JP2010182776A - Conductive film pattern and method of forming the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a conductive film pattern having a fine form, excellent in adhesiveness to a base material, form accuracy and reliability, and formed requiring no complicated and costly equipment and steps and a method of forming the same. <P>SOLUTION: The conductive film pattern at least including the base material 5001, an insulating layer 5002 formed by disposing an insulating ink on the base material, and a conductive layer 5004 formed by disposing a conductive ink on the insulating layer so as to have a predetermined pattern by an inkjet device, characterized by including a coupling agent film 5003 formed with at least one coupling agent selected from a silane coupling agent, a titanium coupling agent, zirconia coupling agent, and an aluminum coupling agent, each containing no fluorine atom, on the insulating layer. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a method for forming a conductive film pattern using an inkjet method and electroless plating and a conductive film pattern formed thereby.

  There has been proposed a technique for forming circuit wirings and electrodes by discharging conductive ink onto a substrate using an inkjet method. The conventional photolithography method requires a large number of steps (conductive film formation, resist coating, exposure, development, etching, etc.) and materials (conductive material, photoresist, developer, cleaning solution, etc.). On the other hand, using the inkjet method has simplified the man-hours and requires a small amount of materials and energy, and has attracted attention as a technology that can form fine wiring patterns at low cost. Yes.

  Furthermore, by using an insulating ink in addition to the conductive ink, short-circuiting between wirings can be prevented (for example, Japanese Patent Application Laid-Open No. 2005-210079), or applied to the production of a multilayer wiring board (for example, Japanese Patent Application Laid-Open No. 11-1999). -163499) is known. However, when producing patterns such as circuit wiring using both conductive ink and insulating ink, it has been necessary to improve the reliability of the circuit by improving the adhesion between them. .

  In order to solve this problem, for example, it is described that the conductive pattern is formed on the semi-cured insulating layer, and then the heat treatment is performed to completely cure, thereby improving the adhesion between the insulating layer and the conductive pattern. (For example, refer to Patent Document 1). However, although this method certainly improves the adhesion itself, the semi-cured insulating layer does not necessarily have a uniform surface state, so that the wettability of the conductive ink on the insulating layer is not uniform and depends on the position. Will be different. As a result, the landed shape of the discharged conductive ink on the insulating layer is not uniform, and the pattern shape to be formed will differ from the desired shape, so only the technology using semi-cured insulating ink However, it is very difficult to form a pattern with a high precision and a fine shape.

JP 2007-158352 A

  The present invention has been made in view of the above problems, and an object of the present invention is to provide a complicated shape, an expensive equipment, and a process having a fine shape, excellent adhesion to the substrate, shape accuracy, and reliability. An object of the present invention is to provide a conductive film pattern formed without necessity and a method of forming the conductive film pattern.

  The above object of the present invention can be achieved by the following constitution.

1. A substrate;
An insulating layer formed by disposing an insulating ink on the substrate;
On the insulating layer, a conductive layer formed by disposing conductive ink in a predetermined pattern by an inkjet device;
In the conductive film pattern having at least
A coupling agent film formed on the insulating layer by at least one coupling agent selected from a silane coupling agent not containing a fluorine atom, a titanium coupling agent, a zirconia coupling agent, and an aluminum coupling agent. A conductive film pattern comprising:

  2. 2. The conductive film pattern according to 1 above, wherein the insulating layer is disposed on the entire surface of the base material.

  3. 2. The conductive film pattern according to 1 above, wherein the insulating layer is formed by disposing insulating ink in a predetermined pattern by an ink jet apparatus.

4). The substrate is a semiconductor substrate having a plurality of electrode regions;
4. The conductive film pattern according to 3, wherein the conductive film pattern connects the plurality of electrode regions.

  5. 4. The conductive film pattern according to any one of 1 to 3, wherein the substrate has a conductive region and a non-conductive region.

  6). 6. The conductive film pattern according to 5 above, wherein the base material is a base material on which a predetermined pattern is formed with conductive ink.

  7). The inkjet apparatus includes a nozzle plate having discharge holes, a pressure chamber communicating with the discharge holes, a pressure generating element that causes a pressure variation in the liquid in the pressure chamber, and a driving voltage applying unit that applies a voltage to the pressure generating element. 7. The conductive film pattern according to any one of 1 to 6, wherein the conductive film pattern is a device that discharges droplets from a droplet discharge head.

  8). 8. The conductive film pattern according to 7, wherein the ink jet apparatus further includes an electrostatic voltage applying unit, and the liquid droplets are ejected using an electrostatic force in addition to the pressure fluctuation.

  9. 9. The conductive film pattern according to any one of 1 to 8, wherein the conductive ink has a catalytic ability for electroless plating.

  10. The said coupling agent is at least 1 type of coupling agent selected from a titanium coupling agent, a zirconia coupling agent, and an aluminum coupling agent, The said any one of 1-9 characterized by the above-mentioned. Conductive film pattern.

11. Forming an insulating layer by disposing an insulating ink on the substrate;
On the insulating layer, a coupling agent film is formed with at least one coupling agent selected from a silane coupling agent not containing a fluorine atom, a titanium coupling agent, a zirconia coupling agent, and an aluminum coupling agent. Process,
Forming a conductive layer on the coupling agent film by disposing a conductive ink in a predetermined pattern by an ink-jet method.

  12 12. The method for forming a conductive film pattern according to 11 above, wherein the step of forming the insulating layer is a step of disposing an insulating ink on a substrate by an ink jet method.

  13. The inkjet method includes a nozzle plate having discharge holes, a pressure chamber communicating with the discharge holes, a pressure generating element that causes a pressure fluctuation in the liquid in the pressure chamber, and a driving voltage applying unit that applies a voltage to the pressure generating element. 13. The method for forming a conductive film pattern according to the item 11 or 12, which is an inkjet method in which droplets are ejected from a droplet ejection head.

  14 14. The conductive film pattern according to 13, wherein the inkjet method further includes an electrostatic voltage applying unit, and the droplets are ejected using electrostatic force in addition to the pressure fluctuation. Forming method.

  15. 15. The coupling agent according to any one of 11 to 14, wherein the coupling agent is at least one coupling agent selected from a titanium coupling agent, a zirconia coupling agent, and an aluminum coupling agent. Method for forming conductive film pattern.

  According to the present invention, a conductive film pattern having a fine shape, excellent adhesion to a base material, shape accuracy and reliability, formed without requiring complicated and expensive equipment and processes, and the conductive film pattern thereof Can be provided.

  In the present invention, when a conductive ink pattern is formed on a base material on which an insulating layer is formed by an inkjet method to form a conductive layer pattern, the insulating layer is surface-treated with a predetermined coupling agent in advance. As a result, the surface state of the insulating layer can be made uniform in a desired state, so that the pattern shape of the conductive layer by the conductive ink can be improved and the pattern of the insulating layer and the conductive layer can be improved. It is possible to obtain a conductive layer pattern and a conductive film pattern with improved adhesion.

  In addition, by using a method utilizing electrostatic force as an ink jet method, it is possible to easily arrange minute droplets on an insulating layer and further on a substrate with good positional accuracy. It is preferably used for the formation of a conductive film pattern having.

  In addition, an ink having electroless plating catalytic ability is used as the ink disposed by the inkjet method, and the electroless plating process is further performed on the conductive layer pattern (conductive film pattern) formed on the insulating layer. Even when the plating film is formed by the above method, since the plating metal can be favorably deposited on the ink pattern (pattern of the conductive layer), it is preferably used for the formation of the film pattern having excellent reliability of the present invention. It is done.

1 is a perspective view illustrating an example of an internal configuration of an ink jet recording apparatus according to an embodiment. 1 is a schematic diagram illustrating an overall configuration of a droplet discharge device (inkjet device) using an electrostatic force that is preferably used in the present invention. 1 is an exploded perspective view showing an example of a schematic configuration of a multi-nozzle head of an electrostatic suction type ink jet device used in the present invention. An example of a cross-sectional view of the multi-nozzle head 500 is shown in FIG. Sectional drawing which shows the shape of the electrically conductive film pattern of Example 1. FIG. Sectional drawing which shows the shape of the electrically conductive film pattern of Example 2. FIG. Sectional drawing which shows the shape of the electrically conductive film pattern of Example 3. FIG.

  Hereinafter, although the best mode for carrying out the present invention will be described, the present invention is not limited to these.

  In the present invention, when a conductive layer pattern is prepared by disposing a conductive ink on an insulating layer on a substrate by an inkjet method, the surface of the insulating layer is subjected to a surface treatment with a predetermined coupling agent in advance. This makes it possible to make the wettability of the conductive ink uniform and form a desired fine pattern, and to improve the adhesion between the insulating layer and the pattern of the conductive layer. . That is, the surface properties of the insulating layer are controlled by the action of the functional group of the coupling agent film formed by chemical bonding with the surface of the insulating layer, and the pattern of the conductive ink droplets placed is formed into a fine pattern. It is possible to control to such an extent that it does not spread more than a certain amount and maintains an appropriate adhesion.

(Insulating ink)
The insulating ink used in the present invention is obtained by dissolving an insulating resin composition with a solvent, and may contain various additives as necessary.

  The insulating resin composition of the insulating ink may be any material containing an electrically insulating material, such as an epoxy resin, a phenol resin, a polyimide resin, a polyamide resin, a polyamideimide resin, or a silicone-modified polyamideimide. Examples include compositions containing monomers, oligomers, polymers, and the like that constitute resins, polyester resins, cyanate ester resins, BT resins, acrylic resins, methacrylic resins, melamine resins, urethane resins, alkyd resins, and the like. These can be used alone or in combination of two or more. Moreover, it is preferable that the said resin composition contains a thermosetting resin. An insulating layer made of a cured product of an insulating ink containing a thermosetting resin is excellent in heat resistance and has excellent insulation reliability and connection reliability in a printed wiring board.

  In the present invention, it is particularly preferable that the resin composition contains an epoxy resin among the resins described above. By using an epoxy resin, the adhesiveness with respect to a coupling agent film | membrane and also a conductive layer can be improved.

  Examples of the epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, biphenol type epoxy resin, alicyclic epoxy resin, aliphatic chain epoxy resin, glycidyl ester type epoxy resin, phenol Examples thereof include glycidyl ether compounds obtained by subjecting a compound and an aldehyde compound to a condensation reaction. These may be contained in combination of two or more. Furthermore, in this invention, it is preferable that the said resin composition contains the hardening | curing agent which hardens the said epoxy resin and an epoxy resin.

  Examples of the curing agent include amines such as diethylenetriamine, triethylenetetramine, metaxylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, m-phenylenediamine, and dicyandiamide; phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyl Acid anhydrides such as tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyl nadic anhydride, pyromellitic anhydride, trimellitic anhydride; imidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2 -Phenylimidazole, 2-undecylimidazole, 1-benzyl-2-methylimidazole, 2-heptadecylimidazole, 4,5-diphenylimidazole, 2-methylimidazoline, 2-phenyl Nilimidazoline, 2-undecylimidazoline, 2-heptadecylimidazoline, 2-isopropylimidazole, 2,4-dimethylimidazole, 2-phenyl-4-methylimidazole, 2-ethylimidazoline, 2-isopropylimidazoline, 2,4- Imidazoles such as dimethylimidazoline and 2-phenyl-4-methylimidazoline; imidazoles whose imino group is masked with acrylonitrile, phenylene diisocyanate, toluidine isocyanate, naphthalene diisocyanate, methylene bisphenyl isocyanate, melamine acrylate, etc .; bisphenol F, bisphenol A And phenol compounds such as bisphenol S; condensates of phenol compounds and aldehyde compounds. In addition, you may contain these hardening | curing agents individually by 1 type or in combination of 2 or more types. In addition to the above-described components, the resin composition may contain a curing accelerator, a coupling agent, an antioxidant, a filler and the like according to desired properties.

  The solvent contained in the insulating ink used in the present invention may be any solvent that can disperse or dissolve the components of the resin composition described above, and examples thereof include γ-butyrolactone and cyclohexanone.

(Coupling agent)
The coupling agent used in the present invention is selected from the group consisting of a silane coupling agent not containing a fluorine atom, a titanium coupling agent, a zirconia coupling agent, and an aluminum coupling agent. In the present invention, it is possible not only to use one kind of compound selected from the above group, but also to use two or more kinds in combination.

  The coupling agent used in the present invention does not contain a fluorine atom. By using a coupling agent containing a fluorine atom, a relatively high value can be obtained for the contact angle between the conductive ink applied to the insulating layer and the substrate in a later step (that is, liquid repellency). However, in the present invention, a coupling agent that does not contain a fluorine atom is used from the viewpoint of adhesion between the insulating layer and the conductive ink and from the viewpoint of use as circuit wiring.

  Further, from the viewpoint of adhesion of the film itself to the insulating layer on the substrate, stability of film properties, and ease of handling during film formation, in the present invention, a titanium coupling agent, a zirconia coupling agent, and an aluminum coupling. A compound selected from the group consisting of an agent is preferably used.

  Examples of the silane coupling agent used in the present invention include vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and 3-glycidoxypropyltrimethoxysilane. 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacrylic Loxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2 Aminoethyl) 3-aminopropyltrimethoxysilane, N-2 (aminoethyl) 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, hexamethyldisilazane, 3- ( 2-aminoethylaminopropyl) dimethoxymethylsilane, 3- (2-aminoethylaminopropyl) trimethoxysilane, 2- (2-aminoethylthioethyl) diethoxymethylsilane, 2- (2-aminoethylthioethyl) Triethoxysilane, 3- [2- (2-aminoethylaminoethylamino) propyl] trimethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N-phenyl-3- Aminopropyltrimethoxysilane, N- (vinyl base Gil) -2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride, 3-ureidopropyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, bis (triethoxysilylpropyl) tetrasulfide, imidazolylalkyl-trialkoxysilane, diphenyldimethoxysilane, hexyltrimethoxysilane, decyltrimethoxysilane, tetramethoxysilane, tetraethoxysilane, methyltrimethoxy Examples thereof include silane, methyltriethoxysilane, dimethyltriethoxysilane, and phenyltriethoxysilane.

  Among them, N-2 (aminoethyl) 3-aminopropylmethyldimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, diphenyldimethoxysilane, hexyltrimethoxysilane, decyltrimethoxysilane Etc. are preferred.

  Examples of the titanium coupling agent used in the present invention include titanium tetraisopropoxide, titanium tetranormal butoxide, butyl titanate dimer, titanium tetra-2-ethylhexoxide, titanium dioctyloxybis (octylene glycolate), tetra Methyl titanate, titanium acetylacetonate, titanium diisopropoxybis (acetylacetonate), titanium tetraacetylacetonate, titanium diisopropoxybis (ethylacetoacetate), titanium ethylacetoacetate, titanium octanediolate, titanium diisopropoxy Bis (triethanolamate), Titanium triethanolamate, Titanium lactate ammonium salt, Titanium lactate, Polyhydroxytitanium stearate, KR38S In-Techno), KR44 (Ajinomoto Fine-Techno), KR46B (Ajinomoto Fine-Techno), KR55 (Ajinomoto Fine-Techno), KR9SA (Ajinomoto Fine-Techno), KRTTS (Ajinomoto Fine-Techno) , KR41B (manufactured by Ajinomoto Fine Techno), KR138S (manufactured by Ajinomoto Fine Techno), KR238S (manufactured by Ajinomoto Fine Techno), KR338X (manufactured by Ajinomoto Fine Techno), and the like.

  Among them, titanium dioctyloxybis (octylene glycolate), titanium diisopropoxybis (ethyl acetoacetate), polyhydroxytitanium stearate, KR44 (manufactured by Ajinomoto Fine Techno), KR46B (manufactured by Ajinomoto Fine Techno), KR55 (Ajinomoto) Fine Techno), KR9SA (Ajinomoto Fine Techno), KR41B (Ajinomoto Fine Techno), and the like are preferable.

  Examples of the zirconia coupling agent used in the present invention include zirconium tetranormal propoxide, zirconium tetranormal butoxide, zirconium tetraacetylacetonate, zirconium tributoxymonoacetylacetonate, zirconium monobutoxyacetylacetonate bis (ethylacetoacetate). ), Zirconium dibutoxybis (ethyl acetoacetate), zirconium tetraacetylacetonate, zirconium tributoxy monostearate, zirconium chloride compound aminocarboxylic acid, zirconium monoacetylacetonate, zirconium bisacetylacetonate, zirconium monoethylacetoacetate, Zirconium acetylacetonate bisethylacetoacetate, zirconium acetate Over DOO, zirconium monostearate, and the like.

  Of these, zirconium dibutoxybis (ethyl acetoacetate), zirconium tributoxy monostearate and the like are preferable.

  Examples of the aluminum coupling agent used in the present invention include aluminum isopropylate, monosec-butoxyaluminum diisopropylate, aluminum sec-butyrate, aluminum ethylate, ethyl acetoacetate aluminum diisopropylate, aluminum tris (ethyl acetoacetate), Alkyl acetoacetate aluminum diisopropylate, aluminum diisopropoxy monooleyl acetoacetate, aluminum monoacetylacetonate bis (ethyl acetoacetate), aluminum tris (acetylacetonate), aluminum monoisopropoxy monooleoxyethyl acetoacetate, cyclic aluminum Oxide isopropylate, cyclic aluminum oxide octylene , Cyclic aluminum oxide stearate, and the like.

  Of these, alkyl acetoacetate aluminum diisopropylate is preferred.

(Base material)
The base material used in the present invention may be appropriately selected and used depending on the application, but examples include resin films such as polyimide films, polyamideimide films, polyamide films, and polyester films, glass-epoxy substrates, and silicon. Examples include a substrate, a ceramic substrate, and a glass substrate.

  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.

  The present invention can also be used for manufacturing a multilayer wiring board having a plurality of conductive layers. In this case, only one layer of the plurality of conductive layers may be formed by the method of the present invention, or a plurality of conductive layers or all the conductive layers may be formed by the method of the present invention.

  When only a part of the conductive layers is formed by the method of the present invention, the method of the present invention is applied to a base material on which conductive regions and non-conductive regions are already formed. In other words, an insulating layer is formed on the conductive region and non-conductive region that have already been formed, a coupling agent film is formed on the surface of the insulating layer, and then a conductive ink is disposed to create a pattern of the conductive layer. To do. As a result, a conductive layer can be further formed on a wiring board that already has a conductive layer, and a multilayer wiring board can be manufactured.

  When a plurality of conductive layers are formed by the method of the present invention, the method of the present invention is further applied on the substrate on which the conductive layer is formed by the method of the present invention. That is, an insulating layer is formed on a base material on which a predetermined pattern has already been formed with a conductive ink, a film of a coupling agent is formed on the surface of the insulating layer, and then the conductive ink is arranged to dispose the conductive layer Create a pattern.

  In the present invention, a conductive layer made of conductive ink may be formed so as to connect the electrodes using a substrate having a plurality of electrode regions as a base material. Specifically, electrode patterns that are formed in advance on a substrate such as a semiconductor are connected with a conductive layer made of conductive ink, or terminals on the substrate and electronic components mounted on the substrate Electrodes can be connected. In this case, the conduction | electrical_connection by an electrode part can be ensured by forming the insulating layer formed prior to a conductive layer on base materials other than the electrode part to connect.

(Formation of insulating layer on substrate)
As a method of forming an insulating layer by disposing an insulating ink on a substrate, existing coating methods (screen printing, gravure printing, ink jet printing, spin coating, wire bar coating, blade coating, roll coating, dip coating, etc. In the present invention, it is preferable to use a dispenser device or an ink jet device. In particular, when an insulating layer is provided only in the vicinity of the position where the pattern of the conductive layer is formed, instead of providing the insulating layer on the entire surface of the substrate, an ink jet apparatus is preferably used. However, an inkjet apparatus may be used even when an insulating layer is provided on the entire surface of the substrate.

  When using a dispenser apparatus, it is possible to use the existing insulating ink for screen printing. The viscosity is preferably 1000 to 20000 mPa · S, more preferably 3000 to 15000 mPa · S. It is preferable that it is 3000 mPa · S or more from the viewpoint that wet thinning fine lines can be formed, and if it is 15000 mPa · S or less, it is preferable from the viewpoint that injection with a thin needle is possible. The thickness of the needle is preferably 0.10 to 1.0 μm.

  In the case of using an ink jet device, the viscosity of the insulating ink is preferably 50 mPa · S or less. The ink viscosity when using the ink jet apparatus according to the present invention is preferably 20 mPa · S or less at the injection temperature. Furthermore, 2.0 to 8.0 mPa · S is more preferable. 2.0 mPa · S or more is preferable from the viewpoint of obtaining desired insulating properties from the viewpoint of the concentration of the insulating ink, and 8.0 mPa · S or less is preferable from the viewpoint of ejection properties. Moreover, when it becomes 8.0 mPa * S or more, the injection | pouring defect may come out. The injection temperature is preferably 20 to 60 ° C, more preferably 25 to 50 ° C.

  The surface tension of the ink is preferably 20 mN / m or more, and more preferably 25 to 45 mN / m from the viewpoint of ejection stability and drawing reliability.

  In addition, when drawing using an inkjet device using electrostatic force, the electrical conductivity of the ink is preferably 0.1 μS / cm or more, and more preferably 1 μS / cm or more from the viewpoint of high-precision drawing. preferable.

  In the present invention, after the insulating ink is disposed on the substrate, the insulating ink is cured by heating, light irradiation, or the like to form the insulating layer. As a means for curing, an apparatus or a method such as a hot-air circulating furnace (oven), a hot plate, or ultraviolet irradiation may be used according to the physical properties of the insulating ink.

(Formation of coupling agent film on insulating layer)
The film forming method for forming the coupling agent film on the insulating layer formed on the substrate is not particularly limited. For example, a solution obtained by diluting the coupling agent in a solvent is applied to the substrate surface. And a method of applying by a method such as spray coating, spin coating, dip coating, roll coating, and ink jet. In this case, an appropriate solvent can be selected and used according to the type of coupling agent to be used. For example, isopropanol or 1-butanol can be used.

  In addition, the concentration of the coupling agent in the diluent can be any value, but if the concentration is too high, it becomes difficult to handle and difficult to apply uniformly on the substrate, and conversely if the concentration is too low Since the formed film may not exhibit desired physical properties, it may be set to any value within a range of 0.01 to 20% by mass, for example.

  Further, the substrate to which the coupling agent has been applied is heated and dried using a hot-air circulating furnace (oven) or a hot plate. By drying by heating, the coupling agent provided on the insulating layer exhibits desired physical properties and functions on the surface of the insulating layer.

  In addition, prior to applying the coupling agent on the insulating layer, the insulating layer may be subjected to surface treatment in advance from the viewpoint of improving the adhesion between the insulating layer and the coupling agent film. Examples of the surface treatment include plasma treatment, corona discharge treatment, flame treatment, ozone treatment, ultraviolet treatment, radiation treatment, and chemical treatment.

(Manufacture of multilayer wiring boards)
The present invention can be used for manufacturing a multilayer wiring board having a plurality of conductive film patterns as well as a single conductive film pattern. The following method can be mentioned as an example of a preferable method when the present invention is applied to the production of a multilayer wiring board.
1) Insulating ink is placed on a substrate and dried to form a first insulating layer 2) A coupling layer is formed on the surface of the first insulating layer and dried 3) Conductive ink is placed by an inkjet method 4) Firing and drying to form the first conductive layer 5) Disposing the insulating ink and drying to form the second insulating layer 6) Forming and drying the coupling layer on the surface of the second insulating layer 7 ) Disposing the conductive ink by the ink jet method 8) Firing and drying to form the second conductive layer Further, after repeating the above steps, the steps 5) to 8) are repeated to further form the insulating layer and the conductive layer. You may laminate.

(Conductive ink)
As the conductive ink used in the present invention, a dispersion liquid in which conductive fine particles are dispersed in a dispersion medium can be used.

  The form of the ink is not particularly limited, but a preferable form includes a form containing metal fine particles as conductive fine particles.

  Examples of the metal fine particles used in the present invention include Au, Pt, Ag, Cu, Ni, Cr, Rh, Pd, Zn, Co, Mo, Ru, W, Os, Ir, Fe, Mn, Ge, Sn, Ga, In and the like can be mentioned, among which Au, Ag, Pt, Pd, Rh, Ir, Cu or alloys containing these are preferably used. These metal fine particles are preferably metal nanocolloids having an average particle diameter of 100 nm or less.

  In the fine metal particle-containing ink used in the present invention, a polymer or a surfactant can be used as a protective colloid of fine metal particles. Particularly, a block copolymer of polyester, polyacrylonitrile, polyurethane and alkanolamine is preferable. .

  Examples of the metal fine particle-containing ink used in the present invention include water-based ink and oil-based ink. A water-based conductive ink constituted by dispersing metal fine particles in a dispersion medium mainly containing water can be prepared, for example, according to the following method.

  A water-soluble polymer is dissolved in a metal ion source aqueous solution such as chloroauric acid or silver nitrate, and an alkanolamine such as dimethylaminoethanol is added with stirring. Metal ions are reduced in several tens of seconds to several minutes, and metal fine particles having an average particle diameter of 100 nm or less are deposited. Thereafter, chlorine ions and nitrate ions are removed by a filtration method such as ultrafiltration, and then concentrated and dried to obtain a water-based ink containing metal fine particles at a high concentration. This water-based ink can be stably dissolved and mixed in water, an alcohol-based solvent, a sol-gel process binder such as tetraethoxysilane or triethoxysilane.

  An oil-based ink in which metal fine particles are dispersed in an oil-based dispersion medium can be prepared, for example, according to the following method.

  The oil-soluble polymer is dissolved in a water-miscible organic solvent such as acetone, and the polymer solution is mixed with an aqueous metal ion source solution. Although the mixture is heterogeneous, when alkanolamine is added while stirring the mixture, metal fine particles are precipitated on the oil phase side in a form dispersed in the polymer. By washing, concentrating and drying this, an oil-based ink containing dense metal fine particles similar to the water-based ink can be obtained. This oil-based conductive ink can be stably dissolved and mixed in aromatic, ketone-based, ester-based solvents, polyesters, epoxy resins, acrylic resins, polyurethane resins, and the like.

  The concentration of the metal fine particles in the ink dispersion medium can be about 80% by mass at maximum, but can be appropriately diluted depending on the application. Usually, the content of metal fine particles in the ink is preferably 2 to 50% by mass, the content of the surfactant and the resin component is 0.3 to 30% by mass, and the viscosity is preferably 3 to 30 mPa · s.

  In addition, the ink used in the present invention has a surface tension of 20 mN / m or more and 50 mN / m or less from the viewpoint that it can be ejected satisfactorily from an inkjet head and exhibits appropriate wetting and spreading properties when placed on a substrate. It is preferable to adjust the value. Furthermore, it is more preferable to set it as 25 mN / m or more and 45 mN / m or less.

  In addition, the ink used in the present invention preferably has an electric conductivity of 0.1 μS / cm or more and 1000 μS / cm or less. More preferably, the value is 1 μS / cm or more and 100 μS / cm or less. As a result, when electrostatic force is used as the ink jet method, ink ejection becomes stable, and variations in the landing position of the ink on the base material are reduced, which can be preferably used.

  In the present invention, when an ink containing metal fine particles is used as the conductive ink, a film pattern having a predetermined shape is formed on the substrate by an inkjet device, and then heated using a hot air circulation furnace (oven) or a hot plate. It is preferable to perform firing. Thereby, an organic substance such as a dispersant or a solvent contained in the ink is evaporated, and the electric conductivity of the formed pattern can be increased. The temperature at the time of firing is not particularly limited, but when a resin base material is used as the base material, it is necessary to carry out at a temperature lower than the softening point or melting point of the base material.

  The conductive ink used in the present invention may have electroless plating catalytic ability. In this case, after forming a conductive film pattern on a base material, the thickness of the conductive film pattern can be increased by performing an electroless plating process. The plating solution used for the electroless plating treatment is a solution in which metal ions to be deposited as a plating material are dissolved, and contains a reducing agent together with a metal salt. It can be used without particular limitation.

  Examples of metal salts contained in the plating solution include halides, nitrates, sulfates, phosphates, borates, acetic acids of at least one metal selected from Au, Ag, Cu, Ni, Co, and Fe. Salt, tartrate, citrate and the like.

  As the reducing agent, hydrazine, hydrazine salt, borohalide salt, hypophosphite, hyposulfite, alcohol, aldehyde, carboxylic acid, carboxylate and the like are applicable. Elements such as boron, phosphorus and nitrogen contained in these reducing agents may be precipitated together with the metal. Or you may take the form which an alloy precipitates using the plating solution containing 2 or more types of metal salts.

  The plating solution may contain additives such as a buffer for adjusting pH and a surfactant as necessary. Moreover, you may make it add organic solvents, such as alcohol, a ketone, and ester other than water as a solvent.

  The composition of the plating solution is composed of a metal salt of the metal to be deposited, a reducing agent, and an additive and an organic solvent as necessary, but the concentration and composition can be adjusted according to the deposition rate. . In addition, the deposition rate can be adjusted by adjusting the temperature of the plating solution. As a method for adjusting the temperature, a method of adjusting the temperature of the plating solution, and, for example, when immersed in the plating solution, the substrate (the substrate on which the coupling agent film is formed) is heated and cooled before immersion. And adjusting the temperature. Furthermore, the film thickness of the metal which deposits by the time immersed in a plating solution can also be adjusted.

  Moreover, it is preferable to pre-process a base material before processing the base material in which the electrically conductive film pattern was formed with a plating solution. Examples of the pretreatment include heat drying treatment, washing treatment, catalyst activation treatment and the like of the base material, and a known treatment method may be selected as necessary. In particular, it is preferable to perform a treatment step that selectively imparts catalytic ability to the ink pattern.

  Further, after the electroless plating process is performed to form the wiring pattern, electroplating may be further performed to increase the thickness of the wiring. In this case, it is preferable that a pattern for use as an electrode for use in energization when performing electroplating is formed with ink in the same manner as the wiring pattern.

(Inkjet device, method)
By using an ink jet device that uses electrostatic force as the ink jet device, it is possible to easily arrange minute droplets on a substrate with good positional accuracy. It can be preferably used for formation.

(Outline of inkjet recording apparatus)
Hereinafter, an exemplary embodiment of an ink jet recording apparatus according to the present invention will be described with reference to the drawings. FIG. 1 is a perspective view showing an internal configuration of the ink jet recording apparatus according to the present embodiment. The ink jet recording apparatus 100 according to the present embodiment includes a bottom plate 1 and a guide rail support 3 that supports the horizontal guide rail 2 from below at a predetermined height position. The horizontal guide rail 2 supports a carriage 7 via a vertical guide rail 6, and the vertical guide rail 6 and the carriage 7 are integrated into a horizontal main scan in a predetermined transport direction by a moving mechanism (not shown). In the direction X, it reciprocates along the horizontal guide rail 2. The carriage 7 reciprocates along the vertical guide rail 6 in the vertical direction Z by a moving mechanism (not shown). A support base 4 that supports a base material (not shown) from the non-recording surface side and a maintenance device 5 that performs maintenance of the ink jet recording head 8 are arranged on the bottom plate 1 side by side in the longitudinal direction of the horizontal guide rail 2. Yes. The support 4 transports the recording medium in the sub-scanning direction Y orthogonal to the main scanning direction X by a transport mechanism (not shown).

  Further, the support base 4 also has a function as an electrode of an electrostatic voltage application unit when ink is ejected using an electrostatic attraction force.

  An ink jet recording head 8 that discharges the ink according to the present invention to the substrate is mounted on the carriage 7. The ink jet recording head will be described in detail later.

  When using the above-described inkjet recording apparatus in the present invention, the carriage and the support base are arranged so that an arbitrary pattern is drawn by the ink ejected from the ink jet recording head on the substrate arranged on the support base. Control is performed so that it can be arbitrarily moved, and ink ejection from the recording head is controlled.

(Droplet discharge means using electrostatic force)
FIG. 2 is a schematic diagram showing an overall configuration of a droplet discharge device (inkjet device) using electrostatic force, which is preferably used in the present invention. The ink jet recording head 402 used in the present invention can be applied to various liquid ejection devices such as a so-called serial method or line method.

  The droplet discharge device 401 of the present embodiment has a liquid discharge head 402 in which a nozzle 410 for discharging a droplet D of chargeable ink L is formed, and a facing surface that faces the nozzle 410 of the liquid discharge head 402. The counter electrode 403 that supports the base material K that receives the landing of the droplet D on the opposing surface is provided.

  A resin nozzle plate 411 having a plurality of nozzles 410 is provided on the side of the inkjet recording head (hereinafter also referred to as a liquid discharge head) 402 facing the counter electrode 403. The liquid discharge head 402 is configured as a head having a flat discharge surface in which the nozzle 410 does not protrude from the discharge surface 412 facing the counter electrode 403 of the nozzle plate 411.

  Each nozzle 410 is formed by perforating the nozzle plate 411. Each nozzle 410 has a small diameter portion 414 having a discharge hole 413 on the discharge surface 412 of the nozzle plate 411 and a larger diameter formed behind the small diameter portion 414. A two-stage structure with the large diameter portion 415 is adopted. In this embodiment, the small diameter portion 414 and the large diameter portion 415 of the nozzle 410 are each formed in a tapered shape having a circular cross section and a smaller diameter on the counter electrode side. , The nozzle diameter) is, for example, 10 μm, and the inner diameter of the open end of the large diameter portion 415 farthest from the small diameter portion 414 is, for example, 75 μm.

  On the surface opposite to the ejection surface 412 of the nozzle plate 411, a charging electrode 416 made of a conductive member such as nickel, for charging the liquid L in the nozzle 410 is provided. In the present embodiment, the charging electrode 416 extends to the inner peripheral surface 417 of the large-diameter portion 415 of the nozzle 410 and comes into contact with the ink L in the nozzle.

  Further, the charging electrode 416 is connected to a charging voltage power source 418 as an electrostatic voltage applying unit that applies an electrostatic voltage that generates an electrostatic attraction force, and the single charging electrode 416 includes all the nozzles 410. When the electrostatic voltage is applied to the charging electrode 416 from the charging voltage power source 418, the liquid L in all the nozzles 410 is charged at the same time, and the liquid ejection head 402 and the counter electrode 403 are in contact with the liquid L inside. In particular, an electrostatic attraction force is generated between the liquid L and the substrate K.

  A body layer 419 is provided behind the charging electrode 416. A portion of the body layer 419 facing the opening end of the large diameter portion 415 of each nozzle 410 is formed with a substantially cylindrical space having an inner diameter substantially equal to the opening end, and each space is a liquid to be discharged. The cavity 420 communicates with L.

  A flexible layer 421 made of a flexible metal thin plate, silicon, or the like is provided behind the body layer 419. The flexible layer 421 defines the liquid ejection head 402 from the outside.

  In the body layer 419, a flow path (not shown) for supplying the liquid L to the cavity 420 is formed. Specifically, the silicon plate as the body layer 419 is etched to provide a cavity 420, a common flow path, and a flow path that connects the common flow path and the cavity 420. A supply pipe (not shown) for supplying the liquid L from a liquid tank (not shown) is connected, and a flow path, a cavity 420, a nozzle 410, etc. are provided by a supply pump (not shown) provided in the supply pipe or by a differential pressure depending on the position of the liquid tank. A predetermined supply pressure is applied to the liquid L.

  Piezo elements 422, which are piezoelectric element actuators as pressure generating means, are provided in portions corresponding to the respective cavities 420 on the outer surface of the flexible layer 421. A driving voltage is applied to the piezoelectric elements 422 to the elements. A drive voltage power source 423 for deforming the device is connected. The piezo element 422 is deformed by the application of a driving voltage from the driving voltage power source 423 to generate a pressure on the liquid L in the nozzle and form a meniscus of the liquid L in the discharge hole 413 of the nozzle 410. . In addition to the piezoelectric element actuator as in the present embodiment, for example, an electrostatic actuator, a heating element, or the like can be adopted as the pressure generating means.

  The charging voltage power source 418 for applying an electrostatic voltage to the driving voltage power source 423 and the charging electrode 416 is connected to the operation control means 424, and is controlled by the operation control means 424, respectively.

  In this embodiment, the operation control means 424 is composed of a computer in which a CPU 425, a ROM 426, a RAM 427, etc. are connected by a BUS (not shown). The CPU 425 is based on a power control program stored in the ROM 426. The power supply 418 and each drive voltage power supply 423 are driven to discharge the liquid L as ink from the discharge hole 413 of the nozzle 410.

  In this embodiment, the liquid repellent layer 428 for suppressing the oozing of the liquid L from the ejection holes 413 is disposed on the ejection surface 412 other than the ejection holes 413 on the ejection surface 412 of the nozzle plate 411 of the liquid ejection head 402. It is provided on the entire surface. For the liquid repellent layer 428, for example, a material having water repellency is used if the liquid L is aqueous, and a material having oil repellency is used if the liquid L is oily. Fluorine resins such as hexafluoropropylene), PTFE (polytetrafluoroethylene), fluorine siloxane, fluoroalkylsilane, and amorphous perfluoro resin are often used, and a film is formed on the discharge surface 412 by a method such as coating or vapor deposition. Has been. The liquid repellent layer 428 may be formed directly on the ejection surface 412 of the nozzle plate 411 or may be formed through an intermediate layer in order to improve the adhesion of the liquid repellent layer 428. .

  Below the liquid discharge head 402, a plate-like counter electrode 403 that supports the substrate K is disposed in parallel to the discharge surface 412 of the liquid discharge head 402 and spaced apart by a predetermined distance. The separation distance between the counter electrode 403 and the liquid ejection head 402 is appropriately set within a range of about 0.1 mm to 3 mm.

  In this embodiment, the counter electrode 403 is grounded and is always maintained at the ground potential. Therefore, when an electrostatic voltage is applied to the charging electrode 416 from the charging voltage power source 418, an electric field is generated between the liquid L in the ejection hole 413 of the nozzle 410 and the opposing surface of the counter electrode 403 facing the liquid ejection head 402. Has come to occur. Further, when the charged droplet D lands on the substrate K, the counter electrode 403 releases the electric charge by grounding. On the contrary, a configuration may be adopted in which an electrostatic voltage is applied to the electrode 403 on the substrate side and the electrode 416 in contact with the liquid L is grounded.

  The counter electrode 403 or the liquid ejection head 402 is provided with positioning means (not shown) for positioning the liquid ejection head 402 and the substrate K by relatively moving them. The droplet D discharged from each nozzle 410 can be landed on the surface of the substrate K at an arbitrary position.

  Next, a preferred embodiment of the ink jet head (droplet discharge head) preferably used in the present invention will be described below with reference to the drawings. However, the present invention is not limited to these.

  As an example of the ink jet head used in the present invention, a multi-nozzle head 500 is shown in FIG. The multi-nozzle head 500 includes a nozzle plate 531, a body plate 532, and a piezoelectric element 533. The nozzle plate 531 is a silicon substrate or a silicon oxide substrate having a thickness of about 150 μm to 300 μm. A plurality of nozzles 501 are formed on the nozzle plate 531, and the plurality of nozzles 501 are arranged in a line.

  The body plate 532 is a silicon substrate having a thickness of about 200 μm to 500 μm. An ink supply port 601, an ink storage chamber 602, a plurality of ink supply paths 603, and a plurality of pressure chambers 604 are formed in the body plate 532.

  The ink supply port 601 is a circular through hole having a diameter of about 400 μm to 1500 μm.

  The ink storage chamber 602 is a groove having a width of about 400 μm to 1000 μm and a depth of about 50 μm to 200 μm.

  The ink supply path 603 is a groove having a width of about 50 μm to 150 μm and a depth of about 30 μm to 150 μm. The pressure chamber 604 is a groove having a width of about 150 μm to 350 μm and a depth of about 50 μm to 200 μm.

  The nozzle plate 531 and the body plate 532 are joined to each other, and in the joined state, the nozzle 501 of the nozzle plate 531 and the pressure chamber 604 of the body plate 532 are in a one-to-one correspondence. .

  When ink is supplied to the ink supply port 601 in a state where the nozzle plate 531 and the body plate 532 are joined, the ink is temporarily stored in the ink storage chamber 602, and then each ink supply from the ink storage chamber 602. Each pressure chamber 604 is supplied through a passage 603.

  The piezoelectric element 533 is bonded to a position corresponding to the pressure chamber 604 of the body plate 532. The piezoelectric element 533 is an actuator composed of PZT and an electrode, and is deformed when a voltage is applied to discharge ink inside the pressure chamber 604 from the nozzle 501.

  Next, an example of a cross-sectional view of the multi-nozzle head 500 is shown in FIG. Although not shown in FIG. 3, a borosilicate glass plate 534 (see FIG. 4) is interposed between the nozzle plate 531 and the body plate 532. Further, a charging electrode (not shown) for applying an electrostatic voltage to the liquid inside the nozzle is provided.

  As shown in FIG. 4, one nozzle 501 and one pressure chamber 604 are formed corresponding to one piezoelectric element.

  In the nozzle plate 531, a step is formed in the nozzle 501, and the nozzle 501 includes a lower step portion 501a and an upper step portion 501b. Both the lower step 501a and the upper step 501b have a cylindrical shape, and the diameter D1 (the distance in the left-right direction in FIG. 4) of the lower step 501a is smaller than the diameter D2 (the distance in the left-right direction in FIG. 3) of the upper step 501b. It has become.

  The lower part 501a of the nozzle 501 is a part that directly ejects ink circulated from the upper part 501b. The lower step portion 501a has a diameter D1 of 1 μm to 10 μm and a length L (a distance in the vertical direction in FIG. 4) of 1.0 μm to 5.0 μm. The reason why the length L of the lower step portion 501a is limited to the range of 1.0 μm to 5.0 μm is that the ink landing accuracy can be remarkably improved.

  On the other hand, the upper portion 501b of the nozzle 501 is a portion for allowing the ink flowing from the pressure chamber 604 to flow to the lower portion 501a, and its diameter D2 is 10 μm to 60 μm.

  The lower limit of the diameter D2 of the upper part 501b is limited to 10 μm or more. If the diameter D2 is less than 10 μm, the flow resistance of the upper part 501b cannot be ignored with respect to the flow resistance of the entire nozzle 501 (the lower part 501a and the upper part 501b). This is because the ink ejection efficiency tends to decrease.

  On the other hand, the upper limit of the diameter D2 of the upper step 501b is limited to 60 μm or less. The larger the diameter D2 of the upper step 501b, the weaker the lower step 501a as the ink ejection site (the lower step 501a increases in area). This is because the mechanical strength is reduced), and the ink is easily deformed when ejected, and as a result, the ink landing accuracy is lowered. That is, when the upper limit of the diameter D2 of the upper step portion 501b exceeds 60 μm, the deformation of the lower step portion 501a becomes very large as the adhesive liquid is discharged, and the landing accuracy is suppressed within a specified value (= 0.5 °). This is because there is a possibility that it will not be possible.

  A borosilicate glass plate 534 having a thickness of about several hundred μm is provided between the nozzle plate 531 and the body plate 532, and the borosilicate glass plate 534 has an opening for communicating the nozzle 501 and the pressure chamber 604. A portion 534a is formed. The opening 534 a is a through-hole that communicates with the pressure chamber 604 and the upper portion 501 b of the nozzle 501, and is a part that functions as a flow path through which ink flows from the pressure chamber 604 toward the nozzle 501. The pressure chamber 604 is a portion that applies pressure to ink inside the pressure chamber 604 in response to deformation of the piezoelectric element 533.

  In the multi-nozzle head 500 having the above configuration, when the piezoelectric element 533 is deformed, pressure is applied to the ink inside the pressure chamber 604, and the ink flows from the pressure chamber 604 through the opening 534 a of the borosilicate glass plate 534. Thus, the nozzle 501 is reached and finally discharged from the lower step portion 501a of the nozzle 501.

  As an aspect of the ink jet recording apparatus according to the present invention, a base electrode is provided at a position facing the nozzle plate 531 of the multi-nozzle head 500 (not shown), and the nozzle 501 and the base electrode An electrostatic voltage can be applied between them.

  Therefore, a liquid droplet ejection head capable of efficiently ejecting liquid droplets can be obtained by a synergistic effect between the application of pressure to the liquid by the piezoelectric element and the electrostatic attraction force to the liquid by the charging electrode. In other words, when the electrostatic attraction force does not work, electrostatic attraction is effective even when ejecting minute droplets that cannot reach the normal landing position due to the flight speed being reduced due to the air resistance during flight. Due to the action of force, it is possible to land at a regular landing position with high accuracy, and a pattern having a good shape can be formed.

  In the present invention, when a linear pattern is formed by an inkjet apparatus, so-called thinning drawing (a method of forming a linear pattern by first arranging droplets at intervals that do not contact each other and then filling the intervals) A method of forming a linear pattern by continuously arranging droplets without performing the above is preferably used. When this method is used, it is said that disconnection (interruption of the line) or overflow of ink from the pattern often occurs when forming a linear pattern. By controlling the physical properties and changing the surface physical properties in accordance with the ink physical properties to be used, the above-described problems can be solved without performing thinning drawing that requires complicated control.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated in detail, this invention is not limited to these.

Example 1
After mixing the main component of EPOTEC 330 (manufactured by Epoxy Technology), which is an epoxy adhesive, and γ-butyrolactone so as to have a mass ratio of 1: 3, the curing agent of EPOTECH 330 becomes 2.5% by mass of the total. Was added as follows. The obtained ink was filtered through a 0.45 μm filter to prepare an insulating ink.

  After performing surface cleaning by performing oxygen plasma treatment on a silicon substrate, insulating ink is applied by a spin coat method and dried in a thermostat set at 150 ° C. for 60 minutes to insulate on the substrate. A layer was formed.

  A solution in which the coupling agent was diluted with a solvent was prepared. The types of coupling agents and solvent types are shown in the following table (coupling agent concentrations are all 0.5% by mass).

  T1770: triethoxy-1H, 1H, 2H, 2H-tridecafluoro-n-octylsilane (manufactured by Tokyo Chemical Industry Co., Ltd.)

KBM-7103: trifluoropropyltrimethoxysilane (manufactured by Shin-Etsu Silicone)
CF ₃ CH ₂ CH ₂ Si (OCH ₃ ) ₃
KBM-202SS: Diphenyldimethoxysilane (manufactured by Shin-Etsu Silicone)

KBM-3063: Hexyltrimethoxysilane (manufactured by Shin-Etsu Silicone)
CH ₃ (CH ₂ ) ₅ Si (OCH ₃ ) ₃
KBM-602: N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane (manufactured by Shin-Etsu Silicone)

  KBM-573: N-phenyl-3-aminopropyltrimethoxysilane (manufactured by Shin-Etsu Silicone)

KBM-803: 3-mercaptopropyltrimethoxysilane (manufactured by Shin-Etsu Silicone)
(CHO ₃ ) ₃ SiC ₃ H ₆ SH
KBM-3103: Decyltrimethoxysilane (manufactured by Shin-Etsu Silicone)
CH ₃ (CH ₂ ) ₉ Si (OCH ₃ ) ₃
KR 44: isopropyl-tri (N-aminoethyl-aminoethyl) titanate (manufactured by Ajinomoto Fine Techno Co., Ltd.)
_{i-C 3 H 7 O-} Ti [-O- (CH 2) 2 -NH- (CH 2) 2 -NH 2] 3
KR 41B: (Ajinomoto Fine Techno Co., Ltd.)
_{(I-C 3 H 7 O-} ) 4 Ti [(P (OC 8 H 17) 2 OH) 2]
KR 46B: (Ajinomoto Fine Techno Co., Ltd.)
(C ₈ H ₁₇ O—) ₄ Ti [(P (OC ₁₃ H ₂₇ ) ₂ OH) ₂ ]
KR 55: (Ajinomoto Fine Techno Co., Ltd.)

  KR 9SA: (Ajinomoto Fine Techno Co., Ltd.)

  KR TTS: (Ajinomoto Fine Techno Co., Ltd.)

PC-605: Titanium oligomer compound (Orgatics PC-605) (Matsumoto Fine Chemical Co., Ltd.)
TC-750: Titanium diisopropoxybis (ethyl acetoacetate) (manufactured by Matsumoto Fine Chemical Co., Ltd.)
_{(I-C 3 H 7 O} ) 2 Ti (C 6 H 9 O 3) 2
TC-200: Titanium dioctyloxybis (octylene glycolate) (manufactured by Matsumoto Fine Chemical Co., Ltd.)
(C ₈ H ₁₇ O) ₂ Ti (O ₂ C ₈ H ₁₇ ) ₂
TPHS: Polyhydroxytitanium stearate (Matsumoto Fine Chemical Co., Ltd.)

ZC-580: zirconium dibutoxybis (ethyl acetoacetate) (manufactured by Matsumoto Fine Chemical Co., Ltd.)
_{Zr (O-n-C 4} H 9) 2 (C 6 H 9 O 3) 2
ZB-320: zirconium tributoxy monostearate (Matsumoto Fine Chemical Co., Ltd.)
_{Zr (O-n-C 4} H 9) 3 (OCOC 17 H 35)
AL-M: Alkyl acetoacetate aluminum diisopropylate (manufactured by Ajinomoto Fine Techno Co., Ltd.)

  After immersing the silicon substrate on which the insulating layer was formed in these coupling agent solutions, various coupling agent films were formed on the insulating layer by drying for 20 minutes in a thermostatic bath set at 100 ° C.

  Next, an ink prepared by adding pure water and ethylene glycol to a silver nanoparticle-containing ink (AGIN-W4A manufactured by Sumitomo Electric Industries) to have a viscosity at 25 ° C. of 5 mPa · s and a surface tension of 30 mN / m is inkjet. It was prepared as a silver ink. The silver ink pattern is ejected from the head (nozzle diameter 10 μm) using the ink jet apparatus (electrostatic / piezoelectric ink jet apparatus) described in FIGS. Formed. The injection frequency and discharge voltage of the apparatus, and the relative movement speed of the head and the substrate were appropriately adjusted so that the pattern shape was a shape in which 20 linear patterns having a line width of 30 μm and a length of 1 mm were arranged at intervals of 50 μm.

  The substrate on which the pattern was formed was baked for 30 minutes in a thermostat at 150 ° C. to obtain a sample on which a conductive film pattern was formed (FIG. 5).

  The following evaluation was performed about the sample in which the electrically conductive film pattern was formed.

(Conductive pattern shape)
The sample on which the conductive film pattern was formed was observed with a microscope, and the shape of the conductive pattern (the pattern of the conductive layer) was evaluated in three stages according to the following criteria.
A: The variation in line width was small, and the formed pattern shape was good.
Δ: Although there was a variation in line width, there was no disconnection or a portion that was too wet and shorted with an adjacent line.
X: Many portions where the conductive ink was greatly wetted and short-circuited with adjacent lines or where the lines were interrupted were observed.

(Adhesion)
The adhesion was evaluated according to the following criteria by a tape peeling test in accordance with the cross-cut method shown in Japanese Industrial Standard JIS K 5600-5-6, and the results were shown in three stages of ◯ Δ ×.
○: Adhesiveness is good (corresponding to cross-cut test result classification 0)
Δ: Medium adhesion (corresponding to cross-cut test result classification 1-2)
X: Adhesion is poor (corresponds to test result classification 3 of the cross-cut method or worse)
The results are shown in Table 2.

  As is apparent from the results shown in Table 2, by forming the coupling agent film of the present invention on the base material, the pattern of the conductive layer formed by the arrangement of the conductive ink can be obtained with a good pattern shape. Further, it can be seen that the adhesion between the insulating layer and the conductive layer can be improved.

Example 2
(Insulating ink pattern formation)
The insulating ink produced in Example 1 was ejected onto a silicon substrate by an inkjet apparatus in the same manner as in Example 1, and then dried at 150 ° C. for 60 minutes to form an insulating layer pattern on the substrate. .

(Coupling agent treatment)
Next, various coupling agent films were formed on the insulating layer forming substrate by performing immersion treatment in a coupling agent solution and drying in the same manner as in Example 1.

  Next, in the same manner as in Example 1, a silver ink pattern was formed on the insulating layer pattern on which the base material coupling agent film was formed by an ink jet apparatus, dried, and a linear pattern as shown in FIG. Formed. The shape of the linear pattern of the silver ink was good, and the adhesion was also good.

  For comparison, an attempt was made to form a similar silver ink pattern on an insulating layer-formed substrate that was not treated with a coupling agent. However, there were many portions where the linear pattern was interrupted or widely spread. A linear pattern having a good shape could not be formed.

Example 3
A pattern in which two conductive patterns were laminated as shown in FIG. 7 was formed by the following steps (the contents of the steps are in accordance with the methods described in Examples 1 and 2).
1) Insulating ink is placed on a silicon substrate and dried to form a first insulating layer 2) A coupling layer is formed on the surface of the first insulating layer and dried 3) Conductive ink is placed by an inkjet method 4) Firing And drying to form the first conductive layer 5) disposing the insulating ink and drying to form the second insulating layer 6) forming a coupling layer on the surface of the second insulating layer, and drying 7) inkjetting the conductive ink 8) Firing and drying to form the second conductive layer The conductive pattern formed by the above steps has good adhesion, insulation between adjacent wiring lines, and further, the first conductive layer and the second conductive layer. Insulation between the conductive layers was also ensured.

  On the other hand, in the case of forming the two-layer laminated pattern in the same manner except that 2) and 6) (coupling layer forming step) are omitted from the above steps, disconnection due to disconnection of the conductive layer (conductivity failure), Leakage (short circuit) between adjacent lines and peeling of wiring due to poor adhesion were observed everywhere.

DESCRIPTION OF SYMBOLS 1 Bottom plate 2 Horizontal guide rail 3 Guide rail support stand 4 Support stand which supports a base material 5 Maintenance apparatus 6 Vertical guide rail 7 Carriage 8, 11, 402 Inkjet recording head 401 Droplet discharge apparatus 403 Counter electrode 410, 501 Nozzle 416 Charging Electrode 500 Multi-nozzle head 533 Piezoelectric element 604 Pressure chamber 5001 Base material (silicon base material)
5002 Insulating layer 5003 Coupling agent layer 5004 Conductive layer (pattern)
6001 Base material (silicon base material)
6002 Insulating layer (pattern)
6003 Coupling agent layer 6004 Conductive layer (pattern)
7001 Base material (silicon base material)
7002 First insulating layer 7003 First coupling agent layer 7004 First conductive layer (pattern)
7012 2nd insulating layer 7013 2nd coupling agent layer 7014 2nd conductive layer (pattern)

Claims (15)

A substrate;
An insulating layer formed by disposing an insulating ink on the substrate;
On the insulating layer, a conductive layer formed by disposing conductive ink in a predetermined pattern by an inkjet device;
In the conductive film pattern having at least
A coupling agent film formed on the insulating layer by at least one coupling agent selected from a silane coupling agent not containing a fluorine atom, a titanium coupling agent, a zirconia coupling agent, and an aluminum coupling agent. A conductive film pattern comprising:   The conductive film pattern according to claim 1, wherein the insulating layer is disposed on the entire surface of the base material.   The conductive film pattern according to claim 1, wherein the insulating layer is formed by disposing insulating ink in a predetermined pattern by an ink jet apparatus. The substrate is a semiconductor substrate having a plurality of electrode regions;
The conductive film pattern according to claim 3, wherein the conductive film pattern connects the plurality of electrode regions.   The conductive film pattern according to claim 1, wherein the base material has a conductive region and a non-conductive region.   The conductive film pattern according to claim 5, wherein the base material is a base material on which a predetermined pattern is formed using a conductive ink.   The inkjet apparatus includes a nozzle plate having discharge holes, a pressure chamber communicating with the discharge holes, a pressure generating element that causes a pressure fluctuation in the liquid in the pressure chamber, and a driving voltage applying unit that applies a voltage to the pressure generating element. The conductive film pattern according to claim 1, wherein the conductive film pattern is a device that discharges droplets from a droplet discharge head.   The conductive film pattern according to claim 7, wherein the ink jet apparatus further includes an electrostatic voltage applying unit, and the liquid droplets are ejected using an electrostatic force in addition to the pressure fluctuation.   The conductive film pattern according to claim 1, wherein the conductive ink has a catalytic ability for electroless plating.   10. The coupling agent according to claim 1, wherein the coupling agent is at least one coupling agent selected from a titanium coupling agent, a zirconia coupling agent, and an aluminum coupling agent. The electrically conductive film pattern of description. Forming an insulating layer by disposing an insulating ink on the substrate;
On the insulating layer, a coupling agent film is formed with at least one coupling agent selected from a silane coupling agent not containing a fluorine atom, a titanium coupling agent, a zirconia coupling agent, and an aluminum coupling agent. Process,
Forming a conductive layer on the coupling agent film by disposing a conductive ink in a predetermined pattern by an ink-jet method.   The method for forming a conductive film pattern according to claim 11, wherein the step of forming the insulating layer is a step of disposing an insulating ink on a substrate by an inkjet method.   The inkjet method includes a nozzle plate having discharge holes, a pressure chamber communicating with the discharge holes, a pressure generating element that causes a pressure fluctuation in the liquid in the pressure chamber, and a driving voltage applying unit that applies a voltage to the pressure generating element. The method for forming a conductive film pattern according to claim 11, wherein the method is an inkjet method in which droplets are ejected from a droplet ejection head.   The conductive film pattern according to claim 13, wherein the inkjet method further includes an electrostatic voltage applying unit, and the droplets are ejected using an electrostatic force in addition to the pressure fluctuation. Forming method.   15. The coupling agent according to any one of claims 11 to 14, wherein the coupling agent is at least one coupling agent selected from a titanium coupling agent, a zirconia coupling agent, and an aluminum coupling agent. Forming a conductive film pattern.

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