JPH058599B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a method of manufacturing a substrate having a conductive circuit while continuously winding the substrate.

Substrates with conductive circuits include liquid crystal displays, electrochromic displays, electrophotographic recording bodies, electrophoretic recording bodies, transparent switches, connectors, flexible circuits, antistatic bodies, planar heating elements, solar cells, and conductive It is widely used as a material for bodies, etc. in various industrial fields, including the electrical and electronic industries.

<Prior Art> Conventionally, the following method is known as a method for manufacturing a substrate having such a conductive circuit. That is, metal films such as gold, silver, copper, tin, nickel, and palladium, or metal oxide films such as tin oxide, indium oxide, and antimony oxide are deposited by vacuum evaporation,
After forming it on the entire surface of a substrate such as a glass substrate or a plastic substrate by sputtering method or printing method, a masking layer is formed on the required conductive circuit portion by photoresist method or screen printing method, and then wet or dry method is used. There is a method of manufacturing a substrate having a desired conductive circuit by removing unnecessary metal film portions or metal oxide film portions by etching and then removing the masking layer.

However, the above-described method requires many steps such as a masking layer formation step, an etching step, and a masking layer removal step, and has extremely poor workability.

As a method to solve the problems of the above-mentioned method,
Methods disclosed in JP-A-56-13789 and JP-A-58-113376 have been proposed. In both of these methods, ink containing a corrosive agent for the conductive film is printed on a conductive film provided on a substrate in a predetermined area to be removed by corrosion, and unnecessary parts of the conductive film are removed. This is a method of manufacturing a substrate having a desired conductive circuit by removing the ink portion containing the corrosive after corrosion.

According to this method, the step of forming a masking layer,
This has a great effect in that the process of removing the masking layer is no longer necessary, which reduces the number of work steps in production.

<Problems to be Solved by the Present Invention> However, although this method has a good effect in terms of reducing the number of work steps,
It was extremely unsuitable for continuous mass production. This is because in all of the above methods, the corrosive agent used is liquid at room temperature, so after printing the ink containing the corrosive agent, the ink printed on the conductive film is left as is, i.e., the ink printed on the conductive film is used as is. This is because it is necessary to proceed to the next step, an etching step and an unnecessary matter removal step, without contact, and therefore it is not possible to print while continuously winding up the substrate.

<Object of the present invention> An object of the present invention is to provide a continuous manufacturing method for substrates having conductive circuits particularly suitable for continuous production, in order to solve all the problems of various conventional methods. It's about doing.

<Technical Means for Solving the Problems> The present inventors have repeatedly conducted research and experiments on various raw material-related conditions, processing conditions, work procedures, etc. for many years in order to solve the problems of the above-mentioned conventional techniques. As a result of their dedicated efforts, they have finally completed the present invention as a new and remarkable method. That is, the present inventors used an ink containing a solid corrosive agent that generates acidic gas or atomized acidic gas when heated at 50°C to 300°C in the presence of coexisting materials to coat a long substrate. After printing a predetermined pattern on the conductive film, it is dried and then
The corrosive effect is completed by heating to ℃~300℃ to perform an etching reaction, and then the printed pattern part is washed and removed to form a conductive circuit, and the substrate is continuously rolled up in the process after printing and drying. He invented a continuous manufacturing method for substrates having conductive circuits, which is characterized by the following.

The present invention will be explained in detail below.

50℃ ~ in the presence of coexisting materials according to the present invention
The acidic gas generated by heating to 300°C is a relatively pure gas that does not substantially contain water (dry gas) or a mixture of this and an organic compound gas (mixed gas). In addition to the above acidic gases, water, mineral acids, hydrogen fluoride,
It is a heavy gas-liquid mixture (wet gas) with relatively poor diffusivity, in which fine droplets of organic acids or organic acid anhydrides are mixed.

Solid corrosives that generate such gases include acidic sulfates, acidic hydrofluorides, acidic phosphates, mineral acid salts of amino group-containing compounds, boron fluoride complex salts, and boroborohydrofluoric acid compounds that contain amino groups. Salts, amino group-containing compounds, hydrofluoric acid salts, etc. may be used alone or in mixtures of two or more. Although its content is not limited, it is usually 5 to 30% by weight of the ink.
It is.

Although some inks according to the present invention can be used with the above-mentioned solid corrosive agent alone, in reality, an ink containing a binder as a coexisting material with the above-mentioned solid corrosive agent is used. Coexisting materials include water-soluble compounds containing active hydrogen such as dextrin, polyvinyl alcohol, hydroxycellulose, polyacrylamide, and polyacrylic acid, and organic solvent-soluble materials such as polystyrene and polyvinyl acetate. , polyvinyl chloride, acrylate resins, methacrylate resins, soluble phenolic resins, soluble urea resins, soluble melamine resins, and the like. Although the content of this coexisting material is not limited, it is usually
20-50% by weight.

Further, the ink according to the present invention may contain a reaction accelerator in addition to the binder. This reaction accelerator is a third substance with catalytic or cocatalytic performance that is added to the mixed system of solid corrosive and coexisting materials to promote the gas generation reaction.For example, maleic anhydride, succinic anhydride, Acid, adipic acid, zebacic acid, azelaic acid, benzoic acid, nuclear-substituted benzoic acid, naphthalenecarboxylic acid, trimellitic anhydride, itaconic anhydride, phthalic anhydride, isophthalic acid, terephthalic acid, norbornene dicarboxylic anhydride, humic acid, tannin Refers to organic acids or organic acid anhydrides with a melting point of 50°C or higher, such as acids. The amount added is not limited, but it is usually preferably 10% by weight or less of the solid corrosive.

In the present invention, first, a predetermined pattern is printed on a conductive film provided on a substrate using the above-mentioned ink and then dried.

Printing methods according to the present invention include screen printing, gravure printing, flexographic printing, offset printing, letterpress printing, and the like.

What is also important in the present invention is that in the above printing method, the corrosive agent used to corrode the conductive film formed on the substrate is a solid that is stable at temperatures below 50°C. Preferably, it can be dried once at 5 to 40° C. and then rolled up, and therefore has the advantage that a continuous winding screen printing method or a continuous winding type gravure printing method can be applied.

As the substrate according to the present invention, any substrate conventionally used for this type of substrate can be used, but various plastic films are particularly suitable for the present invention, such as polyester film, nylon film, and polyester film. Sulfon film, polyester sulfon film, etc. are preferable for printing.

The conductive film according to the present invention includes gold, silver, copper,
There are metal coatings such as tin, nickel, and palladium.
Also tin oxide, indium oxide, antimony oxide,
There are transition metal oxide films such as zinc oxide, cadmium oxide, indium oxide-tin oxide, and tin oxide-antimony oxide, but considering etching processability and economical efficiency, copper, nickel, indium oxide, and tin oxide are preferable. type is most preferred. The thickness of these conductive films is 10 Å to 3000 Å, and the resistance value is 1 Ω□ to 10 ⁴ Ω/□ depending on the use of the electric circuit, and particularly preferably 10 Ω/□ to 2000 Ω/.

The etching reaction is then completed by heating the substrate to 50°C to 300°C.

Heating in the present invention means that the material is devised so that the desired purpose can be achieved at a temperature of 50°C to 300°C, particularly preferably 70°C to 150°C. There is a method using a tunnel furnace etc. An example of heating conditions is:
Corrosion treatment for 30 seconds to 1 minute at 80° C. to 120° C. is set as practically preferable.

The etching reaction referred to in the present invention refers to an etching reaction in which a pattern is printed and dried, and then the pattern portion of the conductive film is brought into contact with the solid corrosive agent described above, either by winding it up once or without winding it up, at an appropriate temperature, that is, from 50°C to 300°C. Particularly preferably at 70°C to 150°C, acidic salts, acidic oxides,
A phenomenon in which soluble compounds, releasable substances, powdered substances, etc. undergo chemical changes on a substrate in a dry state.
Furthermore, the term "corrosion action" refers to an action in which, as a result of an etching reaction, a required portion is obviously corroded, resulting in a change in form or appearance that differs from that before treatment.

Next, the printed pattern portion is washed and removed.

The cleaning removal method according to the present invention includes shower cleaning with water or a polar solvent, cleaning in a bathtub,
Methods such as ultrasonic cleaning and microwave cleaning are employed.

The present inventors conducted a number of experiments regarding the method for manufacturing a substrate having a conductive circuit according to the present invention described above, and confirmed the superiority of the present invention.However, the technical content of the present invention will be further explained. Therefore, typical examples are shown below as examples. It goes without saying that the method of the present invention should not be construed as being limited only to the examples shown below, and that the embodiments thereof can be carried out as appropriate.

Example 1 A commercially available continuous polyester film was
Indium/tin oxide having a composition of indium oxide: tin oxide = 90:10 was deposited by a sputtering method. Sputtering was performed at a vacuum level of 10 ^-4 torr with argon gas introduced, and the deposited film thickness was approximately 100 Å.
It was hot. Next, 5 parts by weight of sodium hydrogen sulfate and 25 parts by weight of aluminum silicate were mixed with 20 parts by weight of polyacrylamide to prepare an ink suitable for continuous silk screen printing. Using this ink, the line width is 5.0 mm, the line spacing is 10 mm, i.e.
Ten thin lines with a length of 100 mm and a pitch of 15.0 mm were printed and wound using a continuous winding screen printing machine, and then the printed film was heat-treated at 80°C for 30 seconds in a hot air circulation oven. The etching reaction took place simultaneously with the drying of the ink, and the corrosive action was completed.

Next, the film was washed with water to completely remove the ink portion, and then dried. The surface resistance between both ends of each thin wire was 500Ω/□, and each thin wire was completely insulated.

Example 2 Copper was deposited on a commercially available polyester sulfon film to a thickness of 1000 Å by vapor deposition to produce a film with a copper thin film. Next, 20 parts by weight of glucose, 20 parts by weight of polyvinyl alcohol, 8 parts by weight of sodium hydrogen phosphate, and aluminum silicate.
An ink consisting of 12 parts by weight, 8 parts by weight of alkylbenzenesulfonic acid, and 8 parts by weight of bentonite was prepared.

Using this ink, 50 fine lines with a line width of 1.27 mm and a line spacing of 1.27 mm, that is, a pitch of 2.54 mm and a length of 50 mm, were printed and rolled on the copper thin film coated film using a continuous winding screen printing machine. After that, using an arch-type far-infrared heater tunnel furnace,
Heat treatment was performed at 120°C for 20 seconds to cause an etching reaction of the copper to complete the corrosion action, and then the film was washed with water to completely remove the ink and dried, resulting in a predetermined fine copper line pattern. was gotten.

Example 3 100 parts by weight of methacrylic resin was added to a polyester film with a 200 Å thick indium-tin oxide thin film.
30 parts by weight of aluminum tetrafluoroborate, 20 parts by weight of aluminum silicate, ethyl alcohol
Printing was carried out using an ink consisting of 200 parts by weight of a water mixed solvent and 1 part by weight of maleic anhydride using a continuous winding type gravure printing machine. Next, the rolled polyester film was heat-treated at 90℃ for 1 minute using an arch-type far-infrared heater tunnel furnace.
When the ink was completely removed, the desired conductive circuit made of indium-tin oxide was obtained.

<Effects of the Invention> Since the present invention has the above configuration, it has the following effects. That is, since the corrosive agent used to corrode the conductive film formed on the substrate is solid at room temperature, a predetermined pattern is printed using ink containing this corrosive agent. After that, it can be continuously rolled up, and therefore a continuous winding printing method can be applied as a printing method, so it has an extremely large effect on continuous mass production. It is. As a result, the manufacturing process can be streamlined and the etching process can be shortened. Furthermore, if it is predicted that the product will be defective due to printing defects when printing with ink containing corrosive agents, this step Since the ink can be washed away and the expensive substrate can be reused, it also has effects such as improving the yield rate and reducing costs.

Therefore, the continuous manufacturing method of a substrate having a conductive circuit according to the present invention is extremely useful industrially and has high utility value.

Note that the continuous manufacturing method of a substrate having a conductive circuit according to the present invention does not necessarily require the application of a continuous winding printing method, and even when a continuous winding printing method is applied, winding is not necessarily necessary. It goes without saying that the sheet may be cut into a predetermined size immediately after printing and drying in preparation for a subsequent process, or it may be dried after printing and simultaneously moved to a subsequent heating step.

Claims (1)

[Claims] 1. Provided on a long substrate using an ink containing a solid corrosive that generates acidic gas or atomized acidic gas when heated at 50 to 300°C in the presence of coexisting materials. After printing a predetermined pattern on the conductive film, it is dried, and then heated to 50 to 300°C to perform an etching reaction to complete the corrosion action, and then the printed pattern is washed away to form a conductive circuit. A continuous manufacturing method for a substrate having a conductive circuit, characterized in that the substrate is continuously wound up in a step after printing and drying. 2. The continuous manufacturing method of a substrate having a conductive circuit according to claim 1, wherein the conductive film is a conductive metal film. 3. A continuous manufacturing method for a substrate having a conductive circuit according to claim 1, wherein the conductive film is a transition metal oxide film. 4 Claim 1, characterized in that the ink contains a binder as a coexisting material with a solid corrosive agent.
A continuous manufacturing method for a substrate having a conductive circuit as described in 1. 5. The continuous manufacturing method of a substrate having a conductive circuit according to claim 4, wherein the ink contains a binder and a reaction accelerator as coexisting materials with the solid corrosive agent.