JP2009049274A - Manufacturing method for conductive pattern sheet and conductive pattern sheet - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a manufacturing method for conductive pattern sheet having improved adhesion property between a conductive pattern and a base material and having sufficient electrical conductivity, and also to provide a conductive pattern sheet manufactured by the manufacturing method. <P>SOLUTION: In the manufacturing method for conductive pattern sheet, a base layer including a metal oxide, a binder and a compound containing a mercapt group or a carboxyl group is provided on a base material, then ink containing metal having a pattern shape is provided over the base layer and then a metal film is formed over formed metal catalytic nuclei. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a method for producing a conductive pattern sheet with improved electrical adhesion between a conductive pattern and a substrate and sufficient electrical conductivity, and a conductive pattern sheet produced by the production method. is there.

  Conventionally, to produce an electronic circuit or the like having a fine conductive pattern, a resist layer is laminated on a substrate on which a conductive layer is formed, irradiated with light through a photomask having a desired pattern, and then developed. Thereafter, a photolithographic method for removing an unnecessary resist layer has been performed. However, this photolithographic method is troublesome because it requires a large number of steps, and there is also a problem in terms of cost. Further, the disposal of the removed resist layer has a problem in that it has a burden on the environment.

  In order to solve such a problem, there has been proposed a method of forming a conductive pattern by directly injecting conductive ink onto a substrate surface using a printing apparatus such as an ink jet apparatus (for example, Patent Document 1). reference).

In the method proposed in Patent Document 1, a conductive circuit forming pattern is formed on a predetermined portion of a substrate surface using an ink-jet ink containing a metal colloid as a conductive ink, heated and dried, and melted to form a metal colloid. It is intended to improve the electrical conductivity by improving the contact between them. However, when the metal colloid is melted, a high temperature of 180 degrees or more is required. When the metal and the substrate are heated to 180 degrees or more at the same time, the thermal expansion coefficients of the metal and the substrate are different, so that different volume changes occur, so that the adhesion between the substrate and the metal is reduced, and the metal from the substrate to the metal There is a problem that a problem of peeling occurs easily.
JP 2004-247667 A

  The present invention has been made in view of the above problems, and its purpose is to improve the adhesion between the conductive pattern and the substrate, and to produce a conductive pattern sheet with sufficient electrical conductivity, and the method It is providing the electroconductive pattern sheet produced with the preparation method.

  The above object of the present invention is achieved by the following configurations.

  1. A base layer containing a compound containing a metal oxide, a binder, a mercapto group or a carboxyl group is provided on a base material, and an ink containing a metal is applied in a pattern on the base layer, and the formed metal catalyst core is formed on the base layer. A method for producing a conductive pattern sheet, comprising forming a metal film.

  2. 2. The method for producing a conductive pattern sheet according to 1 above, wherein light irradiation is performed after the ink containing the metal is applied in a pattern.

  3. 3. The method for producing a conductive pattern sheet according to 1 or 2, wherein an electroless plating process is performed after forming the metal catalyst nucleus to form a metal film.

  4). 4. The conductive pattern sheet according to any one of 1 to 3, wherein the means for applying the metal-containing ink in a pattern is an ink jet recording means that performs injection drawing using an ink jet recording apparatus. Method.

  5). 5. The method for producing a conductive pattern sheet as described in 4 above, wherein the ink jet recording means is a method using a pressure applying means and an electric field applying means.

  6). 6. The conductive pattern sheet according to any one of 1 to 5, wherein the metal of the ink containing the metal is at least one selected from copper, silver, gold, nickel, palladium, and zinc. Method.

  7. The ink containing a metal contains a ligand compound capable of forming a complex having a complex stability constant smaller than a complex stability constant of a complex formed from the metal and a compound containing a carboxyl group or a mercapto group. The manufacturing method of the electroconductive pattern sheet of any one of said 1-6.

  8). 8. The method for producing a conductive pattern sheet according to any one of 1 to 7, wherein the metal oxide is at least one selected from titanium oxide, silicon oxide, and aluminum oxide.

  9. 9. The method for producing a conductive pattern sheet according to any one of 1 to 8, wherein the compound containing the mercapto group or the carboxyl group is immobilized on the metal oxide.

  10. 10. The method for producing a conductive pattern sheet according to any one of 1 to 9, wherein the underlayer is porous.

  11. 11. A conductive pattern sheet produced by the method for producing a conductive pattern sheet according to any one of 1 to 10 above.

  By the method for producing a conductive pattern sheet of the present invention, it was possible to provide a conductive pattern sheet with improved adhesion to a substrate and sufficient electrical conductivity.

  Hereinafter, the best mode for carrying out the present invention will be described in detail.

  In the method for producing a conductive pattern sheet of the present invention, a base layer containing a compound containing a metal oxide, a binder, a mercapto group or a carboxyl group is provided on a substrate, and the ink containing the metal is patterned on the base layer. And a metal film is formed on the formed metal catalyst core.

〔Base material〕
Examples of the substrate used in the present invention include resin films such as polyimide films, polyamideimide films, polyamide films, and polyester films, glass-epoxy substrates, silicon substrates, ceramic substrates, and glass substrates.

  The material of the resin film used in the present invention is not particularly limited. For example, polyester film (polyethylene terephthalate, polyethylene naphthalate, etc.), polycarbonate film, polyarylate film, polysulfone (including polyethersulfone). Film, polyethylene film, polypropylene film, polyvinylidene chloride film, polyvinyl alcohol film, ethylene vinyl alcohol film, syndiotactic polystyrene film, polycarbonate film, cycloolefin polymer film (Arton (manufactured by JSR), Zeonex, Zeonea (and above) , Manufactured by Nippon Zeon)), polyethersulfone film, polysulfone film, polymethylpentene film, poly Chromatography ether ketone film, polyether ketone imide film, a polyamide film, a fluororesin film, a nylon film, polymethyl methacrylate film, polyacrylate films, and polyarylate films. The film which laminated | stacked the film of the different material which has these materials as a main component may be sufficient.

  Further, in the present invention, from the viewpoint of enhancing the adhesion between the base material and the underlying layer provided thereon, the surface of the base material is pretreated with corona discharge treatment, flame treatment, ozone treatment, primer treatment, desmear treatment, ultraviolet treatment. It is preferable to perform chemical treatment including radiation treatment, surface roughening treatment, silane coupling agent, acid, alkali, surfactant and the like.

  Examples of the mechanism for improving the adhesion include cleaning of the surface by removing foreign substances adhering to the surface that inhibits adhesion, using an anchor effect due to unevenness of the member interface, and inserting an adhesive compound at the interface with both members. . Moreover, it is preferable to select the compound with good adhesiveness of a base material and a binder previously for the binder contained in a base layer. For example, a polyester-based substrate includes a polyurethane-based binder, a polyimide-based substrate, and a glass fiber kneaded epoxy-based substrate includes a polyacrylic binder and a polyepoxy-based binder.

[Underlayer]
The underlayer according to the present invention is composed of a compound containing a metal oxide, a binder, a mercapto group, or a carboxyl group. The metal oxide carries a mercapto group or carboxyl group to control the metal film formation site, to control the spread of the ink from the wettability between the ink and the metal oxide surface, or to make the underlayer porous Thus, it has a function of increasing the permeability of the ink. Binder is a function to provide physical strength by interposing between the base material, metal oxide and metal film, a function to relieve stress generated during the formation of metal film, a function to improve the adhesion between the base material and the base layer, etc. Have A compound containing a mercapto group or a carboxyl group has a function of forming a metal catalyst complex by forming a complex with a metal to form a metal film.

(Metal oxide)
Examples of the metal oxide according to the present invention include barium sulfate, calcium carbonate, aluminum oxide, zinc oxide, magnesium oxide and zinc hydroxide, magnesium hydroxide, magnesium phosphate, magnesium hydrogen phosphate, alkaline earth metal salt, Talc, kaolin, zeolite, acid clay, glass, titanium oxide, silicon oxide, zinc oxide, tin oxide, Sn-doped indium oxide (ITO), antimony-doped tin oxide (ATO), fluorine-doped tin oxide (FTO), aluminum-doped oxidation Zinc, etc., titanium dioxide surface-treated with inorganic oxides (Al ₂ O ₃ , AlO (OH), SiO _2, etc.), in addition to these surface treatments, trimethylolethane, triethanolamine acetate, trimethylcyclosilane, etc. Titanium dioxide treated with organic matter or these Compounds, and the like. In the present invention, particularly preferred metal oxides include titanium oxide, silicon oxide, and aluminum oxide.

The metal oxide may bind or contact a plurality of fine particles. The average particle diameter of the metal oxide fine particles is preferably 5 nm to 10 μm, more preferably 20 nm to 1 μm. It is preferable that the specific surface area of the metal oxide particles is ^{1 × 10 -3 ~1 × 10 2} m 2 / g by a simple BET method, more preferably from ^{1 × 10 -2 ~10m 2 / g} . The metal oxide fine particles may have any shape such as an indefinite shape, a needle shape, and a spherical shape.

  As a method for forming or binding metal oxide fine particles, a known sol-gel method or sintering method can be employed. For example, 1) Journal of the Ceramic Society of Japan, 102, 2, p200 (1994), 2 ) Ceramics Association Journal 90, 4, p157, 3) J. of Non-Cryst. Solids, 82, 400 (1986) and the like. In addition, a method of obtaining a porous electrode by dispersing titanium oxide dendrimer particles produced by a vapor phase method on a solution, applying the solution on a substrate, drying in a temperature range of about 120 to 150 ° C., and removing the solvent. It can also be used.

  The metal oxide fine particles are preferably bound, and preferably have a resistance of 0.1 g or more, preferably 1 g or more with a continuous load type surface property measuring instrument (for example, a scratch tester).

  The porous referred to in the present invention refers to a film having a space that can receive ink when ink is applied.

(binder)
As the binder according to the present invention, a known polymer compound can be used as long as it can bind a substrate, a metal oxide, a metal film and the like. Preferred binders include proteins such as gelatin and gelatin derivatives, or cellulose derivatives, natural compounds such as polysaccharides such as starch, gum arabic, dextran, pullulan and carrageenan, polyvinyl alcohol, polyvinyl pyrrolidone, acrylamide polymers, Examples thereof include synthetic polymer compounds such as derivatives thereof.

  Examples of gelatin derivatives include acetylated gelatin, phthalated gelatin, polyvinyl alcohol derivatives include terminal alkyl group-modified polyvinyl alcohol, terminal mercapto group-modified polyvinyl alcohol, and cellulose derivatives include hydroxyethyl cellulose, hydroxypropyl cellulose, carboxymethyl cellulose, and the like. It is done.

Further, Research Disclosure and those described on pages (71) to (75) of JP-A No. 64-13546, US Pat. No. 4,960,681, and JP-A No. 62-245260 Or the like, ie, a homopolymer of vinyl monomers having —COOM or —SO ₃ M (M is a hydrogen atom or an alkali metal), or vinyl monomers or other vinyl monomers (for example, sodium methacrylate) , Ammonium methacrylate, potassium acrylate, etc.). Two or more of these binders can be used in combination.

  These binders may be cured. Examples of hardeners include, for example, US Pat. No. 4,678,739, column 41, US Pat. No. 4,791,042, JP-A-59-116655, JP-A-62-245261, Examples thereof include hardeners described in JP-A-61-18942, JP-A-61-249054, JP-A-61-245153, and JP-A-4-218044.

  More specifically, aldehyde hardeners (formaldehyde, etc.), aziridine hardeners, epoxy hardeners, vinyl sulfone hardeners (N, N'-ethylene-bis (vinylsulfonylacetamide) Ethane, etc.), N-methylol hardeners (dimethylolurea, etc.), boric acid, metaboric acid or polymer hardeners (compounds described in JP-A-62-234157). When gelatin is used as the aqueous compound, it is preferable to use a vinyl sulfone type hardener or a chlorotriazine type hardener alone or in combination. Moreover, when using polyvinyl alcohol, it is preferable to use boron-containing compounds such as boric acid and metaboric acid.

  These hardeners are used in an amount of 0.001 to 1 g, preferably 0.005 to 0.5 g, per 1 g of the aqueous compound. In order to increase the film strength, it is also possible to adjust the humidity during heat treatment or curing reaction.

  Polymers dispersed in aqueous solvents include natural rubber latex, styrene butadiene rubber, butadiene rubber, nitrile rubber, chloroprene rubber, isoprene rubber and other latexes, polyisocyanate, epoxy, acrylic, silicone, polyurethane, Examples thereof include a thermosetting resin and a photocurable resin in which urea, phenol, formaldehyde, epoxy-polyamide, melamine, alkyd resin, vinyl resin and the like are dispersed in an aqueous solvent. Of these polymers, it is preferable to use an aqueous polyurethane resin described in JP-A-10-76621.

(Compounds containing mercapto groups or carboxyl groups)
The compound containing a mercapto group or carboxyl group according to the present invention may be any compound as long as it contains a mercapto group or carboxyl group in its chemical structure.

<Compound containing mercapto group>
In the present invention, a preferred mercapto compound is a compound represented by the following general formula (A).

General formula (A): R-SM
In the formula, R represents an alkyl group, an aryl group, or a heterocyclic group. M represents a hydrogen atom, a metal atom or ammonium.

  Here, the alkyl group means a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms. The aryl group means a monocyclic or condensed ring substituted or unsubstituted aromatic hydrocarbon ring such as a phenyl group or a naphthyl group. The heterocyclic group means an aromatic or non-aromatic monocyclic or condensed ring substituted or unsubstituted heterocyclic group containing at least one heteroatom.

Here, the substituent is, for example, a mercapto group, (alkyl, aryl or heterocycle) thio group, (alkyl, aryl or heterocycle) dithio group, (alkyl or aryl) sulfonyl group, (alkyl or aryl) sulfinyl group. , Sulfo group or a salt thereof, sulfamoyl group, N-acylsulfamoyl group, N-sulfonylsulfamoyl group or a salt thereof, halogen atom (fluorine atom, chlorine atom, bromine atom or iodine atom), alkyl group (straight chain) Branched, cyclic alkyl groups, including bicycloalkyl groups and active methine groups), alkenyl groups, alkynyl groups, aryl groups, heterocyclic groups (regardless of the position of substitution), acyl groups, alkoxycarbonyl groups, aryloxy Carbonyl group, heterocyclic oxycarbonyl group, carbamoyl group, N- Roxycarbamoyl group, N-acylcarbamoyl group, N-sulfonylcarbamoyl group, N-carbamoylcarbamoyl group, thiocarbamoyl group, N-sulfamoylcarbamoyl group, carbazoyl group, carboxy group or a salt thereof, oxalyl group, oxamoyl group, cyano Group, carbonimidoyl group (Carbonimidoyl group), formyl group, hydroxy group, alkoxy group (including a group containing repeating ethyleneoxy group or propyleneoxy group units), aryloxy group, heterocyclic oxy group,
Acyloxy group, (alkoxy or aryloxy) carbonyloxy group, carbamoyloxy group, sulfonyloxy group, amino group, (alkyl, aryl or heterocyclic) amino group, acylamino group, sulfonamido group, ureido group, thioureido group, N- Hydroxyureido group, imide group, (alkoxy or aryloxy) carbonylamino group, sulfamoylamino group, semicarbazide group, thiosemicarbazide group, hydrazino group, ammonio group, oxamoylamino group, N- (alkyl or aryl) sulfonylureido Group, N-acylureido group, N-acylsulfamoylamino group, hydroxyamino group, nitro group, quaternized heterocyclic group containing nitrogen atom (for example, pyridinio group, imidazolio group, quinolinio group Isoquinolinio group), an isocyano group, an imino group, a phosphino group, phosphinyl group, phosphinyloxy group, phosphinylamino group, a silyl group, trialkoxysilyl group, and the like.

  Here, the active methine group means a methine group substituted with two electron-withdrawing groups, and the electron-withdrawing group here means an acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl. Group, an alkylsulfonyl group, an arylsulfonyl group, a sulfamoyl group, a trifluoromethyl group, a cyano group, a nitro group, and a carbonimidoyl group (Carbonimidoyl group). Here, the two electron withdrawing groups may be bonded to each other to form a cyclic structure. The salt means a cation such as alkali metal, alkaline earth metal or heavy metal, or an organic cation such as ammonium ion or phosphonium ion.

  These substituents may be further substituted with these substituents.

  Examples of the mercapto compound preferably used include the following compounds.

<Compound containing carboxyl group>
In the present invention, a preferred compound containing a carboxyl group is a compound represented by the following general formula (3).

  In the formula, each A represents a cycloalkyl group, a phenyl group or a heterocyclic group which may have a substituent, and may form a condensed ring. M may be the same or different and represents an alkali metal, an ammonium ion or an organic base.

  As the cycloalkyl ring and heterocyclic group represented by A, the number of atom groups constituting the cycloalkyl ring and heterocyclic group is not particularly limited, but a 5-membered ring or 6-membered ring is preferable. Among the compounds represented by the general formula (3), A may have a substituent each having a pyridyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, pyrrolyl group, pyrazolyl group, imidazolyl group, tetrazolyl group, and furyl group. From the viewpoint of glossiness of the surface of the image forming surface, a compound that is a heterocyclic group selected from the above, or a phenyl group that may have a substituent is preferable. Further, A is more preferably a phenyl group or a pyridyl group which may have a substituent.

  Although the specific example of a compound represented by General formula (3) below is given, it is not limited to this.

  These complex-forming compounds can be purchased as commercial products. Also, Beilsteins Handbuch der Organischen Chemie, Annan der Chemy, Chemical Abstracts, Journal of American Abstracts. Described in Chemical Society (J. Am. Chem. Soc.), Monashshte Hül Hemy (Monatsch. Chem), Jurnar der Russien Physisch, etc. Can be synthesized according to That.

  Of these compounds containing a mercapto group or a carboxyl group, compounds having a trialkoxysilyl group are particularly preferred. Specific examples include compounds such as 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 1-triethoxysilylamino-3,5-dimercaptotriazine.

  Examples of the method for immobilizing a compound containing a mercapto group or a carboxyl group of the present invention on a metal oxide include a method of adsorbing the compound by van der Waals force between the compound and the metal oxide, a carboxyl group or a hydroxyl group of the compound And a method of immobilizing by providing an ionic bond or a coordination bond at a metal site of a metal oxide, a method of immobilizing a chemical group by reacting a functional group contained in the compound and a metal oxide surface atom, etc. Can be mentioned.

  As a method for supplying the compound to the metal oxide, a method in which a solution in which the compound is dissolved or dispersed is brought into contact with the metal oxide is preferable. At that time, in the case of the solvent type, acid basicity, and aqueous system of the solution, the pH and the like are combined with the solubility of the compound, and the solubility of the compound is changed from the high solubility to the low solubility of the compound. Thus, the compound can be easily fixed to the metal oxide.

[Pattern formation method]
The method for applying the ink containing the metal according to the present invention in a pattern is not particularly limited as long as it is a method capable of applying the ink in a pattern, and a known pattern forming method can be applied. For example, as a coating method, a liquid spraying method, or a spraying method via a gas phase, a method of flying droplets using vibration of a piezoelectric element, for example, a piezo ink jet head or a thermal head using bumping Examples thereof include a bubble jet (registered trademark) type ink jet head that causes droplets to fly, and a spray type that sprays liquid by air pressure or liquid pressure.

  Examples of the printing method include screen printing, flexographic printing, letterpress and intaglio printing. The coating method can be appropriately selected from known coating methods. For example, an air doctor coater, blade coater, rod coater, knife coater, squeeze coater, impregnation coater, reverse roller coater, transfer roller coater, curtain coater, double coater Examples include roller coaters, slide hopper coaters, gravure coaters, kiss roll coaters, bead coaters, cast coaters, spray coaters, calendar coaters, and extrusion coaters.

  Of these, the ink jet system can be preferably used in the present invention. In particular, it is preferable to apply an ink jet method using an ink jet recording apparatus. Further, from the viewpoint of forming a thin line having a line width of 20 μm or less used in an electric circuit or the like with high accuracy, the conductive ink of the ink jet recording apparatus is used. The discharge method is preferably a method using pressure applying means and electric field applying means.

  Hereinafter, an ink jet recording method using a pressure applying unit and an electric field applying unit will be described.

  In general, in order to draw a fine line width pattern required in an electronic circuit or the like with high definition, it is necessary to further refine the ink droplets ejected from the ink jet recording apparatus.

  However, electro-mechanical conversion methods (eg, single cavity type, double cavity type, bender type, piston type, shear mode type, shared wall type, etc.) and electro-thermal conversion methods (eg, thermal ink jet type, bubble jet type) When a very small ink droplet is ejected using only (registered trademark type) output means, the kinetic energy imparted to the ink droplet ejected from the nozzle is proportional to the cube of the radius of the ink droplet Therefore, the microdroplet cannot secure sufficient kinetic energy enough to withstand air resistance, and is subject to disturbance due to air convection, making accurate landing difficult.

  Furthermore, since the effect of surface tension increases as the ink droplets become finer, the vapor pressure of the droplets increases and the amount of evaporation increases. For this reason, fine droplets cause a significant loss of mass during flight, and there is a problem that it is difficult to maintain the shape of the droplets upon landing. As described above, increasing the accuracy of the landing position is a problem that contradicts the miniaturization of ink droplets, and has an obstacle to realizing these two simultaneously.

  In the present invention, it is preferable to apply an injection method using a pressure applying means and an electric field applying means as a method for solving the above problems.

  This ejection method uses a nozzle having an ejection port with an inner diameter of 0.1 to 100 μm, applies an arbitrary waveform voltage to the conductive ink, and charges the conductive ink to discharge the ink droplets. This is a method of discharging from an outlet to a substrate having a resin layer. That is, in this ejection method, the inner diameter of the nozzle outlet is 0.1 to 100 μm and the electric field strength distribution is narrow, so by applying an arbitrary waveform voltage to the conductive ink supplied into the nozzle. The electric field can be concentrated.

  As a result, the formed ink droplets can be made minute and the shape can be stabilized. Therefore, it is possible to form an ink droplet pattern composed of a plurality of ink droplets, for example, less than 1 pl (picoliter), on the surface of the resin layer. In addition, since the electric field strength distribution is narrow, the total applied voltage applied to the conductive ink in the nozzle can be reduced. Further, immediately after the ink droplet is ejected from the nozzle, the ink droplet is accelerated by an electrostatic force acting between the electric field and the electric charge. However, the ink droplets that are fine droplets and the electric field is concentrated are accelerated by the mirror image force as they approach the resin layer. By balancing the deceleration by the air resistance and the acceleration by the mirror image force, it is possible to stably fly the fine droplets and improve the landing accuracy.

  FIG. 1 is a schematic cross-sectional view showing an example of a conductive ink discharge apparatus using a pressure applying unit and an electric field applying unit that can be preferably applied to the present invention.

  In FIG. 1, a conductive ink discharge device 20 includes a superfine nozzle 21 that discharges a droplet of conductive ink that can be charged from a tip portion toward a substrate K having a resin layer, and a tip portion of the nozzle 21. The counter electrode 23 is disposed on the surface side opposite to the substrate 21 and supports the base material K on the opposite surface, the conductive ink supply means for supplying the conductive ink to the flow path 22 in the nozzle 21, and the conductivity in the nozzle 21. Discharge voltage applying means (voltage applying means) 25 for applying a discharge voltage having an arbitrary waveform to the ink. The nozzle 21 and a part of the conductive ink supply unit and a part of the discharge voltage application unit 25 are formed integrally with the nozzle plate 26.

  The nozzle 21 is suspended from the lower surface layer 26c of the nozzle plate 26, and is formed integrally with the lower surface layer 26c. The tip of the nozzle 21 is directed to the counter electrode 23. Inside the nozzle 21, an in-nozzle flow path 22 is formed that penetrates from the tip portion along the center line.

  The nozzle 21 is formed with an ultrafine diameter using, for example, an electrical insulator such as glass. Specific examples of the dimensions of each part of the nozzle 21 are as follows: the inner diameter of the nozzle flow path 22 is 1 μm, the outer diameter at the tip of the nozzle 21 is 2 μm, the root of the nozzle 21, that is, the diameter of the upper end is 5 μm, The height of 21 is set to 100 μm. Moreover, the shape of the nozzle 21 is formed in a truncated cone shape close to a conical shape. The nozzle 21 as a whole is formed of an insulating resin material together with the lower surface layer 26 c of the nozzle plate 26.

  Each dimension of the nozzle 21 is not limited to the above example. In particular, the inner diameter of the discharge port is a range in which the discharge voltage that enables the discharge of droplets by the effect of electric field concentration is less than 1000 V, for example, 100 μm or less, more preferably 20 μm or less, An inner diameter, for example, 0.1 μm, in a range where it is feasible to form a through hole through which a solution passes by the current nozzle forming technique is set as the lower limit.

  The conductive ink supply means is provided inside the nozzle plate 26 at a position that is the root of the nozzle 21 and communicates with the flow path 22 in the nozzle, and an ink chamber from an external conductive ink tank (not shown). A supply path 27 that guides conductive ink to 24 and a supply pump (not shown) that applies supply pressure of the solution to the ink chamber 24 are provided.

  The supply pump supplies conductive ink to the tip of the nozzle 21 and supplies the conductive ink while maintaining a supply pressure in a range that does not spill from the tip.

  The discharge voltage application means 25 applies a discharge voltage to the conductive ink in the nozzle 21 to charge the conductive ink, thereby causing the droplets of the conductive ink to move from the discharge port of the nozzle 21 toward the substrate K. To be discharged. The discharge voltage application means 25 is provided inside the nozzle plate 26 and at a boundary position between the ink chamber 24 and the nozzle flow path 22, and the discharge voltage application discharge electrode 28 is always on the discharge electrode 28. A bias power source 30 that applies a DC bias voltage and an ejection voltage power source 29 that applies a pulse voltage that is superimposed on the bias voltage to a potential required for ejection on the ejection electrode 28 are provided.

  The discharge electrode 28 directly contacts the conductive ink inside the ink chamber 24 to charge the conductive ink and apply a discharge voltage.

  The bias voltage from the bias power supply 30 is always applied within a range in which conductive ink is not discharged, thereby reducing the width of the voltage to be applied at the time of discharge, thereby improving the reactivity at the time of discharge. I am trying. As an example, the bias voltage is applied at 300V DC and the pulse voltage is marked at 100V. Therefore, the superimposed voltage at the time of ejection is 400V.

  The nozzle plate 26 includes an upper surface layer 26a positioned at the uppermost layer, a flow path layer 26b forming a conductive ink supply path positioned therebelow, and a lower surface layer 26c formed further below the flow path layer 26b. The discharge electrode 28 is interposed between the flow path layer 26b and the lower surface layer 26c.

  The counter electrode 23 has a counter surface perpendicular to the nozzle 21 and supports the substrate K along the counter surface. The distance from the tip of the nozzle 21 to the facing surface of the counter electrode 23 is kept constant, for example, 100 μm.

  Further, since the counter electrode 23 is grounded, the ground potential is always maintained. Accordingly, when a pulse voltage is applied, the liquid droplets ejected by the electrostatic force generated by the electric field generated between the tip of the nozzle 21 and the opposing surface are guided to the opposing electrode 23 side.

  The conductive ink discharge device 20 discharges droplets by increasing the electric field strength by concentrating the electric field at the tip of the nozzle 21 due to the ultra-miniaturization of the nozzle 21, so that there is no induction by the counter electrode 23. In both cases, it is possible to discharge liquid droplets, but it is desirable that induction is performed between the nozzle 21 and the counter electrode 23 by electrostatic force. In this case, the droplet discharged from the nozzle 21 and decelerated by air resistance can be accelerated by the mirror image force. Therefore, by balancing the deceleration by the air resistance and the acceleration by the mirror image force, it is possible to stably fly the fine droplets and improve the landing accuracy. Furthermore, the charge of the charged droplets can be released by grounding the counter electrode 23.

  The conductive ink discharge device 20 as described above may be a scanning type conductive ink discharge device that can be scanned in a direction orthogonal to the conveyance direction of the substrate K by a drive mechanism (not shown). In this case, a plurality of nozzles 21 may be arranged in the conductive ink discharge device 20. Further, the conductive ink discharge device 20 may be a line-type conductive ink discharge device in which a large number of nozzles 21 are arranged in a direction orthogonal to the conveyance direction of the substrate K.

[Light irradiation]
In the present invention, it is preferable to perform light irradiation after applying a metal-containing ink in a pattern.

In the present invention, irradiation with actinic rays may be visible light irradiation or ultraviolet irradiation, and ultraviolet irradiation is particularly preferable. When performing ultraviolet irradiation, ultraviolet ray irradiation quantity is 150 mJ / cm ² or more, preferably 250 mJ / cm ² or more and 2000 mJ / cm ² or less, preferably performed at 1000 mJ / cm ² or less. An ultraviolet irradiation amount within such a range is advantageous because a sufficient curing reaction can be performed and the influence on the conductive pattern can be prevented by the ultraviolet irradiation.

  Examples of the ultraviolet irradiation light source include lamps such as metal halide lamps, xenon lamps, carbon arc lamps, chemical lamps, low-pressure mercury lamps, and high-pressure mercury lamps. For example, a commercially available product such as an H lamp, a D lamp, or a V lamp manufactured by Fusion System can be used.

  The metal halide lamp has a continuous spectrum as compared with a high-pressure mercury lamp (main wavelength is 365 nm), has high luminous efficiency in the range of 200 to 450 nm, and has a long wavelength range.

  Irradiation of actinic light is a method of applying actinic light in a region different from the conductive pattern, or an actinic light source is attached to a conductive ink application device, and actinic light is emitted along with the emission of conductive ink It may be a method to do. The basic method is disclosed in JP-A-60-132767.

  According to this, the light source is provided on both sides of the head unit, and the head and the light source are scanned by the shuttle method. Irradiation is performed after a certain period of time after ink landing. Further, the curing is completed by another light source that is not driven. In US Pat. No. 6,145,979, as an irradiation method, a method using an optical fiber or a method of irradiating a recording unit with UV light by applying a collimated light source to a mirror surface provided on the side surface of the head unit is disclosed. Has been. Any of these irradiation methods can be used in the image forming method of the present invention.

  In addition, irradiation with actinic rays is divided into two stages. First, the actinic rays are irradiated by the above-described method within 0.001 second or more and 2 seconds or less after ink landing, and after the formation of all conductive patterns, further activation is performed. A method of irradiating with light is also one of the preferred embodiments. By dividing the irradiation of actinic rays into two stages, it is possible to further suppress the shrinkage of the recording material that occurs during ink curing.

  In the present invention, it is preferable to use an actinic ray having a maximum illuminance in a wavelength region of 254 nm, and a high-definition conductive pattern image can be formed even when a light source having a total power consumption of 1 kW · hr or more is used. The impact on the environment is also within a practically acceptable level.

  In the present invention, it is preferable that the total power consumption of the light source for irradiating actinic rays is less than 1 kW · hr. Examples of the light source having a total power consumption of less than 1 kW · hr include, but are not limited to, a fluorescent tube, a cold cathode tube, a hot cathode tube, and an LED.

[Metal film formation]
The conductive pattern formed by the conductive ink according to the present invention, particularly the conductive ink containing metal fine particles that act as a plating catalyst, has good conductivity by the drying and baking treatment according to the present invention after the pattern is formed. However, after performing the treatment step with the above-described plating catalyst activator, it is more excellent to perform the plating treatment using the metal fine particles contained in the conductive pattern and the plating catalyst activator as a plating catalyst. This is preferable from the viewpoint of obtaining conductivity.

  Hereinafter, a plating method applicable to the present invention will be described.

  In the present invention, a conventionally known plating method can be applied. Among them, an electroless plating method is applied from the viewpoint that a low-resistance conductive pattern can be easily and inexpensively plated without a complicated process. It is preferable to do.

  The plating process by the electroless plating method is a method in which a plating agent is brought into contact with a conductive pattern containing metal fine particles that act as a plating catalyst according to the above-described method. Thereby, the metal fine particle which is a plating catalyst and a plating agent contact, electroless plating is given to a conductive pattern part, and more excellent electroconductivity can be obtained.

  As a plating agent that can be used in the plating treatment according to the present invention, for example, a solution in which metal ions to be deposited as a plating material are uniformly dissolved is used, and a reducing agent is contained together with a metal salt. Here, a solution is usually used. However, the present invention is not limited to this as long as it causes electroless plating, and a gaseous or powder plating agent can also be applied.

  Specifically, as this metal salt, a halide, nitrate, sulfate, phosphate, borate, acetate of at least one metal selected from Au, Ag, Cu, Ni, Co, Fe, Tartrate, citrate, etc. are applicable. As the reducing agent, hydrazine, hydrazine salt, borohalide salt, hypophosphite, hyposulfite, alcohol, aldehyde, carboxylic acid, carboxylate, and the like are applicable. In addition, you may contain in the electrode which elements, such as boron, phosphorus, and nitrogen contained in these reducing agents, precipitate. Alternatively, an alloy may be formed using a mixture of these metal salts.

  As the plating agent, a mixture of the metal salt and the reducing agent may be applied, or the metal salt and the reducing agent may be applied separately. Here, in order to form a conductive pattern more clearly, it is preferable to apply a mixture of a metal salt and a reducing agent. When the metal salt and the reducing agent are applied separately, a more stable electrode pattern can be formed by arranging the metal salt first in the conductive pattern portion and then arranging the reducing agent.

  If necessary, the plating agent may contain additives such as a buffer for adjusting pH and a surfactant. Moreover, as a solvent used for the solution, an organic solvent such as alcohol, ketone, ester or the like may be added in addition to water.

  The composition of the plating agent is composed of a metal salt of the metal to be deposited, a reducing agent, and, if necessary, an additive and an organic solvent, but the concentration and composition can be adjusted according to the deposition rate. . Further, the deposition rate can be adjusted by adjusting the temperature of the plating agent. Examples of the method for adjusting the temperature include a method for adjusting the temperature of the plating agent, and a method for adjusting the temperature by heating and cooling the substrate before the immersion, for example, when immersed in the plating agent. Furthermore, the film thickness of the metal thin film deposited by the time immersed in a plating agent can also be adjusted.

〔ink〕
The ink containing the metal of the present invention may have any composition as long as it is a solution containing metal ions, metal fine particles, metal complexes and the like. Examples of the metal species that are preferably used include copper, silver, gold, nickel, palladium, zinc, and mixtures thereof.

  When the ink according to the present invention is an inkjet ink, various additives can be applied as necessary in addition to the above description.

  In the ink according to the present invention, a water-soluble organic solvent can be used. Examples of the water-soluble organic solvent that can be used in the present invention include alcohols (for example, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, secondary butanol, tertiary butanol, pentanol, hexanol, cyclohexanol, benzyl). Alcohol), polyhydric alcohols (for example, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol, hexanediol, pentanediol, glycerin, hexanetriol, thiodiglycol Etc.), polyhydric alcohol ethers (for example, ethylene glycol monomethyl ether, ethylene glycol) Ether monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether , Triethylene glycol monobutyl ether, ethylene glycol monophenyl ether, propylene glycol monophenyl ether, etc.), amines (for example, ethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, mole) Phosphorus, N-ethylmorpholine, ethylenediamine, diethylenediamine, triethylenetetramine, tetraethylenepentamine, polyethyleneimine, pentamethyldiethylenetriamine, tetramethylpropylenediamine, etc.), amides (eg, formamide, N, N-dimethylformamide, N , N-dimethylacetamide, etc.), heterocyclic rings (for example, 2-pyrrolidone, N-methyl-2-pyrrolidone, cyclohexylpyrrolidone, 2-oxazolidone, 1,3-dimethyl-2-imidazolidinone, etc.), sulfoxides ( For example, dimethyl sulfoxide etc.), sulfones (for example, sulfolane etc.), urea, acetonitrile, acetone etc. are mentioned.

  In addition to the ink according to the present invention, various other known additives such as ejection stability, print head and ink cartridge compatibility, storage stability, image storability, and other various performance enhancement purposes such as , Viscosity modifier, Surface tension modifier, Specific resistance modifier, Film forming agent, Dispersant, Surfactant, Ultraviolet absorber, Antioxidant, Anti-fading agent, Antifungal agent, Rust inhibitor, etc. For example, polystyrene, polyacrylates, polymethacrylates, polyacrylamides, polyethylene, polypropylene, polyvinyl chloride, polyvinylidene chloride, or a copolymer thereof, urea resin, or melamine Organic latex such as resin, liquid paraffin, dioctyl phthalate, tricresyl phosphate, oil droplets such as silicone oil, Various surfactants of thione or nonion, ultraviolet absorbers described in JP-A-57-74193, JP-A-57-87988, and JP-A-62-261476, JP-A-57-74192, and 57-87989 No. 60-72785, 61-146591, JP-A-1-95091 and JP-A-3-13376, etc., and JP-A-59-42993, 59- Fluorescent brighteners, sulfuric acid, phosphoric acid, citric acid, sodium hydroxide, potassium hydroxide described in Japanese Patent Nos. 52689, 62-280069, 61-242871, and JP-A-4-219266 And a pH adjuster such as potassium carbonate.

  There is no particular limitation on the preparation of the ink according to the present invention, but when preparing an ink containing various additives, it is preferable to prepare the ink so that aggregation and sedimentation do not occur in the preparation process. If necessary, it is possible to adopt a blending method such as adjusting the order of addition of additives and the rate of addition.

  Although there is no restriction | limiting in particular in the viscosity which concerns on this invention, It is preferable that the viscosity in 25 degreeC is 2 mPa * s or more and 10 mPa * s or less. Further, it is preferable that the viscosity of the inkjet ink according to the present invention does not have a share rate dependency.

  Moreover, in the ink which concerns on this invention, it is preferable that surface tension is 40 mN / m or less, More preferably, it is 25-35 mN / m. The surface tension (mN / m) of the ink as referred to in the present invention is a value measured by a surface tension measured at 25 ° C., and the measuring method is described in general interface chemistry, colloid chemistry reference books, etc. For example, New Experimental Chemistry Course Volume 18 (Interface and Colloid), The Chemical Society of Japan, published by Maruzen Co., Ltd. 68-117 can be referred to.

  In the ink according to the present invention, from the viewpoint of ink storage stability, the electrical conductivity is preferably 1 mS / m or more and 500 mS / m or less, more preferably 1 mS / m or more and 200 mS / m or less. More preferably, it is 10 mS / m or more and 100 mS / m or less. In the preparation of the ink according to the present invention, it is preferable to adjust the ion concentration as appropriate.

[Ligand compound]
The ink containing a metal according to the present invention contains a ligand compound capable of forming a complex having a complex stability constant smaller than a complex stability constant of a complex formed from the metal and a compound containing a carboxyl group or a mercapto group. Is preferred. This ligand compound has a function of binding to metal fine particles or metal ions in the ink and improving the pot life of the ink, and examples thereof include ammonium compounds, amine compounds, compounds containing imino groups and ether groups. .

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. In addition, although the display of "part" or "%" is used in an Example, unless otherwise indicated, "part by mass" or "mass%" is represented.

[Preparation of a sample having a conductive pattern]
<< Preparation of Sample 1 >>
(Preparation of underlayer 1)
Polyurethane latex containing 10% titanium dioxide (average particle size 27 nm) and 0.3% 2-mercaptotriazole on a commercially available glass-epoxy substrate having a surface subjected to a corona discharge treatment of 12 W · min / m ² for 2 seconds (Solid content 3%) was applied so as to have a dry film thickness of 0.8 μm and dried to prepare a porous base layer 1.

(Preparation of ink 1)
Ink 1 was prepared by dissolving copper sulfate in a mixed solution of water / ethylene glycol = 1/3 to a concentration of 50 mmol / L.

(Formation of conductive pattern)
A 20 mm square pattern with a wet film thickness of 0.6 μm was formed on the base layer 1 by the offset printing method, and then the solvent of the ink 1 was dried. Next, it was immersed in the following electroless copper plating bath and subjected to electroless plating at 75 ° C. for 20 minutes to form a conductive pattern having an average film thickness of 4.5 μm. .

(Electroless copper plating solution)
Copper sulfate 0.04 mol Formaldehyde (37% by mass) 0.08 mol Sodium hydroxide 0.10 mol Triethanolamine 0.05 mol Polyethylene glycol 100 ppm
Add water to bring the total volume to 1L.

<< Preparation of Sample 2 >>
Sample 2 was prepared in the same manner as Sample 1, except that 2-mercaptotriazole of Sample 1 was changed to equimolar Exemplified Compound 3-7 and copper sulfate was changed to nickel acetate.

<< Preparation of Sample 3 >>
Sample 3 was prepared in the same manner as Sample 1 except that 2-mercaptotriazole was removed from Sample 1.

<< Preparation of Sample 4 >>
Sample 4 was prepared in the same manner as Sample 1 except that the underlayer of Sample 1 was removed.

<< Preparation of Sample 5 >>
Sample 5 was produced in the same manner as Sample 1 except that 230 mJ / cm ² of ultraviolet light was irradiated using a high-pressure mercury lamp before immersion of Sample 1 in the electroless plating bath.

<< Preparation of Sample 6 >>
The 2-mercaptotriazole of sample 1 was changed to 3-mercaptopropyltriethoxysilane, and after the preparation of the underlayer 1, it was heated at 60 ° C. for 1 hour to fix the mercapto compound to titanium oxide, and the ink application was shown in FIG. Sample 6 was prepared in the same manner as Sample 1, except that the application was performed by an ink jet recording apparatus including the pressure applying unit and the electric field applying unit described in 1 above.

<< Preparation of Sample 7 >>
The copper sulfate of Sample 6 was irradiated with 230 mJ / cm ² of ultraviolet light using a high-pressure mercury lamp before immersion in the electroless plating bath, and the electroless plating solution was applied to silver p-toluenesulfonate and the following electroless plating solution. Sample 7 was produced in the same manner as Sample 6, except for the above.

(Electroless silver plating solution)
0.84 g of silver nitrate
Potassium phosphate 15.0g
Potassium borate 5.0g
Hydantoin 10.0g
Triethanolamine 0.05 mol Polyethylene glycol 100 ppm
Add water to bring the total volume to 1L.

<< Preparation of Sample 8 >>
Sample 8 was changed in the same manner as Sample 7 except that the electroless plating solution of Sample 7 was changed to the ink solution of Sample 7, the electroless plating bath was removed, and the ultraviolet irradiation with the high-pressure mercury lamp was changed to 5 J / cm ^2. Produced.

[Evaluation]
(Electrical conductivity)
When the volume resistivity of each sample was calculated from the resistance value obtained according to the four-terminal method of Japanese Industrial Standard JIS K 7194, a value within twice the volume resistivity of the pure metal of each material was obtained, and each sample was sufficient It was found to have a good electrical conductivity.

(Adhesion)
The adhesion of the sample was evaluated according to Japanese Industrial Standard JIS K 5600-5-6. After forming squares on the grid with a razor on a square conductive pattern of 20 mm square of the sample, a tape peeling test is performed to determine the area ratio of the peeled conductive pattern. Evaluated.

A: No peeling of conductive pattern (equivalent to test result classification 0)
○: Peeling area of the conductive pattern is greater than 0% and 1.0% or less Δ: Peeling area of the conductive pattern is greater than 1.0% and 5.0% or less ×: Peeling area of the conductive pattern is 5 Greater than 0.0%.

  It turns out that the adhesiveness of the sample which satisfy | fills the structure of this invention is excellent.

1 is a schematic cross-sectional view showing an example of a conductive ink discharge apparatus using a pressure application unit and an electric field application unit that can be preferably applied to the present invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 20 Conductive ink discharge apparatus 21 Nozzle 22 Inner flow path 23 Counter electrode 24 Ink chamber 25 Discharge voltage application means 26 Nozzle plate 27 Supply path 28 Discharge electrode 30 Bias power supply K Base material

Claims (11)

A base layer containing a compound containing a metal oxide, a binder, a mercapto group or a carboxyl group is provided on a base material, and an ink containing a metal is applied in a pattern on the base layer, and the formed metal catalyst core is formed on the base layer. A method for producing a conductive pattern sheet, comprising forming a metal film. The method for producing a conductive pattern sheet according to claim 1, wherein light irradiation is performed after the ink containing the metal is applied in a pattern. 3. The method for producing a conductive pattern sheet according to claim 1, wherein after forming the metal catalyst core, an electroless plating treatment is performed to form a metal film. 4. The conductive pattern sheet according to any one of claims 1 to 3, wherein the means for applying the metal-containing ink in a pattern is an ink jet recording means that performs injection drawing using an ink jet recording apparatus. Manufacturing method. 5. The method for producing a conductive pattern sheet according to claim 4, wherein the ink jet recording means is a method using a pressure applying means and an electric field applying means. The conductive pattern sheet according to any one of claims 1 to 5, wherein the metal of the ink containing the metal is at least one selected from copper, silver, gold, nickel, palladium, and zinc. Manufacturing method. The ink containing a metal contains a ligand compound capable of forming a complex having a complex stability constant smaller than a complex stability constant of a complex formed from the metal and a compound containing a carboxyl group or a mercapto group. The manufacturing method of the electroconductive pattern sheet of any one of Claims 1-6. The method for producing a conductive pattern sheet according to any one of claims 1 to 7, wherein the metal oxide is at least one selected from titanium oxide, silicon oxide, and aluminum oxide. The method for producing a conductive pattern sheet according to any one of claims 1 to 8, wherein the compound containing a mercapto group or a carboxyl group is immobilized on the metal oxide. The method for producing a conductive pattern sheet according to claim 1, wherein the underlayer is porous. A conductive pattern sheet produced by the method for producing a conductive pattern sheet according to claim 1.

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