JP2015032734A - Conducting pattern and conducting circuit - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a conducting pattern which has good conductivity and which suffers no bleeding of a conducting ink nor crack at drying even in making an ink jet print on a support member with the conducting ink, and allows a conducting pattern of a desired wiring form to be obtained.SOLUTION: A conducting pattern is arranged by laminating: a support obtained by applying a fluid (a) to a coating film (x) formed on a surface of the support by primer, and then drying the fluid (a), provided that the fluid (a) contains alcohol (a1) containing mono alcohol (a1-1) with 2C-4C and the conducting substance (a2); a primer layer (X) formed by the coating film (x); and a layer (Y) containing the conducting substance (a2). With a fine droplet of the fluid (a) discharged onto the coating film (x), the contact angle formed by the coating film (x) and the fluid (a)is in a range of 15-70°. The rate of change of the fine droplet in a period of time right after the impingement of the fine droplet on the coating film (x) to 200 ms later is within a range of ±30%.

Description

  The present invention relates to a conductive pattern that can be used in the manufacture of electromagnetic shielding, integrated circuits, organic transistors, and the like.

  In recent years, ink-jet printer-related industries, where growth has been remarkable, have dramatically improved the performance of ink-jet printers and improved ink, making it easy to produce high-definition and clear printability images similar to silver halide photographs. It is becoming possible to obtain. For this reason, inkjet printers are not only used in homes, but are also being used in the printed electronics field in which electronic circuits are formed by inkjet printing using conductive ink, including the manufacture of large advertising signs. However, after the conductive ink is printed on the support, the conductive ink bleeds or cracks are generated during the drying process of the conductive ink, and the conductive pattern having the desired wiring shape cannot be obtained. There was a problem to become.

  Among the above problems, as a method of suppressing the spread (bleeding) of the conductive ink, non-fluorine and non-silicon hydrocarbon epoxy resin and non-fluorine and non-silicon hydrocarbon acrylic compound having no substituent capable of hydrogen bonding And a surface of a support on which inkjet printing is performed for the hydrocarbon-based pressure-sensitive adhesive composition for substrate surface treatment, which contains at least one additive selected from the group consisting of a dispersant and a surfactant, a curing agent, and a solvent. A method has been proposed in which a conductive ink receiving layer is applied and dried (see, for example, Patent Document 1).

  However, the method using the hydrocarbon adhesive composition for substrate surface treatment described above has a problem that the cracking of the conductive ink can be suppressed to some extent, but the bleeding cannot be sufficiently suppressed during the drying process of the conductive ink.

  Therefore, in a method of forming a conductive pattern by printing a conductive ink by ink jet printing, there has been a demand for a method or material that does not cause conductive ink bleeding or cracking during drying, and does not cause poor conductivity.

Special table 2012-532243 gazette

  The problem to be solved by the present invention is that when conductive ink is inkjet printed on a support, the conductive ink does not bleed or crack when dried, and a conductive pattern having a desired wiring shape is obtained. It is to provide a conductive pattern having good conductivity.

  As a result of diligent research to solve the above-mentioned problems, the present inventors have found that the contact angle when the conductive ink, which is a fluid, is ejected onto the coating film having the primer applied to the surface of the support, and the conductive ink By making the rate of change of the droplet diameter in a certain time within a specific range, the conductive ink bleeds or cracks when dried when ink-jet printing is performed on a support having a primer coating film. Thus, the present inventors have found that a conductive pattern having a desired wiring shape can be obtained and a conductive pattern having good conductivity can be obtained, and the present invention has been completed.

  That is, in the present invention, a coating film (x) is formed by applying a primer to a part or all of the surface of the support, and a part or all of the surface of the coating film (x) has 2 carbon atoms. The support obtained by apply | coating the fluid (a) containing the alcohol (a1) containing the monoalcohol (a1-1) of ~ 4, and the electroconductive substance (a2), and drying, The said coating film ( x) a conductive layer in which a primer layer (X) formed from a layer (Y) containing the conductive substance (a2) is laminated, and the fluid ( The contact angle between the coating film (x) and the fluid (a) when the fine droplets a) are ejected is in the range of 15 to 70 °, and the liquid 200 ms after immediately after the landing of the fine droplets A conductive pattern having a drop rate change rate in a range of ± 30% and the conductive pattern It relates to the conductive circuit used.

  The conductive pattern of the present invention does not cause conductive ink bleeding or drying cracks when ink-jet printing of the conductive ink on a support, and the conductive pattern is obtained in a desired wiring shape. Is good. Therefore, the conductive pattern of the present invention includes, for example, formation of electronic circuits, organic solar cells and electronic book terminals, organic EL, organic transistors, flexible printed circuit boards, RFIDs such as non-contact IC cards, and the like, plasma displays It can be optimally used in the field of printed electronics such as the production of electromagnetic shielding wires, integrated circuits, and organic transistors.

  In the conductive pattern of the present invention, a coating film (x) is formed by applying a primer to part or all of the surface of the support, and carbon atoms are formed on part or all of the surface of the coating film (x). A support obtained by applying and drying a fluid (a) containing an alcohol (a1) containing a monoalcohol (a1-1) of formula 2-4 and a conductive substance (a2), and the coating A conductive pattern in which a primer layer (X) formed from a film (x) and a layer (Y) containing the conductive substance (a2) are laminated, and the flow of the primer layer (X) on the coating film (x) The contact angle between the coating film (x) and the fluid (a) when the fine droplets of the body (a) are discharged is in the range of 15 to 70 °, and 200 ms after immediately after the landing of the fine droplets The change rate of the droplet diameter is in the range of ± 30%.

  The conductive pattern of the present invention comprises at least a support, a primer layer (X), and a layer (Y) containing a conductive substance (a2).

  First, the primer layer (X) will be described. Examples of the primer layer (X) include a primer layer composed of the coating film (x), and after applying the fluid (a) to the surface of the coating film (x), active energy rays such as heating and ultraviolet rays. The primer layer (X-1) formed by irradiating is mentioned. That is, the coating film (x) can be used as the primer layer (X) as it is, and a primer layer (X newly formed by heating or irradiating active energy rays to the coating film (x). -1) can also be used as the primer layer (X).

  The primer layer (X) has an effect of bringing the support into close contact with a conductive substance (a2) such as silver contained in the fluid (a) such as conductive ink. Specifically, the coating film (x) formed using a primer absorbs the solvent contained in the fluid (a) when the fluid (a) contacts the surface thereof, and the coating (x) The conductive substance (a2) contained in the fluid (a) is supported on the surface of the film (x). Thereafter, the conductive material (a2) supported on the surface of the primer layer (X) by passing through a drying step at room temperature or a heating step such as firing if imparting conductivity. A conductive pattern is formed.

  The primer layer (X) may be provided on a part or the whole of the surface of the support, or may be provided on one side or both sides of the support. For example, the conductive pattern has a primer layer (X) on the entire surface of the support, and a layer containing the conductive substance (a2) only in a necessary portion of the primer layer (X) ( Those having Y) can be used. Moreover, the electroconductive pattern in which the said primer layer (X) was provided only in the part in which the said layer (Y) is provided among the surfaces of a support body may be sufficient.

  The primer layer (X) varies depending on the use of the conductive pattern of the present invention, but can maintain its good flexibility when a support having a foldable level of flexibility is used. The thickness is preferably 0.01 to 300 μm, and more preferably 0.05 to 20 μm.

  Next, the layer (Y) constituting the conductive pattern of the present invention will be described. The said layer (Y) is a layer comprised by the electroconductive substance (a2) contained in the said fluid (a), and has a role as a conductive layer or a plating nucleus layer. If the layer (Y) is, for example, a conductive ink containing silver as the fluid (a), the layer (Y) is constituted by a conductive substance (a2) such as silver contained in the conductive ink. It corresponds to a printed image or pattern composed of the conductive material (a2) such as silver.

  The layer (Y) is mainly composed of the conductive substance (a2), but other components contained in the fluid (a), for example, monoalcohols having 1 to 4 carbon atoms such as ethanol ( a1-1), a substance represented by the general formula (I) to be described later may remain in the layer (Y).

  The layer (Y) may be a layer provided on the entire surface of the primer layer (X), or may be a layer provided on a part of the surface of the primer layer (X). . Specifically, the layer (Y) present on a part of the surface of the primer layer (X) refers to a fine line-shaped layer formed on the surface of the primer layer (X). The thin line layer is suitable when the conductive pattern of the present invention is used as an electric circuit or the like.

  The width (line width) of the thin-line layer (pattern) is usually about 0.01 to 200 μm, but it is about 0.01 to 150 μm when increasing the density of the conductive pattern. preferable.

  The layer (Y) preferably has a thickness of 0.01 to 100 μm because a conductive pattern having low resistance and excellent conductivity can be formed. Moreover, when the said layer (Y) is a thin wire-like thing, it is preferable that the thickness (height) is the range of 0.1-50 micrometers.

  Next, the support which comprises the electroconductive pattern of this invention is demonstrated. Examples of the support used in the present invention include polyimide resin, polyamideimide resin, polyamide resin, polyethylene terephthalate, polyethylene naphthalate, polycarbonate, acrylonitrile-butadiene-styrene copolymer (ABS resin), and poly (meth) acrylic acid. Examples include a support made of an acrylic resin such as methyl, polyvinylidene fluoride, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, polyethylene, polypropylene, polyurethane, cellulose nanofiber, silicon, ceramics, and glass. The support may be porous.

  In addition, as the support, for example, synthetic fibers such as polyester fibers, polyamide fibers, and aramid fibers, and natural fibers such as cotton and hemp can be used. The fibers may be processed in advance.

  As the support, in general, a support made of polyimide resin, polyethylene terephthalate, polyethylene naphthalate, glass, cellulose nanofiber, etc., which is often used as a support when forming a conductive pattern such as a circuit board. Is preferably used.

  As the support, when the conductive pattern of the present invention is used for applications where flexibility is required, it is possible to use a material that is relatively flexible and capable of being bent, etc., to impart flexibility to the conductive pattern. It is preferable for obtaining a foldable final product. Specifically, it is preferable to use a film or sheet-like support formed by uniaxial stretching or the like.

  For example, a polyethylene terephthalate film, a polyimide film, or a polyethylene naphthalate film is preferably used as the film or sheet-like support.

  The support preferably has a thickness of about 1 to 2,000 μm and a thickness of about 1 to 200 μm from the viewpoint of realizing a lightweight and thin conductive pattern and a final product used for the conductive pattern. More preferably, it is a thickness. When a relatively flexible material is required as the laminate, it is preferable to use a material having a thickness of about 1 to 80 μm.

  A book having the primer layer (X) on part or all of the surface of the support, and a layer (Y) containing a conductive substance (a2) on part or all of the primer layer (X). In order to reduce the thickness of an electric circuit or the like, the conductive pattern of the invention is the thickness of the constituent parts other than the support, specifically, the total of the primer layer (X) and the layer (Y). The thickness is preferably in the range of 0.01 to 300 μm, more preferably 0.05 to 80 μm.

  Next, the fluid (a) used for production of the conductive pattern of the present invention will be described. The fluid (a) contains an alcohol (a1) containing a monoalcohol (a1-1) having 2 to 4 carbon atoms and a conductive substance (a2).

  The fluid (a) preferably has a viscosity at 23 ° C. in the range of 0.1 to 500,000 mPa · s, and is a liquid or viscous liquid in the range of 0.5 to 10,000 mPa · s. Those are more preferred.

  Further, when the fluid (a) is applied (printed) at a desired position by an ink jet printing method described later, the viscosity at 23 ° C. of the fluid (a) is 0.1 to 10,000 mPa. -The range of s is preferable, the range of 0.5-1,000 mPa * s is more preferable, and the range of 1-500 mPa * s is further more preferable. The viscosity is a value measured using an E-type viscometer (“TVE-22LT” manufactured by Toki Sangyo Co., Ltd.).

  Specific examples of the fluid (a) include a conductive ink and a plating nucleating agent that can be used when plating is performed.

  As the alcohol (a1) containing the monoalcohol (a1-1) used in the fluid (a), the monoalcohol (a1-1) is essential, and other alcohols are used as necessary. can do. The monoalcohol (a1-1) is used to form a conductive pattern excellent in thin lineability without impairing the adhesion and conductivity at a level that does not cause peeling of the conductive substance from the conductive pattern. , And used in combination with the primer layer (X).

  Examples of the monoalcohol (a1-1) include ethanol, n-propanol, isopropyl alcohol, n-butanol, isobutyl alcohol, sec-butanol, tert-butanol and the like. Among these, the use of ethanol is excellent in adhesion at a level that does not cause peeling of the conductive material from the conductive pattern, has low resistance and excellent conductivity, and is a fluid such as conductive ink ( It is particularly preferable for forming a conductive pattern excellent in fineness without causing repelling or bleeding from the coated surface of a). The monoalcohol (a1-1) is preferably contained in the range of 5 to 70% by mass and more preferably in the range of 10 to 50% by mass in the total amount of the fluid (a). .

  Moreover, as said alcohol (a1), it is preferable to use together the diol (a1-2) represented by the following general formula (1) with the monoalcohol (a1-1) illustrated above. When the diol (a1-2) is used in combination, the ejection stability can be improved when the fluid (a) such as conductive ink is applied by an ink jet method.

（一般式（Ｉ）中のＲは、水素原子又はアルキル基を表す。）

(R in the general formula (I) represents a hydrogen atom or an alkyl group.)

  The diol (a1-2) is a compound represented by the general formula (1). When R in the general formula (I) is an alkyl group, the alkyl group having 1 to 10 carbon atoms is Preferably, an alkyl group having 1 to 5 carbon atoms is more preferable, and an alkyl group having 1 to 3 carbon atoms is more preferable.

  As the diol (a1-2), it was possible to suppress the peeling of the layer (Y) formed from the conductive substance (a2) contained in the fluid (a) from the primer layer (X), and the diol (a1-2) was printed. Since the occurrence of cracks in the wiring pattern can be suppressed and a conductive pattern having excellent conductivity can be obtained, 1,3-butylene glycol in which R in the general formula (I) is a hydrogen atom, or R is methyl It is preferred to use the group isoprene glycol.

  When the diol (a1-2) is used, it is possible to improve the discharge stability of the fluid (a) and form a wiring pattern having excellent conductivity, so that the total amount of the fluid (a) is 5 to 5. It is preferably contained in the range of 60% by mass, more preferably in the range of 15-50% by mass, and further preferably in the range of 20-40% by mass.

  Examples of other alcohols that can be used in addition to the monoalcohol (a1-1) and the diol (a1-2) as the alcohol (a1) include 2-ethyl-1,3-hexanediol, ethylene glycol, and diethylene glycol. , Triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, 1,2-butanediol, 1,4-butanediol, 2,3-butanediol, glycerin and the like. In addition, a solvent other than those described above may be added to the fluid (a) as long as the gist of the present invention is not impaired.

  Examples of the conductive substance (a2) include transition metals or compounds thereof. Among them, an ionic transition metal is preferable because it has a low electrical resistance and can form a conductive pattern resistant to corrosion, and transition metals such as copper, silver, gold, nickel, palladium, platinum, and cobalt are more preferable, and copper Silver, gold and the like are more preferable, and silver is particularly preferable.

  In addition, when the fluid (a) is used as a plating nucleating agent, the metal particles made of the transition metal used as the conductive material (a2) exemplified above, and the surface thereof is formed by the oxide or organic substance of the transition metal. One or more types of coated ones can be used.

  In addition, since the oxide of the transition metal is usually in an inactive (insulating) state, even if the fluid (a) containing it is simply applied to the surface of the support, it does not exhibit conductivity. There are many cases. Therefore, when the fluid (a) containing the oxide is applied to the surface of the support, the surface is treated with a reducing agent such as dimethylaminoborane to expose the transition metal and activate (conductive) ) Is preferable.

  In addition, examples of the metal whose surface is coated with the organic substance include those in which a metal is contained in resin particles (organic substance) formed by an emulsion polymerization method or the like. Since these are usually inactive (insulating) like the transition metal oxides, even if the fluid containing them is simply applied to the surface of the support, it does not exhibit conductivity. There are many cases. Therefore, when a fluid containing a metal surface-coated with the organic substance is applied to the surface of the support, the transition metal is exposed by irradiating the surface with a laser or the like to remove the organic substance. A layer having activity (conductivity) is preferable.

  The conductive substance (a2) preferably has an average particle diameter of 1 to 100 nm, but has a fine conductive pattern as compared with the case of using a conductive substance having an average particle diameter on the order of micrometers. Since it can form and the resistance value after a heating can be reduced more, what has an average particle diameter of 1-50 nm is more preferable. The “average particle size” is a volume average value measured by a dynamic light scattering method after diluting the conductive substance (a2) with a dispersion good solvent. For this measurement, “Nanotrack UPA-150” manufactured by Microtrack Co. can be used.

  The conductive substance (a2) is preferably included in the total amount of the fluid (a) in a range of 5 to 90% by mass, more preferably in a range of 5 to 85% by mass, More preferably, it is contained in the range of 60% by mass, and particularly preferably in the range of 20-40% by mass.

  The fluid (a) used in the present invention contains a solvent such as an aqueous medium or an organic solvent as necessary together with the alcohol (a1) and the conductive substance (a2). It is preferable when used as an ink or plating nucleating agent.

  Examples of the aqueous medium include distilled water, ion exchange water, pure water, and ultrapure water. Examples of the organic solvent include heptanol, hexanol, octanol, nonanol, decanol, undecanol, dodecanol, tridecanol, tetradecanol, pentadecanol, stearyl alcohol, allyl alcohol, cyclohexanol, terpineol, terpineol, dihydroterpineol, Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, tetraethylene glycol monobutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, triplicate Alcohol solvents such as pyrene glycol monomethyl ether, propylene glycol monopropyl ether, dipropylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monobutyl ether and tripropylene glycol monobutyl ether; ketone solvents such as acetone, cyclohexanone and methyl ethyl ketone; acetic acid Ester solvents such as ethyl, butyl acetate, 3-methoxybutyl acetate, 3-methoxy-3-methyl-butyl acetate; toluene, octane, nonane, decane, dodecane, tridecane, tetradecane, cyclooctane, xylene, mesitylene, ethylbenzene, dodecyl Hydrocarbon solvents such as benzene, tetralin and trimethylbenzenecyclohexane; mineral spirits And solvents such as solvent naphtha.

  The fluid (a) of the present invention can be produced, for example, by mixing the alcohol (a1), the conductive substance (a2) and the solvent as necessary. Among them, a composition containing the conductive substance (a2) and the solvent is produced, and then the composition and the alcohol (a1) containing the monoalcohol (a1-1) or the diol (a1-2). Is preferable to improve the dispersion stability of the conductive material and prevent cracks in the layer (Y).

  As the composition containing the conductive substance (a2) and the solvent, a dispersion in which the conductive substance (a2) is dispersed in a solvent such as the aqueous medium or the organic solvent can be used.

  The dispersion can be produced by mixing and stirring the conductive substance (a2) and the solvent. Specifically, SW1000 (manufactured by Bando Chemical Co., Ltd.), Silk Auto A-1 (manufactured by Mitsubishi Materials Corporation), MDot-SLP (manufactured by Mitsuboshi Belting Co., Ltd.), etc. can be used as the dispersion. .

  The dispersion and the alcohol (a1) can be mixed with an apparatus generally used for mixing and dispersing, such as a mixer, a disper, a bead mill, or an ultrasonic homogenizer.

  The fluid (a) used in the present invention further improves the dispersion stability of the conductive substance (a2) in a solvent such as an aqueous medium or an organic solvent, In order to improve the wettability to the surface of the coating film (x), a surfactant, an antifoaming agent, a rheology adjusting agent and the like may be contained as necessary.

  As the fluid (a), from the viewpoint of removing impurities and the like after being manufactured by the above-described method, a fluid filtered using a micropore filter or the like, or a material processed using a centrifugal separator or the like is used. You can also

  Next, the primer used when manufacturing the electroconductive pattern of this invention is demonstrated. The primer forms a coating film (x) that can carry the conductive substance (a2) contained in the fluid (a) and can form the conductive pattern layer (Y) of the present invention. is there.

  As a primer which can form the said coating film (x), what contains various resin and a solvent can be used.

  Examples of the resin include urethane resin (x1), vinyl resin (x2), urethane-vinyl composite resin (x3), phenol resin, epoxy resin, melamine resin, urea resin, unsaturated polyester resin, alkyd resin, polyimide resin, A fluororesin or the like can be used.

  Among the resins, urethane resin having a polycarbonate structure as urethane resin (x1), urethane resin having an aliphatic polyester structure, acrylic resin having a structural unit derived from methyl methacrylate as vinyl resin (x2), and urethane-vinyl As the composite resin (x3), one or more resins (x-1) selected from the group consisting of urethane-acrylic composite resins are preferable, and urethane-acrylic composite resins are more preferable.

  As said primer, since the outstanding applicability | paintability can be maintained, what contains 10-70 mass% of said resins in the whole quantity of the said primer is preferable, and what contains 10-50 mass% is more preferable.

  Moreover, as a solvent which can be used for the primer, various organic solvents and aqueous media can be used.

  As the organic solvent, for example, toluene, ethyl acetate, methyl ethyl ketone, or the like can be used. Examples of the aqueous medium include water, organic solvents miscible with water, and mixtures thereof.

  Examples of the organic solvent miscible with water include alcohol solvents such as methanol, ethanol, n- and isopropanol, ethyl carbitol, ethyl cellosolve, and butyl cellosolve; ketone solvents such as acetone and methyl ethyl ketone; ethylene glycol, diethylene glycol, propylene glycol, and the like Polyalkylene glycol solvents; alkyl ether solvents of polyalkylene glycols; lactam solvents such as N-methyl-2-pyrrolidone.

  In the present invention, only water may be used, a mixture of water and an organic solvent miscible with water may be used, or only an organic solvent miscible with water may be used.

  The primer is preferably one containing 25 to 90% by mass of the solvent in the total amount of the primer, and more preferably 50 to 85% by mass because it is easy to apply.

  In the case of using an aqueous medium as the solvent, it is preferable to use a resin having a hydrophilic group as the resin in order to impart good water dispersibility to the primer and improve storage stability. Examples of the hydrophilic group include an anionic group, a cationic group, and a nonionic group.

  Examples of the anionic group include a carboxyl group, a carboxylate group, a sulfonic acid group, and a sulfonate group. Among them, a carboxylate group or a sulfonate group partially or wholly neutralized with a basic compound or the like It is preferable for imparting good water dispersibility.

  Examples of basic compounds that can be used for neutralizing the anionic group include organic amines such as ammonia, triethylamine, pyridine, and morpholine; alkanolamines such as monoethanolamine; metals including sodium, potassium, lithium, calcium, and the like Examples include basic compounds. In the case of forming a conductive pattern or the like, the ammonia, organic amine or alkanolamine is preferable because the metal base compound may lower the conductivity.

  When the carboxylate group or the sulfonate group is used as the anionic group, the presence of the carboxylate group or the sulfonate group in the range of 50 to 2,000 mmol / kg with respect to the whole resin can improve the water dispersion stability of the resin. It is preferable in maintaining.

  Moreover, as said cationic group, a tertiary amino group etc. can be used, for example. Examples of the acid that can be used for neutralizing a part or all of the tertiary amino group include organic acids such as acetic acid, propionic acid, lactic acid, and maleic acid; organic acids such as sulfonic acid and methanesulfonic acid. Sulfonic acid; inorganic acids such as hydrochloric acid, sulfuric acid, orthophosphoric acid and orthophosphorous acid can be used alone or in combination of two or more. In the case of forming the conductive pattern, it is preferable to use acetic acid, propionic acid, lactic acid, maleic acid and the like because chlorine, sulfur, and the like may lower the conductivity.

  Moreover, as said nonionic group, polyoxyalkylene groups, such as a polyoxyethylene group, a poly (oxyethylene-oxypropylene) group, a polyoxyethylene-polyoxypropylene group, can be used, for example. Among them, it is preferable to use a polyoxyalkylene group having an oxyethylene unit because hydrophilicity can be further improved.

  As the urethane resin (x1) that can be used as the resin contained in the primer, a urethane resin obtained by reacting a polyol, a polyisocyanate, and, if necessary, a chain extender can be used. Especially, it is preferable to use the urethane resin which has a polycarbonate structure, and the urethane resin which has an aliphatic polyester structure.

  The polycarbonate structure and the aliphatic polyester structure are preferably derived from a polyol used for the production of the urethane resin. Specifically, the polycarbonate structure-containing urethane resin can be produced by using a polycarbonate polyol that will be described later as the polyol. Moreover, the urethane resin having the aliphatic polyester structure can be produced using a resin containing an aliphatic polyester polyol described later as the polyol.

  As a polyol that can be used in the production of the urethane resin (x1), other polyols can be used in combination with the polycarbonate polyol and the aliphatic polyester polyol as necessary.

  Examples of the polycarbonate polyol include those obtained by reacting a carbonate and polyol, and those obtained by reacting phosgene and bisphenol A.

  Examples of the carbonic acid ester include methyl carbonate, dimethyl carbonate, ethyl carbonate, diethyl carbonate, cyclocarbonate, diphenyl carbonate, and the like.

  Examples of the polyol that can react with the carbonate ester include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, dipropylene glycol, 1,4-butanediol, 1,3. -Butanediol, 1,2-butanediol, 2,3-butanediol, 1,5-pentanediol, 1,5-hexanediol, 2,5-hexanediol, 1,6-hexanediol, 1,7- Heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 3-methyl-1,5-pentanediol, 2 -Ethyl-1,3-hexanediol, 2-methyl-1,3-pro Diol, 2-methyl-1,8-octanediol, 2-butyl-2-ethylpropanediol, 2-methyl-1,8-octanediol, neopentyl glycol, hydroquinone, resorcin, bisphenol-A, bisphenol-F, And relatively low molecular weight dihydroxy compounds such as 4,4′-biphenol.

  Examples of the aliphatic polyester polyol include aliphatic polyester polyols obtained by esterification reaction of low molecular weight polyols and polycarboxylic acids; ring-opening polymerization of cyclic ester compounds such as ε-caprolactone and γ-butyrolactone. Aliphatic polyesters obtained by reaction; these copolyesters and the like.

  Examples of the low molecular weight polyol include ethylene glycol, 1,2-propanediol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, and 3-methyl-1,5-pentane. Diol, neopentyl glycol, diethylene glycol, dipropylene glycol, glycerin, trimethylolpropane and the like can be used alone or in combination of two or more. In addition, ethylene glycol, 1,2-propanediol, 1,3-butanediol, 1,4-butanediol, etc., and 3-methyl-1,5-pentanediol, neopentyl glycol, etc. should be used in combination. Is preferred.

  Examples of the polycarboxylic acid include succinic acid, adipic acid, sebacic acid, dodecanedicarboxylic acid, azelaic acid and anhydrides or ester-forming derivatives thereof, and aliphatic polycarboxylic acids such as adipic acid. It is preferred to use an acid.

  As said polycarbonate polyol and aliphatic polyester polyol, it is preferable to use a thing with a number average molecular weight of 500-4,000, and it is more preferable to use a 500-2,000 thing.

  Moreover, as a polyol which can be used for manufacture of the said urethane resin (x1), another polyol can be used together as needed other than an above-described thing.

  Examples of the other polyol include ethylene glycol, 1,2-propanediol, 1,3-butanediol, 1,4-butanediol, 3-methyl-1,5-pentanediol, and 1,6-hexanediol. 1,4-cyclohexanedimethanol, neopentyl glycol, diethylene glycol, dipropylene glycol, glycerin, trimethylolpropane, and other polyols, acrylic polyols with hydroxyl groups introduced into acrylic copolymers, and butadiene containing hydroxyl groups in the molecule Polymers such as polybutadiene polyol, hydrogenated polybutadiene polyol, partially saponified product of ethylene-vinyl acetate copolymer, and the like can be used.

  Moreover, when manufacturing the urethane resin which has a hydrophilic group as said urethane resin (x1), it is preferable to use the polyol which has a hydrophilic group as said other polyol.

  Examples of the polyol having a hydrophilic group include a polyol having a carboxyl group such as 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid and 2,2-dimethylolvaleric acid; 5-sulfoisophthalic acid And polyols having a sulfonic acid group such as sulfoterephthalic acid, 4-sulfophthalic acid, and 5- (4-sulfophenoxy) isophthalic acid. Examples of the polyol having a hydrophilic group include a polyester polyol having a hydrophilic group obtained by reacting the above-described polyol having a low molecular weight hydrophilic group with various polycarboxylic acids such as adipic acid. Can also be used.

  Examples of the polyisocyanate capable of reacting with the polyol to form a urethane resin include, for example, 4,4′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate, carbodiimide-modified diphenylmethane diisocyanate, crude diphenylmethane diisocyanate, phenylene diisocyanate, tolylene diisocyanate, Polyisocyanates having an aromatic structure such as naphthalene diisocyanate; aliphatic polyisocyanates or aliphatic cyclic structures such as hexamethylene diisocyanate, lysine diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate Poly with Isocyanate, and the like.

  Moreover, as a chain extender which can be used when manufacturing the said urethane resin, a polyamine, a hydrazine compound, the compound which has an active hydrogen atom, etc. are mentioned, for example.

  Examples of the polyamine include ethylenediamine, 1,2-propanediamine, 1,6-hexamethylenediamine, piperazine, 2,5-dimethylpiperazine, isophoronediamine, 4,4′-dicyclohexylmethanediamine, and 3,3′-. Diamines such as dimethyl-4,4′-dicyclohexylmethanediamine, 1,4-cyclohexanediamine; N-hydroxymethylaminoethylamine, N-hydroxyethylaminoethylamine, N-hydroxypropylaminopropylamine, N-ethylaminoethylamine, N -Methylaminopropylamine, diethylenetriamine, dipropylenetriamine, triethylenetetramine, etc. are mentioned, Among these, ethylenediamine is preferable.

  Examples of the hydrazine compound include hydrazine, N, N′-dimethylhydrazine, 1,6-hexamethylenebishydrazine, succinic acid dihydrazide, adipic acid dihydrazide, glutaric acid dihydrazide, sebacic acid dihydrazide, isophthalic acid dihydrazide, β-semicarbazide. Examples include propionic acid hydrazide, 3-semicarbazide-propyl-carbazate, semicarbazide-3-semicarbazidemethyl-3,5,5-trimethylcyclohexane, and the like.

  Examples of the other active hydrogen-containing compounds include ethylene glycol, diethylene recall, triethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, hexamethylene glycol, Glycols such as saccharose, methylene glycol, glycerin, sorbitol; phenolic compounds such as bisphenol A, 4,4′-dihydroxydiphenyl, 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxydiphenylsulfone, hydrogenated bisphenol A, hydroquinone , Water and the like.

  The chain extender is preferably used, for example, in an amount ratio [amino group / isocyanate group] between the amino group of the polyamine and the isocyanate group of 1.9 or less, 0.3 to 1 It is more preferable to use in the range.

  The urethane resin (x1) is produced, for example, by reacting the polyol, the polyisocyanate, and, if necessary, the chain extender by a known method in the absence of a solvent or in the presence of an organic solvent. be able to.

  The reaction between the polyol and the polyisocyanate is preferably performed at a reaction temperature of 50 to 120 ° C., more preferably 80 to 100 ° C. in consideration of safety, paying careful attention to sudden heat generation and foaming. And the polyisocyanate can be mixed at once or sequentially supplied by a method such as dropping one of them to the other and allowed to react for about 1 to 15 hours.

  Moreover, the primer containing the water dispersion of the said urethane resin (x1) manufactures a urethane resin (x1) by making the said polyol, the said polyisocyanate, and a chain extender react as needed by the above-mentioned method. If necessary, after neutralizing a part or all of hydrophilic groups such as anionic groups of the urethane resin (x1), it is mixed with an aqueous medium used as a solvent for the primer. Thus, a primer composed of an aqueous dispersion of urethane resin (x1) in which urethane resin (x1) is dispersed or partially dissolved in an aqueous medium can be obtained.

  More specifically, by reacting the polyol and the polyisocyanate by the method described above, a urethane prepolymer having an isocyanate group at the terminal is produced, and if necessary, the anionic group possessed by the urethane prepolymer. After neutralizing a part or all of the hydrophilic group such as the like, the urethane resin (x1) is aqueous by mixing it with the aqueous medium and extending the chain using the chain extender as necessary. A primer comprising a urethane resin (x1) aqueous dispersion dispersed or dissolved in a medium can be obtained.

  The reaction between the polyisocyanate and the polyol is preferably performed, for example, in a range where the equivalent ratio [isocyanate group / hydroxyl group] of the isocyanate group of the polyisocyanate and the hydroxyl group of the polyol is 0.90-2. .

  When manufacturing the said urethane resin (x1), an organic solvent can also be used as a solvent as above-mentioned. Examples of the organic solvent include ketone solvents such as acetone and methyl ethyl ketone; ether solvents such as tetrahydrofuran and dioxane; acetate solvents such as ethyl acetate and butyl acetate; nitrile solvents such as acetonitrile; dimethylformamide, N-methylpyrrolidone and the like. Examples include amide solvents.

  The organic solvent is preferably removed by distillation or the like after the production of the urethane resin (x1). Moreover, when using what contains the said urethane resin (x1) and an organic solvent as said primer, the organic solvent used when manufacturing the said urethane resin (x1) is used as a solvent of the said primer. May be.

  The urethane resin (x1) has a weight average molecular weight of 5,000 to 500,000 because it can form a conductive pattern with excellent adhesion to the conductive substance (a2) and excellent conductivity. A thing of 20,000-100,000 is more preferable.

  As said urethane resin (x1), what has various functional groups can be used as needed. Examples of the functional group include crosslinkable functional groups such as an alkoxysilyl group, a silanol group, a hydroxyl group, and an amino group. The crosslinkable functional group is preferable because a pattern having excellent durability (the layer (Y)) can be formed by forming a crosslinked structure in the primer layer (X) carrying the fluid (a).

  The alkoxysilyl group or silanol group can be introduced into the urethane resin by using γ-aminopropyltriethoxysilane or the like when the urethane resin (x1) is produced.

  Moreover, when using the said urethane resin (x1) in combination with the crosslinking agent (D) mentioned later, what has the functional group which can react with the functional group which the said crosslinking agent (D) has can be used. . As the functional group, although depending on the selection of the crosslinking agent (D) to be used in combination, for example, when a crosslinking agent such as a blocked isocyanate compound is used, a hydroxyl group or an amino group can be used.

  Moreover, as a vinyl resin (x2) which can be used as resin contained in the said primer, the polymer of the monomer which has a polymerizable unsaturated double bond can be used. Specifically, polyethylene, polypropylene, polybutadiene, ethylene-propylene copolymer, natural rubber, synthetic isopropylene rubber, ethylene-vinyl acetate copolymer, acrylic resin, etc. can be used, and a structure derived from methyl methacrylate It is preferable to use an acrylic resin having units.

  As the acrylic resin, a polymer or copolymer obtained by polymerizing a (meth) acrylic monomer can be used. In addition, a (meth) acryl monomer points out any one or both of an acrylic monomer and a methacryl monomer.

  As said acrylic resin, it can manufacture by polymerizing the various (meth) acryl monomers mentioned later, for example.

  Examples of the (meth) acrylic monomer include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, and (meth) acrylic acid. t-butyl, 2-ethylhexyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, dodecyl (meth) acrylate, (meth) (Meth) acrylic esters such as stearyl acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate; (meth) acrylic acid 2,2,2-trifluoroethyl, 2,2,3,3-pentafluoropropyl (meth) acrylate, ( And (meth) acrylic acid alkyl esters such as perfluorocyclohexyl acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, and β- (perfluorooctyl) ethyl (meth) acrylate. Can be mentioned.

  Among the above (meth) acrylic monomers, methyl methacrylate is excellent in the primer layer (X) and the support regardless of the influence of heat or the like in the heating step or the like in producing the conductive pattern. It is preferable because it can provide high adhesion. In addition, a fine line having a line width of about 0.01 to 200 μm, preferably about 0.01 to 150 μm, when forming a conductive pattern such as an electronic circuit is printed without causing bleeding (improving the fine line property). ), It is preferable to use methyl methacrylate.

  Moreover, since it can improve adhesiveness and electroconductivity more and can form the electroconductive pattern excellent in fine-line property without the bleeding etc. of the said fluid (a), it is C2-C12 alkyl with the said methyl methacrylate. It is preferable to use a (meth) acrylic acid alkyl ester having a group, more preferably an acrylic acid alkyl ester having an alkyl group having 3 to 8 carbon atoms, and n-butyl acrylate to be used. Further preferred.

  The methyl (meth) acrylate is preferably used in the range of 10 to 70% by mass and more preferably in the range of 30 to 65% by mass in the total amount of the (meth) acrylic monomer mixture. . In addition, the acrylic acid alkyl ester having an alkyl group having 2 to 12 carbon atoms or the acrylic acid alkyl ester having an alkyl group having 3 to 8 carbon atoms is 20% in the total amount of the (meth) acrylic monomer mixture. It is preferable to use in the range of -80 mass%, and it is more preferable to use in the range of 35-70 mass%. It is.

  Moreover, as a (meth) acryl monomer which can be used when manufacturing the said acrylic resin, in addition to what was mentioned above, acrylic acid, methacrylic acid, (meth) acrylic acid beta-carboxyethyl, 2- (meth) acryloyl It has a carboxyl group such as propionic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, itaconic acid half ester, maleic acid half ester, maleic anhydride, itaconic anhydride, β- (meth) acryloyloxyethyl hydrogen succinate Vinyl monomers can be used. The vinyl monomer having a carboxyl group may be neutralized with ammonia, potassium hydroxide or the like.

  The (meth) acrylic monomer includes one or more amide groups selected from the group consisting of a methylolamide group and an alkoxymethylamide group, an amide group other than the above, a hydroxyl group, and a glycidyl group. From the viewpoint of introducing the crosslinkable functional group such as amino group, silyl group, aziridinyl group, isocyanate group, oxazoline group, cyclopentenyl group, allyl group, carboxyl group, acetoacetyl group, etc. A mer can be used.

  Examples of the vinyl monomer having one or more amide groups selected from the group consisting of a methylolamide group and an alkoxymethylamide group that can be used for the (meth) acrylic monomer having a crosslinkable functional group include, for example, N -Methylol (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-methoxyethoxymethyl (meth) acrylamide, N-ethoxymethyl (meth) acrylamide, N-propoxymethyl (meth) acrylamide, N-isopropoxymethyl ( (Meth) acrylamide, Nn-butoxymethyl (meth) acrylamide, N-isobutoxymethyl (meth) acrylamide, N-pentoxymethyl (meth) acrylamide, N-ethoxymethyl-N-methoxymethyl (meth) acrylamide, N , N'-dimethylol (Meth) acrylamide, N-ethoxymethyl-N-propoxymethyl (meth) acrylamide, N, N′-dipropoxymethyl (meth) acrylamide, N-butoxymethyl-N-propoxymethyl (meth) acrylamide, N, N-di Butoxymethyl (meth) acrylamide, N-butoxymethyl-N-methoxymethyl (meth) acrylamide, N, N′-dipentoxymethyl (meth) acrylamide, N-methoxymethyl-N-pentoxymethyl (meth) acrylamide, etc. Is mentioned. Among these, the use of Nn-butoxymethyl (meth) acrylamide and N-isobutoxymethyl (meth) acrylamide can prevent peeling of the conductive substance (a2) in the plating process described later. It is preferable because a conductive pattern having the above durability can be formed.

  Examples of the (meth) acrylic monomer having a crosslinkable functional group include, in addition to those described above, vinyl monomers having an amide group such as (meth) acrylamide, 2-hydroxyethyl (meth) acrylate, and the like. 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, (meth) acrylic acid (4-hydroxy) Vinyl monomers having a hydroxyl group such as methylcyclohexyl) methyl, glycerol (meth) acrylate, polyethylene glycol (meth) acrylate, N-hydroxyethyl (meth) acrylamide: glycidyl (meth) acrylate, (meth) acrylic acid Polymerizable monomer having a glycidyl group such as allyl glycidyl ether Polymerizable monomer having an amino group such as aminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, N-monoalkylaminoalkyl (meth) acrylate, and N, N-dialkylaminoalkyl (meth) acrylate Mer: vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, γ- (meth) acryloxypropyltrimethoxysilane, γ- (meth) acryloxypropyltriethoxysilane, γ- (meth) acryloxypropylmethyldimethoxysilane, γ- (meth) acryloxypropylmethyldiethoxysilane, γ- (meth) acryloxypropyltriisopropoxysilane, N-β- (N-vinylbenzylaminoethyl) -Γ-aminopropyltrimeth Polymerizable monomer having silyl group of silane and its hydrochloride; Polymerizable monomer having aziridinyl group such as (meth) acrylic acid 2-aziridinylethyl; (meth) acryloyl isocyanate, (meth) acryloyl isocyanate Polymerizable monomers having (blocked) isocyanate groups such as ethyl phenol and their methyl ethyl ketoxime adducts; Polymerizability having oxazoline groups such as 2-isopropenyl-2-oxazoline and 2-vinyl-2-oxazoline Monomer; polymerizable monomer having a cyclopentenyl group such as (meth) acrylate dicyclopentenyl; polymerizable monomer having an allyl group such as allyl (meth) acrylate; acrolein, diacetone (meth) acrylamide It is possible to use a polymerizable monomer having a carbonyl group such as That.

  The (meth) acryl monomer having the crosslinkable functional group can be used in the range of 0 to 50% by mass in the total amount of the (meth) acryl monomer mixture. In addition, when using what carries out a self-crosslinking reaction as said crosslinking agent (D), it is not necessary to use the (meth) acryl monomer which has the said crosslinkable functional group.

  Among the (meth) acrylic monomers having the crosslinkable functional group, the (meth) acrylic monomer having the amide group has a (meth) acrylic group for introducing a self-crosslinking reactive methylolamide group. It is preferable to use in the range of 0.1-50 mass% in the whole quantity of a monomer mixture, and it is more preferable to use in the range of 1-30 mass%. In addition, the (meth) acryl monomer having another amide group and the (meth) acryl monomer having a hydroxyl group used in combination with the self-crosslinking reactive methylolamide group are the (meth) acryl monomer. It is preferable to use in the range of 0.1-30 mass% in total in the whole quantity of, and it is more preferable to use in the range of 1-20 mass%.

  Among the (meth) acrylic monomers having a crosslinkable functional group, the (meth) acrylic monomer having a hydroxyl group and the (meth) acrylic monomer having an acid group are used as a crosslinking agent. Although it depends on the type of (D), it is preferably used in the range of 0.05 to 50% by mass and used in the range of 0.05 to 30% by mass in the total amount of the (meth) acrylic monomer mixture. It is preferable to use it at 0.1 to 10% by mass.

  In addition, when the acrylic resin is produced, together with the (meth) acrylic monomer, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl versatate, methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, amyl Vinyl ether, hexyl vinyl ether, (meth) acrylonitrile, styrene, α-methyl styrene, vinyl toluene, vinyl anisole, α-halostyrene, vinyl naphthalene, divinyl styrene, isoprene, chloroprene, butadiene, ethylene, tetrafluoroethylene, vinylidene fluoride, N -Vinylpyrrolidone, polyethylene glycol mono (meth) acrylate, glycerol mono (meth) acrylate, vinyl sulfonic acid, styrene sulfonic acid, Ryl sulfonic acid, 2-methylallyl sulfonic acid, 2-sulfoethyl (meth) acrylate, 2-sulfopropyl (meth) acrylate, “Adekaria soap PP-70, PPE-710” (manufactured by ADEKA Corporation) or those A combination of salts and the like can also be used.

  The acrylic resin can be produced by polymerizing a mixture of various vinyl monomers as described above by a conventionally known method, but produces a conductive pattern having excellent adhesion and excellent conductivity. In addition, it is preferable to apply an emulsion polymerization method.

  As the emulsion polymerization method, for example, water, a (meth) acrylic monomer mixture, a polymerization initiator, and, if necessary, a chain transfer agent, an emulsifier, a dispersion stabilizer, and the like are collectively supplied into a reaction vessel. , A method of mixing and polymerizing; a monomer dropping method in which a (meth) acrylic monomer mixture is dropped into a reaction vessel and polymerizing; a (meth) acrylic monomer mixture, an emulsifier and the like and water mixed in advance; Examples thereof include a pre-emulsion method in which the reaction is dropped and polymerized in a reaction vessel.

  The reaction temperature of the emulsion polymerization method varies depending on the type of (meth) acrylic monomer and polymerization initiator used, but is preferably about 30 to 90 ° C., for example, and the reaction time is 1 to 10 for example. It is preferable that it is about time.

  Examples of the polymerization initiator include persulfates such as potassium persulfate, sodium persulfate, and ammonium persulfate; organic peroxides such as benzoyl peroxide, cumene hydroperoxide, and t-butyl hydroperoxide; hydrogen peroxide Radical polymerization using only these peroxides, or metal salts of ascorbic acid, erythorbic acid, sodium erythorbate, formaldehyde sulfoxylate, sodium thiosulfate, bisulfite Polymerization can also be achieved by a redox polymerization initiator system in combination with a reducing agent such as sodium or ferric chloride, and 4,4′-azobis (4-cyanovaleric acid), 2,2′-azobis (2 An azo initiator such as -amidinopropane) dihydrochloride can also be used. These compounds may be used alone or in combination of two or more.

  Examples of emulsifiers that can be used in the production of the acrylic resin include anionic surfactants, nonionic surfactants, cationic surfactants, and zwitterionic surfactants.

  Examples of the anionic surfactant include sulfates of higher alcohols and salts thereof, alkylbenzene sulfonates, polyoxyethylene alkylphenyl sulfonates, polyoxyethylene alkyl diphenyl ether sulfonates, and polyoxyethylene alkyl ethers. Examples include non-ionic surfactants such as polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene alkyl phenyl ether, and polyoxyethylene alkyl phenyl ether. Examples thereof include ethylene diphenyl ether, polyoxyethylene-polyoxypropylene block copolymer, and acetylenic diol surfactant.

  Examples of the cationic surfactant include alkyl ammonium salts.

  Examples of zwitterionic surfactants include alkyl (amido) betaines and alkyldimethylamine oxides.

  As the emulsifier, in addition to the above surfactants, fluorine surfactants, silicone surfactants, and emulsifiers having a polymerizable unsaturated group generally called “reactive emulsifier” in the molecule. It can also be used.

  Examples of the reactive emulsifier include “Latemul S-180” (manufactured by Kao Corporation) having a sulfonic acid group and a salt thereof, “Eleminol JS-2, RS-30” (manufactured by Sanyo Chemical Industries, Ltd.) and the like; “AQUALON HS-10, HS-20, KH-1025” (Daiichi Kogyo Seiyaku Co., Ltd.), “ADEKA rear soap SE-10, SE-20” (manufactured by ADEKA Corporation) having a sulfate group and a salt thereof, etc. "New Frontier A-229E" having a phosphate group (Daiichi Kogyo Seiyaku Co., Ltd.) and the like; "Aqualon RN-10, RN-20, RN-30, RN-50" having a nonionic hydrophilic group ( Daiichi Kogyo Seiyaku Co., Ltd.) can be used.

  Moreover, as a chain transfer agent which can be used for manufacture of the said acrylic resin (x2-1), a lauryl mercaptan etc. can be used, and 0-1 mass% in the whole quantity of the said (meth) acryl monomer mixture. It is preferable to use in the range, and it is more preferable that it is the range of 0-0.5 mass%.

  Moreover, as urethane-vinyl composite resin (x3) which can be used as resin contained in the primer, urethane resin (x3-1) and vinyl polymer (x3-2) form composite resin particles in an aqueous medium. Can be dispersed.

  Specific examples of the composite resin particles include those in which part or all of the vinyl polymer (x3-2) is contained in the resin particles formed by the urethane resin (x3-1). It is preferable to form core-shell type composite resin particles composed of the vinyl polymer (x3-2) as the core layer and the urethane resin having the hydrophilic group as the shell layer. In particular, when forming a conductive pattern, it is preferable to use the core-shell type composite resin particles that do not require the use of a surfactant or the like that can lower the electrical characteristics. As the composite resin particles, it is preferable that the vinyl polymer (x3-2) is almost completely covered with the urethane resin (x3-1), but it is not essential and the effect of the present invention is impaired. A part of the vinyl polymer (x3-2) may be present on the outermost part of the composite resin particle as long as it is not present.

  Further, as the composite resin particles, when the vinyl polymer (x3-2) is more hydrophilic than the urethane resin (x3-1), the vinyl polymer (x3- In the resin particles formed by 2), part or all of the urethane resin (x3-1) may be present to form composite resin particles.

  The urethane resin (x3-1) and the vinyl polymer (x3-2) may form a covalent bond, but preferably do not form a bond.

  Moreover, as said urethane-vinyl composite resin (x3), it is preferable to use the urethane-acrylic composite resin whose said vinyl polymer (x3-2) is an acrylic resin.

  Moreover, it is preferable that the said composite resin particle is an average particle diameter of the range of 5-100 nm from a viewpoint of maintaining favorable water dispersion stability. The average particle diameter here refers to the average particle diameter on a volume basis measured by a dynamic light scattering method.

  The mass ratio of the urethane resin (x3-1) and the vinyl polymer (x3-2) constituting the urethane-vinyl composite resin is [urethane resin (x3-1) / vinyl polymer (x3-2)]. ] = 90/10 to 5/95 is preferable, 70/30 to 10/90 is more preferable, and 40/60 to 20 to 80 is even more preferable.

  As urethane resin (x3-1) which comprises the said urethane-vinyl composite resin, the thing similar to the said urethane resin (x1) can be used. Moreover, as urethane resin (x3-1) which comprises the said urethane-vinyl composite resin, in addition to what was illustrated as said urethane resin (x1), it has a urethane resin which has a polyether structure, and an aromatic polyester structure, for example. Urethane resin can also be used.

  Examples of the polyol, polyisocyanate, and chain extender that can be used in the production of the urethane resin (x3-1) include the polyol, polyisocyanate, and chain extension exemplified as those that can be used when the urethane resin (x1) is produced. The same agent can be used.

Moreover, the urethane resin which has the said polyether structure can be manufactured by using what contains the polyether polyol mentioned later as the said polyol.
As the polyether polyol, for example, one obtained by addition polymerization of alkylene oxide using one or more compounds having two or more active hydrogen atoms as an initiator can be used.

  Examples of the initiator include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, trimethylene glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, and glycerin. , Trimethylolethane, trimethylolpropane and the like.

  Examples of the alkylene oxide include ethylene oxide, propylene oxide, butylene oxide, styrene oxide, epichlorohydrin, and tetrahydrofuran.

  Moreover, when using the urethane resin which has the said aromatic polyester structure, an aromatic polyester polyol can also be used as said polyol.

  Examples of the aromatic polyester polyol include those obtained by esterifying a low molecular weight polyol and an aromatic polycarboxylic acid.

  Examples of the low molecular weight polyol that can be used in the production of the aromatic polyester polyol include ethylene glycol, 1,2-propanediol, 1,3-butanediol, 1,4-butanediol, and 1,6-hexanediol. , 3-methyl-1,5-pentanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, glycerin, trimethylolpropane and the like can be used alone or in combination of two or more thereof. It is preferable to use propanediol, 1,3-butanediol, 1,4-butanediol, or the like in combination with 3-methyl-1,5-pentanediol, neopentyl glycol, or the like.

  Examples of the aromatic polycarboxylic acid include terephthalic acid, isophthalic acid, phthalic acid, naphthalenedicarboxylic acid, and anhydrides or esterified products thereof.

  The polyether polyol and aromatic polyester polyol preferably have a number average molecular weight of 500 to 4,000, more preferably 500 to 2,000.

  As the vinyl polymer (x3-2) constituting the urethane-vinyl composite resin, it is possible to use a polymer having a glass transition temperature of 10 to 70 ° C. The adhesiveness to a2) and the conductivity of the resulting conductive pattern can be further improved, which is preferable. In addition, the glass transition temperature of the said vinyl polymer (x3-2) is a value determined by calculation mainly based on the composition of the vinyl monomer used for manufacture of this vinyl polymer (x3-2). is there. Specifically, the vinyl polymer (x3-2) having the predetermined glass transition temperature can be obtained by using a combination of the vinyl polymer (x3-2) described later.

  Moreover, as said vinyl polymer (x3-2), the adhesiveness with the electroconductive substance (a2) contained in the said fluid (a) and the electroconductivity of the electroconductive pattern obtained are improved more, and it is electroconductive. In view of the fact that the property pattern can be further thinned, those having a weight average molecular weight of 800,000 or more are preferable, and those having a weight average molecular weight of 1,000,000 or more are more preferable.

  Although it does not specifically limit as an upper limit of the weight average molecular weight of the said vinyl polymer (x3-2), It is preferable that it is 10 million or less, and it is more preferable that it is 5 million or less.

  The vinyl polymer (x3-2) may have various functional groups as necessary. Examples of the functional group include an amide group, a hydroxyl group, a glycidyl group, an amino group, and a silyl group. Crosslinkable functional groups such as aziridinyl group, isocyanate group, oxazoline group, cyclopentenyl group, allyl group, carboxyl group, and acetoacetyl group.

  As said vinyl polymer (x3-2), the thing similar to the said vinyl polymer (x2) can be used. Specifically, as the (meth) vinyl monomer that can be used for the production of the vinyl polymer (x3-2), the vinyl monomers exemplified as those that can be used for the production of the vinyl resin (x2). Can be used, and preferably the same as the (meth) acrylic monomer can be used. Especially, as a vinyl polymer (x3-2), it is preferable to use the thing similar to the acrylic resin which has a structural unit derived from the methyl methacrylate illustrated as what can be used for the said vinyl resin (x2).

  For example, the urethane-vinyl composite resin (x3) is produced by reacting the polyisocyanate, polyol, and, if necessary, a chain extender and dispersing in water to produce an aqueous dispersion of the urethane resin (x3-1). The step (V) and the step (W) of polymerizing the (meth) acrylic monomer in the aqueous dispersion to produce a vinyl polymer (x3-2).

  Specifically, the urethane resin (x3-1) is reacted by reacting the polyisocyanate and the polyol in the absence of a solvent or in an organic solvent or in the presence of a reactive diluent such as a (meth) acrylic monomer. Then, a part or all of the hydrophilic group of the urethane resin (x3-1) is neutralized with a basic compound as necessary, and further reacted with a chain extender as necessary. And dispersing it in an aqueous medium to produce an aqueous dispersion of urethane resin (x3-1).

  Next, a vinyl monomer such as the (meth) acrylic monomer is supplied into the aqueous dispersion of the urethane resin (x3-1) obtained above, and within the urethane resin (x3-1) particles. The vinyl monomer is radically polymerized to produce a vinyl resin (x3-2). When the urethane resin (x3-1) is produced in the presence of a vinyl monomer, the production of the urethane resin (x3-1) is followed by supplying a polymerization initiator and the like. A vinyl resin (x3-2) is produced by radical polymerization of a vinyl monomer such as a (meth) acrylic monomer.

  Thereby, the primer which the composite resin particle which a part or all of the said vinyl resin (x3-2) contained in the said urethane resin (x3-1) particle | grains disperse | distributed to the aqueous medium can be manufactured.

  When the composite resin particles are produced, when the urethane resin (x3-1) has a high viscosity, the usual resin such as methyl ethyl ketone, N-methyl pyrrolidone, acetone, dipropylene glycol dimethyl ether is used for the purpose of improving workability. The viscosity may be lowered using an organic solvent or a reactive diluent. In particular, the use of a vinyl monomer such as a (meth) acrylic monomer that can be used in the production of the vinyl polymer (x3-2) as the reactive diluent is a primer that eliminates the solvent removal step. This is preferable because the production efficiency can be further improved.

  In addition to the above-mentioned resins that can be used for the primer, for example, phenol resin, epoxy resin, melamine resin, urea resin, unsaturated polyester resin, alkyd resin, polyimide resin, fluororesin, etc. should be used. Can do.

  The resins exemplified as resins that can be used for the primer may be used in combination. For example, two or more of the urethane resin (x1), vinyl resin (x2), and urethane-vinyl composite resin (x3) can be used in appropriate combination. Further, as the urethane resin (x1), a urethane resin having a polyether structure and a urethane resin having a polycarbonate structure can be used in combination.

  As the primer, the urethane resin (x1) and the vinyl resin (x2) can be used in combination. When used in such a combination, the mass ratio [(x1) / (x2)] of the urethane resin (x1) and the vinyl resin (x2) is preferably in the range of 90/10 to 5/95, 70 The range of / 30 to 10/90 is more preferable, and the range of 40/60 to 20 to 80 is more preferable.

  As the resin contained in the primer, those having a crosslinkable functional group can be used as described above.

  The crosslinkable functional group forms a crosslink structure in the primer layer (X) carrying the fluid (a), thereby causing a pattern (layer (excellent in adhesion) and conductivity without causing bleeding or the like. Y)) can be used suitably.

  The coating film (x) formed using the primer may have a crosslinked structure before the fluid (a) is applied (printed) on a part or all of the surface thereof.

  In addition, the coating film (x) does not have a crosslinked structure before the fluid (a) is applied (printed) to the surface thereof, and after the fluid (a) is applied (printed). A primer layer having a crosslinked structure may be formed as the primer layer (X).

  Examples of the crosslinkable functional group include an alkoxysilyl group and a silanol group, as well as an amino group and a hydroxyl group.

  When the resin having the alkoxysilyl group and the silanol group is used, the alkoxysilyl group and the silanol group are hydrolyzed and condensed in an aqueous medium that is a solvent for the primer to form a crosslinked structure. By applying a primer having a crosslinked structure to the surface of the support and drying it, a coating film (x) having a crosslinked structure is formed before applying (printing) the fluid (a).

  Moreover, as said crosslinkable functional group, it can carry out a crosslinking reaction between crosslinkable functional groups or the crosslinking agent (D) mentioned later by heating to 100 degreeC or more, Preferably it is 120 degreeC or more, and the said crosslinked structure can be formed. Specifically, it is preferable to use one or more thermally crosslinkable functional groups selected from the group consisting of a methylolamide group and an alkoxymethylamide group.

  Specific examples of the alkoxymethylamide group include an amide group formed by bonding a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, a butoxymethyl group or the like to a nitrogen atom, and among them, a methylolamide group and It is preferable to use one having at least one selected from the group consisting of alkoxymethylamide groups because the durability of the primer layer (X) and the adhesion to various supports can be greatly improved.

  When using a primer including a resin having a functional group capable of undergoing a crosslinking reaction by heating to 100 ° C. or higher, preferably about 120 ° C. as described above, the primer is applied to the surface of the support and dried. The temperature is preferably less than 100 ° C. Thereby, the coating film which does not have a crosslinked structure substantially as said coating film (x) can be formed.

  After applying (printing) the fluid (a) to the coating film having no crosslinked structure, the primer layer is heated at a temperature of 100 ° C. or higher, or by heating separately from the heating step. A primer layer having a cross-linked structure can also be formed as (X).

  In this way, after coating (printing) with the fluid (a), a plating agent made of a strong alkali or strong acid substance is formed in the plating process described later by forming a crosslinked structure in the primer layer (X). Even when exposed to the above, it is possible to form a conductive pattern having exceptional durability without causing peeling of the primer layer (X) from the support. The phrase “substantially has no cross-linked structure” includes an embodiment in which the cross-linked structure is not formed at all, and within about 5% of the number of functional groups capable of forming the cross-linked structure is partially cross-linked. Refers to the structure formed.

  The crosslinkable functional group is preferably included in a total range of 0.005 to 1.5 equivalent / kg with respect to the total amount of resin used in the primer.

  Moreover, the said primer is a range which does not impair the effect of this invention, A crosslinking agent (D) as needed, A pH adjuster, a film formation adjuvant, a leveling agent, a thickener, a water repellent, a defoaming agent You may use suitably well-known things, such as an agent.

  As the crosslinking agent (D), for example, a metal chelate compound, a polyamine compound, an aziridine compound, a metal base compound, an isocyanate compound, or the like, which can react at a relatively low temperature of less than 25 to 100 ° C. to form a crosslinked structure. One or more types selected from the group consisting of agent (d1-1), melamine compound, epoxy compound, oxazoline compound, carbodiimide compound, and blocked isocyanate compound react at a relatively high temperature of 100 ° C. or higher to form a crosslinked structure. The thermal crosslinking agent (d1-2) which can be used, and various photocrosslinking agents can be used.

  The primer containing the thermal crosslinking agent (d1-1) is, for example, applied to the surface of the support, dried at a relatively low temperature, and then applied (printed) to the temperature of less than 100 ° C. By forming a cross-linked structure by heating to a temperature, a conductive pattern with exceptional durability that can prevent the loss of conductive materials regardless of the effects of heat and external forces over a long period of time is formed. be able to.

  On the other hand, the primer containing the thermal crosslinking agent (d1-2) forms a crosslinked structure by, for example, applying it to the support surface and drying at a low temperature of room temperature (25 ° C.) to less than 100 ° C. After producing the coating film (x) not applied and then applying (printing) the fluid (a), for example, it is heated at a temperature of 150 ° C. or higher, preferably 200 ° C. or higher to form a crosslinked structure. Thus, it is possible to obtain a conductive pattern having a remarkably excellent durability that does not cause peeling of the conductive material regardless of the influence of heat, external force, etc. over a long period of time.

  However, when using a support made of polyethylene terephthalate or the like that is relatively heat-sensitive as a support, heating is performed at a temperature of 150 ° C. or less, preferably 120 ° C. or less, from the viewpoint of preventing deformation of the support. Therefore, it is preferable to use the thermal crosslinking agent (d1-1) instead of the thermal crosslinking agent (d1-2) as the crosslinking agent.

  Examples of metal chelate compounds that can be used for the thermal crosslinking agent (d1-1) include polyvalent metals such as aluminum, iron, copper, zinc, tin, titanium, nickel, antimony, magnesium, vanadium, chromium, and zirconium. An acetylacetone coordination compound, an acetoacetate coordination compound and the like can be used, and it is preferable to use acetylacetone aluminum which is an acetylacetone coordination compound of aluminum.

  Moreover, as a polyamine compound which can be used for the said thermal crosslinking agent (d1-1), tertiary amines, such as a triethylamine, a triethylenediamine, a dimethylethanolamine, can also be used, for example.

  Examples of the aziridine compound that can be used for the thermal crosslinking agent (d1-1) include 2,2-bishydroxymethylbutanol-tris [3- (1-aziridinyl) propionate], 1,6-hexamethylenediethylene. Urea, diphenylmethane-bis-4,4′-N, N′-diethyleneurea and the like can be used.

  Examples of the metal base compound that can be used as the crosslinking agent (d1-1) include aluminum sulfate, aluminum alum, aluminum sulfite, aluminum thiosulfate, polyaluminum chloride, aluminum nitrate nonahydrate, and aluminum chloride hexahydrate. Water-soluble metal salts such as Japanese products, titanium tetrachloride, tetraisopropyl titanate, titanium acetylacetonate, and titanium lactate can be used.

  Examples of the isocyanate compound that can be used for the thermal crosslinking agent (d1-1) include tolylene diisocyanate, hydrogenated tolylene diisocyanate, triphenylmethane triisocyanate, methylenebis (4-phenylmethane) triisocyanate, isophorone diisocyanate, hexa Polyisocyanates such as methylene diisocyanate and xylylene diisocyanate; isocyanurate-type polyisocyanate compounds obtained by using them; adducts composed of them with trimethylolpropane; and the like; the polyisocyanate compound and a polyol such as trimethylolpropane are reacted. It is possible to use urethane having a polyisocyanate group obtained by the above process. Among them, hexamethylene diisocyanate nurate, adduct of hexamethylene diisocyanate and trimethylolpropane, adduct of tolylene diisocyanate and trimethylolpropane, adduct of xylylene diisocyanate and trimethylolpropane, etc. are used. It is preferable.

  Examples of the melamine compound that can be used in the thermal crosslinking agent (d1-2) include hexamethoxymethyl melamine, hexaethoxymethyl melamine, hexapropoxymethyl melamine, hexabutoxymethyl melamine, hexapentyloxymethyl melamine, and hexahexyl. Oxymethyl melamine or a mixed etherified melamine obtained by combining these two types can be used. Of these, trimethoxymethyl melamine and hexamethoxymethyl melamine are preferably used. As a commercial item, becamine M-3, APM, J-101 (made by DIC Corporation) etc. can be used. The melamine compound can form a crosslinked structure by a self-crosslinking reaction.

  When the melamine compound is used, a catalyst such as an organic amine salt may be used to promote the self-crosslinking reaction. As a commercial item, catalyst ACX, 376 etc. can be used. The catalyst is preferably in the range of 0.01 to 10 parts by mass with respect to 100 parts by mass of the melamine compound.

  Examples of the epoxy compound that can be used for the thermal crosslinking agent (d1-2) include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, hexamethylene glycol diglycidyl ether, cyclohexanediol diglycidyl ether, and glycerin diglycidyl. Polyglycidyl ethers of aliphatic polyhydric alcohols such as ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, pentaerythritol tetraglycidyl ether; polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, polytetramethylene glycol diglycidyl ether Polyglycidyl ethers of polyalkylene glycols such as 1,3-bis (N, N ′ Polyglycidylamines such as diglycidylaminoethyl) cyclohexane; polyglycidyl esters of polycarboxylic acids [succinic acid, adipic acid, butanetricarboxylic acid, maleic acid, phthalic acid, terephthalic acid, isophthalic acid, benzenetricarboxylic acid, etc.]; bisphenol A Bisphenol A-based epoxy resins such as condensates of chlorophenol and epichlorohydrin and ethylene oxide adducts of bisphenol A and epichlorohydrin condensates; phenol novolac resins; various vinyl (co) polymers having an epoxy group in the side chain. Among these, it is preferable to use polyglycidylamines such as 1,3-bis (N, N'-diglycidylaminoethyl) cyclohexane; polyglycidyl ethers of aliphatic polyhydric alcohols such as glycerin diglycidyl ether.

  Examples of the epoxy compound include, in addition to those described above, for example, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, and γ-glycid. Xylpropylmethyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethylmethyldi Examples also include silane compounds having a glycidyl group such as ethoxysilane or γ-glycidoxypropyltriisopropenyloxysilane.

  Examples of the oxazoline compound that can be used in the thermal crosslinking agent (d1-2) include 2,2′-bis- (2-oxazoline), 2,2′-methylene-bis- (2-oxazoline), 2,2′-ethylene-bis- (2-oxazoline), 2,2′-trimethylene-bis- (2-oxazoline), 2,2′-tetramethylene-bis- (2-oxazoline), 2,2 ′ -Hexamethylene-bis- (2-oxazoline), 2,2'-octamethylene-bis- (2-oxazoline), 2,2'-ethylene-bis- (4,4'-dimethyl-2-oxazoline), 2,2'-p-phenylene-bis- (2-oxazoline), 2,2'-m-phenylene-bis- (2-oxazoline), 2,2'-m-phenylene-bis- (4,4 ' -Dimethyl-2-oxa Phosphorus), bis - (2-oxazolinyl sulfonyl cyclohexane) sulfide, bis - (2-oxazolinyl sulfonyl norbornane) sulfide, and the like.

  Moreover, as said oxazoline compound, the polymer which has an oxazoline group obtained by superposing | polymerizing combining the following addition polymerizable oxazoline and another monomer as needed can also be used, for example.

  Examples of the addition polymerizable oxazoline include 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, and 2-isopropenyl-2-oxazoline. 2-isopropenyl-4-methyl-2-oxazoline, 2-isopropenyl-5-methyl-2-oxazoline, 2-isopropenyl-5-ethyl-2-oxazoline, etc., alone or in combination. be able to. Among these, it is preferable to use 2-isopropenyl-2-oxazoline because it is easily available industrially.

  Examples of the carbodiimide compound that can be used for the thermal crosslinking agent (d1-2) include poly [phenylenebis (dimethylmethylene) carbodiimide] and poly (methyl-1,3-phenylenecarbodiimide). it can. Commercially available products include Carbodilite V-01, V-02, V-03, V-04, V-05, V-06 (manufactured by Nisshinbo Co., Ltd.), UCALINK XL-29SE, XL-29MP (manufactured by Union Carbide Corporation). Etc.

  Moreover, as a block isocyanate compound which can be used for the said thermal crosslinking agent (d1-2), a part or all of the isocyanate group which the isocyanate compound illustrated as the said thermal crosslinking agent (d1-1) has by a blocking agent is used. Examples include sealed ones.

  Examples of the blocking agent include phenol, cresol, 2-hydroxypyridine, butyl cellosolve, propylene glycol monomethyl ether, benzyl alcohol, methanol, ethanol, n-butanol, isobutanol, dimethyl malonate, diethyl malonate, and methyl acetoacetate. , Ethyl acetoacetate, acetylacetone, butyl mercaptan, dodecyl mercaptan, acetanilide, acetic acid amide, ε-caprolactam, δ-valerolactam, γ-butyrolactam, succinimide, maleic imide, imidazole, 2-methylimidazole, urea, thiourea , Ethylene urea, formamide oxime, acetald oxime, acetone oxime, methyl ethyl ketoxime, methyl isobutyl ketoxime, cyclohexa N'okishimu, diphenylaniline, aniline, carbazole, ethyleneimine, polyethyleneimine and the like.

  As the blocked isocyanate compound, Elastolon BN-69 (Daiichi Kogyo Seiyaku Co., Ltd.) can be used as a water-dispersed commercial product.

  When using the said crosslinking agent (D), it is preferable to use what has a group which can react with the crosslinkable functional group which the said crosslinking agent (D) has as resin contained in the said primer. Specifically, it is preferable to use the (block) isocyanate compound, the melamine compound, the oxazoline compound, and the carbodiimide compound as a crosslinking agent, and use a resin having a hydroxyl group or a carboxyl group as the resin.

  Although the said crosslinking agent (D) changes with kinds etc., it is preferable to use normally in the range of 0.01-60 mass parts with respect to a total of 100 mass parts of resin contained in the said primer. More preferably, it is used in the range of 10 to 10 parts by mass, and it is used in the range of 0.1 to 5 parts by mass to form a conductive pattern excellent in adhesion and conductivity and excellent in the durability. This is preferable because it is possible.

  The crosslinking agent (D) is preferably added and used in advance before the primer of the present invention is applied or impregnated on the surface of the support.

  Moreover, as said additive, various fillers, such as an inorganic particle, can also be used. However, as the primer of the present invention, the amount of the filler and the like used is preferably as small as possible, and more preferably 5% by mass or less based on the total amount of the primer of the present invention.

  Although the usage-amount of the said additive will not be specifically limited if it is a range which does not impair the effect of this invention, It is preferable that it is the range of 0.01-40 mass% in the total amount of the solid content in a primer.

  Next, the manufacturing method of the electroconductive pattern of this invention is demonstrated.

  In the conductive pattern of the present invention, a primer is applied to part or all of the surface of the support, and then the fluid is applied to part or all of the surface of the coating film (x) formed using the primer. After the body (a) is applied (printed), it can be produced by drying.

  First, a method for forming the coating film (x) by applying a primer to a part or all of the surface of the support will be described.

  The said coating film (x) can be formed by the method of apply | coating the said primer to the said support body, and removing solvents, such as an aqueous medium and an organic solvent contained in the said primer.

  The primer that can be applied to a part or all of the surface of the support to form the coating film (x) can form the primer layer (X) of the conductive pattern of the present invention.

  Examples of a method for applying the primer to the surface of the support include a gravure method, a coating method, a screen method, a roller method, a rotary method, a spray method, a spin coater method, and an ink jet method.

  Moreover, as a method of removing the solvent contained in the primer, for example, a method of drying using a dryer and volatilizing the solvent is common. The drying temperature may be set to a temperature that can volatilize the solvent and does not adversely affect the support.

  The coating amount of the primer on the support is preferably in the range where the film thickness of the coating film (x) is 0.01 to 300 μm from the viewpoint of imparting excellent adhesion and conductivity. A range of 0.05 to 20 μm is more preferable.

  The film thickness of the coating film (x) obtained by the above method is preferably in the range where the thickness of the primer layer (X) constituting the finally obtained conductive pattern is 0.01 to 300 μm. .

  The conductive pattern of the present invention has a contact angle of 15 between the coating film (x) and the fluid (a) when the droplets of the fluid (a) are ejected onto the coating film (x). It is a range of ˜70 °, and the change rate of the droplet diameter after 200 ms from immediately after the landing of the minute droplet is in a range of ± 30%. In the present invention, the term “microdroplets” refers to those having a capacity in the range of 0.5 to 200 pl (picoliter).

  The contact angle and the droplet diameter are, for example, an ink jet type local contact angle meter (“Automatic Minimal Contact Angle Meter MCA-J” manufactured by Kyowa Interface Science Co., Ltd.), a droplet landing device (“DropMeasure 800” manufactured by MicroJet Corporation). Etc. can be measured.

  The rate of change of the droplet diameter is determined by the droplet diameter immediately after the landing of the fine droplet of the fluid (a) on the coating film (x), and the droplet diameter after 200 ms (milliseconds) immediately after the landing. Are respectively calculated and calculated by the following equation.

  The contact angle is in the range of 15 to 70 °, but is preferably in the range of 30 to 70 ° and more preferably in the range of 45 to 65 ° because the thin line property of the conductive pattern is improved.

  Further, the rate of change of the droplet diameter is in the range of ± 30%. However, since the linear reproducibility of the conductive pattern is improved, the range of ± 20% is preferable, and the range of ± 10% is more preferable.

  Further, in the present invention, by setting the contact angle and the rate of change of the droplet diameter within a predetermined range, the conductive ink bleeds when ink-jet printing is performed on the support as the fluid (a). In addition, a conductive pattern having a desired wiring shape can be obtained without causing cracks during drying. In order to make the change rate of the contact angle and the droplet diameter within a predetermined range, it is preferable to adjust the composition of the fluid (a), and does not depend on the composition of the coating film (x).

  The said coating film (x) is a film | membrane used as the precursor of the said primer layer (X) formed by active energy ray irradiation, such as a heating and an ultraviolet-ray. Moreover, the said coating film (x) can also be made into the primer layer (X) by drying at normal temperature etc., for example.

  Next, a method for producing a conductive pattern by applying (printing) the fluid (a) to a part or all of the surface of the coating film (x) obtained above and then drying it will be described. To do.

  As a method of applying (printing) the fluid (a) to a part or all of the surface of the coating film (x), an ink jet printing method is preferable, but other printing methods such as a screen printing method and an offset method are used. Can be applied (printed) using printing methods, reversal printing methods such as letterpress reversal printing methods, spin coating methods, spray coating methods, bar coating methods, die coating methods, slit coating methods, roll coating methods, dip coating methods, etc. Good.

  0.01 required for realizing high-density electronic circuits and the like by applying (printing) the fluid (a) to part or all of the surface of the coating film (x) by an ink jet printing method. A thin linear conductive pattern of about 100 μm can be obtained more easily.

  As the ink jet printing method, what is generally called an ink jet printer can be used. Specific examples of the inkjet printer include Konica Minolta EB100, XY100 (manufactured by Konica Minolta IJ Co., Ltd.), Dimatics Material Printer DMP-3000, Dimatics Material Printer DMP-2831 (manufactured by Fuji Film Co., Ltd.), and the like. Can be mentioned.

  The fluid (a) coated (printed) can be dried by, for example, room temperature or heating. Especially, when providing electroconductivity by closely_contact | adhering and joining between electroconductive substances (a2), such as a metal contained in the said fluid (a), it is preferable to heat. On the other hand, when a plating nucleating agent is used as the fluid (a), the conductivity by the conductive substance (a2) is not necessarily required. In such a case, the conductive substance (a2) may be supported on the surface of the primer layer made of the coating film (x) by drying at room temperature or the like.

  The heating is preferably performed at 80 to 300 ° C. for about 2 to 200 minutes. Although the said heating may be performed in air | atmosphere, you may perform a part or all of heating process in a reducing atmosphere from a viewpoint of preventing the oxidation of the said metal. The conductive pattern of the present invention can form a pattern with excellent adhesion and conductivity even when heated at a relatively low temperature of 80 to 120 ° C.

  The heating step can be performed using, for example, an oven, a hot air drying furnace, an infrared drying furnace, laser irradiation, microwave, or the like.

  In addition, as the resin contained in the primer, the fluid (a) is applied by using a resin having a crosslinkable functional group that undergoes a crosslinking reaction at a relatively high temperature, or by using the crosslinking agent (d1-2). When a crosslinked structure is to be formed in the primer layer (X) after (printing), the crosslinked structure is formed after coating (printing) by passing through the heating step. Thereby, durability of a conductive pattern can be improved to each step.

  When the crosslinking reaction step and the heating step are carried out, the heating temperature is in the range of 80 to 300 ° C., although it varies depending on the type of the crosslinking agent (D) used, the combination of crosslinkable functional groups, and the like. Is preferable, 100-300 degreeC is more preferable, 120-300 degreeC is further more preferable. In addition, when the said support body is comparatively weak to heat, it is preferable that the upper limit of temperature shall be 150 degrees C or less, and it is more preferable to set it as 120 degrees C or less.

  On the surface of the conductive pattern obtained through the heating step, a conductive pattern is formed by a conductive substance (a2) such as a metal contained in the fluid (a). This conductive pattern can be used to form electronic circuits using silver ink, organic solar cells and electronic book terminals, organic EL, organic transistors, flexible printed circuit boards, RFID layers, peripheral wiring, plasma display It is useful in the field of printed electronics such as wiring for electromagnetic shielding.

  In addition, as the conductive pattern, a plating process using a metal such as copper was performed in order to form a highly reliable wiring pattern capable of maintaining good conductivity without causing disconnection or the like over a long period of time. Things can be used. Specifically, as the conductive pattern, for example, a part or all of the surface of the support has a coating film (x) formed using the primer, and the surface of the coating film (x) By applying (printing) a plating nucleating agent as the fluid (a) to a part or all of the coating nuclei, the plating nuclei are supported on the surface of the coating film (x), and a heating step or the like is performed as necessary. After passing, what has a plating layer (Z) which consists of an electroplating process, an electroless-plating process, or the plating film formed by performing an electroplating process after the said electroless-plating process is mentioned.

  The electroless plating treatment step is included in the electroless plating solution by contacting the electroless plating solution with the surface of the plating layer such as palladium or silver supported on the primer layer (X), for example. This is a step of forming an electroless plating layer (coating) made of a metal coating by depositing a metal such as copper.

  As the electroless plating solution, for example, a solution containing a conductive substance made of a metal such as copper, nickel, chromium, cobalt, tin, a reducing agent, and a solvent such as an aqueous medium or an organic solvent is used. Can do.

  Examples of the reducing agent include dimethylaminoborane, hypophosphorous acid, sodium hypophosphite, dimethylamine borane, hydrazine, formaldehyde, sodium borohydride, and a phenol compound.

  In addition, as the electroless plating solution, if necessary, monocarboxylic acids such as acetic acid and formic acid; dicarboxylic acids such as malonic acid, succinic acid, adipic acid, maleic acid, fumaric acid; malic acid, lactic acid, glycolic acid Hydroxycarboxylic acids such as gluconic acid and citric acid; amino acids such as glycine, alanine, arginine, aspartic acid and glutamic acid; aminopolycarboxylic acids such as iminodiacetic acid, nitrilotriacetic acid, ethylenediaminediacetic acid, ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid Organic acids such as: Soluble salts of these organic acids (sodium salts, potassium salts, ammonium salts, etc.), and complexing agents such as amines such as ethylenediamine, diethylenetriamine, and triethylenetetramine may also be used.

  The temperature of the electroless plating solution when the electroless plating solution is brought into contact with the surface of the primer layer (X) carrying the plating nuclei in the plating nucleating agent is in the range of 20 to 98 ° C. preferable.

  In addition, the electrolytic plating treatment step is performed, for example, by applying an electrolytic plating solution to the surface of the primer layer (X) on which the plating nucleus is supported or the surface of the electroless plating layer (coating) formed by the electroless treatment. By energizing in the contact state, a metal such as copper contained in the electrolytic plating solution is used to form the primer layer (X) placed on the negative electrode or the electroless plating layer (coating) formed by the electroless treatment. It is a step of depositing on the surface to form an electrolytic plating film (metal film).

  As said electroplating liquid, what contains the electroconductive substance which consists of metals, such as copper, nickel, chromium, cobalt, tin, a sulfuric acid, etc., and an aqueous medium can be used.

  The temperature of the electrolytic plating solution when the electrolytic plating solution is brought into contact with the surface of the primer layer (X) carrying the plating nucleus in the plating nucleating agent is preferably in the range of 20 to 98 ° C. .

  In the process of electroless plating and electrolytic plating as described above, the above strong acid or strong alkaline plating solution is used. Therefore, in the normal primer layer, the primer layer is affected by the plating solution, and the primer layer is supported. May peel from the body.

  On the other hand, after applying (printing) the fluid (a) containing the plating nucleating agent or the like on the coating film (x), the coating film (x) is coated with the primer layer (X) having a crosslinked structure formed thereon. In this case, the primer layer (X) is preferably not peeled off from the support in the plating treatment step. In particular, even when the support is a polyimide resin, it is possible to suppress the peeling of the primer layer (X), which is extremely useful for producing the conductive pattern of the present invention.

  The conductive pattern as described above includes, for example, formation of electronic circuits using silver ink or the like, organic solar cells, electronic book terminals, organic EL, organic transistors, flexible printed boards, RFID, etc. It can be suitably used for forming and forming a conductive pattern, more specifically, a circuit board in manufacturing an electromagnetic wave shield wiring of a plasma display.

  Moreover, after apply | coating (printing) fluid (a), such as electroconductive ink or a plating nucleating agent, among the electroconductive patterns obtained by the said method, a crosslinked structure is formed in the said primer layer (X). Even when the conductive pattern obtained through the plating treatment step, the primer layer (X) does not peel off from the support and can maintain high conductivity, thereby providing outstanding durability. Each layer constituting a circuit forming substrate used for electronic circuits, integrated circuits, etc. using silver ink, organic solar cells, electronic book terminals, organic EL, organic transistors, flexible printed boards, RFIDs, etc. It is suitable for applications that require particularly high durability among the formation of peripheral wiring, wiring for electromagnetic shielding of plasma displays, and the like. In particular, since the conductive pattern subjected to the plating treatment does not cause a problem such as disconnection over a long period of time and can form a highly reliable wiring pattern capable of maintaining high conductivity, for example, a copper-clad laminate is generally used. (CCL: Copper Clad Laminate), which is suitable for applications such as flexible printed circuit board (FPC), automatic tape bonding (TAB), chip on film (COF), printed wiring board (PWB) and the like.

  Hereinafter, the present invention will be described in detail by way of examples.

[Preparation Example 1: Preparation of primer (1)]
In a reaction vessel equipped with a stirrer, reflux condenser, nitrogen inlet tube, thermometer, and dropping funnel, 115 parts by mass of deionized water and emulsifier (“Latemul E-118B” manufactured by Kao Corporation: 25% by mass of active ingredient) 4 A mass part was added, and the temperature was raised to 75 ° C. while blowing nitrogen.

  Under stirring, a vinyl monomer mixture consisting of 60 parts by weight of methyl methacrylate, 3 parts by weight of methacrylic acid and 37 parts by weight of n-butyl acrylate and a reactive emulsifier (“AQUALON” manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) KH-1025 ": active ingredient 25% by mass) 4 parts by mass and 15 parts by mass of deionized water were added and a part (5 parts by mass) of the monomer pre-emulsion was added, followed by potassium persulfate 0.1 parts by mass was added, and polymerization was performed in 60 minutes while maintaining the temperature in the reaction vessel at 75 ° C.

  Next, while maintaining the temperature in the reaction vessel at 75 ° C., the remaining monomer pre-emulsion (114 parts by mass) and 30 parts by mass of an aqueous solution of 1% by mass potassium persulfate were separately used using separate dropping funnels. For 180 minutes. After completion of dropping, the mixture was stirred at the same temperature for 60 minutes.

  The temperature in the reaction vessel was cooled to 40 ° C., and 10% by mass of ammonia water was added so that the pH of the aqueous dispersion in the reaction vessel was 8.5.

  Subsequently, after adding deionized water so that a non volatile matter might be 30 mass%, the primer (1) was prepared by filtering with a 200 mesh filter cloth.

[Preparation Example 2: Preparation of primer (2)]
Polyester polyol obtained by reacting 1,4-cyclohexanedimethanol, neopentyl glycol and adipic acid in a nitrogen-substituted container equipped with a thermometer, a nitrogen gas inlet tube and a stirrer (hydroxyl equivalent of 1,000 g) / Equivalent) 100 parts by mass, 17.6 parts by mass of 2,2-dimethylolpropionic acid, 21.7 parts by mass of 1,4-cyclohexanedimethanol and 106.2 parts by mass of dicyclohexylmethane diisocyanate in 178 parts by mass of methyl ethyl ketone The organic solvent solution of the urethane prepolymer which has an isocyanate group at the terminal was obtained by making it react by.

  Next, 13.3 parts by mass of triethylamine is added to the organic solvent solution of the urethane prepolymer to neutralize part or all of the carboxyl groups of the urethane prepolymer, and 380 parts by mass of water is further added to the solution. By stirring, an aqueous dispersion of urethane prepolymer was obtained.

  Next, 8.8 parts by mass of a 25% by mass aqueous ethylenediamine solution is added to the aqueous dispersion, and the urethane resin is chain-extended by stirring and aged / desolved to obtain a urethane resin having a non-volatile content of 30% by mass. An aqueous dispersion of (L-1) was obtained. The urethane resin (L-1) obtained here had an acid value of 30 and a weight average molecular weight of 53,000.

  Next, 140 parts by mass of deionized water in a reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, a thermometer, a dropping funnel for dropping the monomer mixture, and a dropping funnel for dropping the polymerization catalyst, the urethane resin obtained above 100 parts by mass of the aqueous dispersion (L-1) was added, and the temperature was raised to 80 ° C. while blowing nitrogen.

  A monomer mixture containing 50 parts by mass of methyl methacrylate and 50 parts by mass of n-butyl acrylate and 20 parts by mass of a 0.5% by mass aqueous ammonium persulfate solution in a reaction vessel heated to 80 ° C. with stirring. Was dropped from a separate dropping funnel over 120 minutes while maintaining the temperature in the reaction vessel at 80 ± 2 ° C. to polymerize.

  After completion of dropping, by stirring for 60 minutes at the same temperature, a shell layer made of the urethane resin (L-1) and a core layer made of a vinyl polymer formed by polymerizing the monomer mixture An aqueous dispersion of constituted urethane-acrylic composite resin particles was obtained.

  Primer (2) was prepared by cooling the temperature in the reaction vessel to 40 ° C., adding deionized water so that the non-volatile content was 20% by mass, and then filtering through a 200 mesh filter cloth. .

[Preparation Example 3: Preparation of primer (3)]

  A reaction vessel equipped with a stirrer, reflux condenser, nitrogen inlet tube, thermometer, dropping funnel for dropping the monomer mixture, dropping funnel for dropping the polymerization catalyst, 140 parts by mass of deionized water, urethane resin (L- 100 parts by mass of the aqueous dispersion 1) was added, and the temperature was raised to 80 ° C. while blowing nitrogen.

  A monomer mixture containing 50 parts by mass of methyl methacrylate, 45 parts by mass of n-butyl acrylate, and 5 parts by mass of Nn-butoxymethylacrylamide with stirring in a reaction vessel heated to 80 ° C; 20 parts by mass of a 5% by mass ammonium persulfate aqueous solution was dropped from a separate dropping funnel over 120 minutes while maintaining the temperature in the reaction vessel at 80 ± 2 ° C., and polymerized.

  After completion of dropping, by stirring for 60 minutes at the same temperature, a shell layer made of the urethane resin (L-1) and a core layer made of a vinyl polymer formed by polymerizing the monomer mixture An aqueous dispersion of composite resin particles constituted was obtained.

  Primer (3) was prepared by cooling the temperature in the reaction vessel to 40 ° C., adding deionized water so that the non-volatile content was 20% by mass, and then filtering through a 200 mesh filter cloth. . In addition, since the urethane-acrylic composite resin particle contained in primer (3) has a methylolamide group, the coating film of primer (3) has a crosslinked structure.

[Preparation Example 4: Preparation of primer (4)]
Polyester polyol (hydroxyl equivalent: 1) obtained by reacting 1,4-cyclohexanedimethanol, neopentyl glycol and adipic acid in a nitrogen-substituted container equipped with a thermometer, a nitrogen gas inlet tube, and a stirrer , 1,000 g / equivalent) 100 parts by weight, 2,2-dimethylolpropionic acid 17.6 parts by weight, 1,4-cyclohexanedimethanol 21.7 parts by weight, dicyclohexylmethane diisocyanate 106.2 parts by weight, methyl ethyl ketone 178 parts by weight The organic solvent solution of the urethane prepolymer which has an isocyanate group at the terminal was obtained by making it react in this.

  Next, 10 parts by mass of γ-aminopropyltriethoxysilane (“Aminosilane A1100” manufactured by Nihon Unicar Co., Ltd.) is mixed with the organic solvent solution of the urethane prepolymer, and the urethane prepolymer and γ-aminopropyltriethoxysilane are mixed. And an organic solvent solution of urethane resin was obtained.

  Next, 13.3 parts by mass of triethylamine is added to the organic solvent solution of the urethane resin to neutralize part or all of the carboxyl groups of the urethane resin, and 380 parts by mass of water is further added and sufficiently stirred. As a result, an aqueous dispersion of urethane resin was obtained.

  Next, 8.8 parts by mass of a 25% by mass ethylenediamine aqueous solution is added to the aqueous dispersion, and the urethane resin is chain-extended by stirring, followed by aging and desolvation, whereby a non-volatile content of 30% by mass is obtained. An aqueous dispersion of urethane resin (L-2) was obtained. The urethane resin (L-2) obtained here had an acid value of 30 and a weight average molecular weight of 88,000.

  Next, 140 parts by mass of deionized water in a reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, a thermometer, a dropping funnel for dropping the monomer mixture, and a dropping funnel for dropping the polymerization catalyst, the urethane resin obtained above 100 parts by mass of the aqueous dispersion (L-2) was added, and the temperature was raised to 80 ° C. while blowing nitrogen.

  In a reaction vessel heated to 80 ° C., with stirring, a monomer mixture containing 50 parts by mass of methyl methacrylate and 50 parts by mass of n-butyl acrylate, and 20 parts by mass of a 0.5% by mass aqueous ammonium persulfate solution were added. From a separate dropping funnel, polymerization was carried out by dropping over 120 minutes while maintaining the temperature in the reaction vessel at 80 ± 2 ° C.

  After completion of dropping, by stirring for 60 minutes at the same temperature, a shell layer made of the urethane resin (L-2) and a core layer made of a vinyl polymer formed by polymerizing the monomer mixture An aqueous dispersion of constituted urethane-acrylic composite resin particles was obtained.

  Primer (4) was prepared by cooling the temperature in the reaction vessel to 40 ° C., adding deionized water so that the non-volatile content was 20% by mass, and then filtering through a 200 mesh filter cloth. .

[Preparation Example 5: Preparation of primer (5)]
First, ethylene glycol, 1,4-butanediol, 1,4-butanediol, isophthalic acid, and terephthalic acid were reacted in a nitrogen-substituted container equipped with a thermometer, a nitrogen gas inlet tube, and a stirrer. 64 parts by mass of the obtained polyester polyol (hydroxyl equivalent: 840 g / equivalent), 7 parts by mass of 2,2-dimethylolpropionic acid, 6 parts by mass of 1,4-cyclohexanedimethanol and 47 parts by mass of dicyclohexylmethane diisocyanate were added to methyl ethyl ketone. By making it react in 80 mass parts, the organic solvent solution of the urethane prepolymer which has an isocyanate group at the terminal was obtained.

  Next, 5 parts by mass of triethylamine is added to the organic solvent solution of the urethane prepolymer to neutralize part or all of the carboxyl groups of the urethane prepolymer, and 264 parts by mass of water is further added and sufficiently stirred. As a result, an aqueous dispersion of urethane prepolymer was obtained.

  Next, 5.6 parts by mass of a 25% by mass ethylenediamine aqueous solution is added to the aqueous dispersion, and the urethane resin is chain-extended by stirring and then subjected to aging and desolvation, so that the nonvolatile content is 30% by mass. An aqueous dispersion of urethane resin (L-3) was obtained. The urethane resin (L-3) obtained here had an acid value of 30 and a weight average molecular weight of 50,000.

  Next, 140 parts by mass of deionized water in a reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, a thermometer, a dropping funnel for dropping the monomer mixture, and a dropping funnel for dropping the polymerization catalyst, the urethane resin obtained above 100 parts by mass of the aqueous dispersion (L-3) was added, and the temperature was raised to 80 ° C. while blowing nitrogen.

  A monomer mixture containing 50 parts by mass of methyl methacrylate and 50 parts by mass of n-butyl acrylate and 20 parts by mass of a 0.5% by mass aqueous ammonium persulfate solution in a reaction vessel heated to 80 ° C. with stirring. Was dropped from a separate dropping funnel over 120 minutes while maintaining the temperature in the reaction vessel at 80 ± 2 ° C. to polymerize.

  After completion of dropping, the water of urethane-acrylic composite resin particles constituted by the shell layer made of the urethane resin (L-3) and the core layer made of the vinyl polymer is stirred at the same temperature for 60 minutes. A dispersion was obtained.

  The temperature in the reaction vessel was cooled to 40 ° C., deionized water was added so that the non-volatile content was 20% by mass, and then filtered through a 200 mesh filter cloth to prepare primer (5). .

[Preparation Example 6: Preparation of primer (6)]
First, a polycarbonate polyol (hydroxyl equivalent: 1,000 g) obtained by reacting 1,4-cyclohexanedimethanol and carbonate in a nitrogen-substituted container equipped with a thermometer, a nitrogen gas inlet tube, and a stirrer. / Equivalent) of 100 parts by weight, 9.7 parts by weight of 2,2-dimethylolpropionic acid, 5.5 parts by weight of 1,4-cyclohexanedimethanol and 51.4 parts by weight of dicyclohexylmethane diisocyanate, and 111 parts by weight of methyl ethyl ketone. By making it react in, the organic solvent solution of the urethane prepolymer which has an isocyanate group in the molecular terminal was obtained.

  Next, 7.3 parts by mass of triethylamine is added to the organic solvent solution of the urethane prepolymer to neutralize a part or all of the carboxyl groups of the urethane prepolymer, and 355 parts by mass of water is further added and sufficiently stirred. By doing this, an aqueous dispersion of urethane prepolymer was obtained.

  Next, 4.3 parts by mass of a 25% by mass ethylenediamine aqueous solution is added to the aqueous dispersion, and the urethane resin is chain-extended by stirring, followed by aging and desolvation, whereby the urethane resin has a non-volatile content of 30% by mass. An aqueous dispersion of (L-4) was obtained. The urethane resin (L-4) obtained here had an acid value of 30 and a weight average molecular weight of 61,000.

  Next, 140 parts by mass of deionized water in a reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, a thermometer, a dropping funnel for dropping the monomer mixture, and a dropping funnel for dropping the polymerization catalyst, the urethane resin obtained above 100 parts by mass of the aqueous dispersion (L-4) was added, and the temperature was raised to 80 ° C. while blowing nitrogen.

  A monomer mixture containing 50 parts by mass of methyl methacrylate and 50 parts by mass of n-butyl acrylate and 20 parts by mass of a 0.5% by mass aqueous ammonium persulfate solution in a reaction vessel heated to 80 ° C. with stirring. Was dropped from a separate dropping funnel over 120 minutes while maintaining the temperature in the reaction vessel at 80 ± 2 ° C. to polymerize.

  After the completion of dropping, the water of urethane-acrylic composite resin particles composed of the shell layer made of the urethane resin (L-4) and the core layer made of the vinyl polymer by stirring at the same temperature for 60 minutes. A dispersion was obtained.

  Primer (6) was prepared by cooling the temperature in the reaction vessel to 40 ° C., adding deionized water so that the non-volatile content was 20% by mass, and then filtering through a 200 mesh filter cloth. .

[Preparation Example 7: Preparation of primer (7)]
First, in a nitrogen-substituted container equipped with a thermometer, a nitrogen gas inlet tube, and a stirrer, 100 parts by mass of polyethylene glycol having a number average molecular weight of 600, 17.6 parts by mass of 2,2-dimethylolpropionic acid, , 4-cyclohexanedimethanol 21.7 parts by mass and dicyclohexylmethane diisocyanate 106.2 parts by mass in methyl ethyl ketone 178 parts by mass to obtain an organic solvent solution of urethane prepolymer having an isocyanate group at the terminal It was.

  Next, 13.3 parts by mass of triethylamine is added to the organic solvent solution of the urethane prepolymer to neutralize part or all of the carboxyl groups of the urethane prepolymer, and 380 parts by mass of water is further added and sufficiently stirred. By doing this, an aqueous dispersion of urethane prepolymer was obtained.

  Next, 8.8 parts by mass of a 25% by mass ethylenediamine aqueous solution is added to the aqueous dispersion, and the urethane resin is chain-extended by stirring, followed by aging and desolvation, whereby urethane having a nonvolatile content of 30% by mass is obtained. An aqueous dispersion of resin (L-5) was obtained. The urethane resin (L-5) obtained here had an acid value of 30 and a weight average molecular weight of 30,000.

  Next, 140 parts by mass of deionized water in a reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, a thermometer, a dropping funnel for dropping the monomer mixture, and a dropping funnel for dropping the polymerization catalyst, the urethane resin obtained above 333 parts by mass of the aqueous dispersion (L-5) was added, and the temperature was raised to 80 ° C. while blowing nitrogen.

  A monomer mixture containing 100 parts by mass of ethyl acrylate and 20 parts by mass of a 0.5% by mass aqueous solution of ammonium persulfate were added from a separate dropping funnel to the reaction vessel while stirring in a reaction vessel heated to 80 ° C. While maintaining the internal temperature at 80 ± 2 ° C., it was dropped and polymerized over 120 minutes.

  After completion of dropping, the water of urethane-acrylic composite resin particles constituted by the shell layer made of the urethane resin (L-5) and the core layer made of the vinyl polymer is stirred for 60 minutes at the same temperature. A dispersion was obtained.

  The primer (7) was prepared by cooling the temperature in the reaction vessel to 40 ° C., adding deionized water so that the non-volatile content was 20% by mass, and then filtering through a 200 mesh filter cloth. .

[Preparation Example 8: Preparation of primer (8)]
In a reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, a thermometer, and a dropping funnel, 115 parts by mass of deionized water and emulsifier (“Latemul E-118B” manufactured by Kao Corporation: 25% by mass of active ingredient) 4% The temperature was raised to 75 ° C. while blowing nitrogen.

  Under stirring, a vinyl monomer mixture consisting of 90 parts by weight of methacrylic acid and 10 parts by weight of n-butyl acrylate and a reactive emulsifier (“AQUALON KH-1025” manufactured by Daiichi Kogyo Seiyaku Co., Ltd .: active ingredient) 25 parts by mass) Add 4 parts by weight of monomer pre-emulsion obtained by mixing 15 parts by weight of deionized water (5 parts by weight), then add 0.1 parts by weight of potassium persulfate Then, polymerization was carried out for 60 minutes while maintaining the temperature in the reaction vessel at 75 ° C.

  Next, while maintaining the temperature in the reaction vessel at 75 ° C., the remaining monomer pre-emulsion (114 parts by mass) and 30 parts by mass of an aqueous solution of 1% by mass potassium persulfate were separately used using separate dropping funnels. For 180 minutes. After completion of dropping, the mixture was stirred at the same temperature for 60 minutes.

  The temperature in the reaction vessel was cooled to 40 ° C., and 10% by mass of ammonia water was added so that the pH of the aqueous dispersion in the reaction vessel was 8.5.

  Subsequently, deionized water was added so that the non-volatile content would be 30% by mass, and then filtered through a 200 mesh filter cloth to prepare primer (8).

[Preparation Example 9: Preparation of primer (9)]
In a reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, a thermometer, and a dropping funnel, 115 parts by mass of deionized water and emulsifier (“Latemul E-118B” manufactured by Kao Corporation: 25% by mass of active ingredient) 4% The temperature was raised to 75 ° C. while blowing nitrogen.

  Under stirring, a vinyl monomer mixture consisting of 90 parts by mass of t-butyl methacrylate, 3 parts by mass of methacrylic acid and 7 parts by mass of n-butyl acrylate, and a reactive emulsifier (produced by Daiichi Kogyo Seiyaku Co., Ltd.) “AQUALON KH-1025”: active ingredient 25% by mass) 4 parts by mass and deionized water 15 parts by mass were mixed with a part of the monomer pre-emulsion (5 parts by mass). 0.1 parts by mass of potassium sulfate was added, and polymerization was performed for 60 minutes while maintaining the temperature in the reaction vessel at 75 ° C.

  Next, while maintaining the temperature in the reaction vessel at 75 ° C., the remaining monomer pre-emulsion (114 parts by mass) and 30 parts by mass of an aqueous solution of 1% by mass potassium persulfate were separately used using separate dropping funnels. For 180 minutes. After completion of dropping, the mixture was stirred at the same temperature for 60 minutes.

  The temperature in the reaction vessel was cooled to 40 ° C., and 10% by mass of ammonia water was added so that the pH of the aqueous dispersion in the reaction vessel was 8.5.

  Next, deionized water was added so that the non-volatile content was 30% by mass, and then filtered through a 200 mesh filter cloth to prepare primer (9).

[Preparation Example 10: Preparation of fluid (a-1)]
A flow which is a conductive ink is obtained by dispersing 30 parts by mass of silver particles having an average particle diameter of 30 nm in a mixed solvent composed of 35 parts by mass of ethanol, 3 parts by mass of glycerin and 32 parts by mass of ion-exchanged water, and filtering with a micropore filter. Body (a-1) was prepared.

[Preparation Example 11: Preparation of fluid (a-2)]
A flow which is a conductive ink is obtained by dispersing 30 parts by mass of silver particles having an average particle diameter of 30 nm in a mixed solvent composed of 20 parts by mass of ethanol, 15 parts by mass of glycerin and 35 parts by mass of ion-exchanged water, and filtering with a micropore filter. Body (a-2) was prepared.

[Preparation Example 12: Preparation of fluid (a-3)]
In a mixed solvent consisting of 25 parts by mass of ethanol, 25 parts by mass of 1,3-butylene glycol, 10 parts by mass of ion-exchanged water, and 10 parts by mass of glycerin, 30 parts by mass of silver particles having an average particle diameter of 30 nm are dispersed with a micropore filter. The fluid (a-3) which is a conductive ink was prepared by filtering.

[Preparation Example 13: Preparation of fluid (a-4)]
Conductive ink is obtained by dispersing 30 parts by mass of silver particles having an average particle diameter of 30 nm in a mixed solvent composed of 27 parts by mass of ethanol, 40 parts by mass of 1,3-butylene glycol and 3 parts by mass of glycerin and filtering with a micropore filter. A fluid (a-4) was prepared.

[Preparation Example 14: Preparation of fluid (a-5)]
A fluid which is a conductive ink by dispersing 30 parts by mass of silver particles having an average particle diameter of 30 nm in a mixed solvent composed of 27 parts by mass of ethanol, 40 parts by mass of ethylene glycol and 3 parts by mass of glycerin and filtering with a micropore filter. (A-5) was prepared.

[Preparation Example 15: Preparation of fluid (a′-1)]
By dispersing 30 parts by mass of silver particles having an average particle diameter of 30 nm in a mixed solvent consisting of 33 parts by mass of glycerin and 37 parts by mass of ion-exchanged water and filtering with a micropore filter, a fluid (a′− 1) was prepared.

(Example 1-1)
[Preparation of primer coating]
The primer (1) obtained in Preparation Example 1 is coated on the entire surface of one surface of a support made of a polyimide film (“Kapton 200H” manufactured by Toray DuPont Co., Ltd., thickness 50 μm). It apply | coated using the bar coater so that it might become 3 micrometers. Subsequently, the base material which formed the coating film on the surface of the said support body was obtained by drying at 70 degreeC for 3 minute (s) using a hot air dryer.

[Measurement of fluid contact angle]
The fluid (a-1) obtained in Preparation Example 10 was applied to the droplet observation apparatus (Co., Ltd.) on the coating film of the base material on which the coating film of the primer (1) was formed on the support obtained above. It was discharged using “DropMeasure 800” manufactured by Microjet, and the contact angle of the fluid (a-1) was measured.

[Measurement of change rate of droplet diameter of fluid]
The fluid (a-1) obtained in Preparation Example 10 is discharged onto the base material coating film on which the primer (1) coating film has been formed on the support obtained above, and a droplet landing observation apparatus. (DropMeasure 800 manufactured by Microjet Co., Ltd.) was used to measure the droplet diameter immediately after landing and 200 ms after landing, and the rate of change in droplet diameter was calculated using the following equation.

[Evaluation of thinness of conductive pattern]
The fluid (a-1) obtained in Preparation Example 10 was applied to an ink jet printer (Konica Minolta IJ Co., Ltd.) on the base material coating on which the primer (1) coating was formed on the support obtained above. Using a company-made “inkjet testing machine EB100” and evaluation printer head KM512L 42PL), printing a straight line with a line width of 100 μm and a film thickness of 0.5 μm about 1 cm, and then drying at 150 ° C. for 30 minutes A conductive pattern was obtained. The printed part on which the straight line of the obtained conductive pattern was printed was observed using an optical microscope ("Digital Microscope VHX-100" manufactured by Keyence Corporation), and the thinness of the conductive pattern was evaluated according to the following criteria. .
A: The boundary between the printing part and the non-printing part was clear, and there was no difference in height between the outer edge part and the central part of the printing part, and the printing part as a whole was smooth.
B: Although a slight blur was confirmed in a very small part of the outer edge of the printing part, the boundary between the printing part and the non-printing part was clear as a whole, and the whole printing part was smooth.
C: Slight blurring can be confirmed within a range of 1/3 of the outer edge of the printed part, and the boundary between the printed part and the non-printed part is partially unclear at that part, but the entire line part is smooth. It was a usable level.
D: Bleeding can be confirmed in the range of 1/3 to 1/2 of the outer edge portion of the printing portion, and the boundary between the printing portion and the non-printing portion becomes partially unclear at that portion, and the outer edge portion and the center of the printing portion It was not smooth.
E: Bleeding can be confirmed in a range of 1/2 or more of the outer edge portion of the printing portion, and the boundary between the printing portion and the non-printing portion is partially unclear in that portion, and the outer edge portion and the central portion of the printing portion are unclear. It was not smooth.

[Evaluation of conductivity (resistance value) of conductive pattern]
Prepare a conductive pattern (rectangular 3 cm long, 1 cm wide) obtained by evaluating the adhesion of the conductive pattern, and determine the volume resistivity of the surface using a Loresta pointer meter (MCP-manufactured by Mitsubishi Chemical Corporation). T610). From the volume resistivity value obtained by the measurement, the conductivity of the conductive pattern was evaluated according to the following criteria.
A: The volume resistivity was less than 5 × 10 ⁻⁶ Ω · cm.
B: The volume resistivity was 5 × 10 ⁻⁶ Ω · cm or more and less than 9 × 10 ⁻⁶ Ω · cm.
C: The volume resistivity was 9 × 10 ⁻⁶ Ω · cm or more and less than 5 × 10 ⁻⁵ Ω · cm.
D: The volume resistivity was 5 × 10 ⁻⁵ Ω · cm or more and less than 9 × 10 ⁻⁵ Ω · cm.
E: The volume resistivity was 9 × 10 ⁻⁵ or more.

(Example 1-2 to Example 6-5)
Except that the primers and fluids shown in Tables 1 to 3 were used, the same procedure as in Example 1-1 was performed to measure the contact angle of the fluid, calculate the rate of change in the droplet diameter of the fluid, and conductance. The thin line property and conductivity of the pattern were evaluated.

(Comparative Example 1-1 to Comparative Example 4)
Except that the primers and fluids shown in Tables 4 and 5 were used, the same procedure as in Example 1-1 was performed to measure the contact angle of the fluid, calculate the change rate of the droplet diameter of the fluid, and conductance. The thin line property and conductivity of the pattern were evaluated.

  The measurement results and evaluation results in the above Examples and Comparative Examples are shown in Tables 1-5.

[Electroless plating of conductive pattern]
The conductive patterns obtained in Example 1-1, Comparative Example 1-1, Comparative Example 2-1 and Comparative Example 3-1, were used as catalyst baths ("OPC-SALM / OPC" manufactured by Okuno Pharmaceutical Co., Ltd.). -80 ") for 5 minutes and then washed with water. Next, after immersing in an accelerator bath adjusted to 25 ° C. (“OPC-555” manufactured by Okuno Seiyaku Kogyo Co., Ltd.) for 5 minutes and washed with water, an electroless copper plating bath adjusted to 30 ° C. A copper plating layer by electroless plating having a thickness of 8 μm was formed on the surface of the printed portion (conductive layer) of the conductive pattern by immersing in “ATS add copper”) and washing with water. From this, it was confirmed that the electroconductive pattern of this invention can perform electroless plating easily.

[Electrolytic plating of conductive pattern]
The printed surface (conductive layer) of the conductive pattern obtained in Example 1-1, Comparative Example 1-1, Comparative Example 2-1 and Comparative Example 3-1, was used as a cathode, and phosphorous copper was used as an anode. Copper plating by electroplating with a thickness of 8 μm on the surface of the printed part (conductive layer) of the conductive pattern by performing electroplating for 15 minutes at a current density of 2 A / dm ² using an electroplating solution containing copper sulfate A layer was formed. From this, it was confirmed that the electroconductive pattern of this invention can be easily electroplated. The electrolytic plating solution used was a solution containing copper sulfate 70 g / liter, sulfuric acid 200 g / liter, chloride ion 50 mg / liter, and plating brightener (Okuno Pharmaceutical Co., Ltd. “Top Lucina SF”) 5 g / liter. It was.

Claims (7)

  A coating film (x) is formed by applying a primer to part or all of the surface of the support, and a monoalcohol having 2 to 4 carbon atoms (partially or entirely on the surface of the coating film (x) ( A fluid (a) containing an alcohol (a1) containing a1-1) and a conductive substance (a2) is applied and dried, and formed from a support and the coating film (x). A conductive pattern in which a primer layer (X) and a layer (Y) containing the conductive substance (a2) are laminated, and the droplets of the fluid (a) on the coating film (x) The contact angle between the coating film (x) and the fluid (a) when the liquid droplets are discharged is in the range of 15 to 70 °, and the change rate of the droplet diameter after 200 ms immediately after the landing of the minute droplets is A conductive pattern having a range of ± 30%.   The conductive pattern according to claim 1, wherein the monoalcohol (a1-1) is contained in a total amount of the fluid (a) in a range of 5 to 70 mass%.   The coating film (x) is selected from the group consisting of a urethane resin having a polycarbonate structure, a urethane resin having an aliphatic polyester structure, a urethane-acrylic composite resin, and an acrylic resin having a structural unit derived from methyl methacrylate. The conductive pattern according to claim 1, comprising at least one kind of resin (x-1).   The conductive pattern according to claim 1, wherein the coating film (x) has a crosslinked structure.   The conductive pattern according to claim 4, wherein the crosslinkable functional group involved in the formation of the crosslink structure is one or more thermally crosslinkable functional groups selected from the group consisting of a methylolamide group and an alkoxymethylamide group.   The electroconductive pattern of Claim 1 which has a plating layer (Z) further on the surface of the layer (Y) containing the said electroconductive substance.   A conductive circuit comprising the conductive pattern according to claim 1.