disc-shaped sintered body is repeatedly printed with “ABCD1234” over the entire circumference (23% of the entire sheet area) from the end of the outer periphery to 6 mm, and the printed letters and numbers are It was readable with the naked eye. When the depth of the concave portion of the printed portion was measured in the same manner as in Example 1, it was 44 μm (29% of the thickness of the sintered body). Next, an anode paste was applied to the obtained 20 disc-shaped sintered bodies in the same manner as in Example 1 and then fired at 1350 ° C. to obtain an electrolyte with a cathode.

In the obtained electrolyte with a cathode, cracks occurred from the printed portion on 9 sheets out of 20 sheets. The swell height measured in the same manner as in Example 1 was 27 μm.

[0035]

According to the present invention, a thin-film ceramic sheet having a thickness of 0.5 mm or less and a method of manufacturing the same, and a green sheet and a green sheet for obtaining the thin-film ceramic sheet, which can control the history of the manufacturing process of the product, etc. A manufacturing method can be provided.

[Brief description of the drawings]

FIG. 1 is a manufacturing process diagram of an electrolyte with electrodes for a plate-shaped solid oxide fuel cell.

FIG. 2 Schematic diagram of electrolyte with electrodes

[Explanation of symbols]

 1 electrode 2 thin film ceramic sheet of the present invention 3 printed product information

 ────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Kazuo Hata 992, Nishioki, Okihama-shi, Aboshi-ku, Himeji-shi, Hyogo F-term (reference) in Nippon Shokubai Co., Ltd. 4G030 AA12 AA17 BA03 CA08 5H026 AA06 EE11 EE12 EE13 HH02 HH03

Claims (6)

[Claims] 1. A thin-film ceramic sheet having a thickness of 0.5 mm or less and having an area of 20% or less of the total sheet area,
A thin-film ceramic sheet, wherein information for identifying the sheet is written by printing with a laser marker. 2. The thin-film ceramic sheet according to claim 1, wherein the depth of the concave portion of the printing portion is 40% or less of the thickness of the ceramic sheet. 3. The thin-film ceramic sheet according to claim 1, which is an electrolyte used for a plate-shaped solid oxide fuel cell. 4. A method for producing a thin-film ceramic sheet, comprising: printing a green sheet using a laser marker; and firing the printed green sheet. 5. A green sheet having a thickness of 0.7 mm or less, and information for identifying the sheet is printed by a laser marker within an area of 20% or less of the entire sheet area. Green sheet characterized by the following. 6. A method for manufacturing a green sheet, comprising a step of printing a green sheet using a laser marker.