JP5088063B2 - Electrode pattern forming method - Google Patents

Description

The present invention relates to a method of forming a more electrode patterns in the manufacture how the coating film using a suitable printing in key for use in intaglio offset printing to form a fine and highly precise electrode pattern on a semiconductor device.

  Conventionally, a photolithography method has been used to form electrodes and the like in semiconductor devices such as electronic circuit boards and display devices. However, this photolithography method has a complicated manufacturing process and has a lot of material loss, so that pattern formation can be performed. There is a problem that the manufacturing cost becomes extremely high because a huge amount of cost is required for manufacturing equipment such as an exposure apparatus. Furthermore, the cost of processing the waste liquid generated in the development process at the time of pattern formation is high, and the waste liquid has a problem from the viewpoint of environmental protection.

  Thus, various researches have been conducted on pattern formation methods that are low in cost and do not generate harmful waste liquids. In particular, the intaglio offset printing method is attracting attention as an alternative to the photolithography method because it can form a fine pattern with high accuracy. In the intaglio offset printing method, 100% of the printing ink is transferred from the printing blanket to a transfer medium such as a glass substrate. Therefore, a silicone rubber sheet is used for the printing blanket surface, and the silicone rubber on the blanket surface is used for the printing ink. For example, a solvent is added, this solvent is dissolved in silicone rubber, and the interfacial tension at the interface between the printing ink and the silicone rubber is reduced to make it easier to peel the printing ink from the silicone rubber. The image is transferred from the blanket onto the transfer object. As solvents that are easily dissolved in silicone rubber, alcohols such as α-terpineol and alkyl ethers such as butyl carbitol acetate have been used. However, if continuous printing is performed for a long time, the solvent contained in the printing ink gradually permeates into the silicone rubber sheet on the blanket surface, and the silicone rubber sheet swells. There is a problem that the reproducibility of the image quality decreases.

As a measure for solving the above problem, a method of heating the blanket surface after transferring the conductive ink composition from the printing blanket surface to the surface of the glass substrate and then cooling the blanket surface is disclosed ( For example, see Patent Document 1.) Also, the surface of the printing blanket that uses a silicone elastomer is used, and the ink that contains low molecular weight polysiloxane is used as the printing ink, and the printing ink is transferred from the printing blanket to the transfer target. A method of heating the blanket surface after the transfer to the surface to evaporate the solvent of the printing ink absorbed by the blanket and then cooling the blanket surface is disclosed (for example, see Patent Document 2). By the methods disclosed in Patent Documents 1 and 2, the problem that the blanket swells due to the solvent of the ink can be solved.
JP 2002-245931 A (Claim 1) Japanese Patent Laying-Open No. 2004-66804 (Claim 1)

However, in the methods shown in Patent Documents 1 and 2, the heating and cooling steps are added to normal intaglio offset printing, and the steps are complicated, and the silicone rubber sheet on the surface of the blanket is printed with the ink in the ink. It has not been able to prevent the solvent from penetrating, and it has not completely solved the problem.
An object of the present invention is to provide a method of forming an electrode pattern by producing how the coating film using the printing-in key capable of reducing fluctuations in the shape of the printing pattern in the continuous printing by the intaglio offset printing.
Another object of the present invention is to provide an electrode pattern forming method capable of eliminating a decrease in film thickness, variation, line width variation, and the like caused by a piling phenomenon that occurs when continuous printing is performed using intaglio offset printing. It is to provide.

According to the first aspect of the present invention, a printing plate having a concave pattern is filled with printing ink, and after the filled ink is transferred to a printing blanket having a silicone rubber sheet on the surface, the printing blanket is composed of a glass substrate. by producing a coating film by transferring the ink to the transfer object, an improvement of a method of forming an electrode pattern.
1. The characteristic composition is: an inorganic powder component in which the ink contains silver powder; and a resin component containing an acrylic-styrene copolymer, an acrylic-urethane copolymer, an acrylic-epoxy copolymer, an epoxy acrylate, or a urethane acrylate; , 3 propanediol, 2,4 pentanediol, 1,2 propanediol, 1,2 ethanediol, 1,3 butanediol, 1,5 pentanediol, 1,4 pentanediol, 1,2 pentanediol or 1,2 , look containing a solvent component consisting of 3-propanetriol, the printing plate is the line width W: 10 to 1000 [mu] m, the depth D: 5 to 50 [mu] m, the pitch P: consists plane intaglio having a plurality of concave patterns of 10 to 1000 [mu] m The printing blanket has a 0.1 to 3 mm thick silicone rubber sheet attached to the surface Made from the blanket roll, filled with pre-Symbol printing ink on the plane intaglio, after transferring the ink to the filling to the blanket roll, by transferring the ink from the blanket roll to the glass substrate, the predetermined surface of the glass substrate pattern When the intaglio offset printing for printing a coating film having a continuous printing is performed on any one of 2 to 1000 glass substrates, each 2-1000 sheets obtained are continuously printed. About the printed glass substrate, the average value of the measured value when measuring the line width W of 3 to 12 places at a predetermined position of each glass substrate is in the range of 0.9 W to 1.1 W, and the measured value The standard deviation value is in the range of 1-5.
In the invention according to claim 1, the diol solvent or 1,2,3 propanetriol can dissolve the resin component in the printing ink and can swell the silicone rubber sheet on the surface of the printing blanket. Therefore, by using it for printing ink, it is possible to reduce the variation in the shape of the print pattern in continuous printing by intaglio offset printing. Further, it is possible to eliminate film thickness reduction and variation, line width variation, and the like, which are caused by a piling phenomenon that occurs when continuous printing is performed using intaglio offset printing.

The electrode pattern forming method of the present invention comprises: an inorganic powder component in which the printing ink contains silver powder; an acrylic-styrene copolymer, an acrylic-urethane copolymer, an acrylic-epoxy copolymer, an epoxy acrylate, or a urethane acrylate. A resin component containing; 1,3 propanediol, 2,4 pentanediol, 1,2 propanediol, 1,2 ethanediol, 1,3 butanediol, 1,5 pentanediol, 1,4 pentanediol, 1,2 look containing a solvent component consisting of pentane diol or 1,2,3 propane triol, wherein the printing plate is the line width W: 10 to 1000 [mu] m, the depth D: 5 to 50 [mu] m, the pitch P: a plurality of concave patterns of 10 to 1000 [mu] m A blanket for printing with a thickness of 0.1 to 3 mm on the surface. A blanket roll to which a sheet is attached, a transfer object is a glass substrate, the printing ink is filled into the plane intaglio, and the filled ink is transferred to the blanket roll, and then from the blanket roll to the glass substrate. When intaglio offset printing for printing a coating film having a predetermined pattern on the glass substrate surface by transferring ink is continuously printed on any one of 2 to 1000 glass substrates,
About 2 to 1000 printed glass substrates obtained, the average value of the measured values when measuring the line widths W at 3 to 12 locations at predetermined positions on each glass substrate is 0.9 W to 1.1 W, respectively. in the range of, and the standard deviation of the measured values it is characterized and der range of 1 to 5 Turkey. Since these diol solvents or 1,2,3 propanetriol can dissolve the resin component in the printing ink and does not swell the silicone rubber sheet on the printing blanket surface, By using the printing ink, there is an advantage that the variation in the shape of the printing pattern can be reduced in continuous printing by intaglio offset printing. In addition, according to the method for forming an electrode pattern of the present invention, it is possible to eliminate a decrease in film thickness, variation, variation in line width, and the like caused by a piling phenomenon that occurs when continuous printing is performed using intaglio offset printing. .

Next, the best mode for carrying out the present invention will be described with reference to the drawings.
As a result of diligent study on the influence of the solvent on the silicone rubber sheet on the surface of the printing blanket, the present inventors have found that alcohols and alkyl ethers that are generally used as solvents. Instead of using a diol solvent or 1,2,3 propanetriol , it is possible to dissolve the resin component in the printing ink and to swell the silicone rubber sheet on the surface of the printing blanket. It was confirmed that this was not the case and the present invention was reached.

This onset Ming fills the printing ink to the printing plate having a concave pattern, after transfer to the printing blanket having a silicone rubber sheet to the filled ink surface, the transfer member made of a glass substrate from the printing blanket This is a method for forming an electrode pattern by transferring ink to a coating film. The printing ink includes an inorganic powder component containing silver powder; and a resin component containing an acrylic-styrene copolymer, an acrylic-urethane copolymer, an acrylic-epoxy copolymer, an epoxy acrylate, or a urethane acrylate; 3 propanediol, 2,4 pentanediol, 1,2 propanediol, 1,2 ethanediol, 1,3 butanediol, 1,5 pentanediol, 1,4 pentanediol, 1,2 pentanediol, or 1,2, solvent component and the including of 3-propanetriol. In this electrode pattern forming method, the printing plate is composed of a planar intaglio having a plurality of concave patterns with a line width W of 10 to 1000 μm, a depth D of 5 to 50 μm, and a pitch P of 10 to 1000 μm. made from the blanket roll silicone rubber sheet is attached with a thickness of 0.1~3mm the surface, filled with pre-Symbol printing ink on the plane intaglio, after transferring the filled ink to the blanket roll, the glass from the blanket roll by transferring the ink to the substrate, when the intaglio offset printing for printing a coating film having a predetermined pattern on the glass substrate surface was continuously printed for any one of the glass substrates 2 and 1000 sheets, each obtained 2-1000 For 3 printed glass substrates, 3 to 12 labels at predetermined positions on each glass substrate. In the range the average value of the measured value when measured in the width W respectively of 0.9W～1.1W, and the standard deviation of measured values Ru der range of 1-5. When the ink is 100% by weight, it is preferably blended in a proportion of 5 to 20% by weight of the resin component and 7.5 to 30% by weight of the solvent component. The diol solvent or 1,2,3-propanetriol can dissolve the resin component in the printing ink and does not swell the silicone rubber sheet on the surface of the printing blanket. the use of ink, advantages there Ru that it is possible to reduce the shape change of the print pattern in the continuous printing by the intaglio offset printing.

  The printing ink of the present invention may further contain a dispersant. By further containing a dispersant, an effect of smoothing the coated layer surface can be obtained. When the ink is 100% by weight, the dispersant is preferably blended in a proportion of 3 to 10% by weight. In addition, the sharpness at the edge portion of the line to be formed is increased. As the dispersing agent, it is preferable to use a carboxylic acid type or a phosphoric acid ester type, a polycarboxylic acid polymer anion allyl ether copolymer, a polyamine-fatty acid condensate, a polymer surfactant, a polymer fatty acid, or a fatty acid ester condensate. It is.

The intaglio offset printing method using the printing ink of the present invention will be described.
First, as shown in FIG. 1A, a flat intaglio 10 having a desired concave pattern 10a is prepared as a printing plate, and a predetermined amount of the printing ink 11 of the present invention is supplied to the surface of the flat intaglio 10. The supplied printing ink 11 is embedded in the concave pattern 10 a by sliding the squeegee 12 against the surface of the flat intaglio 10. Next, as shown in FIG. 1B, a blanket roll 13 having a silicone rubber sheet 13a attached to the surface is prepared as a printing blanket, and the blanket roll 13 is a plane in which the ink 11 is embedded in the concave pattern 10a. In this state, the blanket roll 13 is rotated and is slid on the flat intaglio 10 so that a part of the ink 11 embedded in the concave pattern 10 a of the flat intaglio 10 is transferred to the silicone resin of the blanket roll 13. Transfer to the surface of the sheet 13a. The transfer rate at this time is approximately 50 to 60%, although it varies depending on the concave pattern of the plane intaglio, the components contained in the ink, the ratio thereof, and the pressure of the blanket. Finally, as shown in FIG. 1 (c), the blanket roll 13 to which the ink 11 has been transferred is pressed against a transfer medium such as a glass substrate 14, and the blanket roll 13 is rotated in this state, By sliding, a desired pattern is transferred to the surface of the glass substrate 14 as shown in FIG. A silicone resin sheet may be attached to the surface of the blanket roll instead of the silicone rubber sheet. In the printing ink 11 of the present invention using a diol solvent as a solvent, the solvent hardly penetrates into the silicone rubber sheet 13a used on the surface of the blanket roll 13, and does not swell the silicone rubber sheet 13a. Variations in the shape of the print pattern can be reduced.

In the printing ink of the present invention, the printing plate is a planar intaglio having a plurality of concave patterns with a line width W: 10 to 1000 μm, a depth D: 5 to 50 μm, and a pitch P: 10 to 1000 μm. A blanket roll having a thickness of 0.1 to 3 mm attached to a silicone rubber sheet, and when the transfer target is a glass substrate, the ink is filled into a flat intaglio, and the filled ink is transferred to the blanket roll. It was obtained when intaglio offset printing for printing a coating film having a predetermined pattern on the surface of the glass substrate was continuously printed on any one of 2 to 1000 glass substrates by transferring ink from the blanket roll to the glass substrate. About 2 to 1000 printed glass substrates each, 3 to 12 at a predetermined position of each glass substrate When the line width W of each part is measured, the average value of the measured values is in the range of 0.9 W to 1.1 W, preferably 0.95 W to 1.05 W, and the standard deviation value of the measured values is 1 to 1. It is suitable to be in the range of 5, preferably 1-3. If the variation in the shape of the printing pattern is within the above range, it is possible to provide an ink that is suitable for use in continuous printing for a long time by intaglio offset printing and excellent in print reproducibility. Here, continuous printing refers to a case where printing is performed at a speed of 0.5 to 1 sheet / min.

  In the electrode pattern forming method of the present invention, silver powder is selected as the powder component contained in the printing ink, and the substrate is selected as the transfer target. And the printing ink containing silver powder is transcribe | transferred on a board | substrate with the manufacturing method of the coating film using the intaglio offset printing method of this invention mentioned above, and an electrode pattern is formed. In this method, since the electrode pattern is formed on the substrate by the method for producing a coating film using the intaglio offset printing method of the present invention, which reduces the occurrence of the pyring phenomenon in continuous printing, the intaglio offset printing is used for continuous printing. The phenomenon and variation of the electrode pattern thickness, variation in line width, and the like caused by the pyring phenomenon that occurs during printing are eliminated. An electrode having a desired pattern on the substrate can be obtained by drying, firing, or the like on the formed electrode pattern.

Next, examples of the present invention will be described in detail together with comparative examples.
<Examples 1 to 45, Comparative Example 1>
By mixing the powder component, resin component, solvent component and dispersant shown in the following Table 1 to Table 10 with a mixer, and further kneading about 5 to 10 Pa · s with a three-roll mill, paste-like printing ink Got.
As printing plates used for intaglio offset printing, 42 alloy planar intaglio plates having a plurality of concave patterns with a line width of 100 μm, a depth of 25 μm, and a pitch of 360 μm were prepared, and glass substrates were prepared as transfer objects. A blanket roll having a 0.3 mm thick silicone resin sheet attached to the surface was used as a printing blanket. First, a predetermined amount of the printing ink obtained on the surface of the intaglio plate was supplied, and the ink was embedded in the indentation pattern of the intaglio plate using a SUS squeegee. Next, the blanket roll was rotated while being pressed against the flat intaglio, and slid on the flat intaglio to transfer a part of the ink embedded in the concave pattern of the flat intaglio onto the silicone resin sheet surface of the blanket roll. . Finally, the blanket roll was rotated while being pressed against the glass substrate, and slid on the glass substrate to obtain a printed substrate having a predetermined pattern on the glass substrate surface. The intaglio offset printing was continuously performed on 500 substrates.

<Comparison test 1>
Of the 500 printed substrates obtained in Examples 1 to 45 and Comparative Example 1, each of the first, 100th, 200th, 300th, 400th and 500th substrates Nine line widths at predetermined positions on the substrate were measured, and the average value and the standard deviation value of the measured values were calculated. The results are shown in Tables 11-16.

  As is apparent from Table 16, in Comparative Example 1, the average value of the line widths at the nine positions at the predetermined positions on each substrate varied depending on the number of continuous prints, resulting in poor printing stability. Further, printing failure occurred on the 500th continuous printing. On the other hand, as is clear from Tables 11 to 15, in Examples 1 to 45 using the printing ink of the present invention, the average value of the line width is stable, which is preferable for use in continuous printing. I understood.

Schematic of the intaglio offset printing method.

Explanation of symbols

DESCRIPTION OF SYMBOLS 10 Plane intaglio 10a Concave pattern 11 Printing ink 12 Squeegee 13 Blanket roll 13a Silicone rubber sheet 14 Glass substrate

Claims (1)

Filled with printing ink to a printing plate having a concave pattern, after transfer to the printing blanket having a silicone rubber sheet to the filled ink surface, the ink from the printing blanket to the transfer receiving material comprising a glass substrate In the method of forming an electrode pattern by producing a coating film by transferring
The ink includes an inorganic powder component including silver powder; a resin component including an acrylic-styrene copolymer, an acrylic-urethane copolymer, an acrylic-epoxy copolymer, an epoxy acrylate, or a urethane acrylate; 2,4 pentanediol, 1,2 propanediol, 1,2 ethanediol, 1,3 butanediol, 1,5 pentanediol, 1,4 pentanediol, 1,2 pentanediol or 1,2,3 propanetriol and a solvent component consisting of only including,
The printing plate is the line width W: 10 to 1000 [mu] m, the depth D: 5 to 50 [mu] m, the pitch P: made flat intaglio having a plurality of concave patterns of 10 to 1000 [mu] m, the printing blanket has a thickness on the surface of 0.1 Ri Do from the blanket roll silicone rubber sheet is attached in to 3 mm,
The planar intaglio is filled with the printing ink, and after the filled ink is transferred to the blanket roll, the ink is transferred from the blanket roll to the glass substrate, thereby having a predetermined pattern on the glass substrate surface. When intaglio offset printing for printing a coating film is continuously printed on any one of 2 to 1000 glass substrates,
About 2 to 1000 printed glass substrates obtained, the average value of the measured values when measuring the line widths W at 3 to 12 locations at predetermined positions on each glass substrate is 0.9 W to 1.1 W, respectively. And the standard deviation value of the measured value is in the range of 1 to 5 .

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