WO2004101174A1

WO2004101174A1 - Method for forming relief image and paatern formed by that method

Info

Publication number: WO2004101174A1
Application number: PCT/JP2004/006888
Authority: WO
Inventors: Shigekatsu Ohnishi
Original assignee: Taiyo Ink Mfg. Co., Ltd.
Priority date: 2003-05-19
Filing date: 2004-05-14
Publication date: 2004-11-25
Also published as: CN1791472A; KR20060009944A; JPWO2004101174A1; KR100708790B1; CN100418643C

Abstract

A method for forming a relief image comprising a step for forming a powder layer by coating a substrate with slurry composed at least of powder of a metal or its oxide and a solvent and then drying it, a step for printing a pattern of binder by ink jet method onto a powder layer obtained in the powder layer forming step, and a step for forming a pattern by removing only such a part as the pattern of binder is not printed in the pattern printing step from the substrate, characterized in that the slurry being used in the powder layer forming step is produced by regulating the solid content of a collected matter of the powder of a metal or its oxide removed in the pattern printing step with the solvent.

Description

Specification

Method of forming a relay image, its pattern formation

The present invention relates to a method for forming a relay image on a substrate, and particularly to a method for forming a conductor pattern in a plasma display panel (hereinafter, referred to as a PDP), a fluorescent display tube, an electronic component, or the like. The present invention relates to a technology for forming a relay image without using a photosensitive conductive paste.

Background art

In general, as a typical method for forming a relay image of a high-definition conductive pattern on a glass substrate or a ceramic substrate of a PDP, a method using a photosensitive conductive paste is used. There is the photolithographic method. This uses a photosensitive paste as a conductor paste for thick film printing, and forms a high-resolution thick film conductor pattern through mask exposure and development after printing. It is possible. As the photosensitive conductive paste, a mixture of a conductive metal powder, glass frit, a photocurable resin, a photopolymerization initiator, a solvent, and other additives is often used (for example, See Japanese Patent Application Laid-Open Nos. Hei 11-246636, Japanese Patent Laid-Open No. 5-271756, Japanese Patent Laid-Open No. 2-268870, etc.).

However, in the photolithography method using the photosensitive conductive paste, most of the conductive paste is removed by development, and metal powder such as gold, silver, and platinum is used. Even if the conductive paste containing the body is reused, the recovered developer contains metal powder, organic resin, solvent, water, and alkalis in the developer. Therefore, it cannot be easily reused, and as a result, there is a problem that valuable resources are wasted.

On the other hand, a method of forming a relay image using the ink jet method has been proposed for a long time.For example, a method of dissolving a polymer film by ink droplets of the ink jet has been proposed. There is known a technique for forming a relief image having a thickness that allows ink droplets to penetrate by changing the property (for example, see British Patent No. 14431462). Specifically, the technique involves spraying an appropriate liquid onto the polymer film by using an ink jet method, and changing the solubility of the polymer film in the developing solution by a chemical change. In the negative type system, the solubility of the polymer film is reduced, and the portion where the solubility is reduced is developed with a developing solution to form a relief image. The polymer film disintegrates to increase the solubility, and the portion is dissolved in a developer to form a relay image.

However, this technique has no point of reusing the polymer coating material that has been developed and removed, and has been recovered because the technique chemically changes the polymer coating. It is difficult to reuse the polymer coating paste from the developer. Disclosure of the invention

As described above, in the photolithography method using a photosensitive conductive paste, which is generally used in the formation of a relay image of a high-definition conductor pattern in a PDP or the like, the In fact, there has not yet been provided a technique for easily reusing the conductive paste removed by the method. There was no other way than to recover precious metals etc. as sludge and scrap.

The present invention has been completed in view of the problems of the prior art, and a main object of the present invention is to provide a method of forming a relay image on a substrate, the method comprising: Another object of the present invention is to provide a method for forming a relay image that facilitates reuse of metal oxide powder and can achieve low cost and is excellent in productivity.

The present inventors have conducted intensive research to achieve the above object, and as a result, a binder was pattern-printed on a powder layer containing a metal powder or an oxide powder thereof by an ink jet method, and the substrate was printed. It has been found that the above object can be achieved by forming a non-removable portion and a removable portion with respect to a predetermined means for partially removing the powder layer from above. . That is, for example, with respect to the means for partially removing the powder layer using a predetermined solvent, the portion where the binder is printed by the ink jet method is regarded as a non-removable portion using the solvent, and Only the portion where the toner is not printed is removed by using this method. In this case, the recovered liquid containing the metal powder or its oxide powder removed from the substrate can be reused for forming a relay image by adjusting the solid content almost completely. In addition, the metal powder or its oxide powder contained in the recovered liquid can be easily and efficiently reused, and the cost required for forming a relay image is greatly reduced. Get.

That is, according to the present invention, at least a metal powder or Is a step of forming a powder layer by applying a slurry prepared using the oxide powder and a solvent and drying the slurry, and the powder obtained in the powder layer forming step. A step of pattern-printing a binder on the layer by an ink jetting method, and removing, from the substrate, only a portion where the pattern is not printed by the binder in the pattern printing step. A step of forming a pattern, wherein the slurry used in the powder layer forming step contains a metal powder or an oxide powder thereof contained in a portion removed in the pattern printing step. A method for forming a relief image, characterized by using a slurry obtained by adjusting the solid content of a recovered material with a solvent, is provided.

Further, according to the present invention, at least a step of preparing a slurry by adjusting a solid content of a metal powder or an oxide powder thereof and a solvent, and the slurry preparing step are provided. A step of applying a slurry on a substrate and drying to form a powder layer; and patterning a binder by an ink jet method on the powder layer obtained in the powder layer forming step. A pattern is formed by removing from the substrate only a portion where the pattern is not printed by the binder in the pattern printing step, and the pattern is not formed. Recovering the metal powder or the oxide powder thereof contained in the portion which is included in the metal powder or the oxide powder used in the slurry preparation step. Includes metal powder or its oxide powder Wherein, the method of forming the Le Li Fui image is provided.

In the present invention, no pattern was printed on the binder. As one mode of the means for removing the portion, there is a means for removing the portion on which the pattern is not printed by using a predetermined solvent. The metal powder or the oxide powder recovered using the removing means with the solvent can be reused in the preparation of the slurry by adjusting the solid content of the recovered liquid.

In this case, the same solvent as the solvent contained in the slurry used to form the powder layer is used as a solvent that can be used to remove portions where the binder has not been subjected to pattern printing. Is preferred.

Further, according to the present invention, there is provided a pattern formed product obtained by the method for forming a relay image.

Examples of the metal powder or its oxide powder that can be used in the slurry of the present invention include powders of silver, palladium, gold, platinum, copper, nickel, ruthenium oxide, and the like. As a result, these precious resources can be easily and efficiently reused, and the cost can be significantly reduced.

BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 is an explanatory view schematically showing one embodiment of a relay image forming method according to the present invention.

BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the present invention will be described in detail.

The substrate that can be used in forming the relay image according to the present invention is not particularly limited, and the present invention provides a glass substrate, a ceramic substrate, and a ceramic substrate. Can be put on green sheets and metal substrates. The slurry used to form the powder layer is a mixture of the powder and a solvent such as water or a solvent, and if necessary, a mixture of a small amount of resin such as polyvinyl alcohol or polyvinyl butyral. Can be obtained by dispersing and slurrying. The powder is not particularly limited, but, for example, silver, silver-palladium alloy, silver alloy, palladium, gold, platinum, copper or nickel, or gold containing glass frit as necessary for forming a conductive pattern. Dielectric powder can be used for forming a capacitor pattern, and ruthenium oxide containing glass frit can be used for forming a resistive pattern.

The slurry can be applied onto the substrate by a known method such as a doctor blade method or a screen printing method, and by drying the formed uniform coating film. Obtain a powder layer.

In the method for forming a relay image according to the present invention, the slurry used for the powder layer formed on the substrate may be a metal powder removed from the substrate in pattern formation or a slurry thereof. By using slurry obtained by adjusting the solid content of the recovered material containing the oxide powder with a solvent, the metal powder or its oxide powder is reused. It is characterized in that

Such reuse is achieved by printing a pattern of a binder on the powder layer using an ink jet method and removing the powder layer from the substrate by a predetermined means for partially removing the powder layer from the substrate. This is made possible by forming a and a removable portion. In other words, with respect to the predetermined removing means, the part printed by the binder by the ink jet method is regarded as an unremovable part, and only the part where the binder is not printed is used by using the means. Remove. Then, The recovered material containing the metal powder and Z or its oxide powder removed from the plate is used as slurry for forming a powder layer by adjusting the solid content with a solvent. And can be easily reused.

Hereinafter, a method for forming a relay image according to the present invention using an ink jet method will be described with reference to the drawings. FIG. 1 is a cross-sectional view schematically showing one embodiment of a step of forming a relay image according to the present invention. As shown in Fig. 1, the binder is jet-printed on the powder layer 1 as an ink droplet 3 by an ink jet (see Fig. 1 (a)). Thus, the portion 4 on which the binder has been jet-printed cannot be removed by the predetermined removing means. That is, a non-removable portion 4 and a removable portion 5 are formed in the powder layer for a predetermined removing means (see FIG. 1 (b)). Here, the binder is not particularly limited. For example, a hot wax is jetted at a temperature equal to or higher than the melting point of the wax using an ink jet. It is also possible to use a method that renders it impossible to remove the specified removal means, or use a thermosetting, UV-curing, or drying-curing ink.

It is also possible to use a method of making the pattern unremovable by curing after pattern printing by the 'method. Next, the powder layer portion 5 other than the portion 4 which cannot be removed by the predetermined removing means by the jet printing is removed by using the removing means to thereby obtain a desired pattern. (See Fig. 1 (c)).

In the present invention, the means for removing the portion where the jetter is not jet-printed includes a means for applying pressure using a medium, Means using a sound wave, means for removing using a solvent, and the like can be given. The medium that can be used in the means for removing by applying pressure may be a gas or a liquid, and examples thereof include means for removing by wind pressure, means for removing by liquid spray, and the like.

In particular, in the present invention, from the viewpoint of reusing the collected material, it is preferable to employ a means for removing the portion where the binder is not subjected to the jet printing using a solvent as a removing means. . More preferably, the same solvent as that used in forming the slurry is used as the solvent. When the same solvent is used, the recovered liquid containing the metal powder or its oxide powder may be removed, for example, by removing the solvent by a method of adjusting the solid content by removing the supernatant or by removing the solvent by filtration When the solid content is finely adjusted, a slurry that can be reused as a slurry used for forming a powder layer can be obtained by an extremely simple method. As described above, in the present invention, it is desirable that the solvent used for removing the powder layer in a portion that is not jet-printed and cannot be removed is the same as the solvent used for forming the slurry. However, other solvents can be used as long as slurry is not hindered. At this time, when a solvent having a low boiling point is used, the solid content of the slurry can be easily adjusted by removing the solvent by heating, and the slurry can be easily reused. Therefore, it is preferable as a solvent for removing the powder layer. Specifically, alcohols, ketones, and glycols having a boiling point of 100 ° C. or less are suitably used, and a mixture of two or more solvents may be used. In addition, the solid content of the slurry is adjusted by removing the solvent by heating before separating the metal powder or its oxide powder from the recovered liquid by filtration. It is easy to keep them apart.

(Example)

Hereinafter, the present invention will be described specifically with reference to Examples, but it is to be understood that the present invention is not limited to the following Examples. In the following, “%” means “% by mass” unless otherwise specified.

(Example 1)

(1) Preparation of slurry

Silver powder and glass powder are mixed in a mixed solution of polyvinyl alcohol and distilled water at the following composition ratio, stirred with a stirrer, and then slurried with a three-roll mill to make a slurry. Was done.

Silver powder 70%

(Spherical monodisperse, average particle size l / m, power strips density 5. 1 g / cm ³⁾

Polyvinylenole call 2% Distilled water 28%

(2) Application of slurry

Next, the slurry obtained in the above (1) by screen printing is subjected to screen printing using a 250 mesh mesh poly stealth screen. Then, it was applied to the entire surface of the substrate and dried at 80 ° C. for 20 minutes to form a coating film (powder layer) having a thickness of 5 m.

(3) Making removal impossible by the ink jet method

While the head of the ink jet is heated to 50 ° C, the wax having a melting point of 40 ° C is jet-printed on the powder layer obtained in the step (2). Then, the dropped portion of the wax is used for the slurry. The solvent (distilled water) used in the preparation was not removed. The pattern that could not be removed was a parallel line with a space of 200 μm and a line width of 80 im.

(4) Removal of non-jet printed area

Distilled water was sprayed on the powder layer obtained in the above step (3), and portions which were not made unremovable by the wax dripped by the ink jet method were removed. At this time, the water temperature was 30 ° C.

(5) Relief image formation

The substrate obtained in the step (4) was fired at 550 ° C. to form a conductive pattern relief image.

(6) Recovery and Reuse of Silver Powder and Glass Frit The silver powder-containing aqueous solution from which the parts that were not made unremovable in step (4) above were removed was recovered. After dust was removed from the solution with a screen, the powder was allowed to settle at rest and the supernatant was removed. A predetermined amount of distilled water and polyvinyl alcohol were added to the mixture, the viscosity was adjusted, and the slurry was reused as slurry for forming a powder layer.

(Example 2)

(1) Preparation of slurry

Silver powder and glass powder are mixed in a mixed solution of polyvinyl butyral and a solvent at the following composition ratio, stirred with a stirrer, and then ground with a three-roll mill to make a slurry. Was performed.

Silver powder 70%

(Spherical monodisperse, mean particle size ₁ μ πι, power strips density 5. 1 g / cm ³ )

Glass frit 2% Polyvinyl butyral 2% Solvent (Ethyl carbitol acetate) 26%

(2) Application of slurry

Next, the slurry obtained in the above (1) by screen printing is subjected to screen printing using a 250 mesh polystyrene screen. Then, it was applied to the entire surface of the substrate and dried at 80 ° C. for 20 minutes to form a coating film (powder layer) having a thickness of 5 μm.

(3) Unremovable by ink jet method

A thermosetting binder is jet-printed on the powder layer obtained in the above step (2) by an ink jet method, and the portion where the thermosetting binder is dropped is heated. After curing, the solvent (ethyl carbitol acetate) used in the preparation of the slurry was not removed. The pattern that could not be removed had the shape of a parallel line with a space of 200 μm _s and a line width of 80 Atm.

(4) Removal of unprinted parts

Ethyl carbitol acetate was sprayed on the powder layer obtained in the above step (3), and the powder layer was made unremovable by a thermosetting binder dripped by an ink jet method. The missing part was removed.

(5) Relief image formation

The substrate obtained in the step (4) was fired at 550 ° C. to form a relief image of a conductive pattern.

(6) Recovery and reuse of silver powder The silver powder-containing solution from which the portions that were not made unremovable in step (4) were removed was recovered. After the dust was removed from the solution by a screen, the powder was settled by standing still, and the supernatant was removed. To this was added a predetermined amount of ethyl carbitol acetate and polyvinyl butyral, the viscosity was adjusted, and the slurry was reused as slurry for forming a powder layer.

(Example 3)

Making slurry

Silver powder and glass powder are mixed in a mixed solution of cellulose ether and distilled water at the following composition ratio, stirred with a stirrer, and ground with a three-roll mill. Slurry was implemented.

Silver powder 76.5%

(Spherical monodisperse, average particle size 1 μπι, tap density 5.1 g / cm ³ )

Glass powder 8.5% Cellulol ether 0.5% Distilled water 14.5% (2) Application of slurry

Next, the slurry obtained in the above (1) by screen printing is subjected to screen printing using a 250-mesh polysteel screen. Then, it was applied to the entire surface of the substrate and dried at 80 ° C. for 20 minutes to form a coating film (powder layer) having a thickness of 5 μm.

(3) Making removal impossible by the ink jet method

A solution consisting of 5% of acrylic polymer and 95% of carbitol acetate was added to the powder layer obtained in the above step (2) by jetting. After printing and drying at 80 ° C. for 20 minutes, the dropped portion of the solution was made unremovable with respect to the solvent (distilled water) used in the preparation of the slurry. The pattern that could not be removed was shaped like a parallel line with a space of 200 μm and a line width of 80 m.

(4) Removal of unprinted parts

Distilled water is sprayed on the powder layer obtained in the above step (3), and the portion which is not made unremovable by the acrylic polymer-containing solution dropped by the ink jet method is removed. Removed. At this time, the water temperature was 30 ° C.

(5) Formation of relief image

The substrate obtained in the above step (4) was fired at 550 ° C. to form a conductive pattern relief image.

(6) Recovery and Reuse of Silver Powder and Glass Frit The silver powder-containing aqueous solution from which the part that was not made unremovable in step (4) was removed was recovered. After removing dust from the solution by means of a screen, the powder was allowed to settle by standing still, and the supernatant was removed. A predetermined amount of distilled water and cellulose ether were added to the mixture, the viscosity was adjusted, and the slurry was reused as slurry for forming a powder layer.

Industrial applications

According to the relay image forming method of the present invention, the conductive pattern can be formed without using the photolithography method. As a result, it is possible to easily reuse metal powder or its oxide powder that was discarded in the photolithographic method. Therefore, a conductive pattern relief image can be formed at a low price.

Claims

The scope of the claims

1. a step of forming a powder layer by applying a slurry prepared using at least a metal powder or its oxide powder and a solvent on a substrate and drying the slurry; A step of pattern-printing a binder by an ink jet method on the powder layer obtained in the body layer forming step, and a step of printing only a part where the binder is not printed in the pattern printing step. A step of forming a pattern by removing the substrate from the substrate, wherein the slurry contained in the portion removed in the pattern printing step is one of the slurries used in the powder layer forming step A method for forming a relay image, comprising using a slurry obtained by adjusting a solid content of a powder or a recovered product containing an oxide powder thereof with a solvent.

2. A step of preparing a slurry by adjusting the solid content of at least a metal powder or its oxide powder and a solvent, and a step of preparing the slurry obtained in the slurry preparation step. A step of forming a powder layer by coating on a substrate and drying, and a step of pattern-printing a binder by an ink jet method on the powder layer obtained in the powder layer forming step. In the pattern printing step, the pattern is formed by removing only the portion where the binder is not printed from the substrate, and the metal powder contained in the portion where the pattern is not formed. Or a step of recovering the oxide powder thereof, wherein the metal powder or the oxide powder used in the slurry preparation step includes the recovered metal powder or the oxide powder thereof. Characterized by the fact that Huy image Formation method.

3. The relay film according to claim 1 or 2, wherein the metal powder is one or more powders selected from silver, palladium, gold, platinum, copper, nickel and ruthenium. How to form the page.

4. The method of forming a relay image according to any one of claims 1 to 3, wherein a portion of the binder where the pattern is not printed is removed using a predetermined solvent.

5. The relay according to claim 4, wherein the predetermined solvent used for removing the portion where the binder has not been pattern-printed is the same as the solvent used in preparing the slurry. -The method of forming the image.

6. A pattern formed product obtained by using the method according to any one of claims 1 to 5.