TW201404263A - Conductive pattern, conductive circuit, and method for producing conductive pattern - Google Patents

Abstract

The present invention addresses the problem of providing a conductive pattern which exhibits excellent adhesion sufficient for preventing separation of a conductive material over time from a primer layer (X), while having low resistance and excellent conductivity, and which is capable of forming a fine wire pattern without causing bleeding and the like. The present invention relates to a conductive pattern in which a supporting body, a primer layer (X) that is formed using a coating film (x) and a layer (Y) that contains a conductive material (a2) are laminated. This conductive pattern is obtained by: forming the coating film (x) by applying a primer over the surface of the supporting body; and applying a fluid (a) that contains the conductive material (a2) and an alcohol (a1) containing a monoalcohol (a1-1) having 1-4 carbon atoms over the surface of the coating film (x) and drying the applied fluid (a) thereon. The coating film (x) absorbs 20-500% by mass of ethanol relative to the mass of the coating film (x).

Description

Conductive pattern, conductive circuit, and method of manufacturing conductive pattern

The present invention relates to a conductive pattern which can be used in the manufacture of an electromagnetic wave mask or an integrated circuit or an organic transistor.

In recent years, with the increase in performance, size, and thickness of electronic devices, in recent years, there has been a strong demand for higher density or thinner electronic circuits or integrated circuits used therein.

The conductive pattern which can be used in the above-mentioned electronic circuit or the like can be produced, for example, by coating (printing) a conductive ink containing a conductive material such as silver on the surface of the support by various printing methods, and heating as needed. Wait.

However, even if the conductive ink is directly applied to the surface of the various supports, the conductive ink is less likely to adhere to the surface of the support, so that it is easily peeled off, and the electronic circuit or the like finally obtained is broken. . In particular, a support comprising a polyimide resin or a polyethylene terephthalate resin is relatively soft, so that it can be used for the production of a bendable flexible device, but inks and the like are not easily adhered to the above-mentioned polyimine. On the support of a resin or the like, these are easily peeled off when bent, and as a result, there is a case where the electronic circuit or the like finally obtained is broken.

As a method for solving the above problems, for example, a method of forming a conductive pattern by drawing a pattern by a specific method using a conductive ink on an ink receiving substrate provided with a latex layer on the surface of a support is known. An acrylic resin is used as the above latex layer (see Patent Document 1).

However, for the conductive pattern obtained by the above method, there is In the case where the adhesion between the ink receiving layer and the conductive ink is insufficient, there is a case where the conductivity is deteriorated due to the peeling of the conductive material contained in the conductive ink.

Further, when the conductive ink is applied to the above-mentioned latex layer in a linear form, bleeding or the like is likely to occur, and for example, a thin line drawing which cannot be used for a circuit or the like can be used.

However, when the conductive pattern is produced, generally, the conductive material contained in the conductive ink is brought into contact with each other to impart conductivity, and the printed matter obtained by printing using a conductive ink is heated at a relatively high temperature. many.

However, the ink receiving layer such as the latex layer disclosed in the above document 1 is easily deformed or deteriorated due to the influence of the high heat received in the heating step, and thus has the adhesion of the interface between the ink receiving layer and the support. Dropped, causing a defect in the conductive pattern (cracks, etc.). Further, when a plastic substrate is used as the support, the support is deformed by the influence of the high heat, and the resistance value of the conductive pattern is increased (conductivity is lowered).

On the other hand, when a conductive pattern is used at a relatively low temperature by using a previously known conductive ink or a receiving layer thereof, the conductive material is insufficiently melted or the support is not sufficiently expressed. The adhesion to the receiving layer or the adhesion between the conductive layer and the receiving layer causes a decrease in conductivity or the like.

As described above, a conductive pattern that does not cause the above-described decrease in adhesion or decrease in conductivity is sought from the industry.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2009-49124

An object of the present invention is to provide an excellent adhesion with a conductive material which does not peel off from the undercoat layer (X) over time, and which is excellent in low electrical resistance and excellent in electrical conductivity, and can form fine lines without causing bleeding or the like. A fine pattern of excellent conductivity of the pattern.

The inventors of the present invention conducted necessary studies on the above problems and found that a specific primer (a) and a primer (X) which forms an acceptable flow body (a) are used in combination (x). In the case of ), the above problems can be solved.

That is, the present invention relates to a conductive pattern characterized in that a coating film (x) is formed by partially or completely coating a primer on a surface of the support, on the surface of the coating film (x). A part or all of the flow body (a) containing the alcohol (a1) having the monoalcohol (a1-1) having a carbon number of 1 to 4 and the conductive substance (a2) is applied and dried to obtain a support and The primer layer (X) formed by using the coating film (x) and the layer (Y) containing the conductive material (a2) are laminated, and the coating film (x) is exposed to an environment of 25 ° C. The ethanol is absorbed in an amount of 20% by mass to 500% by mass based on the mass of the coating film (x).

The conductive pattern of the present invention has excellent adhesion without causing a level of peeling of the conductive material (a2) over time, and has excellent conductivity, and thus can be used, for example, for formation of an electronic circuit to constitute an organic solar cell or The formation of wiring such as RFID (Radio Frequency IDentification) such as an electronic book terminal, an organic EL, an organic transistor, a flexible printed circuit board, and a non-contact IC card, and wiring of an electromagnetic wave mask of a plasma display, an integrated circuit, and The manufacture of electromechanical crystals and the like is often referred to as a novel field in the field of printed electronics.

The conductive pattern of the present invention is characterized in that it is due to the surface of the support Part or all of the primer is applied to form a coating film (x), and a part or all of the surface of the coating film (x) is coated with a plurality of monohydric alcohols (a1-1) having a carbon number of 1 to 4. After the alcohol (a1) and the fluid (a) of the conductive material (a2), the support and the undercoat layer (X) formed by heating the coating film (x) obtained by heating and containing the above The layer (Y) of the conductive material (a2) is laminated, and the coating film (x) before the application of the fluid (a) is absorbed in the environment of 25 ° C with respect to the coating film (x). The mass is 20% by mass to 500% by mass of ethanol.

The conductive pattern of the present invention comprises at least a support and an undercoat layer (X) and a layer (Y) containing a conductive material (a2).

First, the above undercoat layer (X) will be described.

The undercoat layer (X) may, for example, be coated with the above-mentioned fluid (a) on the surface of the coating film (x) having the specific ethanol absorption rate, and then heated or irradiated with ultraviolet rays or the like. The undercoat layer (X-1) formed, and the undercoat layer of the coating film (x) having the above absorption ratio of ethanol. In other words, the above coating film (x) can be used as the above-mentioned undercoat layer (X). Further, the coating film (x) may be formed on the undercoat layer (X-1) which is newly formed by heating or energy ray irradiation or the like.

When the undercoat layer (X) is, for example, the undercoat layer (X-1), the above-mentioned fluid (a) is applied and heated, the above-mentioned specific ethanol absorptivity is not obtained.

The undercoat layer (X) may adhere a conductive material (a2) such as silver contained in the fluid (a) such as a conductive ink to the support. Specifically, when the coating film (x) formed using the primer is in contact with the fluid (a), the solvent contained in the fluid (a) is absorbed on the surface of the coating film (x). The above-mentioned conductive substance (a2) contained in the above-mentioned fluid (a) is carried. Thereafter, the conductive material (a2) supported on the surface of the undercoat layer (X) is formed by a step of heating at a normal temperature or heating such as heating at the time of imparting conductivity. Conductive pattern.

The undercoat layer (X) may be disposed on part or all of the surface of the support body, It can be disposed on one side or both sides of the above support. For example, as the conductive pattern, the entire surface of the surface for the support may have an undercoat layer (X), and only a portion necessary for the undercoat layer (X) may have a layer containing the above-mentioned conductive substance (a2). (Y). Further, among the surfaces of the support, the conductive pattern of the undercoat layer (X) may be provided only in a portion where the layer (Y) is provided.

The undercoat layer (X) differs depending on the use of the conductive pattern of the present invention, etc., and when a support having flexibility at a bendable level is used, from the viewpoint of maintaining good flexibility. Preferably, it is a thickness of about 0.01 μm to 300 μm, more preferably 0.05 μm to 20 μm.

Next, the layer (Y) constituting the conductive pattern of the present invention will be described.

The layer (Y) is a layer containing the conductive material (a2) contained in the fluid (a), and functions as a conductive layer or a plating core layer. In the case where the conductive layer containing silver is used as the fluid (a), the layer (Y) corresponds to a layer containing the silver contained in the conductive ink, and corresponds to the silver. Printing images or patterns.

The layer (Y) mainly contains the conductive material (a2), but other components contained in the fluid (a) may remain in the layer (Y). For example, ethanol has a carbon number of 1~. The monoalcohol (a1-1) of 4, the substance represented by the formula (I) described later, and the like.

The layer (Y) may be a layer provided on the entire surface of the undercoat layer (X), or may be a layer provided on a part of the surface of the undercoat layer (X). The layer (Y) present in a part of the surface of the undercoat layer (X) specifically means a thin line-like layer formed by drawing a line on the surface of the undercoat layer (X). The thin line-like layer is suitable for the case where the conductive pattern of the present invention is used as a circuit or the like.

The width (line width) of the thin line-like layer (pattern) is about 0.01 μm to 200 μm, preferably about 0.01 μm to 150 μm, which is preferable in terms of achieving high density of the conductive pattern.

The layer (Y) preferably has a thickness of 0.01 μm to 100 μm in terms of forming a conductive pattern having low electrical resistance and excellent electrical conductivity. Further, in the case where the layer (Y) is a thin line, the thickness (height) is preferably in the range of 0.1 μm to 50 μm.

Next, a support constituting the conductive pattern of the present invention will be described.

As the support used in the present invention, for example, a polyimine resin or a polyamide amide resin, a polyamide resin, polyethylene terephthalate or polyethylene naphthalate may be used. , polycarbonate, acrylonitrile-butadiene-styrene (ABS), acrylic acid resin such as poly(methyl) acrylate, polyvinylidene fluoride, polyvinyl chloride, polyvinylidene chloride, polyethylene A support for alcohol, polyethylene, polypropylene, polyurethane, cellulose nanofiber, enamel, ceramic, glass, and the like. The above support may be porous.

Further, as the support, for example, synthetic fibers such as polyester fibers, polyamide fibers, and aromatic polyamide fibers, or natural fibers such as cotton or hemp can be used. The above fibers can be processed in advance.

As the support, it is preferable to use a polyimide resin, polyethylene terephthalate or polyethylene naphthalate, which is usually used as a support for forming a conductive pattern such as a circuit board. A support such as glass or cellulose nanofiber.

When the conductive pattern of the present invention is used for applications requiring flexibility, the support is provided with a relatively soft and bendable support to impart flexibility to the conductive pattern and to obtain a bendable final. It is preferred in terms of the product. Specifically, it is preferred to use a film or a sheet-shaped support formed by uniaxial stretching or the like.

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

The support is preferably a thickness of about 1 μm to 2,000 μm, more preferably about 1 μm to 200 μm, from the viewpoint of lightening and thinning of the conductive pattern and the final product using the conductive material. In the case where the above-mentioned laminated body is required to be soft, it is preferable to use a thickness of about 1 μm to 80 μm.

One or all of the surface of the support has the undercoat layer (X), and the conductive layer of the present invention having a layer (Y) containing a conductive substance (a2) in part or all of the undercoat layer (X) In order to reduce the thickness of the circuit or the like, the thickness of the constituent portion other than the support is preferably a total thickness of the undercoat layer (X) and the layer (Y) of 0.01 μm to 300 μm. The range is more preferably 0.05 μm to 80 μm.

Next, the fluid (a) used in the production of the conductive pattern of the present invention will be described.

The fluid (a) contains an alcohol (a1) having a monool (a1-1) having 1 to 4 carbon atoms, a conductive material (a2), and other solvents as necessary.

The above-mentioned fluid (a) is preferably a viscosity of 0.1 mPa as measured by an E-type viscometer (TVE-22LT, manufactured by Toki Sangyo Co., Ltd.) at about 23 ° C. s~500,000mPa. s, preferably 0.5 mPa. s~10,000mPa. s liquid or viscous liquid.

When the fluid (a) is applied (printed) to a desired position by a method such as an inkjet printing method, a lithography method, a gravure printing method or a flexographic printing method which will be described later, it is preferably adjusted to about 5 mPa. . s~1,000mPa. The viscosity of the range of s.

Specific examples of the fluid (a) include a conductive ink, a plating nucleus which can be used in the plating treatment, and the like.

The alcohol (a1) containing the above-mentioned monool (a1-1) used in the above-mentioned fluid (a) may be used, if necessary, containing the above-mentioned monool (a1-1), and if necessary, other alcohol.

The monool (a1-1) does not impair the adhesion or conductivity at a level that does not cause the conductive material to peel off from the conductive pattern, and forms a conductive pattern excellent in fine linearity. Layer (X) is used in combination.

As the above monool (a1-1), for example, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, second butanol, and third butanol can be used, and ethanol is not used. The conductive material is excellent in adhesion at the level of peeling off from the conductive pattern, and has low electrical resistance and excellent electrical conductivity, and the fluid (a) such as the conductive ink does not cause cissing from the coated surface. It is particularly preferable in terms of forming a conductive pattern excellent in fine linearity, such as bleeding or the like.

The total amount of the monool (a1-1) such as ethanol and the above-mentioned fluid (a1) is preferably contained in the range of 5 mass% to 70 mass%, more preferably 10 mass% to 50 mass%. Contained inside.

In addition, as the alcohol (a1), the diol (a1-2) represented by the following formula (I) is used in combination with the above-mentioned monool (a1-1), and the above-mentioned fine linearity is not impaired, and the above is further improved. It is preferable in terms of adhesion or conductivity. Further, when the fluid (a) such as a conductive ink is applied by an inkjet method, the discharge stability can be imparted. Therefore, in this case, the diol (a1-2) is preferably used.

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

As the diol (a1-2), R in the above formula (I) may be a hydrogen atom or an alkyl group, and the alkyl group is preferably an alkyl group having 1 to 10 carbon atoms, more preferably 1 or more. ~5 alkyl, and preferably 1 to 3 alkyl.

As the diol (a1-2), the layer (Y) formed by the conductive material (a2) contained in the fluid (a) is not peeled off from the undercoat layer (X). It is preferable to use R in the general formula (I) as a hydrogen in terms of a level of further excellent adhesion, no crack in the conductive pattern to be described, and a conductive pattern having further excellent electrical conductivity. Atomic 1,3-butanediol or R is an alkyl isopentylene glycol or the like.

The diol (a1-2) is preferably contained in an amount of from 5 to 60% by mass, more preferably from 15 to 50% by mass, based on the total amount of the fluid (a). on In order to improve the discharge stability of the fluid (a) and form a wiring pattern having excellent conductivity, it is preferably contained in the range of 20% by mass to 40% by mass.

As the other alcohol which can be used in combination with the above-mentioned monool (a1-1) and the above diol (a1-2) as the above alcohol (a1), a previously known alcohol can be used, and for example, 2-ethyl-1,3 can be used. - hexanediol, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, 1,2-butanediol, 1,4-butanediol, 2,3-butyl Glycol, glycerin, etc.

As the above-mentioned conductive material (a2), a transition metal or a compound thereof can be used. Preferably, an ionic transition metal is used. For example, a transition metal such as copper, silver, gold, nickel, palladium, platinum, or cobalt is preferably used, and copper, silver, gold, or the like is used to form a low resistance and corrosion resistance. It is better to have a more conductive pattern, and it is better to use silver.

Further, when the fluid (a) is used for a plating agent, as the conductive material (a2), one or more metal particles containing the transition metal as described above may be used, and the transition metal may be used. Oxide or organic matter and surface coating.

Further, since the oxide of the transition metal is usually in an inert (insulating) state, it is often the case that the fluid containing the fluid is coated on the surface of the support and the conductivity cannot be exhibited. Therefore, when a fluid containing the above oxide is applied onto the surface of the support, the transition metal may be exposed by treating the surface with a reducing agent such as dimethylamine borane. A layer having activity (conductivity) is formed.

In addition, as a metal which is surface-coated by the above-mentioned organic substance, the metal is present in the inside of the resin particle (organic substance) formed by the emulsion polymerization method or the like. These are the same as the oxide of the transition metal described above, and are usually in an inert (insulating) state. Therefore, it is often the case that the fluid containing the fluid is coated on the surface of the support and the conductivity cannot be exhibited. Therefore, when a fluid containing a metal surface-coated with the organic substance is coated on the surface of the support, the surface is irradiated with a laser or the like to remove the organic substance, thereby exposing the transition metal. A layer having activity (conductivity) is formed.

As the conductive material (a2), it is preferred to use about 1 nm to 100 nm left. In the case of particles having an average particle diameter of the right, when a particle having an average particle diameter of 1 nm to 50 nm is used, a finer conductive pattern can be formed as compared with the case of using a conductive material having an average particle diameter of a micron order, which can be further reduced. The resistance value after heating is therefore better. Further, the above "average particle diameter" is a volume average value measured by a dynamic light scattering method by diluting the above-mentioned conductive material (a2) with a dispersion of a good solvent. For the measurement, Nanotrac UPA-150 manufactured by Microtrac Co., Ltd. can be used.

The conductive material (a2) is preferably contained in the range of 5 mass% to 90 mass%, more preferably 5 mass%, based on the total amount of the fluid (a) used in the present invention. It is contained in the range of 85 mass%, and is preferably used in the range of 10% by mass to 60% by mass, and more preferably in the range of 20% by mass to 40% by mass.

When the fluid (a) used in the present invention contains a solvent such as an aqueous medium or an organic solvent together with the above-mentioned alcohol (a1) and the above-mentioned conductive material (a2), it is used as a conductive ink or a plating core. It is more suitable in terms of agents and the like.

As the solvent, for example, an aqueous medium such as distilled water, ion-exchanged water, pure water or ultrapure water can be used, and an organic solvent such as an alcohol, an ether, an ester or a ketone can be used.

As the above alcohol, for example, heptanol, hexanol, octanol, decyl alcohol, decyl alcohol, undecyl alcohol, dodecanol, tridecyl alcohol, tetradecanol, pentadecyl alcohol, stearyl alcohol can be used. , allyl alcohol, cyclohexanol, rosinol, terpineol, dihydroterpineol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, two Ethylene glycol monomethyl ether, diethylene glycol monobutyl ether, tetraethylene glycol monobutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, propylene glycol monopropyl ether, dipropylene glycol monopropyl ether , propylene glycol monobutyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monobutyl ether and the like.

Further, as the fluid (a), in addition to the above, a ketone solvent such as acetone, cyclohexanone or methyl ethyl ketone may be used in combination, ethyl acetate, butyl acetate or 3-methoxybutyl acetate. Esters and ester solvents such as 3-methoxy-3-methyl-butyl acetate, toluene, octane, decane, decane, dodecane, tridecane, tetradecane, cyclooctane, xylene, Mesitylene, ethyl A hydrocarbon solvent such as benzene, dodecylbenzene, tetrahydronaphthalene or trimethylbenzenecyclohexane; a solvent such as mineral spirit or solvent naphtha.

The fluid (a) of the present invention can be produced, for example, by mixing the above alcohol (a1) with the above-mentioned conductive material (a2) and, if necessary, the above solvent. Here, a composition containing the conductive material (a2) and the solvent is produced, and then the composition is mixed with the alcohol (a1) containing the monool (a1-1) or the diol (a1-2). The production is more preferable in terms of achieving improvement in dispersion stability of the conductive material or prevention of cracks in the layer (Y).

As a composition containing the above-mentioned conductive material (a2) and the above solvent, a dispersion for dispersing the above-mentioned conductive material (a2) in a solvent such as an aqueous medium or an organic solvent can be used.

The dispersion can be produced by mixing the above-mentioned conductive material (a2) with the above solvent and stirring. Specific examples of the above-mentioned dispersions include SW1000 (manufactured by Bando Chemical Co., Ltd.), Silk Auto A-1 (manufactured by Mitsubishi Materials Co., Ltd.), MDot-SLP (manufactured by Mitsuboshi Belting Co., Ltd.), and the like.

The mixing of the above-mentioned dispersion and the above-mentioned alcohol (a1) can be carried out by a device which can be usually used by mixing or dispersing a mixer, a disperser, a bead mill, an ultrasonic homogenizer or the like.

Further, the fluid (a) used in the present invention further improves the dispersion stability of the conductive material (a2) in a solvent such as an aqueous medium or an organic solvent, and improves the above-mentioned coating film of the fluid (a) (x) In terms of wettability of the surface, etc., a surfactant, an antifoaming agent, a rheology modifier, etc. may be contained as needed.

As the fluid (a), it is also possible to use a microporous filter or the like to perform filtration, and to perform processing using a centrifugal separator or the like, by the above method, from the viewpoint of removing impurities and the like.

Next, the undercoating agent used in the production of the conductive pattern of the present invention will be described.

The primer is formed into a coating film (x) capable of supporting the conductive material (a2) contained in the fluid (a), and forming a layer (Y) of the conductive pattern of the present invention.

As the primer, any coating film (x) capable of absorbing ethanol having a mass of 20% by mass to 500% by mass based on the mass of the coating film (x) in an environment of 25 ° C can be used. By.

As the primer which can form the above-mentioned coating film (x), those containing various resins and solvents can be used.

As the resin, for example, a urethane resin (x1), an ethylene resin (x2), a urethane-ethylene composite resin (x3), a phenol resin, an epoxy resin, a melamine resin, or a urea can be used. Resin, unsaturated polyester resin, alkyd resin, polyimide resin, fluororesin, and the like.

As the above-mentioned resin, a urethane resin selected from the group consisting of a urethane resin having a polycarbonate structure as a urethane resin (x1) and having an aliphatic polyester structure is used as the ethylene system. An acrylic resin having a structural unit derived from methyl methacrylate of the resin (x2), and a urethane-acrylic composite resin as a urethane-ethylene composite resin (x3) It is preferable that the resin (x-1) of one or more of the groups can form the coating film (x) having the specific absorption rate of the above-described ethanol, and it is more preferable to use a urethane-acrylic composite. Resin.

When the primer is used in an amount of 10% by mass to 70% by mass based on the total amount of the above-mentioned primer, it is preferable to maintain the ease of application, etc., and more preferably 10% by mass. 50% by mass.

Further, as the solvent which can be used in 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. Further, examples of the aqueous medium include water, an organic solvent mixed with water, and a mixture thereof.

Examples of the organic solvent to be mixed with water include alcohols such as methanol, ethanol, n- and isopropanol, ethyl carbitol, ethyl cellosolve, and butyl cellosolve; acetone and methyl b. Ketones such as ketones; polyalkylene glycols such as ethylene glycol, diethylene glycol, and propylene glycol; alkyl ethers of polyalkylene glycols; and internal enthalpy of N-methyl-2-pyrrolidone Amines, etc.

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

When the primer is used in an amount of from 25% by mass to 90% by mass based on the total amount of the solvent of the primer, it is preferable to maintain the ease of application, etc., and more preferably 50% by mass. 85 mass%.

When an aqueous medium is used as the above solvent, it is preferred to use a resin having a hydrophilic group as the above resin in terms of imparting good water dispersibility to the undercoating agent and improving storage stability.

Examples of the hydrophilic group include an anionic group, a cationic group, and a nonionic group.

As the anionic group, for example, a carboxyl group, a carboxylate group, a sulfonic acid group, a sulfonate group or the like can be used. Among them, a part or all of a carboxylate group or a sulfonate formed by neutralizing a basic compound or the like is used. The acid ester group is preferred in terms of imparting good water dispersibility.

Examples of the basic compound which can be used for the neutralization of the anionic group include ammonia, triethylamine, and pyridine. An organic amine such as a phenyl group; an alkanolamine such as monoethanolamine; a metal base compound containing sodium, potassium, lithium, calcium or the like. In the case where a conductive pattern or the like is formed, the above metal alkali compound may impair conductivity or the like, and thus it is preferred to use the above ammonia, an organic amine or an alkanolamine.

When the above carboxylate group or sulfonate group is used as the anionic group, the above-mentioned resin is present in the range of 50 mmol/kg to 2,000 mmol/kg as a whole, and the good water of the above resin is maintained. It is preferred in terms of dispersion stability.

Further, as the above cationic group, for example, a tertiary amino group or the like can be used.

As the acid which can be used for neutralizing part or all of the above-mentioned tertiary amine group, for example, an organic acid such as acetic acid, propionic acid, lactic acid or maleic acid; organic sulfonate such as sulfonic acid or methanesulfonic acid; An acid; an inorganic acid such as hydrochloric acid, sulfuric acid, orthophosphoric acid or orthophosphoric acid, or the like, used alone or in combination of two or more. When the conductive pattern or the like is formed, chlorine or sulfur may be used to impair conductivity or the like. Therefore, acetic acid, propionic acid, lactic acid, maleic acid or the like is preferably used.

Further, as the nonionic group, for example, a polyoxyalkylene group such as a polyoxyethylene group, a poly(oxyethylene-oxypropylene) group or a polyoxyethylene-polyoxypropylene group can be used. Among them, the use of a polyoxyalkylene group having an oxyethylene unit is preferred in terms of further improving the hydrophilicity.

As the urethane resin (x1) which can be used as the resin contained in the above primer, an aminocarboxylic acid obtained by reacting a polyol with a polyisocyanate and, if necessary, a chain extender can be used. Ester resin. Among them, from the viewpoint of forming the coating film (x) having the specific absorption rate of ethanol described above, it is preferred to use a urethane resin having a polycarbonate structure and an amine group having an aliphatic polyester structure. Acid ester resin.

The polycarbonate structure or the aliphatic polyester structure is preferably a structure derived from a polyol used in the production of the above urethane resin. Specifically, the polycarbonate-containing urethane resin can be produced by using a polycarbonate polyol described later as the polyol. Moreover, the urethane resin containing an aliphatic polyester structure can be produced by using an aliphatic polyester polyol which will be described later as the above polyol.

As the polyol which can be used in the production of the above urethane resin (x1), a polycarbonate polyol, an aliphatic polyester polyol or the like can be used as described above. Further, the above polyol may be used in combination with other polyols as needed.

Further, as the polycarbonate polyol, for example, those obtained by reacting a carbonate with a polyol or reacting carbonium chloride with bisphenol A or the like can be used.

As the above carbonate, methyl carbonate or dimethyl carbonate, ethyl carbonate, diethyl carbonate, cyclic carbonate, diphenyl carbonate or the like can be used.

As the polyol which can be reacted with the above carbonate, for example, ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propanediol, 1,3-propanediol, dipropylene glycol, 1,4-butane can be used. Alcohol, 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-nonanediol, 1,11-undecanediol, 1,12-dodecanediol, 3-methyl-1,5-pentanediol, 2-ethyl-1,3-hexanediol, 2-methyl-1,3-propanediol, 2-methyl Base-1,8-octanediol, 2-butyl-2-ethylpropanediol, 2-methyl-1,8-octanediol, neopentyl glycol, hydroquinone, resorcinol, double A relatively low molecular weight dihydroxy compound such as phenol-A, bisphenol-F or 4,4'-biphenol.

Further, as the aliphatic polyester polyol, for example, an aliphatic polyester polyol obtained by esterifying a low molecular weight polyol with a polycarboxylic acid, or ε-caprolactone or γ-butyrolactone can be used. An aliphatic polyester obtained by subjecting a cyclic ester compound to ring-opening polymerization or a copolymerized polyester or the like.

As the low molecular weight polyol which can be used in the production of the above polyester polyol, for example, ethylene glycol, 1,2-propanediol, 1,3-butylene glycol, 1,4-butanediol, 1,6 can be used. - hexanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, glycerin, trimethylolpropane, or the like, used alone or in combination of two or more, preferably Ethylene glycol, 1,2-propanediol, 1,3-butanediol or 1,4-butanediol is used in combination with 3-methyl-1,5-pentanediol or neopentyl glycol.

As the polycarboxylic acid, for example, succinic acid, adipic acid, sebacic acid, dodecanedicarboxylic acid, sebacic acid, and an acid anhydride or ester-forming derivative thereof can be used, and adipic acid is preferably used. Such as aliphatic polycarboxylic acids.

The polycarbonate polyol or the aliphatic polyester polyol is preferably one having a number average molecular weight of from 500 to 4,000, more preferably from 500 to 2,000.

Further, as the polyol which can be used in the production of the urethane resin (x1), in addition to the above, other polyols may be used in combination as needed.

As the above other polyhydric alcohol, for example, ethylene glycol, 1,2-propanediol, 1,3-butanediol, 1,4-butanediol, 3-methyl-1,5-pentanediol, and 1 can be suitably used. ,6-hexanediol, 1,4-cyclohexane Alkenyl dimethanol, neopentyl glycol, diethylene glycol, dipropylene glycol, glycerin, trimethylolpropane, etc., or an acrylic polyol in which a hydroxyl group is introduced into an acrylic copolymer, and a butadiene having a hydroxyl group in the molecule The copolymer is a polybutadiene polyol, a hydrogenated polybutadiene polyol, a partial saponified product of an ethylene-vinyl acetate copolymer, and the like.

When a urethane resin having a hydrophilic group is produced as the urethane resin (x1), it is preferred to use a polyol having a hydrophilic group as the other polyol.

As the polyhydric alcohol having a hydrophilic group, for example, a divalent group having a carboxyl group such as 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid or 2,2-dihydroxymethylpentanoic acid can be used. Alcohol; a polyhydric alcohol having a sulfonic acid group such as 5-sulfoisophthalic acid, sulfoterephthalic acid, 4-sulfophthalic acid or 5[4-sulfophenoxy]isophthalic acid. Further, as the polyol having a hydrophilic group, a hydrophilic polyol-based polyester polyol obtained by reacting the low molecular weight hydrophilic group-containing polyol with various polycarboxylic acids such as adipic acid may be used. Wait.

As the polyisocyanate which can be reacted with the above polyol to form a urethane resin, for example, 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate or carbon ruthenium can be used. Polyisocyanate having an aromatic structure such as imine-modified diphenylmethane diisocyanate, crude diphenylmethane diisocyanate, phenyl diisocyanate, toluene diisocyanate, naphthalene diisocyanate; hexamethylene diisocyanate, lysine II Aliphatic polyisocyanates such as isocyanate, cyclohexane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, benzene dimethylene diisocyanate, tetramethyl benzene dimethylene diisocyanate or have an aliphatic ring Polyisocyanate of the formula.

Further, as the chain extender which can be used in the production of the above urethane resin, a polyamine, a hydrazine compound, or another compound having an active hydrogen atom can be used.

As the above polyamine, for example, ethylenediamine, 1,2-propylenediamine, 1,6-hexanediamine, and piperazine can be used. 2,5-Dimethyl pipe , isophorone diamine, 4,4'-dicyclohexylmethanediamine, 3,3'-dimethyl-4,4'-dicyclohexylmethanediamine, 1,4-cyclohexanediamine, etc. Diamine; N-hydroxymethylaminoethylamine, N-hydroxyethylaminoethylamine, N-hydroxypropylaminopropylamine, N-ethylaminoethylamine, N-methyl Aminopropylamine, di-ethyltriamine, di-propyltriamine, tri-ethylidenetetraamine, etc., preferably ethylenediamine.

As the above ruthenium compound, for example, ruthenium, N,N'-dimethylhydrazine, 1,6-hexamethylene biguanide, diammonium succinate, diammonium adipate, and bismuth glutarate can be used. Bismuth, bismuth azelaic acid, bismuth isophthalate, ruthenium beta-urealuminate, 3-aminourea-propyl-carbazate, ureido-3-amine urethane- 3,5,5-trimethylcyclohexane.

As the other compound having active hydrogen, for example, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butylene glycol, 1,4-butanediol, or the like can be used. a diol such as hexanediol, sucrose, methylene glycol, glycerin or sorbitol; bisphenol A, 4,4'-dihydroxybiphenyl, 4,4'-dihydroxydiphenyl ether, 4,4'- Phenols such as dihydroxydiphenyl hydrazine, hydrogenated bisphenol A, hydroquinone, water, and the like.

The chain extender is preferably used in a range in which the equivalent ratio of the amine group to the isocyanate group of the polyamine is 1.9 or less (equivalent ratio), and more preferably in the range of 0.3 to 1 (equivalent ratio). .

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

The reaction of the above polyol with the above polyisocyanate can be carried out by sufficiently paying attention to safety such as intense heat generation or foaming, and preferably from 50 ° C to 120 ° C, more preferably from 80 ° C to 100 ° C. Next, the above polyol is mixed with the above polyisocyanate at a time, or supplied by dropwise addition to one of the other, or the like, and reacted for about 1 hour to 15 hours.

Further, for the primer containing the aqueous dispersion of the urethane resin (x1), the above polyol and the above polyisocyanate and optionally a chain extender are used in the above manner. The reaction is carried out to produce a urethane resin (x1), and if necessary, some or all of the hydrophilic groups such as an anionic group of the urethane resin (x1) are neutralized, etc., and then The aqueous medium used as the solvent of the primer is mixed, whereby the primer of the aqueous dispersion of the urethane resin (x1) containing the urethane resin (x1) dispersed or partially dissolved in the aqueous medium can be obtained. Agent.

More specifically, by reacting the above polyol with the above polyisocyanate in the above manner, a urethane prepolymer having an isocyanate group at the end is produced, and if necessary, the above urethane prepolymer is used. After partially or completely neutralizing one or all of the hydrophilic groups such as an anionic group, it is mixed with the above aqueous medium, and if necessary, chain extension is carried out using the above chain extender, whereby a urethane-containing resin (x1) can be obtained. A primer for the aqueous dispersion of urethane resin (x1) dispersed or dissolved in an aqueous medium.

The reaction between the polyisocyanate and the polyol is preferably carried out in a range of, for example, an equivalent ratio of the isocyanate group of the polyisocyanate to the hydroxyl group of the polyol (isocyanate group/hydroxy group) of 0.90 to 2.

When the above urethane resin (x1) is produced, an organic solvent can also be used as a solvent as described above. As the above organic solvent, for example, a ketone such as acetone or methyl ethyl ketone; tetrahydrofuran or two can be used. An ether such as an alkyl group; an acetate such as ethyl acetate or butyl acetate; a nitrile such as acetonitrile; or a guanamine such as dimethylformamide or N-methylpyrrolidone.

The organic solvent is preferably removed by distillation or the like after the production of the urethane resin (x1). However, when the above-described urethane resin (x1) and an organic solvent are used as the primer, the organic solvent used in the production of the above urethane resin (x1) can be used as the above. The solvent of the primer.

The urethane resin (x1) is preferably used in the form of a weight average molecular weight of 5,000 to 500,000 from the viewpoint of forming a conductive pattern having excellent adhesion and excellent conductivity. 20,000~100,000.

As the above urethane resin (x1), various functional groups can be used as needed. By. Examples of the functional group include a crosslinkable functional group such as an alkoxyalkylene group, a stanol group, a hydroxyl group or an amine group.

The crosslinkable functional group is suitable for forming a crosslinked structure in the undercoat layer (X) of the above-mentioned fluid (a) to form a pattern (layer (Y)) having excellent durability.

The above alkoxyalkylene group or stanol group can be introduced into the above urethane resin by using γ-aminopropyltriethoxysilane or the like in the production of the above urethane resin (x1).

Further, when the above urethane resin (x1) is used in combination with a crosslinking agent (D) to be described later, a functional group having a functional group reactive with the above-mentioned crosslinking agent (D) can be used. By. The functional group may be different 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, an amine group or the like may be used.

Further, as the vinyl resin (x2) which can be used as the resin contained in the primer, a polymer having a monomer having 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, or the like can be used, and it is preferred to use An acrylic resin derived from a structural unit of methyl methacrylate.

As the acrylic resin, a polymer or a copolymer obtained by polymerizing a (meth)acrylic monomer can be used. Further, the (meth)acrylic monosystem refers to either or both of an acrylic monomer and a methacrylic monomer.

As the acrylic resin, from the viewpoint of forming the coating film (x) having the specific absorption rate of ethanol described above, an acrylic resin having a structural unit derived from methyl (meth) acrylate is preferably used.

The acrylic resin can be produced, for example, by polymerizing various (meth)acrylic monomers described later.

As the (meth)acrylic monomer, for example, methyl (meth)acrylate or ethyl (meth)acrylate, n-butyl (meth)acrylate, or isobutyl (meth)acrylate, ( Tert-butyl methacrylate, 2-ethylhexyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, octyl (meth) acrylate, (methyl) Ethyl acrylate, dodecyl (meth)acrylate, stearyl (meth)acrylate, (meth)acrylic acid (meth)acrylates such as esters, dicyclopentanyl (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate; 2,2,2-trifluoro(meth)acrylate Ethyl ester, 2,2,3,3-pentafluoropropyl (meth)acrylate, perfluorocyclohexyl (meth)acrylate, 2,2,3,3-tetrafluoropropyl (meth)acrylate, An alkyl (meth)acrylate such as β-(perfluorooctyl)ethyl (meth)acrylate.

Among the above, from the viewpoint of forming the coating film (x) having a specific absorption ratio of ethanol, it is preferable to use methyl methacrylate, heat from a heating step in the case where a conductive pattern is not produced, and the like. In view of the effect of imparting excellent adhesion between the undercoat layer (X) and the support, the methyl methacrylate is preferably used. Further, in order to form a conductive pattern such as an electronic circuit, a thin line having a width of about 0.01 μm to 200 μm, preferably about 0.01 μm to 150 μm, does not bleed out and is printed (improving fine linearity). More preferably, the above methyl methacrylate is used.

Further, it is preferred to use an alkyl (meth)acrylate having an alkyl group having 2 to 12 carbon atoms together with the above methyl methacrylate, and more preferably having 3 to 8 carbon atoms. The alkyl acrylate of the alkyl group is preferably n-butyl acrylate from the viewpoint of forming the coating film (x) having the specific absorption rate of ethanol described above and further improving the adhesion or conductivity. Further, it is also preferable from the viewpoint that the fluid (a) does not bleed out or the like to form a conductive pattern excellent in fine linearity.

The total amount of the methyl (meth) acrylate relative to the total amount of the (meth)acrylic monomer mixture is preferably 10% by mass to 70% by mass, more preferably 30% by mass to 65% by mass, and has the above-mentioned The alkyl acrylate having an alkyl group having 2 to 12 carbon atoms is preferably an alkyl acrylate having an alkyl group having 3 to 8 carbon atoms, which is relative to the above (meth)acrylic acid. The total amount of the body mixture is preferably 20% by mass to 80% by mass, more preferably 35% by mass. The amount is %~70% by mass.

Further, as the (meth)acrylic monomer which can be used in the production of the above acrylic resin, in addition to the above, acrylic acid, methacrylic acid, β-carboxyethyl (meth)acrylate, 2-(() may be used. Methyl) acrylonitrile propionic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, itaconic acid half ester, maleic acid half ester, maleic anhydride, clothing A carboxyl group-containing vinyl monomer such as acanic anhydride or hydrogen succinate-β-(meth) propylene oxyethyl ester. The vinyl monomer having a carboxyl group can be neutralized by ammonia, potassium hydroxide or the like.

In addition, as the (meth)acrylic monomer, one or more kinds of guanamine groups selected from the group consisting of a hydroxymethyl guanamine group and an alkoxymethyl guanamine group are introduced from the acrylic resin. Or a non-amine group other than the above, a hydroxyl group, a glycidyl group, an amine group, a decyl group, an aziridine group, an isocyanate group, From the viewpoint of the above-mentioned crosslinkable functional group such as an oxazoline group, a cyclopentenyl group, an allyl group, a carboxyl group or an ethyl oxime group, a vinyl monomer having a crosslinkable functional group can be used.

As the above-mentioned (meth)acrylic monomer having a crosslinkable functional group, one or more kinds of guanamines selected from the group consisting of a hydroxymethyl guanamine group and an alkoxymethyl guanamine group can be used. As the vinyl monomer of the group, for example, N-methylol (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-methoxyethoxymethyl (N-methoxyethoxymethyl) can be used. Methyl) acrylamide, N-ethoxymethyl (meth) acrylamide, N-propoxymethyl (meth) acrylamide, N-isopropoxymethyl (meth) propylene Indoleamine, N-n-butoxymethyl (meth) acrylamide, N-isobutoxymethyl (meth) acrylamide, N-pentyloxymethyl (meth) acrylamide, N-ethoxymethyl-N-methoxymethyl (meth) acrylamide, N, N'-dimethylol (meth) acrylamide, N-ethoxymethyl-N- Propyloxymethyl (meth) acrylamide, N, N'-dipropoxymethyl (meth) acrylamide, N-butoxymethyl-N-propoxymethyl (methyl Acrylamide, N,N-dibutoxymethyl(meth)acrylamide, N-butoxymethyl-N-methoxymethyl(meth)acrylamide, N,N' -dipentyloxymethyl (meth) propylene oxime , N- methoxymethyl-pentoxy -N- methyl (meth) acrylamide and the like.

Among them, N-n-butoxymethyl (meth) acrylamide and N-isobutoxymethyl (meth) acrylamide are used to form a conductive material (a2) capable of preventing plating. It is preferable in terms of a conductive pattern such as durability such as peeling.

As the (meth)acrylic monomer having a crosslinkable functional group, in addition to the above, for example, a vinyl monomer having a mercapto group such as (meth)acrylamide or a (meth)acrylic acid can be used. 2-hydroxyethyl ester, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, (meth)acrylic acid (4-hydroxymethylcyclohexyl)methyl ester, (meth)acrylic acid glyceride, (meth)acrylic acid polyethylene glycol, N-hydroxyethyl (meth) acrylamide, etc. having a hydroxyl group a vinyl monomer; a glycidyl group-containing polymerizable monomer such as glycidyl (meth)acrylate or allyl glycidyl (meth)acrylate; aminoethyl (meth)acrylate; Polymerization of amine groups such as dimethylaminoethyl acrylate, N-monoalkylaminoalkyl (meth) acrylate, N,N-dialkylaminoalkyl (meth) acrylate Monomer; vinyl trichlorodecane, vinyl trimethoxy decane, vinyl triethoxy decane, vinyl tris (β-methoxyethoxy) decane, γ-(meth) propylene methoxy propylene base Methoxydecane, γ-(meth)acryloxypropyltriethoxydecane, γ-(meth)acryloxypropylmethyldimethoxydecane, γ-(methyl)propene醯oxypropylmethyldiethoxydecane, γ-(meth)acryloxypropyltriisopropoxydecane, N-β-(N-vinylbenzylaminoethyl)-γ - a polymerizable monomer having a mercaptoalkyl group of -aminopropyltrimethoxydecane and its hydrochloride; a polymerizable monomer having an aziridine group such as 2-aziridineethyl (meth)acrylate; a polymerizable monomer having a (blocking) isocyanate group, such as a methyl propylene decyl isocyanate, a (meth) propylene decyl ethyl isocyanate phenol, or a methyl ethyl ketone oxime adduct; Isopropenyl-2- Oxazoline, 2-vinyl-2- Oxazoline, etc. a polymerizable monomer having an oxazoline group; a polymerizable monomer having a cyclopentenyl group such as dicyclopentenyl (meth)acrylate; or a polymerizable monomer having an allyl group such as allyl (meth)acrylate; A polymerizable monomer having a carbonyl group such as acrolein or diacetone (meth) acrylamide.

The above (meth)acrylic monomer having a crosslinkable functional group, relative to the above The total amount of the acrylic monomer mixture can be used in the range of 0% by mass to 50% by mass. Further, when a self-crosslinking reaction is used as the crosslinking agent (D), the above-mentioned (meth)acrylic monomer having a crosslinkable functional group may not be used.

In the (meth)acrylic monomer having a crosslinkable functional group, the (meth)acrylic monomer having a mercapto group is introduced from a cross-linking reactive hydroxymethylguanamine group. In general, it is preferably used in the range of 0.1% by mass to 50% by mass based on the total amount of the (meth)acrylic monomer mixture, and more preferably in the range of 1% by mass to 30% by mass. Further, another (meth)acrylic monomer having a mercapto group which is used in combination with the above-mentioned self-crosslinking reactive hydroxymethylguanamine group, and a (meth)acrylic monomer having a hydroxyl group are preferably used. The total amount of the (meth)acrylic monomer is used in the range of 0.1% by mass to 30% by mass in total, and more preferably in the range of 1% by mass to 20% by mass.

Further, in the (meth)acrylic monomer having a crosslinkable functional group, the (meth)acrylic monomer having a hydroxyl group or the (meth)acrylic monomer having an acid group is also used. Depending on the type of the crosslinking agent (D) used in combination, etc., it is preferably used in a range of from about 0.05% by mass to 50% by mass based on the total amount of the above (meth)acrylic monomer mixture. It is preferably used in the range of 0.05% by mass to 30% by mass, more preferably 0.1% by mass to 10% by mass.

Further, when the acrylic resin is produced, it may be used in combination with the above (meth)acrylic monomer: vinyl acetate, vinyl propionate, vinyl butyrate, tetraethylene carbonate, methyl vinyl Ether, ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, pentyl 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 or polyethylene glycol mono(meth)acrylate, glycerol mono(meth)acrylate, vinylsulfonic acid, styrenesulfonic acid, allylsulfonic acid, 2-methylallyl Sulfonic acid, 2-sulfoethyl (meth)acrylate, 2-sulfopropyl (meth)acrylate, "ADEKA REASOAP PP-70, PPE-710" (made by ADEKA Co., Ltd.) or such salts.

The acrylic resin can be produced by polymerizing a mixture of the above various vinyl monomers by a conventionally known method, and is preferably emulsified from the viewpoint of producing a conductive pattern having excellent adhesion and excellent electrical conductivity. Polymerization method.

As the above emulsion polymerization method, for example, water, a (meth)acrylic monomer mixture, a polymerization initiator, and, if necessary, a chain transfer agent or an emulsifier or a dispersion stabilizer may be used, and supplied to the reaction container at once. a method of mixing and polymerizing, or a method of dropping a (meth)acrylic monomer mixture into a reaction vessel to polymerize, or premixing a (meth)acrylic monomer mixture with A pre-emulsion method or the like in which an emulsifier or the like is added dropwise to a reaction vessel to polymerize it.

The reaction temperature of the emulsion polymerization method varies depending on the type of the (meth)acrylic monomer and the polymerization initiator to be used, and is preferably, for example, about 30 ° C to 90 ° C, and the reaction time is, for example, 1 hour. About 10 hours.

Examples of the polymerization initiator include persulfates such as potassium persulfate, sodium persulfate, and ammonium persulfate, and benzammonium peroxide, cumene hydroperoxide, and tert-butyl hydroperoxide. Oxides, hydrogen peroxide, etc., may be subjected to radical polymerization using only such peroxides, or may be used in combination with the above-mentioned peroxides and metal salts such as ascorbic acid, isoascorbic acid, sodium erythorbate, formaldehyde sulfoxylate, The redox polymerization initiator of a reducing agent such as sodium thiosulfate, sodium hydrogen sulfite or ferric chloride is polymerized, and 4,4'-azobis(4-cyanovaleric acid) can also be used. An azo-based initiator such as 2,2'-azobis(2-methylmercaptopropane) dihydrochloride may be used singly or in combination of two or more.

Examples of the emulsifier which can be used in the production of the acrylic resin include an anionic surfactant, a nonionic surfactant, a cationic surfactant, and an amphoteric ionic surfactant.

As the above anionic surfactant, for example, a sulfate of a higher alcohol can be mentioned. And its salt, alkylbenzenesulfonate, polyoxyethylene alkylphenylsulfonate, polyoxyethylene alkyl diphenyl ether sulfonate, sulfuric acid half ester of polyoxyethylene alkyl ether, alkyl diphenyl As the nonionic surfactant, for example, an ether disulfonate or a dialkyl succinate sulfonate, for example, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene II can be used. A phenyl ether, a polyoxyethylene-polyoxypropylene block copolymer, an acetylene glycol-based surfactant, or the like.

Further, as the above cationic surfactant, for example, an alkylammonium salt or the like can be used.

Further, as the amphoteric ionic surfactant, for example, an alkyl (decylamino) betaine or an alkyl dimethyl amine oxide can be used.

As the emulsifier, in addition to the above surfactant, a fluorine-based surfactant, a polyfluorene-based surfactant, or a "reactive emulsifier" may be used, and a polymerizable unsaturated group may be used in the molecule. Emulsifier.

As the reactive emulsifier, for example, "Latemul S-180" (manufactured by Kao Corporation) and "Eleminol JS-2, RS-30" having a sulfonic acid group and a salt thereof can be used (Sanyo Chemical Industry Co., Ltd.) "Manufacture", etc.; "AQUALON HS-10, HS-20, KH-1025" (manufactured by First Industrial Pharmaceuticals Co., Ltd.) and "ADEKA REASOAP SE-10, SE-20" (ADEKA (" "Shares), etc.; "Newfrontier A-229E" (manufactured by Daiichi Kogyo Co., Ltd.) having a phosphate group; "AQUALON RN-10, RN-20, RN-30, RN having a nonionic hydrophilic group" -50" (first industrial pharmaceutical (share) manufacturing) and the like.

Further, as the chain transfer agent which can be used in the production of the acrylic resin (x2-1), lauryl mercaptan or the like can be used, and it is preferably 0 mass with respect to the total amount of the above (meth)acrylic monomer mixture. It is used in the range of % to 1% by mass, and more preferably in the range of 0% by mass to 0.5% by mass.

In addition, examples of the urethane-vinyl composite resin (x3) which can be used as the resin contained in the undercoating agent include a urethane resin (x3-1) and a vinyl polymer ( X3-2) The composite resin particles are formed and can be dispersed in an aqueous medium or the like.

Specifically, the composite resin particles may be partially or wholly present in the resin particles formed of the urethane resin (x3-1). It is preferable to form a core-shell type composite resin particle containing the above-mentioned ethylene-based polymer (x3-2) as a core layer and the above-described hydrophilic group-containing urethane resin as an outer layer. In particular, when forming a conductive pattern, it is preferred to use the above-described core-shell type composite resin particles which do not require the use of a surfactant which can lower electrical characteristics. Further, as the composite resin particles, the vinyl polymer (x3-2) is preferably almost completely coated with the urethane resin (x3-1), but it is not essential and may not be damaged. Within the range of the effects of the present invention, a part of the above-mentioned ethylene-based polymer (x3-2) is present at the outermost portion of the composite resin particles.

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

Further, the urethane resin (x3-1) and the vinyl polymer (x3-2) may form a covalent bond, but it is preferred that no bond is formed.

Moreover, as the urethane-ethylene composite resin (x3), a urethane-acrylic composite resin in which the vinyl polymer (x3-2) is an acrylic resin is preferably used.

In addition, the composite resin particles preferably have an average particle diameter in the range of 5 nm to 100 nm from the viewpoint of maintaining good water dispersion stability. The average particle diameter herein means an average particle diameter on a volume basis as measured by a dynamic light scattering method.

The mass ratio of the urethane resin (x3-1) constituting the urethane-ethylene composite resin to the above vinyl polymer (x3-2) is preferably [urethane resin] (x3-1)/ethylene polymer (x3-2)] = 90/10 to 10/90, more preferably 70/30 to 10/90.

The urethane resin (x3-1) constituting the above urethane-ethylene composite resin can be the same as the above urethane resin (x1). In addition, as the urethane resin (x3-1) constituting the urethane-vinyl composite resin, for example, as exemplified as the urethane resin (x1), for example, A urethane resin of a polyether structure, a urethane resin having an aromatic polyester structure.

The polyol, the polyisocyanate, and the chain extender which can be used in the production of the above urethane resin (x3-1) can be used as exemplified by the user as the urethane resin (x1). The same polyol, polyisocyanate, chain extender.

Further, the urethane resin having a polyether structure can be produced by using a polyether polyol described later as the polyol. As the polyether polyol, for example, one or two or more compounds having two or more active hydrogen atoms may be used as a starter to form an alkylene oxide polymerizer.

As the above initiator, for example, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butylene glycol, 1,4-butanediol, 1, may be used. 6-hexanediol, neopentyl glycol, glycerin, trimethylolethane, trimethylolpropane, and the like.

As the alkylene oxide, for example, ethylene oxide, propylene oxide, butylene oxide, styrene oxide, epichlorohydrin, tetrahydrofuran or the like can be used.

Further, in the case of using the above urethane resin having an aromatic polyester structure, an aromatic polyester polyol may be used as the above polyol.

As the aromatic polyester polyol, for example, those obtained by subjecting a low molecular weight polyol and an aromatic polycarboxylic acid to an esterification reaction can be used.

The low molecular weight polyol which can be used in the production of the above aromatic polyester polyol can be used alone or in combination of two or more kinds of ethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol, and 1, 4-butanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, glycerin, trimethylolpropane, etc. Good combination of ethylene glycol, 1,2-propanediol, 1,3-butanediol or 1,4-butanediol with 3-methyl-1,5-pentanediol or new Pentylene glycol and the like.

As the aromatic polycarboxylic acid, for example, terephthalic acid, isophthalic acid, phthalic acid, naphthalenedicarboxylic acid, or an acid anhydride or esterified product thereof can be used.

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

As the ethylene-based polymer (x3-2) constituting the urethane-ethylene composite resin, a coating film having the above-described specific ethanol absorption rate is formed by using a glass transition temperature of 10 ° C to 70 ° C ( x) It is preferable to improve the adhesion with the conductive material (a2) contained in the above-mentioned fluid (a) and the conductivity of the obtained conductive pattern. In addition, the glass transition temperature of the ethylene-based polymer (x3-2) is mainly determined based on the composition of the vinyl-based monomer used in the production of the ethylene-based polymer (x3-2) by calculation. . Specifically, a vinyl polymer (x3-2) having the above specific glass transition temperature can be obtained by using a combination of the vinyl polymer (x3-2) described later.

Further, the vinyl polymer (x3-2) is formed into a coating film (x) having the specific ethanol absorptivity described above, and is densely bonded to the conductive material (a2) contained in the fluid (a). In view of the conductivity of the conductive or obtained conductive pattern and the thinning of the pattern, it is preferred to use a weight average molecular weight of 800,000 or more, and more preferably a weight average molecular weight of 1,000,000 or more.

The upper limit of the weight average molecular weight of the ethylene-based polymer (x3-2) is not particularly limited, but is preferably about 10,000,000 or less, preferably 5,000,000 or less.

In addition, the vinyl polymer (x3-2) may have various functional groups as necessary, and examples of the functional group include a guanamine group, a hydroxyl group, a glycidyl group, an amine group, a decyl group, and an aziridine. Base, isocyanate group, A crosslinkable functional group such as an oxazoline group, a cyclopentenyl group, an allyl group, a carboxyl group or an ethyl oxime group.

As the vinyl polymer (x3-2), the same as the above vinyl polymer (x2) can be used. Specifically, it can be used as a production of the above vinyl polymer (x3-2). As the (meth)acrylic monomer, a vinyl monomer exemplified as the user of the vinyl resin (x2) can be used, and the (meth)acrylic monomer is preferably the same. In addition, as the vinyl polymer (x3-2), it is preferable to use the same acrylic resin as the structural unit derived from methyl methacrylate exemplified as the user of the vinyl resin (x2). .

The urethane-vinyl composite resin (x3) can be produced by, for example, reacting the above polyisocyanate with a polyol and, if necessary, a chain extender to disperse water, thereby producing a urethane resin. a step (V) of the aqueous dispersion of (x3-1); and a step (W) of polymerizing the (meth)acrylic monomer in the aqueous dispersion to produce a vinyl polymer (x3-2) Manufacturing.

Specifically, the above polyisocyanate is reacted with a polyol in the absence of a solvent or an organic solvent or a reactive diluent such as a (meth)acrylic monomer, whereby a urethane resin is obtained ( X3-1), and then, part or all of the hydrophilic group of the urethane resin (x3-1), if necessary, neutralized with a basic compound or the like, and if necessary, reacts with a chain extender It is dispersed in an aqueous medium to thereby produce an aqueous dispersion of the urethane resin (x3-1).

Next, in the aqueous dispersion of the urethane resin (x3-1) obtained above, a vinyl monomer such as the above (meth)acrylic monomer is supplied to the above urethane resin (x3- 1) The vinyl monomer is subjected to radical polymerization in the particles to produce a vinyl resin (x3-2). In the case where the urethane resin (x3-1) is produced in the presence of a vinyl monomer, the polymerization initiator is supplied after the production of the urethane resin (x3-1). The vinyl monomer such as the above (meth)acrylic monomer is subjected to radical polymerization to produce a vinyl resin (x3-2).

Thereby, it is possible to produce a primer in which a part or all of the above-mentioned vinyl resin (x3-2) is dispersed in an aqueous medium in which the composite resin particles present in the urethane resin (x3-1) particles are dispersed.

When the composite resin particles are produced, when the urethane resin (x3-1) has a high viscosity and the workability is insufficient, methyl ethyl ketone or N-methylpyrrolidone or acetone can be used. Or a usual organic solvent or reactive diluent such as dipropylene glycol dimethyl ether. In particular, as the reactive diluent, a vinyl monomer such as a (meth)acrylic monomer which can be used in the production of the above-mentioned vinyl polymer (x3-2) is used, and it is obtained by omitting the solvent removal step. The improvement in the production efficiency of the primer is preferred.

Further, as the resin which can be used in the primer, in addition to the above, for example, a phenol resin, an epoxy resin, a melamine resin, a urea resin, an unsaturated polyester resin, an alkyd resin, or a polyimine can be used. Resin, fluororesin, etc.

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

As the primer, the above urethane resin (x1) and the above vinyl resin (x2) may be used in combination. When used in combination, the mass ratio of the urethane resin (x1) to the vinyl resin (x2) is preferably [(x1) / (x2)] = 90/10 - 10 It is used within the range of /90, and more preferably used in the range of 70/30~10/90.

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

The crosslinkable functional group forms a crosslinked structure in the undercoat layer (X) of the above-mentioned fluid (a), and forms a pattern (layer (Y) which is excellent in adhesion or conductivity without causing bleeding or the like. In terms of)), it can be suitably used.

The coating film (x) formed by using the above primer may have a crosslinked structure before or partially coating (printing) the above-mentioned fluid (a), but the ethanol absorption rate must be adjusted to 20% by mass. A range of 500% by mass.

Further, the coating film (x) may have no crosslinked structure before coating (printing) the fluid (a) on the surface thereof, and after the application of the fluid (a), an undercoat layer having a crosslinked structure is formed as Undercoat (X).

Examples of the crosslinkable functional group include an alkoxyalkyl group and a stanol group, and examples thereof include an amine group and a hydroxyl group.

In the case of using a resin having the above alkoxyalkylene group and a stanol group, the above alkoxyalkylene group and stanol are hydrolyzed and condensed in an aqueous medium based on a solvent as a primer to form a crosslinked structure. The primer having the crosslinked structure is applied onto the surface of the support to be dried or the like, whereby a coating film (x) having a crosslinked structure formed is formed before the application of the fluid (a).

Further, as the crosslinkable functional group, it is also possible to use a crosslinking functional group or a crosslinking agent (D) to be described later by heating to about 100 ° C or higher, preferably 120 ° C or higher. In the case of the above-mentioned crosslinked structure, it is preferred to use one or more kinds of thermally crosslinkable functional groups selected from the group consisting of hydroxymethylguanamine groups and alkoxymethylguanamine groups. .

Specific examples of the alkoxymethylguanamine group include a guanamine group formed by bonding a nitrogen atom such as a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group or a butoxymethyl group. Among them, the use of one or more selected from the group consisting of a hydroxymethyl decylamino group and an alkoxymethyl guanamine group greatly improves the durability of the undercoat layer (X) and various supports. It is preferable in terms of adhesion.

When the primer containing the resin having a functional group capable of crosslinking reaction by heating to about 100 ° C or higher, preferably about 120 ° C, is used, the primer is applied to the support. The temperature at which the surface of the body is dried is preferably less than 100 °C. Thereby, a coating film having substantially no crosslinked structure can be formed as the coating film (x).

After coating (printing) the fluid body (a) on the coating film having no crosslinked structure, the heating step is performed at a temperature of 100 ° C or higher, or the heating step is additionally performed with the heating step. Alternatively, an undercoat layer having a crosslinked structure can be formed as the undercoat layer (X).

After the application of the fluid (a), a crosslinked structure is formed in the undercoat layer (X), thereby being exposed to an electroplating agent containing a strong alkali or a strong acid substance in a plating treatment step to be described later. In this case, it is also possible to form a conductive pattern having particularly excellent durability without causing the undercoat layer (X) to be peeled off from the support. In addition, the above-mentioned "substantially no cross-linking structure" means a state in which the cross-linking structure is not formed at all, and also refers to a portion in which a cross-linking structure is formed within about 5% of the functional group in which the cross-linking structure can be formed. .

The crosslinkable functional group is preferably contained in a total amount of 0.005 equivalent/kg to 1.5 equivalent/kg based on the total amount of the resin used in the primer.

Further, the primer may be added to a pH adjusting agent, a coating forming aid, a leveling agent, and a tackifier, which are preferably a crosslinking agent (D), as long as the effect of the present invention is not impaired. Well-known agents such as water-repellent agents and defoamers.

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 can be used to form a reaction at a temperature lower than about 25 ° C to 100 ° C. The cross-linking structure of the thermal cross-linking agent (d1-1) is selected from the group consisting of a melamine-based compound, an epoxy-based compound, One or more of the group consisting of an oxazoline compound, a carbodiimide compound, and a blocked isocyanate compound can be reacted at a relatively high temperature of about 100 ° C or higher to form a crosslinked structure of a thermal crosslinking agent (d1-2). Various photocrosslinkers.

The primer containing the above thermal crosslinking agent (d1-1) is applied, for example, to the surface of the support, dried at a lower temperature, and then coated (printed) the above-mentioned fluid, and then heated to less than 100 When the temperature of °C forms a crosslinked structure, it is possible to form a conductive pattern having excellent durability which is excellent in the level of preventing the peeling of the conductive material from the influence of long-term heat or external force.

On the other hand, the primer containing the above-mentioned thermal crosslinking agent (d1-2) is applied, for example, to the surface of the support, and dried at a low temperature (normal temperature (25 ° C) to about 100 ° C). After the coating film (x) having no crosslinked structure is formed, and then the fluid body (a) is applied, for example, it is heated at a temperature of 150 ° C or higher, preferably 200 ° C or higher, to form a crosslinked structure. A conductive pattern having excellent durability which is not affected by long-term heat, external force, or the like without causing peeling of the conductive material or the like is formed.

In the case where a support containing a polyethylene terephthalate or the like which is weak in heat is used as the support, it is preferably about 150 ° C or less from the viewpoint of preventing deformation of the support or the like. It is preferred to heat at a temperature of 120 ° C or lower. Therefore, as the above crosslinking agent, it is preferred to use the above thermal crosslinking agent (d1-1) instead of the above thermal crosslinking agent (d1-2).

As the metal chelate compound which can be used in the above thermal crosslinking agent (d1-1), for example, aluminum, iron, copper, zinc, tin, titanium, nickel, ruthenium, magnesium, vanadium, chromium, zirconium or the like can be used. As the metal acetoacetone complex compound, the acetamidine acetate complex compound, etc., it is preferred to use acetoacetate aluminum as the aluminum acetonide acetone coordination compound.

Further, as the polyamine compound which can be used in the above-mentioned thermal crosslinking agent (d1-1), for example, a tertiary amine such as triethylamine, triethylenediamine or dimethylethanolamine can also be used.

Further, as the aziridine compound which can be used in the above thermal crosslinking agent (d1-1), for example, 2,2-bishydroxymethylbutanol-tris[3-(1-aziridine)propane can be used. Acid ester], 1,6-hexamethylene diethylammonium, diphenylmethane-bis-4,4'-N, N'-diethylethyl urea, and the like.

Further, as the metal base compound which can be used as the above crosslinking agent (d1-1), for example, aluminum sulfate, aluminum bismuth, aluminum sulfite, aluminum thiosulfate, polyaluminum chloride, aluminum nitrate nonahydrate, and six can be used. A water-soluble metal salt such as aluminum chloride hydrate, titanium tetrachloride, tetraisopropyl titanate, titanium acetylacetonate or titanium lactate.

As the isocyanate compound which can be used in the above thermal crosslinking agent (d1-1), for example, toluene diisocyanate, hydrogenated toluene diisocyanate, triphenylmethane triisocyanate, methylene bis(4-phenylmethane) III can be used. Polyisocyanate such as isocyanate, isophorone diisocyanate, hexamethylene diisocyanate or benzene dimethylene diisocyanate; isocyanurate type polyisocyanate compound obtained by using the same; Propane, etc. An adduct of a polyisocyanate group obtained by reacting the polyisocyanate compound with a polyhydric alcohol such as trimethylolpropane. Among them, a urate body of hexamethylene diisocyanate, an adduct of hexamethylene diisocyanate and trimethylolpropane, an adduct of toluene diisocyanate and trimethylolpropane, or the like is preferably used. An adduct of benzene dimethylene diisocyanate with trimethylolpropane or the like.

Further, as the melamine compound which can be used in the above thermal crosslinking agent (d1-2), for example, hexamethoxymethyl melamine, hexaethoxymethyl melamine, hexapropoxymethyl melamine or hexabutyloxy can be used. Methyl melamine, hexaethoxyoxymethyl melamine, hexahexyloxymethyl melamine or a combination of these two kinds of mixed etherified melamine or the like. Among them, trimethoxymethyl melamine and hexamethoxymethyl melamine are preferably used. As a commercial item, Beckamine M-3, APM, J-101 (made by DIC (share)), etc. can be used. The above melamine compound can form a crosslinked structure by a self-crosslinking reaction.

In the case of using the above melamine compound, a catalyst such as an organic amine salt can be used from the viewpoint of promoting its self-crosslinking reaction. As a commercial item, Catalyst ACX, 376, etc. can be used. The catalyst is preferably in a range of from about 0.01% by mass to 10% by mass based on the total amount of the melamine compound.

Further, as the epoxy compound which can be used in the above thermal crosslinking agent (d1-2), for example, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, hexanediol diglycidyl ether or cyclohexane can be used. Polyglycidyl ether of an aliphatic polyhydric alcohol such as alcohol diglycidyl ether, glycerol diglycidyl ether, glycerol triglycidyl ether, trimethylolpropane triglycidyl ether, pentaerythritol tetraglycidyl ether; polyethylene glycol dihydrate a polyglycidyl ether of a polyalkylene glycol such as glyceryl ether, polypropylene glycol diglycidyl ether or polybutylene glycol diglycidyl ether; 1,3-bis(N,N'-diglycidylaminoethyl) a polyglycidylamine such as cyclohexane; a polycarboxylic acid [oxalic acid, adipic acid, butane tricarboxylic acid, maleic acid, phthalic acid, terephthalic acid, isophthalic acid, trimellitic acid) Polyglycidyl ester, etc.; condensate of bisphenol A and epichlorohydrin, ethylene oxide adduct of bisphenol A and epichlorohydrin condensate, etc. An epoxy resin; a phenol novolak resin; various vinyl (co)polymers having an epoxy group in a side chain. Among them, polyglycidol of an aliphatic polyol such as polyglycidylamine or glycerol diglycidyl ether such as 1,3-bis(N,N'-diglycidylaminoethyl)cyclohexane is preferably used. ether.

Further, as the epoxy compound, for example, γ-glycidoxypropyltrimethoxydecane, γ-glycidoxypropyltriethoxydecane, γ-glycidyloxy group may be used in addition to the above. Propylmethyldimethoxydecane, γ-glycidoxypropylmethyldiethoxydecane, β-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, β-(3, 4-epoxycyclohexyl)ethyltriethoxydecane, β-(3,4-epoxycyclohexyl)ethylmethyldiethoxydecane or γ-glycidoxypropyltriisopropenyloxy A decane compound having a glycidyl group such as decane.

Further, it can be used as the above thermal crosslinking agent (d1-2) An oxazoline compound, for example, can be used: 2,2'-bis-(2- Oxazoline), 2,2'-methylene-bis-(2- Oxazoline), 2,2'-extended ethyl-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'-extended ethyl-bis-(4,4'-dimethyl-2- Oxazoline), 2,2'-p-phenylene-bis-(2- Oxazoline), 2,2'-meta-phenyl-bis-(2- Oxazoline), 2,2'-meta-phenyl-bis-(4,4'-dimethyl-2- Oxazoline), bis-(2- Oxazolinylcyclohexane) sulfide, bis-(2- Oxazoline Sulfide, etc.

Again, as above As the oxazoline compound, for example, the following addition polymerization property can also be used. The oxazoline is obtained by polymerizing in combination with other monomers as needed An oxazoline-based polymer.

Addition polymerization The oxazoline can be used alone or in combination of two or more: 2-vinyl-2- Oxazoline, 2-vinyl-4-methyl-2- Oxazoline, 2-vinyl-5-methyl-2- Oxazoline, 2-isopropenyl-2- Oxazoline, 2-isopropenyl-4-methyl-2- Oxazoline, 2-isopropenyl-5-methyl-2- Oxazoline, 2-isopropenyl-5-ethyl-2- Oxazoline and the like. Wherein, if 2-isopropenyl-2- is used Oxazolines are preferred because they are readily available in the industry.

Further, as the carbodiimide compound which can be used in the above thermal crosslinking agent (d1-2), for example, poly[phenylphenylbis(dimethylmethylene)carbodiimide] or poly (methyl-1,3-phenylene carbodiimide) and the like. For commercial use, Carbodilite V-01, V-02, V-03, V-04, V-05, V-06 (manufactured by Nisshinbo Co., Ltd.), UCARLINK XL-29SE, XL-29MP (jointed) Carbide (share) manufacturing, etc.

Further, as the blocked isocyanate compound which can be used in the above-mentioned thermal crosslinking agent (d1-2), one or all of the isocyanate groups which are exemplified as the above-mentioned thermal crosslinking agent (d1-1) can be used. Sealed by a blocking agent.

As the above blocking agent, for example, phenol, cresol, 2-hydroxypyridine, butyl cellosolve, propylene glycol monomethyl ether, benzyl alcohol, methanol, ethanol, n-butanol, isobutanol, malonate may be used. Ester, diethyl malonate, ethyl acetate, ethyl acetate, ethyl acetate, butyl mercaptan, dodecyl mercaptan, acetophenone, acetamidine, ε-caprolactam, δ - Valdecylamine, γ-butyrolactam, amber succinimide, maleimide, imidazole, 2-methylimidazole, urea, thiourea, ethylurea, methotrexate, acetaldehyde Anthraquinone, acetone oxime, methyl ethyl ketone oxime, methyl isobutyl ketone oxime, cyclohexanone oxime, diphenylaniline, aniline, carbazole, ethimine, polyethylenimine and the like.

As the blocked isocyanate compound, Elastron BN-69 (manufactured by Daiichi Kogyo Co., Ltd.), which is a commercially available product of a water dispersion type, can be used.

In the case of using the above crosslinking agent (D), as the resin contained in the primer, it is preferred to use a substrate having a crosslinking functional group which can be reacted with the crosslinking agent (D). . Specifically, it is preferred to use the above (blocked) isocyanate compound, melamine compound, As the crosslinking agent, an oxazoline compound or a carbodiimide compound is used, and a resin having a hydroxyl group or a carboxyl group is used as the above resin.

The above-mentioned crosslinking agent (D) varies depending on the type and the like, and is usually preferably in an amount of from 0.01% by mass to 60% by mass based on 100% by mass based on the total mass of the resin contained in the primer. It is preferably used in the range of 0.1% by mass to 10% by mass, and is used in the range of 0.1% by mass to 5% by mass to form an electrical conductivity excellent in adhesion and electrical conductivity and excellent in durability. The pattern is therefore preferred.

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

Further, as the above additive, various fillers such as inorganic particles can also be used. However, as the primer of the present invention, the amount of the filler or 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.

The amount of the above-mentioned additive is not particularly limited as long as it does not impair the effects of the present invention, and is preferably in the range of 0.01% by mass to 40% by mass based on the total amount of the solid content in the primer.

Next, a method of producing the conductive pattern of the present invention will be described.

The conductive pattern of the present invention may be partially or completely coated with a primer by one or both of the surfaces of the support, and then the flow may be partially or completely coated on one of the surfaces of the coating film (x) formed using the primer. After the body (a), it is dried and produced.

First, a method of forming a coating film (x) by applying a primer to a part or the whole of one surface of the above-mentioned support will be described.

The coating film (x) can be formed by applying the primer to the support to remove a solvent such as an aqueous medium or an organic solvent contained in the primer.

The undercoating agent which forms part or all of the surface of the above-mentioned support to form the coating film (x) can form the undercoat layer (X) of the conductive pattern of the present invention.

Examples of the method of applying the primer to the surface of the support include a gravure method, a coating method, a screen method, a roll coating method, a spinning method, a spray method, a spin coating method, and an ink jet method. And other methods.

Moreover, as a method of removing the solvent contained in the primer, for example, a method in which the solvent is volatilized by drying in a dryer is usually used. As the drying temperature, as long as it is set The temperature in which the solvent is volatilized and which does not adversely affect the support may be used.

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

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

In order to solve the above problem, the coating film (x) must be a coating film which can absorb ethanol in an amount of 20% by mass to 500% by mass based on the mass of the coating film (x) in an environment of 25 ° C.

The coating film (x) absorbs the mass ratio of ethanol to the mass of the coating film (x) [absorbency of ethanol] is a value obtained by measurement by the following method.

The primer was applied onto the surface of the release paper by an applicator, dried, and then the release paper was removed to prepare a coating film having a length of 3 cm, a width of 3 cm, and a thickness of 50 μm.

Next, the quality of the coating film obtained above was measured.

Next, the coating film was immersed in 30 g of ethanol adjusted to 25 ° C in an environment of 25 ° C.

Next, after the coating film was immersed in the ethanol for 30 seconds, the coating film was taken out from the ethanol, placed on three sheets of dust-free wiping paper (bemcot), and three pieces of dust-free wiping paper were superposed thereon. Further, it was left for 10 seconds while leaving a weight of 500 g.

After the above 10 seconds, the mass of the coating film was measured, and the mass of the ethanol absorbed in the coating film after the immersion was determined.

Next, the mass of the ethanol absorbed in the coating film after the immersion is divided by the mass of the coating film before the immersion, and multiplied by 100, and the mass ratio obtained thereby is taken as the absorption rate of the ethanol.

When the absorption rate of the above-mentioned ethanol is less than 20% by mass, specifically, when the above-mentioned fluid (a) is applied to a coating film of 10% by mass, there is a case where conductivity is caused. Sexual decline or decreased adhesion. Specifically, the solvent contained in the fluid (a) is hardly absorbed by the coating film (x), and thus the adhesion between the coating film (x) and the conductive pattern may be deteriorated.

On the other hand, when the absorption rate of the above ethanol exceeds 500% by mass, the conductivity may deteriorate.

The absorption rate of the above-mentioned ethanol is preferably in the range of 20% by mass to 300% by mass, more preferably in the range of 20% by mass to 200% by mass, from the viewpoint of imparting further excellent adhesion and conductivity. The range is from 45% by mass to 190% by mass.

The coating film (x) is a film of the precursor of the undercoat layer (X) formed by heating or ultraviolet irradiation or the like. Further, the coating film (x) may be used as the undercoat layer (X) by, for example, drying at normal temperature.

Further, in the present invention, it is not possible to solve the above problem by using only the coating film (x) having the specific absorption ratio described above, and it is necessary to apply the above-described specific fluid (a) to the coating film (x) to print a pattern. The above issues.

Further, the undercoat layer (X) constituting the conductive pattern does not necessarily have to have the specific absorption rate described above. In order to solve the above problem, the coating film (x) before the application of the fluid (a) before the heating described above must have the specific ethanol absorption rate described above.

The coating film (x) is appropriately dissolved by the solvent contained in the fluid (a), and the solvent is absorbed, whereby the conductive material such as the metal contained in the fluid (a) can be fixed with high precision ( The swelling type receiving layer of a2) can contribute to obtaining a non-bleeding conductive pattern. Further, by using the above coating film (x), a transparent undercoat layer can be formed as compared with the previously known porous type undercoat layer.

Next, a method of producing a conductive pattern by applying the above-mentioned fluid (a) partially or completely to one surface of the coating film (x) obtained above will be described.

The method of applying the fluid body (a) partially or completely to one surface of the coating film (x) is, for example, a reverse printing method such as a letterpress reverse printing method, and inkjet printing is used. Brush method, screen printing method, lithography method, spin coating method, spray coating method, bar coating method, die coating method, slit coating method, roll coating method, dip coating A method of printing the conductive ink directly or in reverse on the receiving substrate or the like.

In the case where the fluid (a) is applied (printed) to a thin line shape of about 0.01 μm to 100 μm which is required to achieve high density of an electronic circuit or the like, an ink jet printing method is preferably used.

As the above inkjet printing method, a person called an inkjet printer can be generally used. Specific examples thereof include Konica Minolta EB100, XY100 (manufactured by Konica Minolta IJ Co., Ltd.) or Dimatix Material Printer DMP-3000, Dimatix Material Printer DMP-2831 (manufactured by Fujifilm Co., Ltd.), and the like.

The coating (printing) of the above-mentioned fluid (a) can be dried, for example, at normal temperature or by heating or the like. In the case where the conductive material (a2) such as a metal contained in the fluid (a) is adhered to each other to impart conductivity, it is preferred to perform heating.

On the other hand, when a plating nucleating agent is used as the above-mentioned fluid (a), the conductivity of the above-mentioned conductive material (a2) is not necessarily required. In this case, the conductive material (a2) may be carried on the surface of the undercoat layer containing the coating film (x) by drying at normal temperature or the like.

The above heating is preferably in the range of about 80 ° C to 300 ° C and is carried out for about 2 minutes to 200 minutes. The above heating can be carried out in the atmosphere, and from the viewpoint of preventing oxidation of the above metal, part or all of the heating step can be carried out in a reducing environment. Further, the conductive pattern of the present invention can form a pattern excellent in adhesion or conductivity even when heated at a relatively low temperature of about 80 ° C to 120 ° C.

Further, the heating step can be carried out, for example, using an oven, a hot air drying oven, an infrared drying oven, laser irradiation, microwaves, or the like.

Further, in the case of using a resin having a crosslinkable functional group which undergoes a crosslinking reaction at a relatively high temperature as a resin contained in the undercoating agent, or by using the above crosslinking agent (d1- 2), in the case where the above-mentioned fluid (a) is applied (printed) to form a crosslinked structure in the undercoat layer (X), a crosslinked structure is formed after coating (printing) by the above heating step. . Thereby, the durability of the conductive pattern can be particularly improved.

In the case where the crosslinking reaction step and the heating step are combined, the heating temperature may be different depending on the type of the crosslinking agent (D) or the like, the combination of the crosslinking functional groups, and the like, and is preferably It is in the range of about 80 ° C to 300 ° C, more preferably 100 ° C to 300 ° C, and particularly preferably 120 ° C to 300 ° C. Further, in the case where the support is weak to heat, the upper limit of the temperature is preferably 150 ° C or lower, more preferably 120 ° C or lower.

The conductive pattern is formed on the surface of the conductive pattern obtained by the above heating step by a conductive substance such as a metal contained in the fluid (a). The conductive pattern is also suitable for forming an electronic circuit such as an organic solar cell or an electronic book terminal, an organic EL, an organic transistor, a flexible printed circuit board, an RFID, and the like, and forming a peripheral wiring, and a plasma. In the field of printed electronics such as wiring of electromagnetic wave shields for displays.

In addition, as the conductive pattern, it is possible to use a metal such as copper from the viewpoint of forming a wiring pattern which has a high reliability and can maintain a good electrical conductivity without causing disconnection or the like for a long period of time. Electroplating processor. Specifically, as the conductive pattern, for example, a coating film (x) having a part or all of the surface of the support using the primer may be used, since one part of the surface of the coating film (x) or All of the coating (printing) is used as the plating agent for the fluid (a), and the plating core is supported on the surface of the coating film (x), and if necessary, after the heating step or the like, electrolytic plating treatment is performed, and no electricity is applied. The electroplating treatment or the plating layer (Z) including the plating film formed by performing the electroplating treatment after the electroless plating treatment described above.

In the electroless plating treatment step, for example, a plating core such as palladium or silver is contacted with an electroless plating solution on the surface of the undercoat layer (X) carrier to precipitate a metal such as copper contained in the electroless plating solution. A step of electroless plating (coating) comprising a metal film.

As the electroless plating solution, for example, a conductive material containing a metal such as copper, nickel, chromium, cobalt or tin, a reducing agent, a solvent such as an aqueous medium or an organic solvent can be used.

As the reducing agent, for example, dimethylaminoborane, hypophosphorous acid, sodium hypophosphite, dimethylamine borane, hydrazine, formaldehyde, sodium borohydride, phenol or the like can be used.

Further, the electroless plating solution may contain a monocarboxylic acid such as acetic acid or formic acid; or a dicarboxylic acid such as malonic acid, succinic acid, adipic acid, maleic acid or fumaric acid; Hydroxycarboxylic acid such as malic acid, lactic acid, glycolic acid, gluconic acid or citric acid; amino acid such as glycine, alanine, arginine, aspartic acid, glutamic acid; iminodiacetic acid, nitrogen An organic acid such as an aminopolycarboxylic acid such as triacetic acid, ethylenediamine diacetic acid, ethylenediaminetetraacetic acid or diamethylenetriaminepentaacetic acid, or a soluble salt of the organic acid (sodium salt, potassium salt, ammonium salt) Etc.), such as ethylene diamine, di-ethyltriamine, tri-ethyltetramine and other amines.

The temperature of the electroless plating solution when the surface of the undercoat layer (X) supported by the plating core in the plating agent is brought into contact with the electroless plating solution is preferably in the range of about 20 to 98 °C.

Further, the electrolytic plating treatment step is performed by, for example, contacting the surface of the undercoat layer (X) on which the plating core is supported or the surface of the electroless plating layer (film) formed by the above-described electroless treatment to the electrolytic plating solution. In the state of being energized, the metal such as copper contained in the electrolytic plating solution is deposited on the surface of the undercoat layer (X) provided on the negative electrode or the electroless plating layer (film) formed by the electroless treatment. Thereby, a step of electrolytic plating film (metal film) is formed.

As the electrolytic plating solution, a conductive material containing a metal such as copper, nickel, chromium, cobalt or tin, and an aqueous medium such as sulfuric acid can be used.

The temperature of the electrolytic plating solution when the surface of the undercoat layer (X) supported by the plating core in the plating catalyst is brought into contact with the electrolytic plating solution is preferably in the range of about 20 to 98 °C.

In the steps of electroless plating treatment and electrolytic plating treatment as described above, the use of a strong acid or a strong alkaline plating solution as described above is often the case, and in general, in the above primer layer (X), the undercoat layer ( X) is invaded, causing the above-mentioned undercoat layer (X) to be peeled off from the support.

On the other hand, in the case where the fluidized body (a) such as the above-mentioned plating nucleating agent is used for printing, the crosslinked structure in the undercoat layer (X) is formed, and the above-mentioned primer is not caused in the above plating treatment step. Layer (X) peeling off the support. In particular, even if the support is made of a polyimide resin or the like, the undercoat layer (X) is not peeled off, so that it can be preferably used for the production of the conductive pattern.

The conductive pattern as described above can be preferably used for forming an organic solar cell, an electronic book terminal, an organic EL, an organic transistor, a flexible printed circuit board, an RFID, etc., using an electronic circuit having silver ink or the like. The wiring is formed to form a conductive pattern such as a wiring of an electromagnetic wave mask of a plasma display, and more specifically, a circuit board.

Further, in the conductive pattern obtained by the above method, after a fluid (a) such as a conductive ink or a plating nucleus is applied (printed), a crosslinked structure is formed in the undercoat layer (X). The conductive pattern can provide a particularly excellent durability which can maintain a good electrical conductivity level without causing the undercoat layer (X) to be peeled off from the support even after the plating treatment step. It is used to form a substrate for circuit formation used in an electronic circuit such as silver ink or an integrated circuit, and constitutes an organic solar cell, an electronic book terminal, an organic EL, an organic transistor, a flexible printed circuit board, and an RFID layer. The use of peripheral wiring, wiring of electromagnetic wave shields for plasma displays, and the like are particularly required for durability. In particular, the conductive pattern having the above-described plating treatment can form a wiring pattern which is highly reliable and can maintain good electrical conductivity without causing disconnection or the like for a long period of time, and thus can be used, for example, as a copper foil. CCL (Copper Clad Laminate), Flexible Printed Substrate (FPC), Tape and Reel (TAB, Tape Automated) Bonding), film flip chip package (COF) and printed wiring board (PWB).

[Examples]

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, a reflux cooling tube, a nitrogen gas introduction tube, a thermometer, and a dropping funnel, 115 parts by mass of deionized water and 4 parts by mass of Latemul E-118B (manufactured by Kao (product): 25 mass% of active ingredient) were charged. The temperature was raised to 75 ° C while blowing nitrogen gas.

Under stirring, a vinyl monomer mixture containing 60 parts by mass of methyl methacrylate, 3 parts by mass of methacrylic acid, and 37 parts by mass of n-butyl acrylate was mixed with AQUALON KH-1025 (First Industrial Pharmaceutical Co., Ltd.) Manufactured: 25% by mass of the active ingredient: 2 parts by mass of a part of the monomer pre-emulsion (5 parts by mass) obtained by adding 15 parts by mass of deionized water, and then 0.1 parts by mass of potassium persulfate, and the temperature inside the reaction vessel The polymerization was carried out for 60 minutes while maintaining the temperature at 75 °C.

Then, while maintaining the temperature in the reaction vessel at 75 ° C, a different dropping funnel was used, and the remaining monomer pre-emulsion (114 parts by mass) and potassium persulfate aqueous solution (active ingredient 1.0 mass) were added dropwise over 180 minutes. %) 30 parts by mass. After the completion of the dropwise addition, the mixture was stirred at the same temperature for 60 minutes.

The temperature in the reaction vessel was cooled to 40 ° C, and aqueous ammonia (active ingredient: 10% by mass) was used to adjust the pH of the aqueous dispersion in the reaction vessel to 8.5.

Then, deionized water was used to have a nonvolatile content of 30.0% by mass, and then filtered with a 200 mesh filter cloth to prepare a primer 1.

[Preparation Example 2] Preparation of primer 2

First, 543 parts by mass of polyethylene glycol-diglycidyl ether (epoxy equivalent: 185 g/eq) was placed in a four-necked flask equipped with a thermometer, a stirring device, a reflux cooling tube, and a dropping device, and then nitrogen was placed in the flask. Replacement. Then, the mixture was heated in an oil bath until the temperature in the flask became 70 ° C, and then 380 parts by mass of di-n-butylamine was added dropwise over 30 minutes using a dropping device. After the completion of the dropwise addition, the mixture was reacted at 70 ° C for 10 hours. After completion of the reaction, an infrared spectrophotometer (FT/IR-460 Plus, manufactured by JASCO Corporation) was used to confirm that the absorption peak near 842 cm ^-1 of the epoxy group of the reaction product disappeared, and a tertiary amino group was prepared. Polyol K (amine equivalent 315 g / equivalent, hydroxyl equivalent 315 g / equivalent).

Next, a polyester polyol P obtained by reacting neopentyl glycol with 1,4-butanediol and adipic acid is added to a four-necked flask equipped with a thermometer, a stirring device, a reflux cooling tube, and a dropping device. The number average molecular weight was 2,000), 1070 parts by mass, and 770 parts by mass of ethyl acetate, and the temperature was raised to 70 ° C while stirring. After stirring and mixing, 281 parts by mass of dicyclohexylmethane diisocyanate and 0.2 parts by mass of stannous octoate were added, and the mixture was reacted at 70 ° C for 2 hours.

After the completion of the reaction, 84 parts by mass of the above-obtained polyol K having a tertiary amino group was added, and after reacting for 4 hours, "amino decane A1100" which is a component capable of forming a crosslinked structure was added [manufactured by Nippon Unicar Co., Ltd. 36 parts by mass of γ-aminopropyltriethoxydecane], and reacted for 1 hour, thereby preparing a urethane prepolymer solution having a decylalkyl group. Then, 38 parts by mass of N-aminoethylethanolamine was added to the above urethane prepolymer solution, and a chain elongation reaction was carried out for 1 hour, whereby an organic solvent solution of a cationic urethane resin was obtained.

Next, 1710 parts by mass of ethyl acetate and 22 parts by mass of acetic acid were added, and the mixture was kept at 45 ° C for 1 hour, and then cooled to 40 ° C, and 3850 parts by mass of ion-exchanged water was added to prepare an aqueous dispersion. The undercoating agent 2 having a nonvolatile content of 30% by mass was prepared by subjecting the aqueous dispersion to distillation under reduced pressure.

[Preparation Example 3] Preparation of primer 3

First, a polyester polyol Q obtained by reacting 1,4-cyclohexanedimethanol with neopentyl glycol and adipic acid in a nitrogen-substituted vessel equipped with a thermometer, a nitrogen gas introduction tube, and a stirrer (described above) The hydroxyl equivalent of the polyester polyol Q is 1000 g/eq. 100 parts by mass, 17.6 parts by mass of 2,2-dimethylolpropionic acid, 21.7 parts by mass of 1,4-cyclohexanedimethanol, and dicyclohexylmethane 106.2 parts by mass of isocyanate, reversed in 178 parts by mass of methyl ethyl ketone Thus, an organic solvent solution of a urethane prepolymer having an isocyanate group at the end is obtained.

Next, by adding 13.3 parts by mass of triethylamine to the organic solvent solution of the urethane prepolymer, one or all of the carboxyl groups of the urethane prepolymer are partially or completely neutralized, and then added. 380 parts by mass of water was sufficiently stirred, whereby an aqueous dispersion of the urethane prepolymer was obtained.

Next, by adding 8.8 parts by mass of a 25% by mass aqueous solution of ethylenediamine to the aqueous dispersion and stirring the mixture, the urethane resin chain is elongated, aged, and solvent-removed, thereby obtaining a nonvolatile content of 30. An aqueous dispersion of a mass% of urethane resin (L-1). 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 was placed in a reaction vessel equipped with a stirrer, a reflux cooling tube, a nitrogen gas introduction tube, a thermometer, a dropping funnel for dropping a monomer mixture, and a dropping funnel for a polymerization catalyst dropwise addition. 100 parts by mass of the aqueous dispersion of the urethane resin (L-1) was heated to 80 ° C while blowing nitrogen gas.

In a reaction vessel heated to 80 ° C, 50 parts by mass of methyl methacrylate was added dropwise from a different dropping funnel while maintaining the temperature in the reaction vessel at 80 ± 2 ° C for 120 minutes while stirring. 50 parts by mass of a monomer mixture of butyl ester and 20 parts by mass of an aqueous solution of ammonium persulfate (nonvolatile content: 0.5% by mass) were polymerized.

After the completion of the dropwise addition, the mixture was stirred at the same temperature for 60 minutes, thereby obtaining a core layer comprising the outer layer comprising the above urethane resin (L-1) and a vinyl layer comprising a mixture of the above monomers. An aqueous dispersion of urethane-acrylic composite resin particles.

The temperature in the reaction vessel was cooled to 40 ° C, and then deionized water was used to have a nonvolatile content of 20.0% by mass, and then filtered with a 200 mesh filter cloth to prepare a primer 3.

[Preparation Example 4] Preparation of primer 4

Into a reaction vessel equipped with a stirrer, a reflux cooling tube, a nitrogen gas introduction tube, a thermometer, a dropping funnel for dropping a monomer mixture, and a dropping funnel for a polymerization catalyst dropwise addition, 140 parts by mass of deionized water was charged, and the amine obtained above was obtained. 100 parts by mass of the aqueous dispersion of the urethane resin (L-1) was heated to 80 ° C while blowing nitrogen gas.

In a reaction vessel heated to 80 ° C, 50.0 parts by mass of methyl methacrylate was added dropwise from a different dropping funnel while maintaining the temperature in the reaction vessel at 80 ± 2 ° C for 120 minutes while stirring. A monomer mixture of 45.0 parts by mass of butyl ester and 5 parts by mass of N-n-butoxymethyl acrylamide and 20 parts by mass of an aqueous solution of ammonium persulfate (nonvolatile content: 0.5% by mass) were polymerized.

After the completion of the dropwise addition, the mixture was stirred at the same temperature for 60 minutes, thereby obtaining a core layer comprising the outer layer comprising the above urethane resin (L-1) and a vinyl layer comprising a mixture of the above monomers. An aqueous dispersion of composite resin particles.

The temperature in the reaction vessel was cooled to 40 ° C, and then deionized water was used to make the nonvolatile content 20.0% by mass, and then filtered with a 200 mesh filter cloth to prepare a primer 4.

[Preparation Example 5] Preparation of primer 5

Into a reaction vessel equipped with a stirrer, a reflux cooling tube, a nitrogen gas introduction tube, a thermometer, a dropping funnel for dropping a monomer mixture, and a dropping funnel for a polymerization catalyst dropwise addition, 140 parts by mass of deionized water was charged, and the amine obtained above was obtained. 333 parts by mass of the aqueous dispersion of the urethane resin (L-1) was heated to 80 ° C while blowing nitrogen gas.

In a reaction vessel heated to 80 ° C, 50 parts by mass of methyl methacrylate was added dropwise from a different dropping funnel while maintaining the temperature in the reaction vessel at 80 ± 2 ° C for 120 minutes while stirring. A monomer mixture of 45 parts by mass of butyl ester and 5 parts by mass of N-n-butoxymethyl acrylamide and 20 parts by mass of an aqueous solution of ammonium persulfate (nonvolatile content: 0.5% by mass) were polymerized.

After the completion of the dropwise addition, the mixture was stirred at the same temperature for 60 minutes, thereby obtaining a core layer comprising the outer layer comprising the above urethane resin (L-1) and a vinyl layer comprising a mixture of the above monomers. An aqueous dispersion of urethane-acrylic composite resin particles.

The temperature in the reaction vessel was cooled to 40 ° C, and then deionized water was used to make the nonvolatile content 20% by mass, and then filtered with a 200 mesh filter cloth to prepare a primer 5 .

[Preparation Example 6] Preparation of Primer 6

First, a polyester polyol Q obtained by reacting 1,4-cyclohexanedimethanol with neopentyl glycol and adipic acid in a nitrogen-substituted vessel equipped with a thermometer, a nitrogen gas introduction tube, and a stirrer (described above) The hydroxyl equivalent of the polyester polyol Q is 1000 g/eq. 100 parts by mass, 17.6 parts by mass of 2,2-dimethylolpropionic acid, 21.7 parts by mass of 1,4-cyclohexanedimethanol, and dicyclohexylmethane 106.2 parts by mass of the isocyanate was reacted in 178 parts by mass of methyl ethyl ketone, whereby an organic solvent solution of a urethane prepolymer having an isocyanate group at the end was obtained.

Next, 10 parts by mass of "amino decane A1100" (manufactured by Nippon Unicar Co., Ltd., γ-aminopropyltriethoxy decane) was mixed in an organic solvent solution of the above urethane prepolymer. The above urethane prepolymer is reacted with γ-aminopropyltriethoxysilane to thereby obtain an organic solvent solution of the urethane resin.

Next, by adding 13.3 parts by mass of triethylamine to the organic solvent solution of the urethane resin, a part or all of the carboxyl group of the urethane resin is neutralized, and 380 parts by mass of water is further added. Stirring is carried out to obtain an aqueous dispersion of the urethane resin.

Then, by adding 8.8 parts by mass of a 25% by mass aqueous solution of ethylenediamine to the aqueous dispersion and stirring it, the urethane resin chain is elongated, followed by aging and solvent removal, thereby obtaining a nonvolatile component. 30% by mass of urethane resin (L-2) An aqueous dispersion. 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 was placed in a reaction vessel equipped with a stirrer, a reflux cooling tube, a nitrogen gas introduction tube, a thermometer, a dropping funnel for dropping a monomer mixture, and a dropping funnel for a polymerization catalyst dropwise addition. 100 parts by mass of the aqueous dispersion of the urethane resin (L-2) was heated to 80 ° C while blowing nitrogen gas.

In a reaction vessel heated to 80 ° C, 50 parts by mass of methyl methacrylate was added dropwise from a different dropping funnel while maintaining the temperature in the reaction vessel at 80 ± 2 ° C for 120 minutes while stirring. 50 parts by mass of a monomer mixture of butyl ester and 20 parts by mass of an aqueous solution of ammonium persulfate (nonvolatile content: 0.5% by mass) were polymerized.

After the completion of the dropwise addition, the mixture was stirred at the same temperature for 60 minutes, thereby obtaining a core layer comprising the outer layer comprising the above urethane resin (L-2) and a vinyl layer comprising a mixture of the above monomers. An aqueous dispersion of urethane-acrylic composite resin particles.

The temperature in the reaction vessel was cooled to 40 ° C, and then deionized water was used to make the nonvolatile content 20% by mass, and then filtered with a 200 mesh filter cloth to prepare a primer 6.

[Preparation Example 7] Preparation of primer 7

First, ethylene glycol and 1,4-butanediol and 1,4-butanediol and isophthalic acid and terephthalic acid were placed in a nitrogen-substituted vessel equipped with a thermometer, a nitrogen gas introduction tube, and a stirrer. 64 parts by mass of the polyester polyol S (the hydroxyl equivalent in the above polyester polyol S is 840 g/eq), 7 parts by mass of 2,2-dimethylolpropionic acid, and 1,4-cyclohexane 6 parts by mass of dimethanol and 47 parts by mass of dicyclohexylmethane diisocyanate were reacted in 80 parts by mass of methyl ethyl ketone, whereby an organic solvent solution of a urethane prepolymer having an isocyanate group at the end was obtained.

Secondly, by adding three to the organic solvent solution of the above urethane prepolymer 5 parts by mass of ethylamine, and partially or completely neutralizing one of the carboxyl groups of the urethane prepolymer, and further adding 264 parts by mass of water, and sufficiently stirring, thereby obtaining a urethane prepolymer. Aqueous dispersion.

Then, 5.6 parts by mass of a 25% by mass aqueous ethylenediamine solution is added to the aqueous dispersion and stirred to elongate the urethane resin chain, followed by aging and solvent removal, thereby obtaining a nonvolatile component. An aqueous dispersion of 30% by mass of urethane resin (L-3). 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 was placed in a reaction vessel equipped with a stirrer, a reflux cooling tube, a nitrogen gas introduction tube, a thermometer, a dropping funnel for dropping a monomer mixture, and a dropping funnel for a polymerization catalyst dropwise addition. 100 parts by mass of the aqueous dispersion of the urethane resin (L-3) was heated to 80 ° C while blowing nitrogen gas.

In a reaction vessel heated to 80 ° C, 50 parts by mass of methyl methacrylate was added dropwise from a different dropping funnel while maintaining the temperature in the reaction vessel at 80 ± 2 ° C for 120 minutes while stirring. 50 parts by mass of a monomer mixture of butyl ester and 20 parts by mass of an aqueous solution of ammonium persulfate (nonvolatile content: 0.5% by mass) were polymerized.

After the completion of the dropwise addition, the mixture was stirred at the same temperature for 60 minutes, thereby obtaining a urethane comprising the outer shell layer containing the above urethane resin (L-3) and the core layer containing the above vinyl polymer- An aqueous dispersion of acrylic composite resin particles.

The temperature in the reaction vessel was cooled to 40 ° C, and then deionized water was used to have a nonvolatile content of 20% by mass, and then filtered with a 200 mesh filter cloth to prepare a primer 7.

[Preparation Example 8] Preparation of primer 8

First, a polycarbonate polyol obtained by reacting 1,4-cyclohexanedimethanol with a carbonate in a nitrogen-substituted vessel equipped with a thermometer, a nitrogen gas introduction tube, and a stirrer (in the above polycarbonate polyol) The hydroxyl equivalent is 1000 g / equivalent) 100 parts by mass, 2,2-dihydroxy 9.7 parts by mass of methylpropionic acid, 5.5 parts by mass of 1,4-cyclohexanedimethanol, and 51.4 parts by mass of dicyclohexylmethane diisocyanate were reacted in 111 parts by mass of methyl ethyl ketone, thereby obtaining a molecular terminal having An organic solvent solution of an isocyanate-based urethane prepolymer.

Then, 7.3 parts by mass of triethylamine is added to the organic solvent solution of the urethane prepolymer to partially or completely neutralize one or more of the carboxyl groups of the urethane prepolymer, and further add 355 parts by mass of water was sufficiently stirred, whereby an aqueous dispersion of the urethane prepolymer was obtained.

Then, 4.3 parts by mass of a 25% by mass aqueous solution of ethylenediamine is added to the aqueous dispersion and stirred to agitate the urethane resin chain, followed by aging and solvent removal, thereby obtaining a nonvolatile component. An aqueous dispersion of 30% by mass of urethane resin (L-4). 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 was placed in a reaction vessel equipped with a stirrer, a reflux cooling tube, a nitrogen gas introduction tube, a thermometer, a dropping funnel for dropping a monomer mixture, and a dropping funnel for a polymerization catalyst dropwise addition. 100 parts by mass of the aqueous dispersion of the urethane resin (L-4) was heated to 80 ° C while blowing nitrogen gas.

In a reaction vessel heated to 80 ° C, 50 parts by mass of methyl methacrylate was added dropwise from a different dropping funnel while maintaining the temperature in the reaction vessel at 80 ± 2 ° C for 120 minutes while stirring. 50 parts by mass of a monomer mixture of butyl ester and 20 parts by mass of an aqueous solution of ammonium persulfate (nonvolatile content: 0.5% by mass) were polymerized.

After the completion of the dropwise addition, the mixture was stirred at the same temperature for 60 minutes, thereby obtaining a urethane comprising an outer shell layer containing the above urethane resin (L-4) and a core layer containing the above vinyl polymer- An aqueous dispersion of acrylic composite resin particles.

The temperature in the reaction vessel was cooled to 40 ° C, and then deionized water was used to make the nonvolatile content 20% by mass, and then filtered with a 200 mesh filter cloth to prepare a primer 8.

[Preparation Example 9] Preparation of Primer 9 for Comparative Example

First, a polyester polyol obtained by reacting ethylene glycol with 1,4-butanediol and isophthalic acid and terephthalic acid in a nitrogen-substituted vessel equipped with a thermometer, a nitrogen gas introduction tube, and a stirrer 64 (the hydroxyl equivalent of the polyester polyol S is 840 g / equivalent) of 64 parts by mass, 7 parts by mass of 2,2-dimethylolpropionic acid, 6 parts by mass of 1,4-cyclohexanedimethanol, and a bicyclic ring. 47 parts by mass of hexylmethane diisocyanate was reacted in 80 parts by mass of methyl ethyl ketone, whereby an organic solvent solution of a urethane prepolymer having an isocyanate group at the end was obtained.

Then, by adding 5 parts by mass of triethylamine to the organic solvent solution of the urethane prepolymer, part or all of the carboxyl group of the urethane prepolymer is neutralized, and then added. 264 parts by mass of water was sufficiently stirred, whereby an aqueous dispersion of the urethane prepolymer was obtained.

Then, by adding 5.6 parts by mass of a 25% by mass aqueous solution of ethylenediamine to the aqueous dispersion and stirring it, the urethane resin chain is elongated, followed by aging and solvent removal, thereby obtaining a non-volatile component. A primer 9 was used as a comparative example of an aqueous dispersion of 30% by mass of a urethane resin (L'-5) having a pH of 8. The above urethane resin (L'-5) had an acid value of 30 and a weight average molecular weight of 50,000.

The temperature in the reaction vessel was cooled to 40 ° C, and then deionized water was used to have a nonvolatile content of 20% by mass, and then filtered through a 200 mesh filter cloth to prepare a primer 7 for a comparative example.

[Preparation Example 10] Preparation of Primer 10 for Comparative Example

First, 100 parts by mass of polyethylene glycol having a number average molecular weight of 600 and 17.6 parts by mass of 2,2-dimethylolpropionic acid, 1 in a container equipped with a thermometer, a nitrogen gas introduction tube, and a stirrer in a nitrogen atmosphere. 21.7 parts by mass of 4-cyclohexanedimethanol and 106.2 parts by mass of dicyclohexylmethane diisocyanate were reacted in 178 parts by mass of methyl ethyl ketone, whereby a urethane prepolymer having an isocyanate group at the terminal was obtained. Organic solvent solution.

Then, by adding three in the organic solvent solution of the above urethane prepolymer 13.3 parts by mass of ethylamine, and partially or completely neutralizing one of the carboxyl groups of the urethane prepolymer, and further adding 380 parts by mass of water to sufficiently stir, thereby obtaining a urethane prepolymer. Aqueous dispersion.

Then, 8.8 parts by mass of a 25% by mass aqueous solution of ethylenediamine is added to the aqueous dispersion and stirred to agitate the urethane resin chain, followed by aging and solvent removal, thereby obtaining a nonvolatile component. An aqueous dispersion of 30% by mass of urethane resin (L'-6). The urethane resin (L'-6) 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 was placed in a reaction vessel equipped with a stirrer, a reflux cooling tube, a nitrogen gas introduction tube, a thermometer, a dropping funnel for dropping a monomer mixture, and a dropping funnel for a polymerization catalyst dropwise addition. 333 parts by mass of the aqueous dispersion of the urethane resin (L'-6) was heated to 80 ° C while blowing nitrogen gas.

The monomer mixture containing 100 parts by mass of ethyl acrylate was added dropwise from a different dropping funnel to the dropping vessel at a temperature of 80 ° C in a reaction vessel while maintaining the temperature in the reaction vessel at 80 ± 2 ° C for 120 minutes. 20 parts by mass of an aqueous solution of ammonium persulfate (nonvolatile content: 0.5% by mass) was polymerized.

After the completion of the dropwise addition, the mixture was stirred at the same temperature for 60 minutes, thereby obtaining a urethane comprising an outer shell layer containing the above urethane resin (L'-6) and a core layer containing the above vinyl polymer. - an aqueous dispersion of acrylic composite resin particles.

The temperature in the reaction vessel was cooled to 40 ° C, and then deionized water was used to make the nonvolatile content 20% by mass, and then filtered with a 200 mesh filter cloth to prepare a primer 10 for a comparative example.

[Method for Measuring Ethanol Absorption Rate of Coating Film Formed Using Primer]

The ethanol absorption rate is a mass ratio of ethanol absorbed by the coating film to the mass of the coating film obtained by using the primer.

Applying the above primer to the surface of the release paper using an applicator, drying it, and removing The release paper was removed to prepare a coating film having a length of 3 cm, a width of 3 cm, and a thickness of 50 μm.

Next, the quality of the coating film obtained above was measured.

Next, the coating film was immersed in 30 g of ethanol adjusted to 25 ° C in an environment of 25 ° C.

Next, after the coating film was immersed in the ethanol for 30 seconds, the coating film was taken out from the ethanol, placed on three dust-free wiping papers, and three dust-free wiping papers were superposed thereon, and further 500 g was placed thereon. Place the weight for 10 seconds.

After the above 10 seconds, the mass of the coating film was measured to determine the mass of ethanol absorbed in the coating film after the immersion.

Next, the mass of the ethanol absorbed in the coating film after the immersion is divided by the mass of the coating film before the immersion, and multiplied by 100, and the mass ratio obtained thereby is taken as the absorption rate of the ethanol.

[Preparation of fluid (a-1)]

30 parts by mass of silver particles having an average particle diameter of 30 nm were dispersed in a mixed solvent containing 30 parts by mass of ethanol, 37 parts by mass of ion-exchanged water, and 3 parts by mass of glycerin, and filtered by a micropore filter to prepare a conductive ink. Flow body (a-1).

[Preparation of fluid (a-2)]

30 parts by mass of silver particles having an average particle diameter of 30 nm were dispersed in a mixed solvent containing 15 parts by mass of ethanol, 40 parts by mass of ion-exchanged water, and 15 parts by mass of glycerin, and filtered by a microporous filter to prepare a conductive ink. Flow body (a-2).

[Preparation of fluid (a-3)]

30 parts by mass of silver particles having an average particle diameter of 30 nm dispersed in a mixed solvent containing 20 parts by mass of ethanol, 25 parts by mass of 1,3-butanediol, 15 parts by mass of ion-exchanged water, and 10 parts by mass of glycerin, by microfiltration The filter was filtered to prepare a flow body (a-3) as a conductive ink.

[Preparation of fluid (a-4)]

30 parts by mass of silver particles having an average particle diameter of 30 nm were dispersed in a mixed solvent containing 30 parts by mass of ethanol, 37 parts by mass of 1,3-butanediol, and 3 parts by mass of glycerin, and filtered by a microfilter. As a fluid (a-4) of a conductive ink.

[Preparation of fluid (a-5)]

30 parts by mass of silver particles having an average particle diameter of 30 nm were dispersed in a mixed solvent containing 30 parts by mass of ethanol, 37 parts by mass of ethylene glycol and 3 parts by mass of glycerin, and filtered by a microfilter to prepare a conductive ink. Flow body (a-5).

[Preparation of fluid (a-6)]

10 parts by mass of ethanol, 6 parts by mass of ion-exchanged water, 4 parts by mass of glycerin, and 80 parts by mass of silver particles having an average particle diameter of 30 nm were stirred by a stirrer disperser to prepare a fluid (a-6) as a conductive ink.

[Preparation of fluid (a'-1)]

60 parts by mass of silver particles having an average particle diameter of 30 nm were dispersed in a mixed solvent containing 37 parts by mass of ion-exchanged water and 3 parts by mass of glycerin, and filtered by a micropore filter to prepare a flow body as a conductive ink (a) '-1).

Example 1 <Production of Conductive Pattern>

The undercoating agent 1 obtained above was applied to a polyimide-containing film (Kapton 200H, manufactured by Toray Dupont Co., Ltd., 50 μm thick) by using a bar coater so that the film thickness of the dried coating film was 3 μm. The surface of one side of the body is on the entire surface. Then, it was dried at 70 ° C for 3 minutes using a hot air dryer, whereby a receiving substrate (1) having a coating film formed on the surface of the above support was obtained.

The above-mentioned fluid (a-1) and the above-mentioned fluid (a-2) were produced using an inkjet printer (inkjet tester EB100 manufactured by Konica Minolta IJ Co., Ltd., print head KM512L for evaluation, discharge amount 42 pl). Each of the surfaces (area) having a length of 3 cm and a width of 1 cm was printed on the surface of the coating film formed using the primer of the substrate (1) obtained as described above at a film thickness of 0.5 μm, and then 120 Drying at °C for 30 minutes, thereby obtaining two kinds of guides Electrical pattern.

Further, using the screen of the metal mesh 250, the flow body (a-3) has a film thickness of 1 μm in a rectangular shape (area) of 3 cm in length and 1 cm in width, and is printed and used to form the receiving substrate (1) obtained as described above. The surface of the coating film formed by the above primer was dried at 120 ° C for 30 minutes, thereby obtaining a conductive pattern.

Example 2 <Production of Conductive Pattern>

Three kinds of conductive patterns were obtained by the same method as in Example 1 except that the primer 2 was used instead of the above primer 1. The undercoat layer constituting the above-mentioned conductive pattern and the coating film forming the same have a crosslinked structure.

Example 3 <Production of Conductive Pattern>

Three kinds of conductive patterns were obtained by the same method as in Example 1 except that the primer 3 was used instead of the above primer 1.

Example 4 <Production of Conductive Pattern>

Three kinds of conductive patterns were obtained by the same method as in Example 1 except that the primer 4 was used instead of the above primer 1. The undercoat layer constituting the above-described conductive pattern is formed by forming a crosslinked structure after the above-mentioned fluid is applied.

Example 5 <Production of Conductive Pattern>

Three kinds of conductive patterns were obtained by the same method as in Example 1 except that the primer 5 was used instead of the above primer 1. The undercoat layer constituting the above-described conductive pattern is formed by forming a crosslinked structure after the above-mentioned fluid is applied.

Example 6 <Production of Three Conductive Patterns>

Three kinds of conductive patterns were obtained by the same method as in Example 1 except that the primer 6 was used instead of the above primer 1. The undercoat layer constituting the above-mentioned conductive pattern and the coating film forming the same have a crosslinked structure.

Comparative Example 1 <Production of Conductive Pattern>

The same as in the first embodiment except that the primer 9 is used instead of the primer 1 described above. Method, obtaining (6) a conductive pattern.

Comparative Example 2 <Production of Conductive Pattern (2')>

(6) A conductive pattern was obtained by the same method as in Example 1 except that the primer 10 was used instead of the primer 1 described above.

Comparative Example 3 <Production of Conductive Pattern>

A conductive pattern was obtained by the same method as in Example 3, except that the above-mentioned fluid (a'-1) was used instead of the above-mentioned fluid (a-1) to (a-3).

[Evaluation method of adhesion between undercoat layer and conductive layer]

After the surface of the conductive layer constituting the conductive pattern obtained by the above method was pressed against a cellophane adhesive tape (manufactured by Miqibang Co., Ltd., CT405AP-24, 24 mm), the transparent tape was peeled off. The adhesion surface of the peeled transparent tape was visually observed, and the above adhesion was evaluated based on the presence or absence of adhesion.

When the conductive layer constituting the conductive pattern was not adhered to the adhesive surface of the peeled transparent tape at all, it was evaluated as "A", and the adhesion of a very small portion of the conductive layer was observed, but the disconnection of the conductive pattern (line portion) did not occur. It is evaluated as "B", and a conductive layer having a range of about 30% to 50% with respect to the entire area of the conductive layer is attached to the above-mentioned adhesive surface, and a disconnection is evaluated as "C", and the entire conductive layer is opposed to the conductive layer. A conductive layer having an area of about 50% or more adhered to the above-mentioned adhesive surface, and a disconnection was evaluated as "D".

[Evaluation method of electrical conductivity (resistance value)]

The volume resistivity of the surface of the layer containing the conductive material in the range of a rectangle of 3 cm in length and 1 cm in width formed on the surface of the conductive pattern obtained above was measured using a Loresta pointer meter (MCP-T610 manufactured by Mitsubishi Chemical Co., Ltd.). Those whose volume resistivity is less than 5 × 10 ^-6 Ω ‧ cm are evaluated as "A", and those who are 5 × 10 ^-6 or more and less than 9 × 10 ^-6 Ω ‧ cm and can be fully used are evaluated as "B""the 9 × 10 ^-6 or more, on the evaluation of the level of less than 5 × 10 ^-5 Ω‧cm and can use it as a" C ", the 5 × 10 ^-5 or more and less than 9 × 10 ^-5 Ω‧cm The evaluation of "D" is 9 × 10 ^-5 or more, and it is difficult for the user to evaluate it as "E".

[Evaluation method of adhesion after electroless plating treatment]

The conductive pattern obtained in the above Example 1 and Comparative Examples 1 to 3 was immersed in a catalyst bath (OPC-SALM/OPC-80 manufactured by Okuno Pharmaceutical Co., Ltd.) for 5 minutes, and then washed with water.

Then, it was immersed in an accelerator bath (OPC-555 manufactured by Okuno Pharmaceutical Co., Ltd.) adjusted to 25 ° C for 5 minutes, washed with water, and immersed in an electroless copper plating bath adjusted to 30 ° C (Okuno Pharmaceutical Industry Co., Ltd.) The company manufactures ATS ADCOPPER) and washes it with water to form a plating layer of 8 μm thick.

Thereby, a plating structure including a conductive pattern in which a plating film containing copper is formed on the surface of the plating core is obtained.

After the surface of the electroplated layer of the electroplated structure obtained above was pressed with a transparent tape (manufactured by Miqibang Co., Ltd., CT405AP-24, 24 mm), the transparent adhesive tape was oriented at 90 degrees with respect to the surface of the electroplated structure. Stripped. The adhesive surface of the peeled transparent tape was visually observed, and the above adhesion was evaluated based on the presence or absence of adhesion.

Any one who has no attachment on the adhesive surface of the above-mentioned peeled transparent tape is evaluated as "A", and the adhesion area with respect to the adhesive tape is within about 5% of the plating layer or the conductive layer. The support was peeled off, and the adhesion to the adhesive tape was evaluated as "B", and the plating area or the conductive layer was peeled off from the support in a range of about 5% or more and less than 50% with respect to the adhesion area of the adhesive tape. The adhesion to the adhesive tape was evaluated as "C", and the plating layer or the conductive layer was peeled off from the support in a range of about 50% or more with respect to the adhesion area of the adhesive tape, and the adhesion to the adhesive tape was evaluated as "D".

[Evaluation method of adhesion after electrolytic plating treatment]

The surface (conductive layer) of the conductive pattern obtained in the above Example 1 and Comparative Examples 1 to 3 was set as a cathode, phosphorus-containing copper was set as an anode, and a plating solution containing copper sulfate was used at a current density of 2 A/dm ² . Electroplating was carried out for 15 minutes, whereby a copper plating layer having a surface layer thickness of 8 μm was formed on the above-mentioned conductive layer. As the plating solution, 70 g/liter of copper sulfate, 200 g/liter of sulfuric acid, 50 mg/liter of chloride ion, and 5 g/liter of Top Lucina SF (brightener manufactured by Okino Pharmaceutical Co., Ltd.) were used.

According to the above method, the surface layer of the electroplated coating film containing copper in the electroplated structure is provided with a plating structure including a plating film of copper.

After the surface of the plating film of the electroplated structure obtained above was pressed with a transparent tape (manufactured by Miqibang Co., Ltd., CT405AP-24, 24 mm), the transparent tape was peeled off at a 90-degree angle with respect to the surface of the electroplated structure. . The adhesive surface of the peeled transparent tape was visually observed, and the above adhesion was evaluated based on the presence or absence of adhesion.

Any one who has no attachment on the adhesive surface of the above-mentioned peeled transparent tape is evaluated as "A", and the adhesion area with respect to the adhesive tape is within about 5% of the plating layer or the conductive layer. The support was peeled off, and the adhesion to the adhesive tape was evaluated as "B", and the plating area or the conductive layer was peeled off from the support in a range of about 5% or more and less than 50% with respect to the adhesion area of the adhesive tape. The adhesion to the adhesive tape was evaluated as "C", and the plating layer or the conductive layer was peeled off from the support in a range of about 50% or more with respect to the adhesion area of the adhesive tape, and the adhesion to the adhesive tape was evaluated as "D".

<Evaluation method of fine linearity> [Production of conductive pattern (inkjet printing method)]

The primers 1 to 10 obtained in Preparation Examples 1 to 10, respectively, were prepared using an ink jet printer (inkjet tester EB100 manufactured by Konica Minolta IJ Co., Ltd., print head KM512L for evaluation, and discharge amount 42 pl). A line with a line width of 100 μm and a film thickness of 0.5 μm is respectively about 1 The cm was printed on the surface of one side of a support comprising a polyimide film (Kapton 200H, manufactured by Toray Dupont Co., Ltd., 50 μm thick), and then dried at 150 ° C for 30 minutes, thereby obtaining respective conductive patterns.

[Production of conductive pattern (screen printing method)]

Using the screen of the metal mesh 250, the primers 1 to 10 obtained in Preparation Examples 1 to 10, respectively, were printed on a polyimine film (Toray Dupont) at a line width of 50 μm and a film thickness of 1 μm at about 1 cm. The surface of one side of the support of Kapton 200H, 50 μm thick manufactured by the company, and then dried at 150 ° C for 30 minutes, thereby obtaining respective conductive patterns.

[Method of evaluation of fine linearity]

Using a light microscope (digital microscope VHX-100 manufactured by KEYENCE), a thin line pattern (printing portion) formed on the surface of the conductive pattern obtained by the above method was observed, and it was confirmed whether or not the printed portion was oozing out.

Specifically, the outer edge portion of the drawing portion is not oozing out, and the boundary between the printing portion and the non-printing portion is clear, and the height difference between the outer edge portion and the central portion of the printing portion is evaluated as "A" as the overall smoothness of the printing portion. In the extremely small portion of the outer edge portion of the printing portion, a certain amount of bleeding was observed. However, the boundary between the printing portion and the non-printing portion was clear, and the overall smoothness of the printing portion was evaluated as "B", and the printing portion (line portion) was excluded. It is confirmed that there is a certain amount of bleeding in the range of about 1/3 of the edge portion, and a part of the boundary between the printing portion and the non-printing portion is not clear in this portion, but the line portion is smooth and the usable level is evaluated as "C". In the range of about 1/3 to 1/2 of the outer edge portion of the printing portion (line portion), the bleed is confirmed, and in the portion, the boundary between the printing portion and the non-printing portion is not clear, and the line portion is When the outer edge portion and the central portion are not smooth, the evaluation is "D", and in the range of about 1/2 or more of the outer edge portion of the printing portion (line portion), the bleeding is confirmed, and the printing portion and the non-printing portion are in the portion. Some of the boundaries are not clear, and the outer edge and the central part of the line are not smooth. "E."

The conductive pattern disclosed in Example 1 produced by printing a flow body containing ethanol on a receiving substrate having an undercoat layer having an ethanol absorption rate of 26% by mass is excellent in an undercoat layer and a conductive layer. Adhesion, good linearity and excellent electrical conductivity.

The conductive pattern disclosed in Example 2, which is produced by printing a flow body containing ethanol on a receiving substrate having an undercoat layer having an ethanol absorption rate of 28% by mass, is a primer layer and a conductive layer. Excellent, with good fine linearity and excellent electrical conductivity.

The conductive patterns disclosed in Examples 3 and 4, which were produced by printing a flow body containing ethanol on a receiving substrate having an ethanol absorption rate of 180% by mass and 174% by mass, were densely bonded between the undercoat layer and the conductive layer. Particularly excellent in terms of properties, fine linearity and electrical conductivity.

The conductive patterns disclosed in Examples 5, 6 and 7 which were produced by printing a flow body containing ethanol on a receiving substrate having an ethanol absorptivity of 50% by mass, 21% by mass and 100% by mass were applied to the primer. The layer is particularly excellent in adhesion to the conductive layer, and is excellent in fine linearity and electrical conductivity.

On the other hand, the conductive pattern disclosed in Comparative Example 1 produced by printing a flow body containing ethanol on a receiving substrate having an undercoat layer having an ethanol absorption rate of 1% by mass, in the undercoat layer and the conductive layer The adhesion is not practical enough, and it is insufficient in terms of fine linearity and electrical conductivity.

The adhesion between the undercoat layer and the conductive layer by using the conductive pattern disclosed in Comparative Example 2, which is produced by printing a flow body containing ethanol on a receiving substrate having an undercoat layer having an ethanol absorption rate of 550% by mass. The fine linearity and electrical conductivity are not practical enough.

The conductive pattern disclosed in Comparative Example 3, which was produced by printing on a receiving substrate having an undercoat layer having an ethanol absorption rate of 180% by mass using a flow-free body (a'-1) containing no ethanol, in the undercoat layer The adhesion to the conductive layer, fine linearity, and electrical conductivity are not practically sufficient.

Claims (10)

A conductive pattern characterized in that a coating film (x) is formed by partially or completely coating a primer on a surface of a support, and a part or all of the surface of the coating film (x) is coated or partially a support body and a coating body obtained by drying a fluid (a) having an alcohol (a1) having a monovalent alcohol (a1-1) having 1 to 4 carbon atoms and a conductive material (a2) The undercoat layer (X) formed in (x) and the layer (Y) containing the conductive material (a2) are laminated, and the coating film (x) is absorbed in an environment of 25 ° C with respect to the coating film. The mass of (x) is 20% by mass to 500% by mass of ethanol. The conductive pattern of claim 1, wherein the coating film (x) absorbs the mass relative to the coating film (x) after immersing the coating film (x) in ethanol for 1 minute at 25 ° C. It is 20% by mass to 500% by mass of ethanol. The conductive pattern of claim 1, wherein the monoalcohol (a1-1) is contained in a range of from 5% by mass to 70% by mass based on the total amount of the above-mentioned fluid (a). The conductive pattern of claim 1, wherein the alcohol (a1) comprises the above-mentioned monool (a1-1) having a carbon number of 1 to 4 and a diol represented by the following formula (I) (a1) )By, (R in the formula (I) represents a hydrogen atom or an alkyl group). The conductive pattern of claim 1, wherein the coating film (x) contains a urethane resin selected from the group consisting of a urethane resin having a polycarbonate structure, an aliphatic polyester structure, and an amine group. A layer of one or more of the resin (x-1) composed of an acid ester-acrylic composite resin and an acrylic resin having a structural unit derived from methyl methacrylate. The conductive pattern of claim 1 or 5, wherein the coating film (x) has a crosslinked structure. The conductive pattern of claim 6, wherein the crosslinkable functional group participating in the formation of the crosslinked structure is one or more selected from the group consisting of a hydroxymethyl guanamine group and an alkoxymethyl guanamine group. Crosslinkable functional group. The conductive pattern of claim 1, wherein the surface (Y) of the layer (Y) containing the conductive material further has a plating layer (Z). A conductive circuit comprising the conductive pattern of any one of claims 1 to 8. A method for producing a conductive pattern, wherein a support is formed by laminating an undercoat layer (X-1) formed by heating a coating film (x) and a layer (Y) containing a conductive material (a2), It is characterized in that the mass of the coating film (x) formed by absorption of the primer is partially or completely coated by the surface of the support to form a mass of 20% by mass to 500% by mass. The coating film (x) of the ethanol of %, and then, partially or wholly, one or all of the surface of the coating film (x) is coated with an alcohol (a1) containing a monool (a1-1) having 1 to 4 carbon atoms. The fluid (a) of the conductive material (a2) is heated.