JPS611089A - Conductive pattern forming transfer material and method of producing substrate having conductive pattern using same - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed Description of the Invention] <Object of the Invention and Industrial Field of Application> The present invention provides a transfer material useful for forming conductive patterns on the surface of various substrates, and a substrate having a conductive pattern using the transfer material. The purpose is to transfer conductive patterns, which are often used in electrical products, electronic products, art products, display products, etc., by a transfer method regardless of the size or shape of the object to be transferred. To provide a method for easily and economically manufacturing a substrate having a conductive pattern using this transfer material, and to provide a transfer material necessary for forming such a pattern easily and in large quantities to users. This is what I am trying to do.

<Prior Art> Conventionally, in order to form such a conductive pattern, using a glass substrate as an example, one of the following methods has been used. That is, (1) first, a mask portion having a pattern opposite to the desired pattern is applied on a glass substrate, then a metal or metal oxide is vacuum-deposited, and then the mask portion is removed; First, a metal or metal oxide is vacuum-deposited on the entire surface of the substrate, then a resist with a desired pattern is applied, and then the parts other than the resist are dissolved and removed by an etching operation, or directly on the glass substrate. One of the methods used was to print a pattern on a conductive material and then bake it to produce a conductive pattern.

However, all of these methods involve considerable technical difficulty in continuously performing each transfer on a large number of objects, and are not uniform because the operating conditions differ depending on the material, size, or shape. It is not easy to operate the method on a large scale, and as a result, large-scale production equipment is required for mass production. Furthermore, it is difficult to obtain uniform final products with satisfactory quality, and the production rate of defective products increases, which has been a source of difficulty for those skilled in the art. Furthermore, a method using a transfer film has been proposed as a method to solve the above-mentioned problems, but this method involves forming a transparent conductive film and an adhesive layer on a flexible film in advance, A stamping method (see Japanese Utility Model Application Publication No. 58-38459) has also been devised, in which the transfer film is stacked on a substrate and then stamped from the back side of the transfer film with a convex stamp having a desired design. According to many follow-up experiments conducted by the present inventors, this stamping method had to be uneconomical because not only was it difficult to produce the above-mentioned convex stamp, but the stamping method also resulted in large losses due to failure. be. Furthermore, with this stamp method, it is not easy to align the pattern with the object to be transferred, and there are inherent limits to the accuracy and size of the pattern.
Especially when it came to complex designs, he was bound to fail completely.゛〈Structure of the Invention〉 In view of the above-mentioned problems, the present inventors have devoted their efforts to discovering a technically and economically advantageous method. We have developed a transfer material for forming a conductive pattern having a desired pattern, and have continued to conduct further research and experiments on this material, and have now finally completed the present invention. That is, the present inventors have found that when a transfer material in which a transfer layer is formed on a releasable plastic film contains a compound of an element of Groups 3 to 5 of the periodic table in at least one layer of the transfer material, and The inventors have succeeded in providing a transfer material for forming conductive patterns of extremely high quality when the material is applied onto a substrate, and a method for manufacturing a substrate having a conductive pattern.

Now, the present invention will be explained in more detail below.

First, as the plastic film 1 of the transfer material for forming conductive patterns according to the present invention, films such as a polyester film, a nylon film, a polyolefin film, etc. alone or in combination can be used. For example, specifically, the thickness of polyethylene terephthalate film is 10μ
It is preferable to have a diameter of about m to 50 μm, because it has excellent printability and heat resistance during heat and pressure transfer.

``The properties observed in this polyester film must be fully considered when selecting and using other films.

The transfer material in which a transfer layer is formed on the plastic film 1 will be explained using FIG. Layer 3 is stacked in multiple layers.

This first ink layer 2 generally has releasability, and is coated with an ink containing one or more of acrylic resin, cellulose resin, silicone resin, polypropylene, melamine resin, etc., or by printing means. It was established by.

Next, for the second ink layer 3, various kinds of resin vehicles can be used, but it is particularly important that this ink contains compounds of elements of groups 3 to 5 of the periodic table. This compound is a solvent-soluble organic compound, and must be uniformly mixed, dispersed, or dissolved with a solvent or resin vehicle, and a small amount of pigment or dopant must be mixed as appropriate. It is comprised in the ink composition. Using this ink composition, a second ink layer 3 is superimposed on the first ink layer 2 by coating or printing means.

Examples of compounds of elements from groups 3 to 5 of the periodic table include gallium,
Desirably, an organic compound soluble in an organic solvent of at least one element selected from the group consisting of indium, thallium, silicon, titanium, zirconium, hafnium, germanium, tin, lead, arsenic, antimony and bismuth,
Furthermore, among these, organic compounds such as indium, thallium, tin, and antimony are industrially important. To give more specific examples, organic acid metal compounds such as octylic acid, indium and caprylic acid, tin, etc., and organic metal chelate compounds such as indium acetylacetonate and tin acetylacetonate can be conveniently used. .

Further, as the solvent for the ink composition constituting the second ink layer 3, ethyl acetate, methyl ethyl ketone,
Ethyl cellosolve and the like are preferred, but should not be particularly limited to these. Also, as a tM fat vehicle,
For example, acrylic resins, cellulose resins, vinyl chloride-vinyl acetate copolymers, and other aliphatic synthetic resins generally give good results, but it goes without saying that other resin vehicles can also be used in various combinations. It is.

What is more interesting is that when an adhesive component is used in the resin vehicle of the ink composition constituting the second ink layer 3, the second ink layer 3 also serves as the adhesive layer 4. In this case, the adhesive layer 4 is often unnecessary.

However, in general, it is convenient to provide an adhesive layer 4 on the first ink layer 2 and the second ink layer 3 in terms of the structure of the transfer material, and this allows the transfer layer to be transferred to be in close contact with the substrate to be transferred. Guaranteed. This adhesive layer 4 can be constructed using, for example, acrylic resin, vinyl resin, polyamide resin, or the like.

The second ink layer 3 is formed into a desired pattern shape, but it goes without saying that it may be formed into a solid pattern if necessary.

Next, a method of manufacturing a substrate having a conductive pattern using the above-mentioned transfer material will be explained.

The object (transferred object) of the transfer material according to the present invention is glass,
Products with good heat resistance include quartz glass, sapphire, spinel, rutile, zirconia, garnet, barium titanate, strontium titanate, mica, asbestos, various ceramics, etc., and the most economical materials are glass, quartz glass, mica, and ceramics. It is often used as a substrate (transferred object) such as.

As shown in FIG. 2, first, the transfer material of the present invention is placed on the surface of the transfer target 50, which is a substrate, so that its adhesive layer 4 is in contact with it, and then the plastic film, which is the base, is peeled off.
The first ink N2 and the second ink layer 3 are accurately transferred.

Next, the transferred object 5 is transferred to a heating process, where it is gently thermally decomposed and oxidized. This heating is performed to change the layer of compounds of Group 3 to 5 elements of the periodic table into conductive oxides of Group 3 to 5 metals, and the heating conditions in this case are generally as follows: is 300℃~ in air
It is carried out at 500°C. However, during or after exposure to an atmosphere of strong oxidizing substances, such as ozone,
The present inventors have revealed that a substrate with a lower electrical resistance value can be obtained by heating to 0°C to 500°C.

The present invention relates to a transfer material for forming a conductive pattern as described above and a method of manufacturing a substrate having a conductive pattern using the same. Mass production is possible with simple operations. If appropriate equipment is used, conductive patterns can be easily formed without pollution.
In particular, it is widely used in manufacturing substrates having transparent conductive films. When forming a transparent conductive film with any complicated pattern, it can be done without the need for difficult methods such as mask evaporation, etching, and schumb methods. It also became very easy to form patterns and circuits.

The present inventors conducted numerous experiments regarding the above-mentioned present invention and confirmed its superiority, but in order to further clarify the technical content, a few examples will be explained below.

<Example 1> After coating an acrylic modified melamine resin ink on a polyethylene terephthalate base film and drying it to form a release layer, 50 parts (parts by weight) of indium octylate,
Printing is carried out by gravure using an ink containing 0 parts of polymethyl methacrylate, methyl ethyl ketone as a solvent and a viscosity of 100 cps to form a predetermined pattern layer and drying.

Next, an ink-type adhesive containing a polyamide resin is layered on top of this and dried. A conductive pattern forming transfer material having a three-layer structure was obtained by sequentially constructing the transfer material in this manner.

This transfer material was stacked with an adhesive layer on a glass plate and pressed from above, and thermal transfer was performed at about 220°C.

Then, the polyethylene terephthalate film was peeled off,
The glass plate was placed in a heating furnace and fired at 500°C for 30 minutes. As a result of testing the conductivity of the product after cooling,
An indium oxide thin film with a light transmittance of 85.1% was uniformly formed, and the electrical resistance of the thin film was measured.
1. It was OKΩ/mouth.

If 0.5 part of tin acetate is added as a dopant to the ink containing this indium octylate, the electrical resistance will be 0.
It became Ω/mouth at 8.

<Example 2> A paraffin wax and ethylene-acrylic copolymer layer was provided on a nylon base film, and then 95 parts of tin acetylacetonate and 3 parts of antimony acetylacetonate were added.
20 parts, 5 parts of cellulose resin, and ethyl acetate.
A pattern layer is provided in the same manner as in Example 1 using 0 cps ink. An adhesive layer containing polymethyl methacrylate resin is then provided. A transfer material for forming a conductive pattern is produced by sequentially configuring in this manner.

After performing thermal transfer (230° C.) on a quartz glass plate with a slightly roughened surface using this transfer material, the quartz glass plate is left in an ozone atmosphere for 20 minutes to allow sufficient ozone to be adsorbed onto the surface. Next, this was placed in an electric furnace at 600°C and fired for 30 minutes. An inspection of the product after cooling revealed that a tin oxide (antimony doped) film with a light transmittance of 89% was formed, and the electrical resistance of the film was measured to be 2.5 Ω/mouth.

<Example 3> A release layer consisting of an acrylic modified melamine resin layer was first formed on a polyphenylsulfone base film, and on top of this, 50 parts of tin acetylacetonate, 1 part of antimony acetylacetonate, and a polymethyl methacrylate resin were formed. A five-part ink was used to form the pattern layer.

Furthermore, an adhesive layer containing polybutadiene was layered on top of this to obtain a desired transfer material. In this case, a glass plate made of Pyrex (registered trademark) is used as the transfer target, and after the transfer is completed on the side surface using a roll transfer machine, the polyphenylsulfone base film is peeled off, and then the plate is transferred to an electric furnace. This electric furnace is kept at 500'C to 510C, and after heating and firing in this furnace for about 1 hour, a beautiful pattern of tin oxide doped with antimony oxide was formed on the surface, and its electrical resistance was When measured, it was 2.8 Ω/mouth.

When using a glass plate as a substrate, it is recognized that the conductivity changes considerably depending on the material of the glass. Generally, hard glass has an IKΩ/~5 Ω/Ω, and soft glass has an IOKΩ/~30 It often becomes niΩ/mouth. It was also observed that the conductivity changed slightly depending on the degree of coloring of the glass, but no particular regularity was observed between the coloring component and the conductivity.

<Effects of the Invention> Since the present invention has the above configuration,
This has the following effects.

That is, by using the transfer material for forming conductive patterns of the present invention, conductive patterns can be easily formed on the surface of various substrates regardless of the size or shape of the object to be transferred, since the conductive patterns are formed by a transfer method. It can be mass-produced. Furthermore, the quality of the final product obtained is sufficiently satisfactory, and the production rate of defective products is extremely low. Furthermore, positioning is easy, the pattern accuracy is excellent, and even complex patterns can be formed.

Therefore, the present invention has extremely high industrial utility value.

[Brief explanation of the drawing]

FIG. 1 is a schematic cross-sectional view of a transfer material for forming a conductive pattern according to the present invention, and FIG. 2 is a schematic cross-sectional view of a method of using the transfer material. In the figure, 1 ------- plastic film, 2
-------1st ink layer, 3------m-2nd ink layer, 4------1 adhesive layer, 5--------Transferred object, FIG. 2. Written amendment to procedure 1. Indication of the case 1982 Patent Application No. 122853 2. Name of the invention Transfer material for forming conductive patterns and manufacturing method of substrates having conductive patterns using the same 3. Person making the amendment 4. The "Detailed Description of the Invention" column 5 of the specification to be amended and the "Detailed Description of the Invention" column of the description of contents of the amendment are amended as follows. (In the 11th specification, page 7, line 18 to line 19, [octylic acid, indium and caprylic acid, tin] is corrected to "indium octylate and tin caprylate". (2) On page 8, line 5 of the specification, “ethyl cellosolve”
Correct it to "ethyl cellosolve". that's all

Claims (3)

[Claims] (1) A transfer material in which a transfer layer is formed on a removable plastic film, in which at least one layer contains a compound of an element of Groups 3 to 5 of the periodic table, for forming a conductive pattern. Transfer material. (2) In a transfer material in which a transfer layer is formed on a removable plastic film, at least one layer of the transfer material contains a compound of an element of Groups 3 to 5 of the periodic table. A method for manufacturing a substrate having a conductive pattern, which comprises forming a transfer layer and then firing it. (3) The compound of elements of groups 3 to 5 of the periodic table is gallium,
A patent characterized in that the compound is a solvent-soluble organic compound of at least one element selected from the group consisting of indium, thallium, silicon, titanium, zirconium, hafnium, germanium, tin, lead, arsenic, antimony, and bismuth. A transfer material for forming a conductive pattern according to claims 1 and 2.