JP2006140376A - Forming method for conductive pattern - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a forming method for conductive patterns which forms a conductive pattern having no variation of its line width and its line space, even if a circuit is fine, without receiving such constraints as its cost, the workability required when creating a substrate for it, the selection of the composition constituting an insulating layer for it, and the selection of an electrode material for it. <P>SOLUTION: The forming method for conductive patterns includes a lipophilic-pattern forming process of forming a lipophilic pattern on the substrate which has on a base material an insulating layer containing inorganic particles and having a hydrophilic property, and includes a conductive-pattern forming process of so feeding a fluidic electrode material to the substrate, whereon the lipophilic pattern has been formed in the lipophilic-pattern forming process as to form a conductive pattern. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a method for forming a conductive pattern formed on a substrate such as a circuit board.

  Conventionally, as a method for forming a conductive pattern on a substrate, a circuit shape is generally patterned by a photolithographic technique.

  The photolithographic technique is a method in which a photosensitive resist is applied onto a metal thin film such as copper or aluminum to be patterned, exposed and developed through a photomask, and then the exposed thin film portion is dry etched or wet etched. Usually, after that, the resist is peeled off, and further, the material is formed into a film, and then the photolithography process is repeated.

  However, in the method using such a photolithographic technique, it is necessary to go through various steps such as metal plating on the substrate, formation of a photoresist layer, exposure, development, etc., and the manufacturing method is complicated and costly. In some cases, problems may occur. Further, a large amount of waste liquid generated during development is harmful, and there is also an environmental problem such as a need to perform processing in order to discharge it to the environment.

  On the other hand, with the widespread use of information terminals, there is an increasing need for flat panel displays as computer displays. In addition, with the development of computerization, information that has been provided on paper media in the past has been digitized and provided more and more. As a mobile display medium that is thin, light, and easy to carry, electronic paper or digital The need for paper is increasing, and there is an increasing demand for durability and a large area of a conductive pattern having a line width of about 2 μm to 20 μm and a relatively low degree of integration compared to a semiconductor element. .

  In response to the above problems, a hydrophilic support having a photoactive group is brought into contact with a hydrophobic support to form an image-like energy to form a hydrophilic pattern. A method for forming a conductive pattern in which an electrode material is adsorbed on a pattern has been proposed (see, for example, Patent Document 1).

In addition, by preparing a substrate having a wettability changing layer whose surface characteristics are changed by the action of the photocatalyst and irradiating energy from a predetermined direction in a state where the photocatalyst is in contact, the surface of the wettability changing layer is lyophilic. A method for producing a conductive pattern by forming a conductive pattern and applying a metal colloid solution as an electrode material to the substrate surface to adhere and solidify the metal colloid solution in a pattern has been proposed (for example, , See Patent Document 2).
JP 2003-289178 A JP 2003-209340 A

  However, the composition described in Patent Document 1 and Patent Document 2, such as a hydrophilic polymer having a photoactive group or an organopolysiloxane whose properties are changed by the action of a photocatalyst, is sufficiently hydrophilic in a hydrophilic region. May not be obtained, and the electrode material may not be sufficiently adsorbed to the substrate. In particular, when a fine circuit having a line width of 10 μm or less is formed, the circuit may be short-circuited or disconnected if the electrode material is not sufficiently adsorbed to the substrate.

  On the other hand, in the methods described in Patent Document 1 and Patent Document 2, if a highly hydrophilic composition is selected, the cost and the workability at the time of substrate production are increased. Similarly, even if an electrode material having a high adsorptive power is selected, there are many restrictions.

  Therefore, the present invention is not limited by cost, workability at the time of substrate production, selection of the composition constituting the insulating layer, selection of electrode material, etc. An object is to provide a method for forming a conductive pattern without variation.

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

The invention according to claim 1 comprises an oleophilic pattern forming step of forming an oleophilic pattern on a substrate containing inorganic particles and having a hydrophilic insulating layer on a substrate;
A conductive pattern forming method comprising forming a conductive pattern by supplying a fluid electrode material to the substrate on which the lipophilic pattern is formed in the lipophilic pattern forming step. is there.

  The invention according to claim 2 is the conductive pattern forming method according to claim 1, wherein the fluid electrode material is hydrophilic.

  The discovery according to claim 3 is the method for forming a conductive pattern according to claim 1, wherein the fluid electrode material is lipophilic.

  The invention according to claim 4 is characterized in that, in the lipophilic pattern forming step, the substrate is imagewise exposed to form a lipophilic pattern. This is a method for forming a sex pattern.

  According to a fifth aspect of the present invention, in the oleophilic pattern forming step, an oleophilic pattern is formed on the substrate by an ink jet printer that ejects oleophilic ink imagewise. The method for forming a conductive pattern according to any one of the above.

The discovery according to claim 6 includes a dampening water supply step of supplying dampening water to the substrate on which the lipophilic pattern is formed in the lipophilic pattern formation step,
6. The conductive pattern forming step of forming a conductive pattern by supplying a fluid electrode material to a substrate to which dampening water is supplied in the dampening water supplying step. It is a formation method of the electroconductive pattern of any one.

The invention according to claim 7 comprises: an insulating layer containing inorganic particles and having hydrophilicity on a substrate; and an image forming layer provided on the insulating layer and containing lipophilic thermoplastic particles. An oleophilic pattern forming step of forming an oleophilic pattern by imagewise exposing a substrate containing a photothermal conversion material adjacent to the image forming layer or the image forming layer;
A dampening water supply step of supplying dampening water to the substrate on which the lipophilic pattern is formed in the lipophilic pattern formation step;
Including a conductive pattern forming step of supplying a lipophilic fluid electrode material to the substrate supplied with the dampening water in the dampening water supply step to form a conductive pattern on the lipophilic pattern. It is the formation method of the electroconductive pattern characterized.

According to an eighth aspect of the present invention, an oleophilic pattern is formed on an ink jet printer that ejects an oleophilic ink imagewise on a substrate having a hydrophilic insulating layer containing inorganic particles on a substrate. A lipophilic pattern forming step,
A dampening water supply step of supplying dampening water to the substrate on which the lipophilic pattern is formed in the lipophilic pattern formation step;
Including a conductive pattern forming step of supplying a lipophilic fluid electrode material to the substrate supplied with the dampening water in the dampening water supply step to form a conductive pattern on the lipophilic pattern. It is the formation method of the electroconductive pattern characterized.

The invention according to claim 9 includes: an insulating layer containing inorganic particles and having hydrophilicity on a substrate; and an image forming layer provided on the insulating layer and containing lipophilic thermoplastic particles. An oleophilic pattern forming step of forming an oleophilic pattern by imagewise exposing a substrate containing a photothermal conversion material adjacent to the image forming layer or the image forming layer;
A conductive pattern forming step of forming a conductive pattern by supplying a hydrophilic fluid insulating material and a lipophilic fluid electrode material to the substrate on which the lipophilic pattern is formed in the lipophilic pattern forming step. This is a method for forming a conductive pattern.

  According to the invention described in claims 1 to 3, since the lipophilic pattern is formed on the substrate containing inorganic particles and having a hydrophilic insulating layer, the hydrophilicity of the insulating layer is high. When a hydrophilic or oleophilic fluid electrode material is supplied, even if the circuit has a fine conductive pattern that adsorbs more firmly, there is no short circuit or disconnection of the circuit, and cost and board creation It is possible to create a conductive pattern with no variation in line width or line even in a fine circuit without being restricted by the processability of the process, selection of the composition constituting the insulating layer, selection of the electrode material, etc. .

  According to the invention described in claim 4, since the lipophilic pattern is formed by exposing the substrate imagewise, it becomes possible to easily form a fine lipophilic pattern.

  According to the invention described in claim 5, since the oleophilic pattern is formed by the ink jet printer, the manufacturing process can be simplified, the waste of ink for forming the oleophilic pattern is small, and the environmental load is small. it can.

  According to the invention described in claim 6, the dampening water is supplied to the substrate on which the oleophilic pattern is formed, and the fluid electrode material is supplied to the substrate to which the dampening water is supplied to thereby form the conductive pattern. Thus, the fluid electrode material can be more firmly adsorbed.

  According to invention of Claim 7, it has an insulating layer which contains inorganic particles and has hydrophilicity, and an image forming layer provided on the insulating layer and containing lipophilic thermoplastic particles Since the lipophilic pattern is formed by imagewise exposing the image forming layer or the substrate containing the photothermal conversion material adjacent to the image forming layer, the hydrophilicity of the insulating layer becomes high, When a hydrophilic or lipophilic fluid electrode material is supplied, it adheres more firmly, and even with a fine conductive pattern, there is no short circuit or disconnection of the circuit, cost, processability when creating a substrate, insulation Without being restricted by the selection of the composition constituting the conductive layer, the selection of the electrode material, etc., it is possible to create a conductive pattern having no variation in line width and line even in a fine circuit.

  Furthermore, the imagewise exposure is converted into heat by the photothermal conversion material, and the dampening water is supplied to the substrate on which the oleophilic pattern is formed by melting or fusing the oleophilic thermoplastic particles in an imagewise manner. In addition to making the adsorption of the conductive electrode material stronger, it is possible to easily remove the image forming layer that does not contribute to the formation of the conductive pattern, so that the manufacturing process can be simplified.

  According to the invention described in claim 8, since the oleophilic pattern is formed on the substrate containing the inorganic particles and having the hydrophilic insulating layer by the ink jet printer that ejects the oleophilic ink imagewise. When the insulating layer has high hydrophilicity and hydrophilic or lipophilic fluid electrode material is supplied, the insulating layer is more strongly adsorbed, and even in a fine conductive pattern, short circuit or disconnection of the circuit may occur. There is no variation in line width or line even in a fine circuit without being restricted by cost, workability at the time of substrate production, selection of composition constituting insulating layer, selection of electrode material, etc. A conductive pattern can be created.

  Furthermore, since the oleophilic pattern is formed by the ink jet printer, the manufacturing process can be simplified, and the waste of ink for forming the oleophilic pattern can be reduced, and the environmental load can be reduced.

  According to the ninth aspect of the present invention, it has an insulating layer containing inorganic particles and having hydrophilicity, and an image forming layer provided on the insulating layer and containing lipophilic thermoplastic particles. Since the lipophilic pattern is formed by imagewise exposing the image forming layer or the substrate containing the photothermal conversion material adjacent to the image forming layer, the hydrophilicity of the insulating layer becomes high, When a hydrophilic or lipophilic fluid electrode material is supplied, it adheres more firmly, and even with a fine conductive pattern, there is no short circuit or disconnection of the circuit, cost, processability when creating a substrate, insulation Without being restricted by the selection of the composition constituting the conductive layer, the selection of the electrode material, etc., it is possible to create a conductive pattern having no variation in line width and line even in a fine circuit.

  In addition, since a hydrophilic fluid insulating material and an oleophilic fluid electrode material are supplied to a substrate on which a lipophilic pattern is formed to form a conductive pattern, even in a finer conductive pattern, a short circuit of the circuit Or disconnection does not occur.

  Hereinafter, embodiments of the present invention will be described in more detail.

<Base material>
The base material used for the board | substrate of this invention is comprised with glass or a flexible resin-made sheet | seat, for example, can use a plastic film as a sheet | seat. Examples of the plastic film include polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyethersulfone (PES), polyetherimide, polyetheretherketone, polyphenylene sulfide, polyarylate, polyimide, polycarbonate (PC), Examples thereof include films made of cellulose triacetate (TAC), cellulose acetate propionate (CAP), and the like. Thus, by using a plastic film, the weight can be reduced as compared with the case of using a glass substrate, the portability can be improved, and the resistance to impact can be improved.

<Insulating layer>
The insulating layer according to the present invention has an electric resistance of 1 × 10 ⁸ Ω · cm to 1 × 10 ¹⁸ Ω · cm, particularly 1 × 10 ¹² Ω · cm to 1 in order to form a good conductive pattern. It is preferably within the range of × 10 ¹⁸ Ω · cm. The film thickness is generally 50 nm to 3 μm, preferably 100 nm to 1 μm. Thereby, it becomes possible to constitute an excellent conductive pattern.

  Moreover, the insulating layer according to the present invention has a hydrophilic matrix structure or is made hydrophilic by using a water-soluble resin as a main component.

  The hydrophilic matrix structure means a coating film that is formed from an organic binder, an inorganic binder, other film forming materials, and the like and is insoluble in water and exhibits hydrophilicity.

  Examples of the material used for the insulating layer according to the present invention include the following.

(Material that forms hydrophilic matrix structure)
As the material for forming the hydrophilic matrix structure, a metal oxide is preferable. The metal oxide preferably contains fine metal oxide particles, and examples thereof include colloidal silica, alumina sol, titania sol, and other metal oxide sols. The form of the metal oxide fine particles may be spherical, needle-like, feather-like, or any other form. The average particle diameter is preferably 3 to 100 nm, and several metals having different average particle diameters are used. Oxide fine particles can also be used in combination. Further, the surface of the particles may be subjected to a surface treatment.

  The metal oxide fine particles can be used as a binder by utilizing the film forming property. The decrease in hydrophilicity is less than when an organic binder is used, and it is suitable for use in an insulating layer.

  In the present invention, colloidal silica is particularly preferably used among the above. Colloidal silica has the advantage of high film-forming properties even under relatively low temperature drying conditions, and can provide good strength. The colloidal silica that can be used in the present invention preferably includes necklace-shaped colloidal silica, which will be described later, and fine particle colloidal silica having an average particle size of 20 nm or less, and the colloidal silica preferably exhibits alkalinity as a colloidal solution.

  The necklace-like colloidal silica used in the present invention is a general term for an aqueous dispersion of spherical silica whose primary particle diameter is on the order of nm. The necklace-shaped colloidal silica used in the present invention means “pearl necklace-shaped” colloidal silica in which spherical colloidal silica having a primary particle diameter of 10 to 50 nm is bonded to a length of 50 to 400 nm. The pearl necklace shape (that is, a pearl necklace shape) means that an image in a state in which the silica particles of colloidal silica are connected and connected has a shape like a pearl necklace. The bond between the silica particles constituting the necklace-shaped colloidal silica is presumed to be —Si—O—Si— in which —SiOH groups present on the surface of the silica particles are dehydrated. Specific examples of the colloidal silica in the form of necklace include “Snowtex-PS” series manufactured by Nissan Chemical Industries, Ltd., and the product name is “Snowtex-PS-S (average particles in a connected state). "Snowtex-PS-M (the average particle size in the connected state is about 120 nm)" and "Snowtex-PS-L (the average particle size in the connected state is about 170 nm)" The acidic products corresponding to these are “Snowtex-PS-SO”, “Snowtex-PS-MO” and “Snowtex-PS-LO”, respectively.

  By adding necklace-like colloidal silica, it becomes possible to maintain the strength while ensuring the porosity of the layer, and it can be preferably used as a porous material for a hydrophilic matrix. Among these, alkaline “Snowtex PS-S”, “Snowtex PS-M”, and “Snowtex PS-L” are particularly preferable because the strength of the insulating layer is improved.

  Further, it is known that the colloidal silica has a stronger binding force as the particle size is smaller, and in the present invention, it is preferable to use colloidal silica having an average particle size of 20 nm or less, and more preferably 3 to 15 nm. preferable. In addition, as described above, alkaline colloidal silica is particularly preferable because it has an effect of suppressing the occurrence of soiling. Examples of the alkaline colloidal silica having an average particle diameter in this range include, for example, “Snowtex-20 (particle diameter 10-20 nm)”, “Snowtex-30 (particle diameter 10-20 nm)” manufactured by Nissan Chemical Co., Ltd. “Snowtex-40 (particle diameter 10-20 nm)”, “Snowtex-N (particle diameter 10-20 nm)”, “Snowtex-S (particle diameter 8-11 nm)”, “Snowtex-XS (particle diameter) 4-6 nm) ".

  Colloidal silica having an average particle size of 20 nm or less is particularly preferable because it can be further improved in strength while maintaining the porosity of the layer to be formed, when used in combination with the aforementioned necklace-shaped colloidal silica.

  The ratio of colloidal silica / necklace-like colloidal silica having an average particle diameter of 20 nm or less is preferably 95/5 to 5/95, more preferably 70/30 to 20/80, and even more preferably 60/40 to 30/70.

  As a porous material having a hydrophilic matrix structure, porous metal oxide particles having a particle size of less than 1 μm can be contained. As the porous metal oxide particles, the following porous silica, porous aluminosilicate particles, or zeolite particles can be preferably used.

  The porous silica particles are generally produced by a wet method or a dry method. In the wet method, the gel obtained by neutralizing the aqueous silicate solution can be obtained by drying and pulverizing, or by pulverizing the precipitate deposited by neutralization. In the dry method, silicon tetrachloride is burned together with hydrogen and oxygen to obtain silica. These particles can be controlled in their porosity and particle size by adjusting the production conditions. As the porous silica particles, those obtained from a wet gel are particularly preferable.

  The porous aluminosilicate particles are produced, for example, by the method described in JP-A-10-71764. That is, it is an amorphous composite particle synthesized by hydrolysis using aluminum alkoxide and silicon alkoxide as main components. The ratio of alumina to silica in the particles can be synthesized in the range of 1: 4 to 4: 1. Moreover, what was manufactured as composite particle | grains of 3 or more components by adding the alkoxide of another metal at the time of manufacture can be used for this invention. These composite particles can also control the porosity and particle size by adjusting the production conditions.

  The porosity of the particles is preferably 0.5 ml / g or more in terms of pore volume, more preferably 0.8 ml / g or more, and further preferably 1.0 to 2.5 ml / g. preferable. The pore volume is closely related to the water retention of the coating film. The larger the pore volume, the better the water retention, the less likely to get dirty during printing, and the greater the water volume latitude.

  Zeolite is a crystalline aluminosilicate and is a porous body having regular three-dimensional network voids having a pore diameter of 0.3 to 1 nm. The general formula combining natural and synthetic zeolite is expressed as follows:

_{(M1, (M2) 0.5)} m (Al m Si n O 2) (m + n) · xH 2 O
Here, M1 and M2 are exchangeable cations, and M1 is Li ⁺ , Na ⁺ , K ⁺ , Tl ⁺ , Me ₄ N ⁺ (TMA), Et ₄ N ⁺ (TEA), Pr ₄ N ⁺ ( TPA), C ₇ H ₁₅ N ₂ ⁺ , C ₈ H ₁₆ N ^{+ and the} like, and M2 is Ca ²⁺ , Mg ²⁺ , Ba ²⁺ , Sr ²⁺ , C ₈ H ₁₈ N ₂ ^{2+ and the} like. . Further, n ≧ m, and the value of m / n, that is, the Al / Si ratio is 1 or less. The higher the Al / Si ratio, the greater the amount of exchangeable cations and the higher the polarity and therefore the higher the hydrophilicity. A preferable Al / Si ratio is 0.4 to 1.0, and more preferably 0.8 to 1.0. x represents an integer.

As the zeolite particles, synthetic zeolite having a stable Al / Si ratio and a relatively sharp particle size distribution is preferable. For example, zeolite A: Na ₁₂ (Al ₁₂ Si ₁₂ O ₄₈ ) · 27H ₂ O; Al / Si ratio 1.0, zeolite X: Na ₈₆ (Al ₈₆ Si ₁₀₆ O ₃₈₄ ) · 264H ₂ O; Al / Si ratio 0.811, zeolite Y: Na ₅₆ (Al ₅₆ Si ₁₃₆ O ₃₈₄ ) · 250H ₂ O ; Al / Si ratio 0.412 etc. are mentioned.

  By containing highly hydrophilic porous particles having an Al / Si ratio of 0.4 to 1.0, the hydrophilicity of the insulating layer itself is greatly improved and the water amount latitude is widened. Also, fingerprint marks are greatly improved.

  The hydrophilic matrix structure can contain layered clay mineral particles. Examples of the layered mineral particles include kaolinite, halloysite, talc, smectite (montmorillonite, beidellite, hectorite, sabonite, etc.), clay minerals such as vermiculite, mica (mica), chlorite, hydrotalcite, layered polysilicic acid. Examples thereof include salts (kanemite, macatite, ialite, magadiite, kenyaite, etc.). In particular, the higher the charge density of the unit layer (unit layer), the higher the polarity and the higher the hydrophilicity. The charge density is preferably 0.25 or more, more preferably 0.6 or more. Examples of the layered mineral having such a charge density include smectite (charge density 0.25 to 0.6; negative charge), vermiculite (charge density 0.6 to 0.9; negative charge) and the like. In particular, synthetic fluoromica is preferable because it can be obtained with stable quality such as particle size. Among the synthetic fluorine mica, those that are swellable are preferable, and those that are free swell are more preferable.

  Also used are intercalation compounds of the above-mentioned layered minerals (pillar crystals, etc.), those subjected to ion exchange treatment, and those subjected to surface treatment (silane coupling treatment, compounding treatment with organic binder, etc.) can do.

  The size of the plate-like layered mineral particles is the average particle size (of the particles) from the viewpoint of the uniformity and strength of the coating film in the state of being contained in the layer (including the case where the swelling process and the dispersion peeling process have been performed). The maximum length) is preferably less than 1 μm, and the average aspect ratio is preferably 50 or more from the viewpoint of thickening. When the particle size is in the above range, the continuity and flexibility in the planar direction, which are the characteristics of the thin layered particles, are imparted to the coating film, and it is difficult for cracks to occur, and a tough coating film can be obtained in a dry state. Moreover, in the coating liquid containing many particulate matters, sedimentation of particulate matter can be suppressed by the thickening effect of the layered clay mineral.

  The content of the layered mineral particles is preferably 0.1 to 30% by mass, and more preferably 1 to 10% by mass based on the entire layer. In particular, swellable synthetic fluorinated mica and smectite are preferable because they are effective even when added in a small amount. The layered mineral particles may be added as a powder to the coating solution, but in order to obtain a good degree of dispersion even with a simple preparation method (no need for a dispersion step such as media dispersion), the layered mineral particles are used alone. It is preferable to prepare the gel swollen in water and add it to the coating solution.

A silicate aqueous solution can also be used as another additive material for the hydrophilic matrix structure. Alkali metal silicates such as silicate Na, silicate K, and silicate Li are preferred, and the SiO ₂ / M ₂ O ratio is in a range where the pH of the entire coating solution does not exceed 13 when silicate is added. It is preferable to select such that the inorganic particles are not dissolved.

  Further, an inorganic polymer or an organic-inorganic hybrid polymer using a metal alkoxide by a so-called sol-gel method can also be used. The formation of an inorganic polymer or an organic-inorganic hybrid polymer by the sol-gel method is described in, for example, “Application of the sol-gel method” (Sakuo Sakuo / Agne Jofusha) or the above-mentioned book. Known methods described in the literature cited in the above can be used.

(Water-soluble resin)
Examples of the water-soluble resin include polysaccharides, polyethylene oxide, polypropylene oxide, polyvinyl alcohol, polyethylene glycol (PEG), polyvinyl ether, styrene-butadiene copolymer, conjugated diene polymer latex of methyl methacrylate-butadiene copolymer. Examples thereof include resins such as acrylic polymer latex, vinyl polymer latex, polyacrylamide, and polyvinylpyrrolidone. As the water-soluble resin used in the present invention, it is preferable to use a polysaccharide.

  As polysaccharides, starches, celluloses, polyuronic acids, pullulans and the like can be used, but cellulose derivatives such as methyl cellulose salts, carboxymethyl cellulose salts, hydroxyethyl cellulose salts are particularly preferable, and sodium salts and ammonium salts of carboxymethyl cellulose are preferable. More preferred. This is because an effect of forming the surface shape of the insulating layer in a preferable state can be obtained by including the polysaccharide in the insulating layer.

  The surface of the insulating layer preferably has a concavo-convex structure with a pitch of 0.1 to 20 μm like the aluminum grain of the PS plate, and this concavo-convex improves water retention and electrode material retention. Such a concavo-convex structure can be formed by containing an appropriate amount of a filler having an appropriate particle size in a hydrophilic matrix, but the above-mentioned alkaline colloidal silica and the above-mentioned water-soluble are used in the coating solution for the insulating layer. It is preferable that a structure having better electroconductivity pattern formation suitability can be obtained by containing a polysaccharide and forming it by causing phase separation when the insulating layer is applied and dried.

  The shape of the concavo-convex structure (such as pitch and surface roughness) is determined by the type and amount of alkaline colloidal silica, the type and amount of water-soluble polysaccharides, the type and amount of other additives, the solid content concentration of the coating solution, and the wetness. It is possible to appropriately control the film thickness, drying conditions, and the like.

  It is preferable that the water-soluble resin added to the hydrophilic matrix structure is present in a state in which at least a part thereof is water-soluble and can be eluted in water. This is because even if it is a water-soluble material, when it is cross-linked by a cross-linking agent or the like and becomes insoluble in water, its hydrophilicity is lowered, and there is a concern that the ability to create a conductive pattern is deteriorated. Further, it may further contain a cationic resin. Examples of the cationic resin include polyalkylene polyamines such as polyethylene amine and polypropylene polyamine or derivatives thereof, tertiary amino groups and quaternary ammonium groups. Examples thereof include acrylic resin and diacrylamine. The cationic resin may be added in the form of fine particles, and examples thereof include a cationic microgel described in JP-A-6-161101.

  In addition, the coating liquid for the insulating layer according to the present invention can contain a water-soluble surfactant for the purpose of improving coatability and the like, and a surfactant such as Si-based or F-based should be used. However, it is preferable to use a surfactant containing Si element, because there is no fear of causing contamination. The content of the surfactant is preferably 0.01 to 3% by mass, more preferably 0.03 to 1% by mass of the entire insulating layer (solid content as the coating solution).

  In addition, the insulating layer according to the present invention may contain a phosphate. In the present invention, since the coating solution for the insulating layer is preferably alkaline, it is preferable to add the phosphate as trisodium phosphate or disodium hydrogen phosphate. The addition amount of phosphate is preferably 0.1 to 5% by mass and more preferably 0.5 to 2% by mass as an effective amount excluding hydrate.

  Moreover, the photothermal conversion raw material mentioned later can also be contained. As the photothermal conversion material, in the case of a particulate material, the particle size is preferably less than 1 μm.

<Inorganic particles>
The insulating layer according to the present invention contains inorganic particles.

  As the inorganic particles that can be used in the present invention, known metal oxide particles such as silica, alumina, titania and zirconia can be used in order to maintain the electric resistance of the insulating layer. In the case where the insulating layer is formed by a coating process, it is preferable to use porous metal oxide particles in order to suppress sedimentation in the coating solution. As the porous metal oxide particles, the aforementioned porous silica particles and porous aluminosilicate particles can be preferably used.

  Moreover, it can replace with an inorganic particle and the particle | grains coat | covered with the inorganic raw material can also be used.

  Examples of the particles coated with an inorganic material include particles in which organic particles such as polymethylmethacrylate and polystyrene are used as a core material and are coated with inorganic particles having a particle diameter smaller than that of the core material particles. The particle size of the inorganic particles is preferably about 1/10 to 1/100 of the core particles. As the inorganic particles, known metal oxide particles such as silica, alumina, titania, zirconia, etc. can be used. As the coating method, various known methods can be used, but the core material particles and the coating material particles are collided at high speed in the air like a hybridizer to cause the coating material particles to bite into the surface of the core material particles. A dry coating method of fixing and coating can be preferably used.

  The particle size of the inorganic particles or the particles coated with the inorganic material is preferably 1 to 10 μm, more preferably 1.5 to 8 μm, and further preferably 2 to 6 μm. As addition amount of particle | grains, it is preferable that it is 1-50 mass% of the whole insulating layer, and it is more preferable that it is 5-40 mass%. In order to improve hydrophilicity, the insulating layer as a whole preferably has a low content ratio of carbon-containing materials such as organic resins and carbon black, and the total of these materials is preferably less than 9% by mass. More preferably, it is less than 5 mass%.

<Formation of lipophilic pattern>
The formation of the oleophilic pattern comprises an image forming layer provided on the insulating layer and containing lipophilic thermoplastic particles, and a substrate containing a photothermal conversion material adjacent to the image forming layer or the image forming layer. A method of forming an oleophilic pattern by imagewise exposure with an infrared laser (hereinafter referred to as a laser method) and a method of forming an oleophilic pattern by an inkjet printer that ejects an oleophilic ink imagewise on a substrate (hereinafter referred to as a laser method). And an ink jet method) and a method of applying an oleophilic material directly to the surface of the insulating layer like an image (hereinafter referred to as a direct application type).

  Hereinafter, each method will be described.

<< Laser system >>
(Image forming layer)
The laser system has an image forming layer containing lipophilic thermoplastic particles. Examples of the lipophilic thermoplastic particles include heat-meltable particles and / or heat-fusible particles.

(Hot-melting particles)
The heat-meltable particles are particles made of a material that has a low viscosity when melted, and is generally classified as a wax, among thermoplastic materials. The physical properties are preferably a softening point of 40 ° C. or higher and 120 ° C. or lower, a melting point of 60 ° C. or higher and 150 ° C. or lower, from the viewpoint of storage stability and adhesion strength of the electrode material, and a softening point of 40 ° C. or higher and 100 ° C. or lower. More preferably, it is 120 ° C. or lower.

  Examples of usable materials include paraffin, polyolefin, polyethylene wax, microcrystalline wax, and fatty acid wax. These have a molecular weight of about 800 to 10,000, and in order to facilitate emulsification, these waxes can be oxidized to introduce polar groups such as hydroxyl groups, ester groups, carboxyl groups, aldehyde groups, and peroxide groups. In addition, to reduce the softening point and improve workability, these waxes include, for example, stearamide, linolenamide, laurylamide, myristamide, hardened bovine fatty acid amide, palmitoamide, oleic acid amide, rice sugar fatty acid amide, It is also possible to add fatty acid amides or methylolated products of these fatty acid amides, methylene bisstellaramide, ethylene bisstellaramide and the like. Coumarone-indene resin, rosin-modified phenol resin, terpene-modified phenol resin, xylene resin, ketone resin, acrylic resin, ionomer, and copolymers of these resins can also be used.

  Among these, it is preferable to contain any of polyethylene, microcrystalline, fatty acid ester, and fatty acid. Since these materials have a relatively low melting point and a low melt viscosity, high-sensitivity image formation can be performed. Further, since these materials have lubricity, damage when a shearing force is applied to the surface of the substrate is reduced, and resistance to dirt due to scratches or the like is improved.

  The heat-meltable particles are preferably dispersible in water, and the average particle size thereof is preferably 0.01 to 10 μm, more preferably 0 from the viewpoint of prevention of background contamination and resolution of the conductive pattern. .1 to 3 μm.

  Further, the composition of the heat-meltable particles may be continuously changed between the inside and the surface layer, or may be coated with a different material. As a coating method, a known microcapsule formation method, a sol-gel method, or the like can be used.

  As content of the heat-meltable particle | grains in a structural layer, 1-90 mass% of the whole layer is preferable, and 5-80 mass% is more preferable.

(Heat-bonding particles)
Examples of the heat-fusible particles include thermoplastic hydrophobic polymer particles, and there is no specific upper limit for the softening temperature of the thermoplastic hydrophobic polymer particles. It is preferable that the temperature is lower than the decomposition temperature. Moreover, it is preferable that the weight average molecular weight (Mw) of a high molecular weight polymer is the range of 10,000-1,000,000.

  Specific examples of the polymer that constitutes the polymer particles include, for example, diene (co) polymers such as polypropylene, polybutadiene, polyisoprene, and ethylene-butadiene copolymer, styrene-butadiene copolymer, Synthetic rubbers such as methyl methacrylate-butadiene copolymer, acrylonitrile-butadiene copolymer, polymethyl methacrylate, methyl methacrylate- (2-ethylhexyl acrylate) copolymer, methyl methacrylate-methacrylic acid copolymer, methyl acrylate- ( (N-methylolacrylamide) copolymer, (meth) acrylic acid ester such as polyacrylonitrile, (meth) acrylic acid (co) polymer, polyvinyl acetate, vinyl acetate-vinyl propionate copolymer, vinyl acetate-ethylene copolymer Vinyl such as polymer Ester (co) polymer, vinyl acetate - (2-ethylhexyl acrylate) copolymers, polyvinyl chloride, polyvinylidene chloride, polystyrene and copolymers thereof. Of these, (meth) acrylic acid esters, (meth) acrylic acid (co) polymers, vinyl ester (co) polymers, polystyrene, and synthetic rubbers are preferably used.

  The polymer particles may be made of a polymer polymer polymerized by any known method such as emulsion polymerization, suspension polymerization, solution polymerization, and gas phase polymerization. As a method of granulating the polymer polymer polymerized by the solution polymerization method or the gas phase polymerization method, a method of spraying a solution in an organic solvent of the polymer polymer into an inert gas and drying to form particles, Examples thereof include a method in which a high molecular weight polymer is dissolved in an organic solvent immiscible in water, this solution is dispersed in water or an aqueous medium, and the organic solvent is distilled off to form particles.

  In any of the methods, the heat-meltable particles and the heat-fusible particles may be used as a dispersant or a stabilizer in polymerization or granulation as necessary, for example, sodium lauryl sulfate, sodium dodecylbenzenesulfonate, polyethylene glycol, etc. Alternatively, a water-soluble resin such as a surfactant or polyvinyl alcohol may be used. Further, triethylamine, triethanolamine or the like may be contained.

  The thermoplastic particles are preferably dispersible in water, and the average particle diameter is preferably 0.01 to 10 μm, more preferably 0.1 to 3 μm.

  Further, the thermoplastic particles may be continuously changed in composition between the inside and the surface layer, or may be coated with different materials. As a coating method, a known microcapsule formation method, a sol-gel method, or the like can be used.

  As content of the thermoplastic particle in a structure layer, 1-90 mass% of the whole layer is preferable, and 5-80 mass% is more preferable.

(Water-soluble material)
The image forming layer according to the present invention may further contain a water-soluble material. By including the water-soluble material, the removability can be improved when the image forming layer in the unexposed area is removed using dampening water or an electrode material.

  As the water-soluble material, the water-soluble resins mentioned as materials that can be contained in the insulating layer can be used, but it is preferable to use saccharides as the image-forming functional layer of the present invention, and particularly use oligosaccharides. Is preferred. Since the oligosaccharide quickly dissolves in water, the image forming layer in the unexposed area can be removed very quickly, and the loss of the substrate on which the conductive pattern is formed can be suppressed. In addition, the oligosaccharide can maintain the good suitability for forming the conductive pattern of the insulating layer without concern about reducing the hydrophilicity of the insulating layer. An oligosaccharide is a crystalline substance that is soluble in water and generally sweet, and is obtained by dehydrating and condensing several monosaccharides by glycosidic bonds. Oligosaccharide is a kind of o-glycoside with sugar as aglycone, so it is easily hydrolyzed with acid to produce monosaccharide, and disaccharide, trisaccharide, tetrasaccharide, pentasaccharide, etc. depending on the number of molecules of monosaccharide produced are categorized. The oligosaccharide in the present invention refers to those from disaccharide to decasaccharide.

  These oligosaccharides are roughly classified into reducing oligosaccharides and non-reducing oligosaccharides depending on the presence or absence of a reducing group, and are composed of a homooligosaccharide composed of a single monosaccharide and two or more types of monosaccharides. It is also classified as a configured hetero-oligosaccharide. Oligosaccharides exist naturally as free or glycosides and are also obtained by partial hydrolysis of polysaccharides with acids or enzymes. Various oligosaccharides are also produced by glycosyl transfer by other enzymes.

  Oligosaccharides often exist as hydrates in a normal atmosphere. Further, the melting point is different between hydrate and anhydride, and examples are as shown in Table 1.

  In the present embodiment, it is preferable to coat and form a saccharide-containing layer with an aqueous solution. Therefore, when formed from an aqueous solution, the oligosaccharide present in the layer is an oligosaccharide that forms a hydrate. The melting point is considered to be that of the hydrate. Thus, since it has a relatively low melting point, the oligosaccharide also melts in the temperature range in which the hot melt particles melt or in the temperature range in which the heat melt particles fuse, and the porous insulating layer of the heat melt particles It does not hinder the formation of a conductive pattern such as melt penetration into the resin or fusion of heat fusion particles.

  Among oligosaccharides, trehalose, which is relatively high in purity, can be obtained industrially at low cost, and has a very low hygroscopicity and a hydrophilic electrode despite its high solubility in water. Both the adsorptivity and storage stability of the material are very good.

  In addition, when oligosaccharide hydrate is melted by heat and solidified after removing water of hydration (for a short time after solidification), it becomes an anhydrous crystal, but trehalose has a melting point of anhydride more than hydrate. It is characteristic that it is higher than 100 ° C. This means that the exposed portion is melted by infrared exposure and immediately after re-solidification, the exposed portion is in a state of being difficult to melt at a high melting point, and is effective in causing image defects during exposure such as banding. In order to achieve the object of the present invention, trehalose is particularly preferable among oligosaccharides.

As content of the oligosaccharide in a structure layer, 1-90 mass% of the whole layer is preferable, and 10-80 mass% is more preferable.
(Photothermal conversion material)
In the laser system, the photothermal conversion material is contained in the image forming layer or a layer adjacent to the image forming layer.

  The following materials can be added as the photothermal conversion material.

  General infrared absorbing dyes such as cyanine dyes, croconium dyes, polymethine dyes, azurenium dyes, squalium dyes, thiopyrylium dyes, naphthoquinone dyes, anthraquinone dyes, organic compounds such as phthalocyanine dyes and naphthalocyanine dyes , Azo-based, thioamide-based, dithiol-based, and indoaniline-based organometallic complexes. Specifically, JP-A-63-139191, JP-A-64-33547, JP-A-1-160683, JP-A-1-280750, JP-A-1-293342, JP-A-2-2074, Kaihei 3-26593, JP-A-3-30991, JP-A-3-34891, JP-A-3-36093, JP-A-3-36094, JP-A-3-36095, JP-A-3-42281, JP-A-3-42281 Examples thereof include compounds described in JP-A-3-97589, JP-A-3-103476, and the like. These can be used alone or in combination of two or more.

  Examples of the pigment include carbon, graphite, metal, metal oxide and the like. As carbon, it is particularly preferable to use furnace black or acetylene black. The particle size (d50) is preferably 100 nm or less, and more preferably 50 nm or less.

  As the graphite, particles having a particle size of 0.5 μm or less, preferably 100 nm or less, more preferably 50 nm or less can be used.

  As the metal, any metal having a particle diameter of 0.5 μm or less, preferably 100 nm or less, and more preferably 50 nm or less can be used. The shape may be any shape such as a spherical shape, a piece shape, or a needle shape. Colloidal metal particles (Ag, Au, etc.) are particularly preferable.

As the metal oxide, a material that is black in the visible light region, or a material that has conductivity or is a semiconductor can be used. Examples of the former include black iron oxide (Fe ₃ O ₄ ) and black composite metal oxides containing two or more of the aforementioned metals. Examples of the latter include Sb-doped SnO ₂ (ATO), Sn-added In ₂ O ₃ (ITO), TiO ₂ , TiO ₂ reduced TiO (titanium oxynitride, generally titanium black) Etc. Further, it is also possible to use those obtained by coating the core material _{(BaSO 4, TiO 2, 9Al} 2 O 3 · 2B 2 O, K 2 O · nTiO 2 , etc.) in these metal oxides. These particle sizes are 0.5 μm or less, preferably 100 nm or less, and more preferably 50 nm or less.

  Among these photothermal conversion materials, black composite metal oxides containing two or more metals are more preferable materials, specifically, Al, Ti, Cr, Mn, Fe, Co, Ni, Cu, It is a composite metal oxide composed of two or more metals selected from Zn, Sb, and Ba. These are disclosed by methods disclosed in JP-A-8-27393, JP-A-9-25126, JP-A-9-237570, JP-A-9-241529, JP-A-10-231441, and the like. Can be manufactured.

  The composite metal oxide is particularly preferably a Cu-Cr-Mn-based or Cu-Fe-Mn-based composite metal oxide. In the case of a Cu—Cr—Mn system, it is preferable to perform the treatment disclosed in JP-A-8-27393 in order to reduce the elution of hexavalent chromium. These composite metal oxides are colored with respect to the amount added, that is, they have good photothermal conversion efficiency.

  These composite metal oxides preferably have an average primary particle diameter of 1 μm or less, and more preferably have an average primary particle diameter in the range of 0.01 to 0.5 μm. When the average primary particle diameter is 1 μm or less, the photothermal conversion ability with respect to the addition amount becomes better, and when the average primary particle diameter is within the range of 0.01 to 0.5 μm, the photothermal conversion ability with respect to the addition amount is better. It becomes. However, the photothermal conversion ability with respect to the added amount is greatly affected by the degree of dispersion of the particles, and the better the dispersion, the better. Therefore, it is preferable to disperse these composite metal oxide particles by a known method separately before adding them to the layer coating solution to prepare a dispersion (paste). A dispersing agent can be appropriately used for the dispersion. The addition amount of the dispersant is preferably 0.01 to 5% by mass, and more preferably 0.1 to 2% by mass with respect to the composite metal oxide particles.

  As addition amount of these composite metal oxides, it is 0.1-50 mass% with respect to an insulating layer or a lower layer, 1-30 mass% is preferable, and 3-25 mass% is more preferable.

  The photothermal conversion material is contained in an image forming layer, an insulating layer, a lower layer and an upper layer that can be appropriately provided adjacent to the image forming layer, and a plurality of layers among these layers.

<Method of applying each layer>
The above-described insulating layer, image forming layer, and other layers provided as necessary are obtained by applying a composition constituting each layer on a substrate. As a coating method of the composition of each layer, a known coating method such as dipping, spin coating, knife coating, bar coating, blade coating, squeeze coating, reverse roll coating, gravure roll coating, curtain coating, spray coating, die coating or the like is used. A coating method capable of continuous coating or thin film coating is preferably used.

(Lipophilic pattern formation by laser)
Formation of the lipophilic pattern in the substrate according to the present embodiment can be performed by heat, but it is particularly preferable to form the lipophilic pattern by exposure with an infrared laser.

  Regarding exposure in the laser system, more specifically, scanning exposure using a laser that emits light in the infrared and / or near-infrared region, that is, in the wavelength range of 700 to 1500 nm is preferable. Although a gas laser may be used as the laser, it is particularly preferable to use a semiconductor laser that emits light in the near infrared region.

  As an apparatus suitable for scanning exposure, any apparatus may be used as long as it can form a circuit pattern on the substrate surface in accordance with an image signal from a computer using a semiconductor laser.

  In general, (1) a system in which a substrate held by a plate-like holding mechanism is subjected to two-dimensional scanning using one or a plurality of laser beams to expose the entire surface of the substrate, and (2) fixed. The substrate held along the cylindrical surface inside the cylindrical holding mechanism is scanned in the circumferential direction (main scanning direction) of the cylinder using one or a plurality of laser beams from the inside of the cylinder. A method in which the entire surface of the substrate is exposed by moving it in a direction perpendicular to (sub-scanning direction), and (3) a substrate held on the surface of a cylindrical drum that rotates about an axis as a rotating body, A method of exposing the entire surface of the substrate by moving in a direction perpendicular to the circumferential direction (sub-scanning direction) while scanning in the circumferential direction (main scanning direction) by rotation of a drum using a plurality of laser beams.

<< Inkjet system >>
Examples of the inkjet method include a method using a known inkjet method. As the ink to be used, the oil-based ink disclosed in Japanese Patent No. 2995075, the hot melt ink disclosed in Japanese Patent Laid-Open No. 10-24550, and the Japanese Patent Laid-Open No. 10-157053 are disclosed. An oil-based ink in which solid and hydrophobic resin particles are dispersed at normal temperature, or a water-based ink in which solid and hydrophobic thermoplastic resin particles are dispersed at normal temperature can be used. A radiation curable ink can be preferably used.

(Radiation curable ink)
The radiation curable ink is composed of at least a polymerizable compound. In addition, a coloring material can be added for the purpose of obtaining visible image quality.

  As the color material, a color material that can be dissolved or dispersed in the main component of the polymerizable compound, that is, various dyes and pigments can be used. When a pigment is added, the dispersibility has a great influence on the coloring degree. In order to give A ball mill, a sand mill, an attritor, a roll mill, an agitator, a Henschel mixer, a colloid mill, an ultrasonic homogenizer, a pearl mill, a wet jet mill, a paint shaker, or the like can be used for dispersing the pigment. It is also possible to add a dispersant when dispersing the pigment. As the dispersant, it is preferable to use a polymer dispersant. Examples of the polymer dispersant include Solsperse series manufactured by Zeneca. Moreover, it is also possible to use a synergist according to various pigments as a dispersion aid. These dispersants and dispersion aids are preferably added in an amount of 1 to 50 parts by mass with respect to 100 parts by mass of the pigment. Although the dispersion medium is a solvent or a polymerizable compound, the radiation curable ink used in the present invention is preferably solventless because it reacts and cures immediately after ink landing. If the solvent remains in the cured image, the solvent resistance deteriorates and the VOC of the remaining solvent arises. Therefore, it is preferable in view of dispersibility that the dispersion medium is not a solvent but a polymerizable compound, and among them, a monomer having the lowest viscosity is selected.

  The dispersion aid preferably has an average particle size of 0.08 to 0.5 μm, and the pigment, dispersant, and dispersion medium so that the maximum particle size is 0.3 to 10 μm, preferably 0.3 to 3 μm. Selection, dispersion conditions, and filtration conditions. By controlling the particle size, clogging of the head nozzle can be suppressed, and ink storage stability, ink transparency, and curing sensitivity can be maintained. The colorant is preferably added in an amount of 0.1% to 10% by weight of the total ink.

  The radiation-polymerizable compound is described in radically polymerizable compounds such as JP-A-7-159983, JP-B-7-31399, JP-A-8-224982, and JP-A-10-863. Photo-curing materials using photo-polymerizable compositions and cationic photo-curing resins are known. Recently, photo-curing photo-curing properties that have been sensitized to a longer wavelength range beyond visible light. Examples of the resin are disclosed in JP-A-6-43633 and JP-A-8-324137.

  The radical polymerizable compound is a compound having an ethylenically unsaturated bond capable of radical polymerization, and may be any compound as long as it has at least one ethylenically unsaturated bond capable of radical polymerization in the molecule. , Oligomers, polymers and the like having a chemical form. Only one kind of radically polymerizable compound may be used, or two or more kinds thereof may be used in combination at an arbitrary ratio in order to improve desired properties. A polyfunctional compound having two or more functional groups is more preferable than a monofunctional compound. More preferably, two or more polyfunctional compounds are used in combination in order to control performance such as reactivity and physical properties.

  Examples of compounds having an ethylenically unsaturated bond capable of radical polymerization include unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid and their salts, esters, urethanes, amides. And radically polymerizable compounds such as unsaturated monomers, acrylonitrile, styrene, various unsaturated polyesters, unsaturated polyethers, unsaturated polyamides, and unsaturated urethanes. Specifically, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, butoxyethyl acrylate, carbitol acrylate, cyclohexyl acrylate, tetrahydrofurfuryl acrylate, benzyl acrylate, bis (4-acryloxypolyethoxyphenyl) propane, neopentyl glycol Diacrylate, 1,6-hexanediol diacrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, polypropylene glycol diacrylate, pentaerythritol triacrylate, pentaerythritol Tetraacrylate, dipentaery Acrylic acid derivatives such as lithol tetraacrylate, trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate, oligoester acrylate, N-methylol acrylamide, diacetone acrylamide, epoxy acrylate, methyl methacrylate, n-butyl methacrylate, 2-ethylhexyl methacrylate , Lauryl methacrylate, allyl methacrylate, glycidyl methacrylate, benzyl methacrylate, dimethylaminomethyl methacrylate, 1,6-hexanediol dimethacrylate, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, polypropylene glycol dimethacrylate, trimethylol Methacryl derivatives such as tan trimethacrylate, trimethylolpropane trimethacrylate, 2,2-bis (4-methacryloxypolyethoxyphenyl) propane, and other derivatives of allyl compounds such as allyl glycidyl ether, diallyl phthalate, triallyl trimellitate More specifically, Shinzo Yamashita, “Cross-linking agent handbook” (Taisei, 1981); Kato Kiyomi, “UV / EB curing handbook (raw material)” (1985, Polymer publication) ); Radtech Study Group, “Application and Market of UV / EB Curing Technology”, p. 79, (1989, CMC); Eiichiro Takiyama, “Polyester Resin Handbook”, (1988, Nikkan Kogyo Shimbun) A commercially available product as described above or a radically polymerizable or crosslinkable monomer known in the industry, Oligomers and polymers can be used. The amount of the radical polymerizable compound added is preferably 1 to 97% by mass, more preferably 30 to 95% by mass.

  Cationic polymerization type photo-curing resin includes monomers that are polymerized by cationic polymerization (mainly epoxy type), epoxy-type UV curable prepolymer, prepolymer containing two or more epoxy groups in one molecule. Etc. Examples of such prepolymers include alicyclic polyepoxides, polyglycidyl esters of polybasic acids, polyglycidyl ethers of polyhydric alcohols, polyglycidyl ethers of polyoxyalkylene glycol, and polyglycidyl of aromatic polyols. Examples include ethers, hydrogenated compounds of polyglycidyl ethers of aromatic polyols, urethane polyepoxy compounds, and epoxidized polybutadienes. One of these prepolymers can be used alone, or two or more thereof can be mixed and used.

  In the present invention, (meth) acrylic monomers or prepolymers, epoxy monomers or prepolymers, urethane monomers or prepolymers are preferably used as the polymerizable compound, and the following compounds are more preferable. 2-ethylhexyl-diglycol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxybutyl acrylate, hydroxypivalate neopentyl glycol diacrylate, 2-acryloyloxyethyl phthalate, methoxy-polyethylene glycol acrylate, tetramethylol Methane triacrylate, 2-acryloyloxyethyl-2-hydroxyethylphthalic acid, dimethylol tricyclodecane diacrylate, ethoxylated phenyl acrylate, 2-acryloyloxyethyl succinic acid, nonylphenol EO adduct acrylate, modified glycerin triacrylate Bisphenol A diglycidyl ether acrylic acid adduct, modified bisphenol A diacrylate, phenoxy-polyethylene Glycol acrylate, 2-acryloyloxyethyl hexahydrophthalic acid, bisphenol A PO adduct diacrylate, bisphenol A EO adduct diacrylate, dipentaerythritol hexaacrylate, pentaerythritol triacrylate tolylene diisocyanate urethane prepolymer, lactone Modified towable acrylate, butoxyethyl acrylate, propylene glycol diglycidyl ether acrylic acid adduct, pentaerythritol triacrylate hexamethylene diisocyanate urethane prepolymer, 2-hydroxyethyl acrylate, methoxydipropylene glycol acrylate, ditrimethylolpropane tetraacrylate, penta Erythritol triacrylate hexamethylene Isocyanate urethane prepolymer, stearyl acrylate, isoamyl acrylate, isomyristyl acrylate, and isostearyl acrylate.

  These acrylate compounds have less skin irritation and sensitization (rash) than conventional polymerizable compounds used in UV curable inks, can relatively reduce viscosity, and provide stable ink ejection properties. The polymerization sensitivity is also good. 20-95 mass% of the said compound group is used, Preferably it is 50-95 mass%, More preferably, 70-95 mass% is used.

  The monomers listed in the above-mentioned polymerizable compounds are low in sensitization even with a low molecular weight, and have high reactivity, low viscosity, and excellent permeability and adhesion to the insulating layer. .

  Furthermore, in order to further improve sensitivity, bleeding, and adhesion to the insulating layer, it is sensitivity to use the above-mentioned monoacrylate together with a polyfunctional acrylate monomer or polyfunctional acrylate oligomer having a molecular weight of 400 or more, preferably 500 or more. From the viewpoint of improving adhesion. Sensitivity and bleeding can be further improved while maintaining safety. As the oligomer, an epoxy acrylate oligomer and a urethane acrylate oligomer are particularly preferable.

  It is preferable to use a monoacrylate selected from the above compound group in combination with a polyfunctional acrylate monomer or a polyfunctional acrylate oligomer, since the film can have flexibility and the film strength can be increased. As monoacrylate, stearyl acrylate, isoamyl acrylate, isomystil acrylate, and isostearyl acrylate have high sensitivity, low shrinkage, and can suppress strength reduction due to internal stress in the image area, and also prevent bleeding, substrate odor, irradiation device This is preferable in terms of cost reduction.

  Although methacrylate has better skin irritation than acrylate, sensitization is generally not different from acrylate and is not suitable because it is less sensitive than acrylate, but it has high reactivity and good sensitization. If it is, it can be used suitably. Among the above compounds, alkoxy acrylate has low sensitivity and causes problems such as bleeding, odor, and irradiation light source. Therefore, it is preferable to keep the amount below 70 parts by mass and use other acrylates in combination.

  If necessary, other components can be added to the ink used in the ink jet system.

  When an electron beam, X-ray, or the like is used as irradiation light, an initiator is not necessary. However, when UV light, visible light, or infrared light is used as a radiation source, a radical polymerization initiator or initiator corresponding to each wavelength is used. Add auxiliaries and sensitizing dyes. These amounts require 1-10 parts by weight of the total ink. Various known compounds can be used as the initiator, but the initiator is selected from those that dissolve in the polymerizable compound. Specific examples of the initiator include xanthone or thioxanthone series, benzophenone series, quinone series, and phosphine oxide series.

  Moreover, in order to improve preservability, 200-20000 ppm of polymerization inhibitors can be added. The ink of the present invention is preferably heated and reduced in viscosity in the range of 40 to 80 ° C. and ejected. Therefore, it is preferable to add a polymerization inhibitor in order to prevent head clogging due to thermal polymerization.

  In addition to this, surfactants, leveling additives, matting agents, polyester resins, polyurethane resins, vinyl resins, acrylic resins, rubber resins, and waxes are added to adjust film properties as necessary. can do. In order to improve adhesion to recording media such as olefin and PET, it is preferable to include a tackifier that does not inhibit polymerization. Specifically, high molecular weight adhesive polymers (esters of (meth) acrylic acid and alcohols having an alkyl group having 1 to 20 carbon atoms, described in JP-A-2001-49200 5-6p, (meta ) A copolymer of acrylic acid and an ester of an alicyclic alcohol having 3 to 14 carbon atoms, an ester of (meth) acrylic acid and an aromatic alcohol having 6 to 14 carbon atoms), or a polymerizable unsaturated bond A low molecular weight tackifying resin having In order to improve the adhesion with the insulating layer, it is also effective to add a trace amount of organic solvent. In this case, it is effective to add in a range that does not cause the problem of solvent resistance and VOC, and the amount is 0.1 to 5%, preferably 0.1 to 3%. In addition, as a means for preventing a decrease in sensitivity due to the light-shielding effect due to the ink color material, it is possible to combine a cationically polymerizable monomer having a long initiator lifetime with an initiator to obtain a radical-cation hybrid curable ink.

  The composition ratio of the ink is determined so that the temperature at the time of ejection is preferably 7 to 30 mPa · s, more preferably 7 to 20 mPa · s in consideration of ejection properties. The ink viscosity at 25 ° C. is preferably 35 to 500 mPa · s, and more preferably 35 to 200 mPa · s. By increasing the viscosity at room temperature, it is possible to prevent ink from penetrating into porous recording media, to reduce uncured monomers and odors, and to suppress dot bleeding at the time of landing and improve image quality. Is done.

  The surface tension is preferably 200 to 300 [mu] N / cm, more preferably 230 to 280 [mu] N / cm from the viewpoint of bleeding, penetration, and wettability.

(Lipophilic pattern formation by inkjet)
As a method for forming an oleophilic pattern in the ink jet system, it is preferable from the viewpoint of ejection stability that the ink is heated to 40 to 80 ° C. and ejected at a reduced ink viscosity. Irradiation curable inks generally have higher viscosities than aqueous inks, and therefore have a large viscosity fluctuation range due to temperature fluctuations. Viscosity fluctuations directly affect the droplet size and droplet ejection speed as they are, causing image quality degradation, so it is necessary to keep the ink temperature as constant as possible. The control range of the ink temperature is set temperature ± 5 ° C., preferably set temperature ± 2 ° C., more preferably set temperature ± 1 ° C. The recording apparatus includes ink temperature stabilization means, but the part to be kept at a constant temperature covers all of the piping system and members from the ink tank (intermediate tank if there is an intermediate tank) to the nozzle ejection surface.

  In order to control the temperature, it is preferable to provide a plurality of temperature sensors at each piping site and perform heating control according to the ink flow rate and the environmental temperature. Moreover, it is preferable that the head unit to be heated is thermally shielded or insulated so as not to be affected by the temperature of the manufacturing apparatus main body and outside air. In order to shorten the manufacturing apparatus start-up time required for heating and to reduce the loss of heat energy, it is preferable to insulate from other parts and reduce the heat capacity of the entire heating unit.

  Various light sources such as ultraviolet rays, electron beams, X-rays, visible light, and infrared light can be used for light irradiation after the formation of the lipophilic pattern. Then, ultraviolet rays are preferable. As the ultraviolet ray source, a mercury lamp, a metal halide lamp, an excimer lamp, an ultraviolet laser / LED, or the like can be used.

  A basic irradiation 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 WO 9,954,415, 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 of the head unit is disclosed. . In this embodiment mode, these irradiation methods can be used. Moreover, it is preferable to irradiate from the back of the head.

  The method of exposing from the back of the head can quickly irradiate the ink immediately after landing without using an optical fiber or an expensive optical system. Further, since the irradiation is from the back of the head, there is also an effect of preventing ink curing at the nozzle interface due to a reflection line from the substrate. It is preferable that the radiation source has a projected shape on the substrate in a band shape having a lipophilic pattern forming width for one scanning.

  Specifically, a strip-shaped metal halide lamp tube and an ultraviolet lamp tube are preferable. The radiation source is substantially fixed to the manufacturing apparatus, and the movable portion can be eliminated, so that an inexpensive configuration can be obtained. Further, in any of the exposure methods, it is one of preferable modes that two types of radiation sources are prepared and curing is completed by the second radiation source. This contributes to obtaining wettability of the fluid electrode material, adhesion between inks, and assembling a radiation source at low cost.

  Note that it is preferable to change the exposure wavelength or the exposure illuminance between the first radiation source and the second radiation source. The first irradiation energy is smaller than the second irradiation energy, that is, the first irradiation energy is 1 to 20%, preferably 1 to 10%, more preferably 1 to 5% of the total irradiation energy. By performing irradiation with varying illuminance, the molecular weight distribution after curing becomes preferable. That is, if irradiation with high illuminance is performed at once, the polymerization rate is increased, but the molecular weight of the polymerized polymer is small, and the strength may not be obtained. A composition having an extremely low viscosity such as an ink-jet ink provides a remarkable effect.

  Also, the first irradiation has a longer wavelength than the second, so that the first irradiation cures the ink surface layer and suppresses ink bleeding, and the second irradiation makes it difficult to reach the irradiation line. The ink in the vicinity of the substrate can be cured to improve the adhesion. In order to accelerate curing inside the ink, the second irradiation wavelength is preferably a long wavelength.

  The feature of the present embodiment is that the above ink is used, the ink is heated to a constant temperature, and the time from landing to irradiation is 0.01 to 0.5 seconds, preferably 0.01 to 0.3 seconds, More preferably, the irradiation is performed after 0.01 to 0.15 seconds. Thus, by controlling the time from landing to irradiation to an extremely short time, it is possible to prevent the landing ink from bleeding before curing. In addition, since the ink can be exposed to the porous substrate before the ink penetrates to a deep part where the light source does not reach, the residual unreacted monomer can be suppressed and the odor can be reduced. This brings about a big synergistic effect by using the above-mentioned ink. In particular, when an ink having an ink viscosity of 35 to 500 mPa · s at 25 ° C. is used, a great effect can be obtained. By adopting such a lipophilic pattern forming method, the dot diameter of the landed ink can be kept constant even on various substrates having different surface wettability, and the reproducibility of the conductive pattern is improved. .

  The head unit includes an inkjet nozzle head, an ink liquid supply system, an ink and a temperature control mechanism for the head, a control board, and the like. When irradiating light from the back side, it is preferable that the head unit has as small a projected area as possible on the substrate. Smaller uses the first irradiation more effectively.

  In addition, the inkjet nozzle head is preferably provided with a liquid discharge nozzle described in International Publication No. 2004/028841 pamphlet and Japanese Patent Application Laid-Open No. 2004-114377 in forming a fine lipophilic pattern.

<< Direct grant form >>
In the substrate of the present invention, an oleophilic pattern can also be formed by applying an oleophilic material directly to the surface of the insulating layer in an image-like manner.

  As one of methods for imparting an oleophilic material to the image, a method using a known thermal transfer method can be mentioned. Specifically, there is a method in which a thermal transfer printer is used to image-transfer the heat-meltable ink from the ink ribbon having the heat-meltable ink layer to the surface of the insulating layer using a thermal head.

  Also, using an infrared laser thermal melting transfer type digital proof device, a substrate is wound on the exposure drum with the insulating layer facing outward, and an ink sheet having a thermal melting ink layer is further coated on the ink surface. There can also be mentioned a method of winding in contact with the insulating layer, imagewise exposure with an infrared laser, and image transfer of the heat-meltable ink onto the surface of the insulating layer. In this case, the photothermal conversion material may be contained in the insulating layer, the ink sheet side may be contained in any layer, or both may be contained.

  After forming an image with a heat-meltable ink on the insulating layer, the substrate can be heated to further strengthen the adhesion between the insulating layer and the image. In the case where the insulating layer contains a photothermal conversion material, this heat treatment can also be performed using infrared laser irradiation or flash exposure using a known xenon lamp or the like.

<Flowable electrode material>
A conductive pattern is formed on the substrate on which the lipophilic pattern is formed by supplying a fluid electrode material. The fluid electrode material is specifically a solution, paste, ink, metal thin film precursor material, liquid dispersion, or the like containing the conductive material shown below, and according to the present invention in which an oleophilic pattern is formed. When the fluid electrode material is hydrophilic by being supplied onto the substrate, the fluid electrode material is adsorbed to the region where the lipophilic pattern is not drawn, that is, the hydrophilic insulating layer, and the fluid electrode material is lipophilic. If adsorbed on the lipophilic pattern.

  The conductive material is not particularly limited as long as it has conductivity at a practical level as an electrode. Platinum, gold, silver, nickel, chromium, copper, iron, tin, antimony lead, tantalum, indium, palladium , Tellurium, rhenium, iridium, aluminum, ruthenium, germanium, molybdenum, tungsten, tin oxide / antimony, indium tin oxide (ITO), fluorine doped zinc oxide, zinc, carbon, graphite, glassy carbon, silver paste and carbon paste, Lithium, beryllium, sodium, magnesium, potassium, calcium, scandium, titanium, manganese, zirconium, gallium, niobium, sodium, sodium-potassium alloy, magnesium, lithium, aluminum, magnesium / copper mixture, mug Sium / silver mixture, magnesium / aluminum mixture, magnesium / indium mixture, aluminum / aluminum oxide mixture, lithium / aluminum mixture, etc. are used, but platinum, gold, silver, copper, aluminum, indium, ITO and carbon are particularly preferable. .

  Moreover, as a conductive material, a conductive polymer, metal fine particles, or the like can be suitably used. As a dispersion containing metal fine particles, for example, a known conductive paste may be used, but a dispersion containing metal fine particles having a particle diameter of 1 nm to 50 nm, preferably 1 nm to 10 nm is preferable.

  Platinum, gold, silver, nickel, chromium, copper, iron, tin, antimony lead, tantalum, indium, palladium, tellurium, rhenium, iridium, aluminum, ruthenium, germanium, molybdenum, tungsten, zinc, etc. Can be used. Among these, gold or silver having good conductivity and corrosion resistance is preferable.

  It is preferable to form an electrode using a dispersion in which fine particles made of these metals are dispersed in water or a dispersion medium that is an arbitrary organic solvent using a dispersion stabilizer mainly made of an organic material. The fluid electrode material can be made oleophilic or hydrophilic by appropriately selecting the dispersion stabilizer and the dispersion medium.

  As a method for producing such a dispersion of metal fine particles, metal ions are reduced in a liquid phase, such as a physical generation method such as gas evaporation method, sputtering method, and metal vapor synthesis method, colloid method, and coprecipitation method. Examples of the chemical production method for producing metal fine particles include those described in JP-A-11-76800, JP-A-11-80647, JP-A-11-319538, JP-A-2000-239853, and the like. Colloidal method, gas evaporation method described in JP-A-2001-254185, 2001-53028, 2001-35255, 2000-124157, 2000-123634, etc. This is a dispersion of produced metal fine particles.

  The viscosity of the dispersion of fine metal particles is preferably in the range of 1 to 100 cps, preferably 5 to 50 cps, particularly 10 to 20 cps, and the concentration is 1 to 70% by mass, preferably 10 to 50% by mass. In particular, it is preferably in the range of 20 to 30% by mass.

  Furthermore, the surface tension in the dispersion of metal fine particles is preferably 20 mN / m or more, preferably 50 mN / m or more, and particularly preferably 70 mN / m or more. The upper limit of the surface tension is not particularly limited, but it can be said that it is preferably 80 mN / m or less. When the hydrophilic dispersion is applied to the entire surface of the substrate on which the lipophilic pattern is formed due to the solution having a large surface tension, the dispersion applied to the lipophilic pattern region is removed or the lipophilic pattern is removed. When gathered in an insulating layer where an oily pattern is not formed and a lipophilic dispersion is applied, the dispersion applied to the insulating layer where a lipophilic pattern is not formed is removed, or Collect in the oily pattern area. For this purpose, it is preferable that the contact angle of the dispersion of metal fine particles in the lipophilic pattern region is large.

  The fluid electrode material composed of these metal fine particle dispersions is adsorbed in a pattern-like manner on the substrate in accordance with the lipophilic pattern formed on the substrate, and then the solvent is removed by drying. It heats by a well-known method in -300 degreeC, Preferably it is the range of 150 to 200 degreeC. When the fluid electrode material adsorbed in a pattern on the substrate is heated, the metal fine particles are thermally fused to form a conductive pattern having a desired shape.

  Further, as the electrode material, it is also preferable to use a known conductive polymer whose conductivity has been improved by doping or the like. For example, conductive polyaniline, conductive polypyrrole, conductive polythiophene, polyethylenedioxythiophene and polystyrenesulfonic acid. Complexes and the like are also preferably used. Thereby, the contact resistance between the electrode and the organic semiconductor layer can be reduced.

<Flowable insulating material>
When a conductive pattern is formed by supplying a fluid electrode material to a substrate on which an oleophilic pattern is formed, a fluid insulating material can also be supplied. The fluid insulating material is specifically a solution, paste, ink, metal thin film precursor material, liquid dispersion, or the like containing the insulating material shown below, and according to the present invention in which an oleophilic pattern is formed. When the fluid insulating material is hydrophilic by being supplied onto the substrate, the fluid insulating material is adsorbed to a region where the lipophilic pattern is not drawn, that is, the hydrophilic insulating layer, and the fluid insulating material is lipophilic. If adsorbed on the lipophilic pattern.

  Examples of the insulating material include a rubbery polymer, liquid paraffin, and silicone oil, and a rubbery polymer is preferable. Rubber-like polymers include conjugated diene rubbers such as polybutadiene, natural rubber, polyisoprene, SBR and NBR and hydrogenated products thereof, block copolymers such as styrene butadiene diene block copolymers and styrene isoprene block copolymers. Examples thereof include merging and hydrogenated products thereof, chloroprene, urethane rubber, polyester rubber, epichlorohydrin rubber, silicone rubber, ethylene propylene copolymer, ethylene propylene diene copolymer and the like. When weather resistance is necessary, rubbery polymers other than conjugated diene rubbers are preferred, and silicone rubber is particularly preferred from the viewpoint of moldability and electrical characteristics.

  It is preferable to use a dispersion in which fine particles made of these insulating materials are dispersed in water or a dispersion medium that is an arbitrary organic solvent using a dispersion stabilizer mainly made of an organic material. As the dispersion containing the insulating material fine particles, for example, a known insulating paste may be used. Preferably, the dispersion contains the insulating material fine particles having a particle diameter of 1 nm to 50 nm, preferably 1 nm to 10 nm. It is a thing. The fluid insulating material can be made oleophilic or hydrophilic by appropriately selecting the dispersion stabilizer and the dispersion medium.

<Dampening water>
In the conductive pattern forming method according to the present invention, dampening water can be supplied to the substrate on which the lipophilic pattern is formed. By supplying dampening water to the substrate on which the lipophilic pattern is formed, the region where the lipophilic pattern is not drawn, that is, the hydrophilic insulating layer repels the lipophilic substance, and the hydrophilic A water film that adsorbs to the substance is formed, and if the fluid electrode material supplied later is hydrophilic, it adsorbs to the water film, and if the fluid electrode material is oleophilic, it is repelled by the water film and is strongly oleophilic Adsorb to the pattern.

  Also, due to the repellent action of the water film, the boundary between the area where the lipophilic pattern is not formed and the area where the lipophilic pattern is formed is clearly formed, and even in a fine conductive pattern, the circuit can be short-circuited or disconnected. Even if it is a fine circuit, the line width and the line-to-line variation are not affected by cost, processability when creating the substrate, selection of the composition constituting the insulating layer, selection of the electrode material, etc. It is possible to create a conductive pattern without any defects.

  Further, when the lipophilic pattern is formed by the laser method, the image forming layer containing the unexposed lipophilic thermoplastic particles is removed by supplying dampening water.

  The dampening water is supplied to the substrate by dipping the substrate in the dampening water, contacting a dampening roller or dampening pad impregnated with dampening water to the substrate, or being used in an offset printing machine. A dampening water supply device can be used.

  The fountain solution can contain various additives such as alcohol such as isopropanol in addition to the main component water. The additive is appropriately selected together with its content according to the surface tension and water retention required for the dampening water supplied to the substrate.

(First embodiment)
As a first embodiment according to the present invention, an example of creating a conductive pattern by a laser method will be described with reference to FIG. FIG. 1 is a cross-sectional view showing the state transition of a substrate in a conductive pattern creation process by a laser method.

  An insulating layer 2 containing inorganic particles (not shown) and having hydrophilicity, and an image forming layer 3 containing oleophilic thermoplastic particles (not shown) are provided in this order on the substrate 1 (FIG. 1). (A)). In addition, the photothermal conversion raw material which is not illustrated is contained in the insulating layer 2 in this Embodiment.

  When the substrate 1 is exposed in a pattern with the infrared laser L, the region exposed by a photothermal conversion material (not shown) is heated, and the oleophilic thermoplastic particles contained in the image forming layer 3 are fused to form the oleophilic pattern 3a. It is formed (FIG. 1 (b)). In addition, the area | region 3b which was not exposed with the infrared laser L among the image forming layers 3 is the same state as Fig.1 (a).

  When the fountain solution is supplied, the fountain solution selectively forms a film in the region 3b not exposed by the infrared laser L, and the image forming layer 3b in which the oleophilic pattern 3a is not formed is removed. When the lipophilic fluid electrode material 4 is supplied in a state where a water film is formed by the dampening water 5, the lipophilic fluid electrode material 4 is selectively adsorbed by the lipophilic pattern 3a and is also moistened. It is repelled by the water 5 (FIG. 1 (c)).

  When the substrate is heated, the fountain solution 5 and the solvent of the lipophilic fluid electrode material 4 are removed by drying, and the metal fine particles contained in the lipophilic fluid electrode material 4 are fused to form a conductive pattern. 4a is formed (FIG. 1 (d)).

  In the present embodiment, the image forming layer 3b on which the lipophilic pattern 3a has not been formed is removed by dampening water. However, after the dampening water is supplied, the image forming layer 3b becomes the insulating layer 2. It may be absorbed.

(Second Embodiment)
As another embodiment of the present invention, another example of creating a conductive pattern by a laser method will be described with reference to FIG. FIG. 2 is a cross-sectional view showing the state transition of the substrate in another conductive pattern creation process using a laser system. The second embodiment is different from the first embodiment in that a hydrophilic fluid electrode material and a lipophilic fluid insulating material are supplied to a substrate on which a lipophilic pattern is formed. The following description will focus on differences from the first embodiment.

  The substrate shown in FIG. 2A is the same as that shown in FIG.

  When the substrate 1 is exposed in a pattern with the infrared laser L, the region exposed by a photothermal conversion material (not shown) is heated, and the oleophilic thermoplastic particles contained in the image forming layer 3 are fused to form the oleophilic pattern 3a. It is formed (FIG. 2B). However, the present embodiment is different from the first embodiment in that the area exposed by the infrared laser L is a region where the lipophilic pattern is not formed.

  When the fountain solution is supplied, the fountain solution selectively forms a film in the region 3b not exposed by the infrared laser L, and the image forming layer 3b in which the oleophilic pattern 3a is not formed is removed.

  When the lipophilic fluid insulating material 6 and the hydrophilic fluid electrode material 7 are supplied in a state where a water film is formed by the dampening water, the lipophilic fluid insulating material 6 is selected as the lipophilic pattern 3a. And is repelled by the film formed of the fountain solution 5. Further, the hydrophilic fluid electrode material 7 is selectively adsorbed to a region where the film of the fountain solution 5 is formed and the lipophilic pattern 3a is not formed (FIG. 2 (c)).

  When the substrate is heated, the fountain solution 5 and the solvent of the oleophilic fluid insulating material 6 and the hydrophilic fluid electrode material 7 are removed by drying, and the metal contained in the hydrophilic fluid electrode material 7 is removed. The fine particles are fused to form the conductive pattern 7a (FIG. 2D).

(Third embodiment)
As a third embodiment according to the present invention, an example of creating a conductive pattern by an ink jet method will be described with reference to FIG. FIG. 3 is a cross-sectional view showing the state transition of the substrate in the conductive pattern creating process by the ink jet method.

  An insulating layer 2 containing inorganic particles (not shown) and having hydrophilicity is provided on the substrate 1 in this order (FIG. 3A).

  When the ink 8 ejected in a pattern from an inkjet printer (not shown) is applied to the substrate 1, a part of the ink 8 penetrates into the insulating layer 2. (FIG. 3B).

When the substrate 1 coated with the ink 8 in a pattern is exposed with a radiation source such as an ultraviolet lamp (not shown), the ink 8 is cured to form an oleophilic pattern 8a (FIG. 3C).
When dampening water is supplied to the substrate on which the lipophilic pattern 8a is formed, the dampening water selectively forms a film in a region where the lipophilic pattern 8a is not formed. When the lipophilic fluid electrode material 4 is supplied in a state in which a water film is formed by the dampening water 5, the lipophilic fluid electrode material 4 is selectively adsorbed by the lipophilic pattern 8a and is also moistened. It is repelled by the water 5 (FIG. 3D).

  When the substrate is heated, the fountain solution 5 and the solvent of the lipophilic fluid electrode material 4 are removed by drying, and the metal fine particles contained in the lipophilic fluid electrode material 4 are fused to form a conductive pattern. 4a is formed (FIG. 3E).

  A substrate having a conductive pattern according to the present invention can be obtained by the above manufacturing method. As a specific application example to an electronic device, an image driving element of a display medium using liquid crystal, organic EL, electrophoresis, or the like. Thin film transistor element (TFT) used as an active drive element applied to electronic paper or digital paper, RFID (Radio Frequency Identification) tag, mobile phone or PDA (Personal Digital Assistant), circuit board such as digital still camera, electromagnetic wave A shielding shield etc. are mentioned.

EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto.

<Example 1>
(Substrate 1) A 150 μm thick polyethylene terephthalate film provided with an undercoat layer for aqueous coating was used.

(Preparation of substrate material for infrared laser exposure)
(Preparation of Insulating Layer Coating Solution) Each material shown in Table 2 was sufficiently stirred and mixed using a homogenizer, then mixed and filtered with the composition shown in Table 2 to obtain Insulating Layer Coating Solutions 1-2. Prepared.

In addition, the detail of each raw material described in Table 2 is as follows, and the numerical value in a table | surface represents a mass part.
* 1; Colloidal silica (alkaline): Snowtex-S (Nissan Chemical Co., Ltd., solid content 30% by mass)
* 2; Necklace-shaped colloidal silica (alkaline): Snowtex-PSM (Nissan Chemical Co., Ltd., solid content 20% by mass)
* 3; Cu—Fe—Mn-based metal oxide black pigment: TM-3550 black powder (manufactured by Dainichi Seika Kogyo Co., Ltd., particle size of about 0.1 μm) solid content of 40% by mass (of which 0.2% by mass is Dispersant) Aqueous dispersion * 4; Layered mineral particles Montmorillonite: A mineral colloid MO (manufactured by Southern Clay Products, average particle size of about 0.1 μm) is vigorously stirred with a homogenizer to form a 5% by mass water-swollen gel * 5: 4% by mass aqueous solution of sodium carboxymethylcellulose (reagent manufactured by Kanto Chemical Co., Ltd.) * 6; 10% by mass aqueous solution of trisodium phosphate dodecahydrate (reagent manufactured by Kanto Chemical Co., Ltd.) * 7; porous metal oxidation Particles Silton AMT08 (manufactured by Mizusawa Chemical Co., Ltd., porous aluminosilicate particles, average particle size 0.6 μm)
* 8: Porous metal oxide particles Shilton JC-20 (Mizusawa Chemical Co., Ltd., porous aluminosilicate particles, average particle size 2 μm)
(Coating of insulating layer) Each coating solution shown in Table 2 was coated on a substrate using a wire bar so that the average film thickness after drying was 4 μm, dried at 100 ° C. for 3 minutes, Samples 1 and 2 were produced.

(Formation of image forming layer) The following image forming layer coating solution was applied onto the prepared samples 1 and 2 using a wire bar so that the dry weight was 0.6 g / m ^2, and at 50 ° C. It dried for 3 minutes and produced the samples 11-13 which are board | substrate materials for infrared laser exposure. Each of the prepared samples was subjected to a heat treatment at 80 ° C. for 20 minutes after applying the image forming layer.

(Image forming layer coating solution)
30% by weight of aqueous solution solid content of disaccharide trehalose powder (trade name Trehaose, Hayashibara Shoji Co., Ltd., melting point 97 ° C.) 30 parts by weight 70 parts by mass of a dispersion obtained by diluting a melting point of 80 ° C., a melt viscosity of 8 cps at 140 ° C. and a solid content of 40% by mass with a pure content of 5% by mass with pure water (formation of an oleophilic pattern by an infrared laser system)
The prepared samples 11 to 13 were wound around and fixed to the exposure drum. For the exposure, a laser beam having a wavelength of 830 nm and a spot diameter of about 7 μm was used, and the exposure energy was set to 300 mJ / cm ^2. A straight line of 4000 dots / 25.4 mm with a line width of 7 μm and a length of 30 mm was formed with a line spacing of 7 μm. Ten lipophilic patterns were formed.

<Example 2>
(Preparation of substrate material for inkjet method)
(Coating of insulating layer) Insulating layer coating solutions 1 and 2 prepared in Example 1 were dried on the base material 1 used in Example 1 using a wire bar so that the average film thickness was 4 μm. And heat treatment at 60 ° C. for 24 hours to prepare Samples 21 to 22 which are substrate materials for the inkjet system.

(Lipophilic pattern formation by inkjet method)
(Preparation of magenta ink)
(Preparation of magenta pigment dispersion) A magenta pigment dispersion was prepared by sequentially mixing and dispersing the following compositions. The dispersion conditions were appropriately adjusted so that the average particle diameter of the magenta pigment particles was in the range of 0.2 to 0.3 μm.

C. I. Pigment Red 57: 1 15 parts by weight Polymer dispersing agent (Solsperse manufactured by Zeneca) 5 parts by weight Stearyl acrylate 80 parts by weight Next, the following respective compositions are mixed, and then filtered through a filter having an absolute filtration accuracy of 2 μm. An ink was prepared. The prepared magenta ink had a viscosity at 25 ° C. of 120 mPa · s, a viscosity at 70 ° C. of 15 mPa · s, and a surface tension at 25 ° C. of 250 μN / cm.
(Magenta ink)
Magenta pigment dispersion 20 parts by mass Stearyl acrylate 60 parts by mass Bifunctional aromatic urethane acrylate (molecular weight 1500) 10 parts by mass Hexafunctional aliphatic urethane acrylate (molecular weight 1000) 5 parts by mass Initiator (manufactured by Ciba, Irgacure 184) 5 parts by mass Part (Formation of Inkjet Pattern) Pattern-like ink images were formed on samples 21 to 22 as substrate materials by an inkjet recording apparatus using an inkjet nozzle described in JP-A No. 2004-114377. The ink supply system was composed of an ink tank, a supply pipe, a front chamber ink tank immediately before the head, a pipe with a filter, and a head, and heat insulation and heating were performed from the front chamber ink tank to the head portion. The temperature sensors were provided in the vicinity of the front chamber ink tank and the nozzle of the head, respectively, and the temperature was controlled so that the nozzle portion was always 60 ° C. ± 2 ° C. The piezo head is driven so as to emit multi-size dots of 2 to 8 pl, and with a resolution of 5080 dots / 25.4 mm × 5080 dots / 25.4 mm, a straight line having a line width of 5 μm and a length of 30 mm as in the first embodiment. A pattern in which 10 lines were formed with a line spacing of 5 μm was formed. After landing, UV-A light was condensed to an exposure surface illuminance of 100 mW / cm ² , and the exposure system, main scanning speed, and ejection frequency were adjusted so that irradiation started 0.1 seconds after ink landing. The exposure time was variable, and the irradiation exposure energy was adjustable.

Using the above apparatus, the prepared magenta ink was ejected at an environmental temperature of 25 ° C., and UV light was irradiated immediately thereafter. Irradiation exposure energy was 300 mJ / cm ² .

<Example 3>
(Dampening water supply)
Samples 11, 12, 21, and 22 on which an oleophilic pattern was formed were immersed in a 2% by mass solution of Astro Mark 3 (manufactured by Nikken Chemical Laboratories) as dampening water for 30 seconds, and then a constant speed of 10 mm / second. It was raised at.

(Supply of fluid electrode material)
Samples 11, 12, 21, and 22 pulled up from the fountain solution were immersed in an oleophilic silver fine particle dispersion, which is a fluid electrode material, for 10 seconds, then pulled up at a constant speed of 10 mm / second, and then a nitrogen atmosphere. Under heating at 200 ° C. for 15 minutes, a substrate on which a conductive pattern was formed was produced.

<Example 4>
The samples 11, 12, 21, and 22 on which the lipophilic pattern was formed in Example 1 or Example 2 were immersed in a hydrophilic silver fine particle dispersion that is a fluid electrode material for 10 seconds, and then a constant of 10 mm / second was set. After being pulled up at a high speed, it is immersed in a lipophilic latex particle dispersion, which is a fluid insulating material, for 10 seconds, then pulled up at a constant speed of 10 mm / second, and heated at 200 ° C. for 15 minutes in a nitrogen atmosphere to conduct electricity. Samples 31, 32, 41, and 42 on which a pattern was formed were produced.

<Comparative Example 1>
In place of the insulating layers of Samples 1 and 2 in Example 1, a 5% aqueous solution of a hydrophilic polymer having the following chemical formula was applied using a wire bar, and then dried at 80 ° C. for 5 minutes. Produced. The produced sample was irradiated with light from a 400 W high-pressure mercury lamp for 5 minutes through a squirrel film on which 10 light-transmitting portions having a line width of 10 μm and a length of 30 mm were formed with a line spacing of 10 μm. Thereafter, the unexposed portion was washed with water and removed to obtain a sample 51 on which a hydrophilic pattern was formed.

  The sample 51 on which the hydrophilic pattern was formed was dipped in the hydrophilic silver fine particle dispersion used in Example 4 for 10 seconds, then pulled up at a constant speed of 10 mm / second, and then 15 ° C. at 200 ° C. in a nitrogen atmosphere. A substrate on which a conductive pattern was formed was produced by heating for a minute.

<Evaluation of conductive pattern>
About each produced said sample, the disconnection and short circuit of the formed conductive pattern were evaluated.

  Disconnection is a sample in which a straight line that does not conduct electricity is applied to each of the straight lines that form the conductive pattern by using a LORESTA-FP (manufactured by Mitsubishi Chemical Corp.) and applying a voltage by contacting the probe at both ends. Was determined to be broken.

  For short-circuiting, for each of the straight lines forming the conductive pattern, one end of the probe is brought into contact with the end of the straight line, and the other is brought into contact with the other end of the straight line adjacent to the straight line, using LORESTA-FP. Then, a voltage was applied and a sample having a straight line to conduct was judged to be short-circuited.

  As described above, in Samples 11, 12, 21, 22, 31, 32, 41 and 42 according to the present invention, neither disconnection nor short circuit occurred, but in Sample 51 produced in Comparative Example 1, disconnection occurred. Or a short circuit occurred.

It is sectional drawing which shows the state transition of the board | substrate in the electroconductive pattern creation process which concerns on the 1st Embodiment of this invention. It is sectional drawing which shows the state transition of the board | substrate in the electroconductive pattern creation process which concerns on the 2nd Embodiment of this invention. It is sectional drawing which shows the state transition of the board | substrate in the electroconductive pattern creation process which concerns on the 3rd Embodiment of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Base material 2 Insulating layer 3 Image forming layer 4 Lipophilic fluid electrode material 5 Dampening water 6 Lipophilic fluid insulating material 7 Hydrophilic fluid electrode material 8 Ink

Claims (9)

On the substrate, an oleophilic pattern forming step for forming an oleophilic pattern on a substrate containing inorganic particles and having a hydrophilic insulating layer;
And a conductive pattern forming step of forming a conductive pattern by supplying a fluid electrode material to the substrate on which the lipophilic pattern is formed in the lipophilic pattern forming step. The method for forming a conductive pattern according to claim 1, wherein the fluid electrode material is hydrophilic. The method for forming a conductive pattern according to claim 1, wherein the fluid electrode material is lipophilic. 4. The method for forming a conductive pattern according to claim 1, wherein in the lipophilic pattern forming step, the substrate is imagewise exposed to form a lipophilic pattern. 5. The oleophilic pattern forming step forms an oleophilic pattern on the substrate by an ink jet printer that ejects oleophilic ink imagewise. A method for forming a conductive pattern. A dampening water supply step of supplying dampening water to the substrate on which the lipophilic pattern is formed in the lipophilic pattern formation step;
6. The conductive pattern forming step of forming a conductive pattern by supplying a fluid electrode material to a substrate to which dampening water is supplied in the dampening water supplying step. The method for forming a conductive pattern according to any one of the above. An insulating layer containing inorganic particles and having hydrophilicity on a substrate; and an image forming layer provided on the insulating layer and containing lipophilic thermoplastic particles, the image forming layer or An oleophilic pattern forming step of imagewise exposing a substrate containing a photothermal conversion material adjacent to the image forming layer to form an oleophilic pattern;
A dampening water supply step of supplying dampening water to the substrate on which the lipophilic pattern is formed in the lipophilic pattern formation step;
Including a conductive pattern forming step of supplying a lipophilic fluid electrode material to the substrate supplied with the dampening water in the dampening water supply step to form a conductive pattern on the lipophilic pattern. A method for forming a conductive pattern. An oleophilic pattern forming step for forming an oleophilic pattern on an ink jet printer that ejects an oleophilic ink imagewise on a substrate having a hydrophilic insulating layer containing inorganic particles on a substrate;
A dampening water supply step of supplying dampening water to the substrate on which the lipophilic pattern is formed in the lipophilic pattern formation step;
Including a conductive pattern forming step of supplying a lipophilic fluid electrode material to the substrate supplied with the dampening water in the dampening water supply step to form a conductive pattern on the lipophilic pattern. A method for forming a conductive pattern. An insulating layer containing inorganic particles and having hydrophilicity on a substrate; and an image forming layer provided on the insulating layer and containing lipophilic thermoplastic particles, the image forming layer or An oleophilic pattern forming step of imagewise exposing a substrate containing a photothermal conversion material adjacent to the image forming layer to form an oleophilic pattern;
A conductive pattern forming step of forming a conductive pattern by supplying a hydrophilic fluid insulating material and a lipophilic fluid electrode material to the substrate on which the lipophilic pattern is formed in the lipophilic pattern forming step. A method for forming a conductive pattern.

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