JPH05222326A - Offset ink for forming silver conductor circuit and method for forming silver conductor circuit - Google Patents

Abstract

PURPOSE:To provide the title ink which can readily form a desired printing pattern with high resolution and accuracy by offset printing. CONSTITUTION:The title ink contains a resin component comprising at least one resin selected from the group consisting of an alkyd resin, a modified alkyd resin, a modified epoxy resin, a polyurethane oil, rosin, and a maleinized oil, a solvent component, a metallic silver powder, and, if necessary, a flux component.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a printing ink and a forming method for forming a silver conductor circuit on various substrates used as electronic industrial materials.

[0002]

2. Description of the Related Art Conventionally, a screen printing method using a silver paste has been widely used for forming a silver conductor circuit on a substrate. Although this method is inexpensive and can produce a large amount of printed patterns, it has a drawback that it is difficult to form a fine pattern having a line / space of 50 μm. Further, in screen printing, since a screen mesh is used for the plate, there is a disadvantage in that the positional accuracy deteriorates because of the positional deviation with respect to printing on a large base material.

On the other hand, a photolithography method is used as a method for forming a fine pattern. Although this method can form a fine fine pattern, it requires a large amount of equipment for manufacturing, and the process is complicated and labor-intensive.
It has a drawback that the production cost is high and the product cannot be supplied inexpensively.

[0004]

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned drawbacks of the conventional method. It is an offset for a silver conductor circuit containing a resin component, a solvent component, a metallic silver powder and, if necessary, a flux component. A method for offset printing a pattern on a substrate using a printing ink to provide a fine pattern forming method with high positional accuracy and high line / space resolution.

[0005]

The present invention provides at least one resin component, solvent component, metallic silver powder selected from alkyd resins, modified alkyd resins, modified epoxy resins, urethanized oils, rosins and maleated oils. The present invention also relates to an offset printing ink for a silver conductor circuit, which contains a flux component if necessary.

Furthermore, the present invention provides at least one resin component selected from alkyd resins, modified alkyd resins, modified epoxy resins, urethanized oils, rosin and maleated oils, a solvent component, a silver metal powder, and if necessary. Offset printing ink for silver conductor circuit containing flux component on the base material, the step of offset printing the pattern on the base material, the step of curing the printed pattern as it is or / and the irradiation with active energy rays and / or the heating, the curing The present invention relates to a method for forming a silver conductor circuit, which comprises a step of overprinting the printed pattern as it is or the same pattern, and a step of drying or firing.

As the resin of the present invention, it is necessary to select a resin suitable for the printability of offset printing, and alkyd resin, modified alkyd resin, modified epoxy resin, urethanized oil, rosin, maleated oil, etc. are preferable, and they may be used alone or in a mixture. Use one. The amount of resin varies depending on the content of silver, but is preferably 3 to 40% in consideration of printability.

The solvent used in the present invention has the purpose of dissolving a solid resin or additive in a liquid state and the role of a thickener for decreasing the viscosity. Xylene, toluene, butanol, mineral spirits, petroleum-based solvents (solveso, naphtha), terpinol, etc. are used to dissolve the solid resin, and solvent Nos. 3 to 6 are used to lower the viscosity.

The metallic silver powder is spherical with a particle size of 0.05 to 1.0 μm,
It is preferably monodispersed with a particle size of 0.1 to 0.5 μm. The flake powder is 0.1-10 μm, more preferably
It is preferably 0.5 to 5 μm, and spherical particles may be used alone or flakes may be mixed in a silver ratio of 10% to 75%, preferably 20% to 50%. The purity of silver powder at this time is 95-99.99%.

The particle size of the spherical silver powder is set to 0.05 to 1.0 μm because if the particle size is less than 0.05 μm, the particle size is too small and the elasticity is not obtained, and thus the printability is unsuitable. This is because the handling becomes difficult because of this. On the other hand, if it is 1 μm or more, there is a problem that stable printing cannot be performed because the ink is not evenly deposited on the roller during inking.

The reason why the flaky powder is mixed with the spherical powder is that when the flakes are located on the line, the powder and powder can make a large contact with each other and the resistance of the conductor can be reduced.

The additive components of the present invention are a leveling agent, a polymerization initiator, an oxidation accelerator, an anti-skinning agent, a thickener, a metal chelate resin, a dispersant and a filler, which are added depending on the suitability of the ink. For example, if it is a leveling agent, it is advisable to add 0.1 to several% of a silicon compound. Acrylic oligomers as polymerization initiators, cobalt naphthenate and manganese naphthenate as oxidation promoters, methyl ethyl ketone oxime as an anti-skin agent, thickening varnishes as thickeners, linseed oil fatty acid salts, stearates, oleic acid as metal chelate resins. There is salt etc. The filler is Al ₂ O ₃ , TiO ₂ , B
A fine powder such as iO ₂ or SnO ₂ may be used, and a powder of 0.05 μm to 10 μm or less may be used. The filler is added for the purpose of removing or reducing the strain generated in the silver thin film or the interface between the silver and the substrate during firing. or,
It also leads to improved chemical resistance.

The flux component is an organometallic compound and / or
Alternatively, it may be added with a glass frit. P as a metal component
b, B, Si, Zn, Bi, Sn, Cr, Mn, Ti,
Select one that contains Al, alkali, alkaline earth, etc. As the organic metal compound, 2-ethylhexanoate, naphthenate, neodecanoate, metal alkoxide, linseed oil fatty acid salt, oleate, stearate and the like are used.

The flux component is added for the purpose of improving the adhesion between the silver conductive thin film and the base material. For example, if the base material is a glass substrate, PbO ₂ --B ₂ O ₃ --SiO ₂ , Pb.
O ₂ -B ₂ O ₃ -ZnO ₂ based softening point of the well by using the glass frit of about 350 to 600 ° C., if alumina substrate _{SiO 2 -Al 2 O 3 -CaO,} SiO 2 -PbO-C
An aO-based glass frit having a high softening point may be used.

The above-mentioned resin, solvent, additives, metallic silver powder and, if necessary, flux components are premixed and then melted and kneaded by a triple roll until they are sufficiently homogeneous. A predetermined pattern can be obtained by offset printing using the silver conductor circuit printing ink thus adjusted.

The method for printing the predetermined pattern is offset printing, which may be either a planographic printing plate or an intaglio printing plate, and the predetermined pattern is obtained by transferring the ink from the printing plate to the blanket or from the blanket to the substrate.

When ink transfer of a predetermined pattern is not sufficiently performed once, overprinting may be performed. By performing this overprinting, the total amount of ink transfer and the film thickness can be increased. You can continue overprinting, but
In the case of overprinting, if the transfer amount does not increase due to backtrapping, backtrapping can be prevented by curing the ink on the pattern before overprinting. Irradiation with active energy rays and / or curing method
Alternatively, it can be cured by heating. Active energy rays mean ultraviolet rays, infrared rays, and electron rays, and curing proceeds by combining these active energy rays and heating. In order to further accelerate the curing, it is advisable to add an ultraviolet curable resin, a polymerization initiator and an oxidation accelerator.

When the printed pattern on the base material is not smooth as described above, it is possible to promote the smoothing of the surface by pressing the printed pattern. At this time, increasing the number of presses and the press pressure leads to thickening of the line.

When a silver conductor circuit printing ink containing a flux component is used, the predetermined pattern obtained by offset printing is subjected to a firing step. The firing temperature is the temperature at which organic substances contained in resin components, solvent components, additive components, etc. must evaporate, sublime, or decompose.
It is desired that the temperature is 00 ° C or higher. Also, in order to improve the adhesion between silver and the base material, the flux component must be melted and a reaction phase must be formed at the interface with the base material, and the temperature must be raised to the temperature required for melting and baked. .

[0020]

【Example】

Production Example 1 20 g of an alkyd resin (manufactured by Dainippon Ink and Chemicals, Inc .: Beckosol EL-8001) was premixed with 80 g of 0.3 μm spherical metallic silver powder and then kneaded with a three-roll to prepare a silver ink.

Production Example 2 An ink was prepared by adding 14.5 g of a phenol-modified alkyd resin (manufactured by Dainippon Ink and Chemicals, Inc .: Beccosol 1341) to 85 g of 0.3 μm spherical metallic silver powder and 0.5 g of No. 5 solvent.

Production Example 3 0.8 μm spherical metallic silver powder was added to 13 g of a fatty acid-modified epoxy resin (Dainippon Ink and Chemicals: Becksol P-786-50).
85 g, No. 5 solvent 0.5 g, methyl ethyl ketone oxime 1 g, cobalt naphthenate 0.5 g are mixed and kneaded.
I made an ink.

Production Example 4 Urethane oil (manufactured by Dainippon Ink and Chemicals: Burnock T
D-125) (20 g) was kneaded with 75 g of 0.1 μm spherical metallic silver powder, 0.5 g of No. 5 solvent, 1 g of methyl ethyl ketone oxime and 3.5 g of thickening varnish to prepare an ink.

Production Example 5 Rosin (manufactured by Dainippon Ink and Chemicals, Inc .: Becca Site J-8)
96) To 13 g, 20 g of chloroform and 6 g of No. 5 solvent are added to dissolve rosin, and then chloroform is removed under reduced pressure. 40 g of 0.3 μm spherical metallic silver powder and 40 g of 5 μm flaky silver powder were mixed with 1 g of methyl ethyl ketone oxime and kneaded to prepare an ink.

Production Example 6 40 g of alkyd resin (manufactured by Dainippon Ink and Chemicals, Inc .: Beckosol EL-8001), 1 g of polymerization initiator (acrylic oligomer), 4 g of methyl ethyl ketone, 45 g of 0.3 μm spherical metallic silver powder and 15 g of 8 μm flake silver powder. Mixed with,
Kneading was performed to prepare an ink.

Comparative Example 1 As a resin component, 7.5 g of ethyl cellulose was dissolved in 7.5 g of methyl isobutyl ketone, 80 g of 0.3 μm spherical metallic silver powder and 5 g of α-terpineol were added, premixed, and homogenized with a three-roll mill. Kneaded thoroughly until 1 x 50cm x 50cm glass substrate with this silver paste
Screen printing (325 mesh) was performed.

As a result, the pattern of 30 μm line / space contacts the line adjacent to the whole and is printed solidly,
It was not resolved at all. At the line / space of 50 μm, it was in contact with the adjacent line in some parts and short-circuited. All were resolved at 100 μm line / space.

As a result of measuring the displacement of the pattern printed on the glass substrate, there was a displacement of +180 μm in the longitudinal direction and +80 μm in the lateral direction with respect to the printing direction of 50 cm × 50 cm. At this time, the membrane pressure is 20 μm and the sheet resistance is 40 mΩ.
It was / □.

Example 1 The ink of Production Example 1 was used to perform offset printing by overprinting a predetermined pattern of 50 cm × 50 cm four times on a glass substrate. As a result, a line / space resolution of 30 μm was found. The positional deviation in the vertical and horizontal directions was ± 5 μm or less.

Example 2 The ink of Production Example 1 was used to print 4 times and then irradiated with ultraviolet rays for 1 minute. Repeatedly printing four times and irradiating ultraviolet rays in the same way, totaling 20
Printed twice. The 30 μm line / space was resolved. The positional displacement in the vertical and horizontal directions was ± 5 μm or less.

Example 3 The ink of Production Example 2 was used to print four times, followed by pressing, irradiating with ultraviolet rays for 1 minute, printing in the same manner four times, repeated pressing and irradiation with ultraviolet rays, and printing 20 times in total. As a result, the smoothing of the pattern progressed. The 30 μm line / space was partially unresolved, but the 50 μm line / space was resolved. The vertical and horizontal directions were each 20 μm or less.

Examples 4 to 7 Tables 1 and 2 show the results of the same operations as above.

[0033]

[Table 1]

[0034]

[Table 2]

Production Example 7 20 g of an alkyd resin (manufactured by Dainippon Ink & Chemicals, Inc .: Beckosol EL-8001) was premixed with 80 g of 0.3 μm spherical metallic silver powder and then kneaded with a three-roll mill to prepare a silver ink.

Production Example 8 16 g of alkyd resin (manufactured by Dainippon Ink and Chemicals, Inc .: Beccosol EL-8001) was premixed with 80 g of 0.3 μm spherical metallic silver powder and 4 g of glass frit (1350 manufactured by Asahi Glass Co., Ltd.) and then three rolls were used. Kneading was performed to prepare a silver ink.

Production Example 9 10 g of a phenol-modified alkyd resin (manufactured by Dainippon Ink and Chemicals, Inc .: Beckosol 1341), 0.3 μm spherical metallic silver powder
g, glass frit (Asahi Glass: 1370) 4.5 g, and No. 5 solvent 0.5 g were mixed and kneaded to prepare an ink.

Production Example 10 0.5 μm spherical metallic silver powder 85 per 10 g of fatty acid-modified epoxy resin (manufactured by Dainippon Ink and Chemicals, Inc .: Beckosol P-786-50)
g, No. 5 solvent 0.5 g, methyl ethyl ketone oxime 1 g, cobalt naphthenate 0.5 g, and glass frit (Asahi Glass: 1307) 3.5 g were mixed and kneaded to prepare an ink.

Production Example 11 Urethane oil (manufactured by Dainippon Ink & Chemicals, Inc .: Barnock T
D-125) 15 g 0.1 μm spherical metallic silver powder 75 g, No. 5 solvent 0.5 g, eugenol 1 g, thickening varnish 3.5
g, bismuth octylate 2.5 g, and lead octylate 2.5 g were mixed and kneaded to prepare an ink.

Production Example 12 80 g of 0.3 μm spherical metallic silver powder, 3 g of glass frit (1350 from Asahi Glass Co., Ltd.), 1.5 g of bismuth octylate, and 0.5 g of filler are added to 15 g of alkyd resin (manufactured by Dainippon Ink and Chemicals, Inc .: Beckosol EC-8001). g was mixed and kneaded to prepare an ink.

Production Example 13 Rosin (manufactured by Dainippon Ink and Chemicals, Inc .: Becca Site J-8)
96) 20 g of chloroform and 6 g of No. 5 solvent were added to 10 g to dissolve rosin, and then chloroform was removed under reduced pressure. 40 g of 0.3 μm spherical metallic silver powder, 40 g of 5 μm flake-shaped silver powder, 1 methyl ethyl ketone oxime
g, and 3 g of glass frit (1350 manufactured by Asahi Glass) were mixed and kneaded to prepare an ink.

Production Example 14 35 g of an alkyd resin (manufactured by Dainippon Ink and Chemicals, Inc .: Beckosol EL-8001) was added to 35 g of a polymerization initiator (acrylic oligomer).
1 g, dibutyl carbitol 4 g, 0.3 μm spherical metallic silver powder 45 g, 8 μm flake silver powder 15 g, glass frit (Asahi Glass: 1350) 4 g, and bismuth octylate 1 g were mixed and kneaded to prepare an ink.

Production Example 15 80 g of 0.3 μm spherical metallic silver powder, 3 g of glass frit (1581 made by Asahi Glass), 1.5 g of bismuth naphthenate, and 0.5 g of alumina filler were added to 15 g of alkyd resin (manufactured by Dainippon Ink and Chemicals, Inc .: Beckosol EL-8001). Was mixed and kneaded to prepare an ink.

Comparative Example 2 As a resin component, 7.5 g of ethyl cellulose was dissolved in 7.5 g of methyl isobutyl ketone, and 75 g of spherical metallic silver powder of 0.3 μm, 5 g of α-terpineol and PbO ₂ -B ₂ O were added.
_After 5 g of _3- SiO ₂ -based 1 μm glass frit was added and premixed, it was sufficiently kneaded with a three-roll mill until it became homogeneous. With this silver paste, 50 cm x 50
Screen printing once on cm glass substrate (325 mesh)
I went. The glass substrate on which this predetermined pattern was printed was baked in an electric furnace. The firing profile at this time is 550 ℃
Was heated for 30 minutes, held for 10 minutes, and then cooled for 1 hour.

As a result, the pattern of 30 μm line 1 space contacted the line adjacent to the whole and was printed in a solid pattern, and was not resolved at all.

As a result of measuring the displacement of the pattern printed on the glass substrate, there was a displacement of +180 μm in the vertical direction and a displacement of +80 μm in the horizontal direction. The membrane pressure at this time is 10μ
The sheet resistance at m was 2 mΩ / □.

Comparative Example 3 The ink of Production Example 7 was used to perform offset printing by overprinting a predetermined pattern of 50 cm × 50 cm four times on a glass substrate. As a result, a line / space of 30 μm was resolved. The positional deviation in the vertical and horizontal directions was ± 5 μm or less. This glass substrate was fired at 550 ° C. as in the conventional example.

As a result, the resolution and displacement of the line / space of 30 μm were similar. However, the adhesion was weak enough to peel off in the tape peel test. The sheet resistance was 25 mΩ / □.

Example 8 50 cm × 5 was formed on a glass substrate using the ink of Production Example 8.
As a result of performing offset printing by overprinting a predetermined pattern of 0 cm four times, a line / space of 30 μm was resolved. The positional deviation in the vertical and horizontal directions was ± 5 μm or less. This glass substrate was baked at 550 ° C.

As a result, the resolution and displacement of 30 μm line / space were similar. Adhesion did not come off in the tape peel test.

Example 9 After printing four times with the ink of Production Example 8, the ultraviolet ray is irradiated for 1 minute. Repeatedly printing 4 times and UV irradiation in the same way, total
Printed 20 times. As a result of firing at 550 ° C. for 10 minutes, the line / space of 30 μm was resolved, and the positional deviation in the vertical and horizontal directions was ± 5 μm or less.

Example 10 After printing four times using the ink of Production Example 9, after pressing and irradiating with ultraviolet rays for 1 minute, printing was repeated four times, pressing and irradiation with ultraviolet rays were repeated in the same manner, and a total of 20 times were printed. As a result, the smoothing of the pattern progressed. Some of the 30 μm lines / spaces were not resolved, but the 50 μm lines / spaces were resolved. 20 in each direction
It was less than μm. As a result of firing this glass substrate at 550 ° C. for 10 minutes, the resolution was up to 50 μm line / space, and the positional accuracy was 20 μm or less as before firing.
The sheet resistance was 12 mΩ / □ and the adhesion was good.

Examples 11 to 15 The results of the same operations as above are shown in Tables 3, 4 and 5.

Example 16 The ink of Production Example 15 was used to print on an alumina substrate of 50 × 50 μm four times, after which it was irradiated with ultraviolet rays for 2 minutes, and then repeated 20 times.
Printed twice. The printed alumina substrate was fired at 650 ° C. The 30 μm line / space was resolved.
The positional deviation in the vertical and horizontal directions was 5 μm or less. The results are shown in Tables 3, 4 and 5.

[0055]

[Table 3]

[0056]

[Table 4]

[0057]

[Table 5]

[0058]

According to the method of the present invention, a predetermined pattern can be easily obtained by offset printing, and a print pattern having high resolution and high positional accuracy can be formed.

Claims (16)

[Claims] 1. An alkyd resin, a modified alkyd resin,
An offset printing ink for a silver conductor circuit, which contains at least one resin component selected from a modified epoxy resin, a urethanized oil, a rosin and a maleated oil, a solvent component and a metallic silver powder. 2. The offset printing ink for silver conductor circuits according to claim 1, further comprising a flux component. 3. The method according to claim 1, further comprising one or more of a leveling agent, a polymerization initiator, an oxidation accelerator, an anti-skinning agent, a thickener, a metal chelate resin and a dispersant. Item 2. The offset printing ink for silver conductor circuits according to Item 2. 4. The silver according to claim 1, wherein the metallic silver powder is a spherical powder having a particle diameter of 0.05 to 1.0 μm and / or a flake powder having a particle diameter of 0.5 to 5 μm. Offset printing ink for conductor circuits. 5. An alkyd resin, a modified alkyd resin,
Offset a pattern on a substrate using an offset printing ink for a silver conductor circuit containing at least one resin component selected from a modified epoxy resin, urethanized oil, rosin and maleated oil, a solvent component and metallic silver powder. A step of printing, a step of curing this print pattern as it is / or by irradiation with active energy rays and / or heating, a step of overprinting the cured print pattern as it is / or the same pattern, and a step of drying. A method for forming a characteristic silver conductor circuit. 6. The method for forming a silver conductor circuit according to claim 5, wherein the metallic silver powder is a spherical powder having a particle diameter of 0.05 to 1.0 μm and / or a flake powder having a particle diameter of 0.5 to 5 μm. 7. After printing a predetermined pattern on a substrate,
The method for forming a silver conductor circuit according to claim 5 or 6, wherein the printed pattern is pressed to promote smoothing of the surface of the printed pattern. 8. The method for forming a silver conductor circuit according to claim 5, 6 or 7, wherein the active energy rays are one or more of ultraviolet rays, infrared rays and electron rays. 9. A silver conductor circuit offset printing ink comprising a leveling agent, a polymerization initiator, an oxidation accelerator, an anti-skinning agent,
The method for forming a silver conductor circuit according to claim 5, claim 6, claim 7, or claim 8, containing one or more of a thickener, a metal chelate resin, and a dispersant. 10. Silver containing at least one resin component selected from alkyd resin, modified alkyd resin, modified epoxy resin, urethanized oil, rosin and maleated oil, a solvent component, a metallic silver powder and a flux component. Step of offset printing a pattern on a substrate using an offset printing ink for a conductor circuit, step of curing this printing pattern as it is / or irradiation of active energy rays and / or heating, and printing of the cured pattern as it is / or A method of forming a silver conductor circuit, comprising the steps of overprinting with the same pattern and firing. 11. The method for forming a silver conductor circuit according to claim 10, wherein the firing temperature is 300 ° C. or higher. 12. The method for forming a silver conductor circuit according to claim 10, wherein the metallic silver powder is a spherical powder having a particle diameter of 0.05 to 1.0 μm and / or a flake powder having a particle diameter of 0.5 to 5 μm. 13. After printing a predetermined pattern on a substrate,
The method for forming a silver conductor circuit according to claim 10, 11 or 12, wherein the surface of the printed pattern is promoted by pressing the printed pattern. 14. The active energy rays are ultraviolet rays, infrared rays,
The method for forming a silver conductor circuit according to claim 10, claim 11, claim 12 or claim 13, which is one or more kinds of electron beams. 15. The offset printing ink for silver conductor circuits further comprises one or two of a leveling agent, a polymerization initiator, an oxidation accelerator, an anti-skinning agent, a thickener, a metal chelate resin, a dispersant and a filler. Claim 10 containing the above,
Claim 11, Claim 12, Claim 13 or Claim 14
A method for forming a silver conductor circuit according to. 16. The method according to claim 10, wherein the flux component is an organic metal compound and / or a glass frit.
Claim 12, Claim 13, Claim 14 or Claim 15
A method for forming a silver conductor circuit according to.