TW201406710A - 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 has low resistance and excellent conductivity, while having excellent adhesion enough to prevent separation of a conductive substance from the conductive pattern. The present invention relates to a conductive pattern, which is obtained by applying a primer onto a supporting body, and then applying a fluid (a) containing a polyhydric alcohol (a1) that contains a predetermined diol (a1-1) and a conductive substance (a2) onto the surface of a coating film (x) that is formed using the primer and heating the applied fluid, and in which the supporting body, a primer layer (X) that is formed by heating the coating film (x) and a layer (Y) containing the conductive substance (a2) are laminated. 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 laminate which can be used for a conductive pattern such as an electromagnetic wave mask, an integrated circuit, an organic transistor, or the like.

In recent years, with the increase in the performance, size, and thickness of electronic devices, the industry has been strongly demanding higher density or thinner electronic circuits or integrated circuits.

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

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, and is easily peeled off, eventually causing disconnection of the obtained electronic circuit or the like. . In particular, since the support comprising the polyimide resin or the polyethylene terephthalate resin is relatively soft, it can be used for the production of a flexible flexible device, but it is not easy to be intimately bonded to the above-mentioned polyene. In the case of a support such as an amine resin, the film is easily peeled off when it is bent, and as a result, 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 on an ink-receiving substrate provided with a latex layer on a surface of a support by a specific method using a conductive ink is known, and is known. An acrylic resin is used as the above latex layer (see Patent Document 1).

However, the conductive pattern obtained by the above method has the above-mentioned ink receiving layer and guide In the case where the adhesion of the electrical ink is insufficient, the conductivity may be lowered due to the peeling of the conductive material contained in the conductive ink.

In addition, when the conductive pattern is produced, the conductive material is usually brought into contact with each other to provide conductivity, and in many cases, the printed matter obtained by printing using a conductive ink is heated at a relatively high temperature.

However, the ink receiving layer of the latex layer as described in the above-mentioned Document 1 is easily deformed or deteriorated due to the high heat received in the above heating step, and thus the adhesion between the ink receiving layer and the support is caused. This is caused by a decrease in the conductive pattern (cracks, etc.). Further, when a plastic substrate is used as the support, the support may be deformed by the influence of the high heat, and the resistance value of the conductive pattern may be increased (the conductivity may be lowered).

On the other hand, even if a conductive pattern is produced by using a previously known conductive ink and a receiving layer thereof and heating at a relatively low temperature, there is insufficient fusion between the conductive substances, or the support and the receiving capacity are not sufficiently expressed. The adhesion between the layers or the adhesion between the conductive layer and the receiving layer causes a decrease in conductivity or the like.

As described above, there is a demand for a conductive pattern that does not cause a decrease in the adhesion or a decrease in conductivity.

[Previous Technical Literature] [Patent Literature]

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

The problem to be solved by the present invention is to provide a conductive pattern having excellent adhesion of a conductive material without being peeled off from the undercoat layer (X) over time, and having excellent electrical resistance and low electrical conductivity.

The inventors of the present invention conducted research in order to study the above problems, and as a result, found that when a fluid of a specific composition (a) is used in combination with a specific primer (x) which forms a primer layer (X) which can be accommodated therein, Can solve the above problems.

That is, the present invention relates to a conductive pattern characterized in that it is coated with a primer by a part or the whole of a surface of a support, and then a coating film (x) formed by using the above primer is used. One or all of the surface is coated with a fluid (a) containing a polyol (a1) having a diol (a1-1) having a structure represented by the following formula (I) and a conductive substance (a2), followed by heating And the obtained support layer, the undercoat layer (X) formed by heating the coating film (x), and the layer (Y) containing the conductive material (a2) are laminated, and the coating film (x) Absorbing 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,

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

The conductive pattern of the present invention has excellent adhesion without causing a peeling of the conductive material (a2) over time, and has excellent conductivity, so that it can be used, for example, for forming an electronic circuit, constituting an organic solar cell or Each layer and peripheral wiring such as RFID (Radio Frequency Identification) such as an electronic book terminal, an organic EL (Electroluminescence), an organic transistor, a flexible printed circuit board, and a non-contact IC (Integrated Circuit) card The formation, the wiring of the electromagnetic wave mask of the plasma display, the integrated circuit, the manufacture of the organic transistor, etc. are generally called printing. A novel field in the field of printed electronics.

The conductive pattern of the present invention is characterized in that it is partially or completely coated with a primer by one or both of the surface of the support, and then a part or all of the surface of the coating film (x) formed by using the primer is used. The fluid (a) containing the polyol (a1) having the diol (a1-1) having the structure represented by the following formula (I) and the conductive material (a2) is applied and heated to obtain support. The substrate, the undercoat layer (X) formed by heating the coating film (x), and the layer (Y) containing the conductive material (a2) are laminated, and the coating film (x) is in an environment of 25 ° C Absorbing ethanol in an amount of 20% by mass to 500% by mass based on the mass of the coating film (x) before the application of the fluid (a),

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

The conductive pattern of the present invention contains at least a support, 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) is formed by heating a coating film (x) or the like formed using a primer as described later.

The undercoat layer (X) is in contact with the conductive material (a2) such as silver contained in the fluid (a) such as a conductive ink. Specifically, the primer is used to form the upper layer. The coating film (x) of the precursor of the undercoat layer (X) absorbs the solvent contained in the fluid (a) when the fluid (a) contacts the surface thereof, so that the fluid contained in the fluid (a) The conductive material (a2) is supported on the surface of the coating film (x) to improve the adhesion between the support and the conductive material (a2). Thereafter, a conductive pattern having a layer (Y) containing the conductive material (a2) supported on the surface of the undercoat layer (X) is formed by heating or the like.

The undercoat layer (X) may be provided on part or all of the surface of the support, and may be provided on one side or both sides of the support. For example, as the conductive pattern, the entire surface of the surface of the support may be provided with an undercoat layer (X), and only a portion necessary for the undercoat layer (X) has a layer containing the above-mentioned conductive substance (a2). (Y). Further, a conductive pattern of the undercoat layer (X) may be provided only on a portion of the surface of the support provided with the layer (Y).

The undercoat layer (X) differs depending on the use of the conductive pattern of the present invention or the like, and is preferable in terms of maintaining a good flexibility when using a support having flexibility at a bendable level. It is approximately 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) contains a layer of the conductive material (a2) contained in the fluid (a), and functions as a conductive layer or a plating nucleation layer. The layer (Y) corresponds to, for example, a conductive ink containing silver as the fluid (a), and corresponds to a conductive layer or a plated nucleation layer containing silver contained in the conductive ink. Contains printed images or patterns of silver.

The layer (Y) mainly contains the conductive material (a2), and other components contained in the fluid (a), for example, a polyol (a1) such as a diol (a1-1) represented by the formula (I). It may also remain in the above layer (Y).

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 portion of the surface of the undercoat layer (X). Specifically, it exists on The above layer (Y) which is a part of the surface of the undercoat layer (X) 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 preferable in the case where the conductive pattern of the present invention is used as an electronic circuit or the like.

In order to increase the density of the conductive pattern, the width (line width) of the thin line layer (pattern) is preferably about 0.01 μm to 200 μm, preferably about 0.01 μm to 150 μm.

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, a polyamidimide resin, a polyamide resin, polyethylene terephthalate, polyethylene naphthalate, poly Acrylic resin such as carbonate, acrylonitrile-butadiene-styrene (ABS) or poly(methyl) acrylate, polyvinylidene fluoride, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, poly Supports of carbonates, polyethylenes, polypropylenes, polyurethanes, cellulose nanofibers, enamels, ceramics, glass, etc., containing such porous supports, containing metal such as steel or copper Body and so on.

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

In addition, as the support, it is preferable to use a polyimide resin, polyethylene terephthalate, polyethylene naphthalate, which is generally used as a support for forming a conductive pattern such as a circuit board. , glass, cellulose nanofiber and other supports.

Further, as the support, when it is used for applications requiring flexibility, etc., in terms of imparting flexibility to the conductive pattern and obtaining a bendable final product, it is preferable to use relatively soft and bendable. By. Specifically, it is preferably used by a single axis A film or sheet-like support formed by stretching or the like.

Examples of the film or sheet-like support include a polyethylene terephthalate film, a polyimide film, and a polyethylene naphthalate film.

The support is preferably a thickness of about 1 μm to 2,000 μm, and more preferably a thickness of about 1 μm to 200 μm from the viewpoint of achieving a light-weight and a thinner thickness of the conductive pattern and the final product using the conductive pattern. When it is required to be relatively soft as the above laminated body, it is preferable to use a thickness of about 1 μm to 80 μm.

a conductive pattern of the present invention in which part or all of the surface of the support has the undercoat layer (X) and a part or all of the undercoat layer (X) having a layer (Y) containing a conductive substance (a2) In order to reduce the thickness of the electronic circuit or the like, the thickness of the constituent portion other than the support, specifically, the total thickness of the undercoat layer (X) and the layer (Y) is preferably set to 0.01. The range of μm to 300 μm is more preferably set to 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 a polyol (a1) containing a diol (a1-1) having a structure represented by the following formula (I), a conductive material (a2), and optionally a solvent or an additive. By.

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

Specifically, the fluid (a) is preferably a viscosity of 0.1 mPa ‧ measured by an E-type viscometer (TVE-22LT, manufactured by Toki Sangyo Co., Ltd.) at approximately 23 ° C ~500,000 mPa‧s, more preferably 0.5mPa‧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 quick-drying printing described later, it is preferable to adjust the use to substantially Fluid with a viscosity ranging from 5 mPa ‧ to 1,000 mPa ‧

Specific examples of the fluid (a) include a conductive ink, a plating nucleating agent which can be used for performing a plating treatment, and the like.

As the polyol (a1) containing the diol (a1-1) for the fluid (a), those containing the above diol (a1-1) and optionally containing other polyols can be used.

The above diol (a1-1) can improve the stability over time of the above fluid (a). Further, the diol (a1-1) can be used in combination with the coating film (x) which can form the undercoat layer (X), whereby the adhesion and conductivity of the conductive pattern of the present invention can be improved. Further, when the fluid (a) or the like is ejected by an inkjet method, the diol (a1-1) can improve the discharge stability of the fluid (a).

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

The adhesive layer having the level of peeling from the undercoat layer (X) which does not cause the layer (Y) formed of the conductive material (a2) contained in the fluid (a) is more excellent, and the drawn conductive pattern is obtained. As the diol (a1-1), it is preferred to use R in the general formula (I) as a hydrogen atom in the aspect of the conductive pattern having no more excellent conductivity and having excellent conductivity. Butylene glycol or R is an isopendendiol of an alkyl group.

It is preferable that the diol (a1-1) is contained in an amount of from 5% by mass to 60% by mass based on the total amount of the fluid (a), and more preferably in a range of from 15% by mass to 50% by mass. The discharge stability of the fluid (a) and the formation of a wiring pattern excellent in conductivity are more preferably in the range of 20% by mass to 40% by mass.

As another polyol which can be used in combination with the above diol (a1-1), it can be used first. For the previously known polyol, for example, 2-ethyl-1,3-hexanediol, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, 1,2- can be used. Butylene glycol, 1,4-butanediol, 2,3-butanediol, glycerin, and the like.

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. Since a conductive pattern having a low electrical resistance and a strong corrosion can be formed, it is more It is preferable to use copper, silver, gold, etc., and it is preferable to use silver.

In the case where the fluid (a) is used for a plating nucleating agent, one or more metal particles containing the transition metal as described above may be used as the conductive material (a2), and the transition metal may be used. Oxide or surface coated with organic matter.

Further, since the oxide of the transition metal is usually in an inert (insulating) state, even if the fluid containing the liquid is simply applied to the surface of the support or the like, the conductivity is not often exhibited. Therefore, when the above-mentioned oxide-containing fluid is applied to the surface of the support or the like, the surface of the support is treated with a reducing agent such as dimethylamine borane to form an exposed transition metal and have activity (conductivity). The layer of).

In addition, as the metal coated with the organic material on the surface, a metal particle contained in the resin particle (organic material) formed by an emulsion polymerization method or the like may be mentioned. These are the same as the oxide of the transition metal described above, and are usually in an inert (insulating) state. Therefore, even if the fluid containing the liquid is simply applied to the surface of the support or the like, conductivity is not often exhibited. Therefore, when a fluid containing the metal coated with the organic surface on the surface of the support is applied to the surface of the support or the like, the organic substance is removed by irradiating a surface with a laser or the like, thereby forming an exposed transition metal and being active ( Layer of conductivity).

As the conductive material (a2), those having an average particle diameter of about 1 nm to 100 nm are preferably used, and those having an average particle diameter of 1 nm to 50 nm and having an average particle diameter of a micron order are used. In comparison with the case of a substance, a fine conductive pattern can be formed, and the resistance value after heating can be further reduced, which is more preferable. Again, on The "average particle diameter" is a volume average value measured by a dynamic light scattering method in which the above-mentioned conductive material (a2) is diluted with a dispersion good solvent. Nanotrac UPA-150 manufactured by Microtrac Co., Ltd. can be used for this measurement.

It is preferable that the conductive material (a2) in the range of 5 mass% to 90 mass% is contained in the total amount of the fluid (a) used in the present invention, and more preferably in the range of 5 mass% to 85% mass%. Further, it is preferably contained 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.

Further, from the viewpoint of improving the easiness of coating, etc., it is preferred that the fluid contains a solvent. As the solvent, an organic solvent or an aqueous medium can be used.

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

As the above alcohol, for example, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, second butanol, tert-butanol, heptanol, hexanol, octanol, decyl alcohol, hydrazine can be used. Alcohol, undecyl alcohol, dodecanol, tridecyl alcohol, tetradecanol, pentadecyl alcohol, stearyl alcohol, allyl alcohol, cyclohexanol, terpineol, terpineol, dihydroterpineol, ethylene Alcohol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, tetraethylene glycol monobutyl ether, propylene glycol Monomethyl ether, dipropylene glycol monomethyl ether, 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, and ethyl acetate, butyl acetate or 3-methoxybutyl acetate may be used in combination. Ester solvent such as 3-methoxy-3-methyl-butyl acetate, toluene, octane, decane, decane, dodecane, tridecane, tetradecane, cyclooctane, xylene, A hydrocarbon solvent such as trimethylbenzene, ethylbenzene, dodecylbenzene, tetralin, or trimethylbenzenecyclohexane; a solvent such as mineral spirits or solvent naphtha.

The fluid (a) of the present invention can be obtained, for example, by using the above polyol (a1) and the above conductive substance. (a2) and the above-mentioned solvent added as needed are mixed and produced. In order to improve the dispersion stability of the conductive material and prevent the layer (Y) from being cracked, it is more preferable to produce the composition containing the conductive material (a2) and the solvent, and then The composition is produced by mixing with the polyol (a1) containing the above diol (a1-1).

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

The dispersion can be produced by mixing and stirring the above-mentioned conductive material (a2) with the above solvent. 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.

When the dispersion is mixed with the above polyol (a1), for example, a device such as a stirrer, a disperser, a bead mill, or a ultrasonic homogenizer can be used.

Moreover, the dispersion stability of the conductive material (a2) in the solvent is further improved, and the wettability of the surface of the coating film (x) by the fluid (a) is further improved, and the present invention is used. The fluid (a) may also contain a surfactant, an antifoaming agent, a rheology modifier, and the like.

After the fluid (a) is produced by the above-described method, a filter such as a micropore filter or a processor such as a centrifugal separator may be used as needed in view 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 layer (Y) capable of supporting the coating film (x) of the conductive material (a2) contained in the fluid (a) and forming the conductive pattern of the present invention.

As the primer, it can be absorbed in an environment which can be formed at 25 ° C relative to the upper Any coating film (x) having a mass of the coating film (x) of 20% by mass to 500% by mass can be used.

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

As the above resin, for example, a urethane resin (x1), a vinyl resin (x2), a urethane-ethylene composite resin (x3), a phenol resin, an epoxy resin, a melamine resin, a urea resin, or not Saturated polyester resin, alkyd resin, polyimide resin, fluororesin, and the like.

In the above-mentioned resin, in terms of forming the coating film (x) having the specific ethanol absorptivity described above, it is preferred to use an amine having a polycarbonate structure selected from the group consisting of urethane resin (x1). a urethane resin, a urethane resin having an aliphatic polyester structure, an acrylic resin having a structural unit derived from methyl methacrylate of a vinyl resin (x2), and a urethane One or more kinds of the resin (x-1) in the group consisting of the urethane-acrylic composite resin of the ethylene composite resin (x3), more preferably a urethane-acrylic composite resin.

The primer is preferably used in an amount of 10% by mass to 70% by mass based on the total amount of the primer, and more preferably 10% by mass, in terms of ease of application and the like. %~50% by mass.

Further, as the solvent which can be used as 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-propanol, isopropanol, ethyl carbitol, ethyl cellosolve, and butyl cellosolve; acetone and methyl ethyl ketone; Ketone; polyethylene glycol, diethylene glycol, propylene glycol, etc. polyalkylene glycol; polyalkylene An alkyl ether of a diol; an indoleamine such as N-methyl-2-pyrrolidone.

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.

The primer is preferably used in an amount of 25% by mass to 90% by mass based on the total amount of the primer, and more preferably 50% by mass. %~85% by mass.

When an aqueous medium is used as the solvent, it is preferred to use a resin containing a hydrophilic group as the resin in terms of imparting good water dispersibility to the primer 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 or a sulfonate group can be used. Among them, in terms of imparting good water dispersibility, it is preferred to use a part or all of alkaline. A carboxylate group or a sulfonate group formed by neutralizing a compound or the like.

Examples of the basic compound which can be used for the neutralization of the above 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 of forming a conductive pattern or the like, it is preferable to use the above-mentioned ammonia, an organic amine or an alkanolamine because the above-mentioned metal base compound can suppress conductivity and the like.

In the case where the above-mentioned carboxylate group or sulfonate group is used as the above anionic group, in terms of maintaining good water dispersion stability of the above resin, it is preferred that these are 50 mmol with respect to all of the above resins. There is a range of /kg~2,000mmol/kg.

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

The acid which can be used for neutralizing a part or all of the above-mentioned tertiary amine group can be used singly or in combination of two or more kinds thereof: an organic acid such as acetic acid, propionic acid, lactic acid or maleic acid; Organic sulfonic acid such as acid or methanesulfonic acid; hydrochloric acid, sulfuric acid, orthophosphoric acid, An inorganic acid such as orthophosphoric acid. In the case where the conductive pattern or the like is formed, it is preferable to use acetic acid, propionic acid, lactic acid, maleic acid or the like because the chlorine and sulfur are somewhat inhibited from being conductive.

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

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

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

As the polyol which can be used for 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, as the above polyol, other polyols may be used in combination as needed.

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

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

As the polyol reactive with the above carbonate, for example, ethylene glycol, diethyl ether can be used. Glycol, triethylene glycol, 1,2-propanediol, 1,3-propanediol, dipropylene glycol, 1,4-butanediol, 1,3-butanediol, 1,2-butanediol, 2,3 -butanediol, 1,5-pentanediol, 1,5-hexanediol, 2,5-hexanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octane Glycol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 3-methyl-1,5-pentane Alcohol, 2-ethyl-1,3-hexanediol, 2-methyl-1,3-propanediol, 2-methyl-1,8-octanediol, 2-butyl-2-ethylpropanediol, Relatively low molecular weight such as 2-methyl-1,8-octanediol, neopentyl glycol, hydroquinone, resorcinol, bisphenol-A, bisphenol-F, 4,4'-biphenol Dihydroxy compounds and the like.

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

As the low molecular weight polyol which can be used for the production of the above polyester polyol, for example, two or more kinds of ethylene glycol, 1,2-propanediol, 1,3-butanediol, and 1,4-butane can be used singly or in combination. Alcohol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, glycerin, trimethylolpropane, etc., preferably B A diol, 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 or the like is preferably used. Aliphatic polycarboxylic acid.

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 for the production of the above urethane resin (x1), other polyols may be used in combination as needed.

As the above other polyol, for example, ethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol, 1,4-butanediol, 3-methyl-1,5-pentanediol, and 1 can be suitably used. , 6-hexanediol, 1,4-cyclohexanedimethanol, neopentyl glycol, diethylene glycol, dipropylene glycol, glycerin, trimethylolpropane, etc. A polybutadiene polyol, a hydrogenated polybutadiene polyol, an ethylene-vinyl acetate copolymer, which is a copolymer of an acrylic polyol obtained by introducing a hydroxyl group into an acrylic copolymer and a butadiene having a hydroxyl group in a molecule. Part of the saponification and the like.

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

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

As the polyisocyanate which can form a urethane resin by reacting with the above polyol, for example, 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, carbon diazide can be used. Polyisocyanate having an aromatic structure such as amine-modified diphenylmethane diisocyanate, crude diphenylmethane diisocyanate, phenyl diisocyanate, toluene diisocyanate, naphthalene diisocyanate; hexamethylene diisocyanate, leuco acid diisocyanate An aliphatic polyisocyanate such as cyclohexane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, benzene dimethylene diisocyanate or tetramethyl benzene dimethylene diisocyanate or having an aliphatic ring type Structure of polyisocyanate.

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

As the above polyamine, for example, ethylenediamine, 1,2-propylenediamine, 1,6-hexanediamine, and piperidine can be used. 2,5-Dimethyl pipe , isophorone diamine, 4,4'-dicyclohexylmethyldiamine, 3,3'-dimethyl-4,4'-dicyclohexylmethyldiamine, 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, diterpene succinate, diammonium adipate, diammonium glutarate can be used. , azelaic acid dithizone, isophthalic acid dioxime, β-semicarbazone propionate, 3-semicarba-propyl-carbazate, semi-carboxy-3-half-carbamate Methyl-3,5,5-trimethylcyclohexane.

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

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

The above urethane resin (x1) may be obtained by stretching the above-mentioned polyol, the above polyisocyanate and, if necessary, the above-mentioned chain by a previously known method in the absence of a solvent or in the presence of an organic solvent. The agent is produced by reaction.

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

Further, the undercoating agent containing the aqueous dispersion of the urethane resin (x1) is produced by reacting the above polyol, the polyisocyanate, and optionally a chain extender by the above method to produce an amine. The urethane resin (x1), if necessary, partially or completely neutralizes one or all of the hydrophilic groups such as an anionic group of the urethane resin (x1) Thereafter, it is mixed with an aqueous medium used as a solvent for the primer to obtain an aminocarboxylic acid containing the urethane resin (x1) dispersed in an aqueous medium or partially dissolved in an aqueous medium. Primer for aqueous dispersion of ester resin (x1).

More specifically, by reacting the above polyol with the above polyisocyanate by the above method, a urethane prepolymer having an isocyanate group at the terminal is produced, and the above urethane prepolymer is optionally used. After partially or completely neutralizing one or all of the hydrophilic groups such as an anionic group, the mixture is mixed with an aqueous medium, and if necessary, chain-stretched using the chain extender to obtain a urethane-containing resin (x1). A primer for dispersing an aqueous dispersion of a urethane resin (x1) in an aqueous medium or dissolved in an aqueous medium.

The reaction between the polyisocyanate and the above polyol is preferably carried out, for example, in an amount equivalent to an equivalent ratio of the isocyanate group of the polyisocyanate to the hydroxyl group of the polyol (isocyanate group/hydroxy group) of 0.9 to 2.

In the production of the above urethane resin (x1), an organic solvent may 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-mentioned 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) may be used as the bottom. The solvent of the paint.

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

As the urethane resin (x1), those having various functional groups may be used as needed. Examples of the functional group include a crosslinkable functional group such as an alkoxyalkyl group, a stanol group, a hydroxyl group or an amine group.

The crosslinkable functional group is preferably formed by forming a crosslinked structure in the undercoat layer (X) carrying the fluid (a) to form a pattern (layer (Y)) excellent in durability.

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

Further, in the case where the above urethane resin (x1) is used in combination with the crosslinking agent (D) described later, it is possible to use a reaction group having a functional group which can be copolymerized with the above crosslinking agent (D). Functional base. The above-mentioned functional group is also selected depending on the choice 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 can be used.

Further, as the vinyl resin (x2) which can be used for 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 a source. 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 ethanol absorptivity described above, it is preferred to use an acrylic resin having a structural unit derived from methyl (meth)acrylate.

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, ethyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, (A) can be used. Tertiary butyl acrylate, 2-ethylhexyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, octyl (meth) acrylate, (meth) acrylate Anthracene ester, dodecyl (meth)acrylate, stearyl (meth)acrylate, (meth)acrylic acid (meth)acrylate such as ester, dicyclopentanyl (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate; 2,2,2-trifluoroethyl (meth)acrylate , 2,2,3,3-pentafluoropropyl (meth)acrylate, perfluorocyclohexyl (meth)acrylate, 2,2,3,3-tetrafluoropropyl (meth)acrylate, (A) An alkyl (meth)acrylate such as β-(perfluorooctyl)ethyl acrylate.

In the above, in terms of forming the coating film (x) having a specific ethanol absorption rate, it is preferable to use methyl methacrylate, and it is not affected by heat in a heating step or the like in the case of producing a conductive pattern. The above-mentioned methyl methacrylate is preferably used in terms of imparting excellent adhesion between the undercoat layer (X) and the support. Moreover, it is possible to print a fine line (improvement in fine linearity) having a width of about 0.01 μm to 200 μm, preferably about 0.01 μm to 150 μm, which is required to form a conductive pattern such as an electronic circuit, without causing bleeding. Further, it is more preferable to use the above methyl methacrylate.

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 a n-butyl acrylate in terms of forming the coating film (x) having the specific ethanol absorptivity described above and further improving the adhesion and conductivity. Further, it is also preferable to form a conductive pattern which is excellent in fine linearity and the like without the above-mentioned fluid (a).

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 the above carbon An alkyl acrylate having an alkyl group of 2 to 12 alkyl groups, preferably an alkyl acrylate having an alkyl group having 3 to 8 carbon atoms, relative to the total of the above (meth)acrylic monomer mixture The amount is preferably 20% by mass to 80% by mass, more preferably 35% by mass to 70% by mass.

Further, as a (meth)acrylic single sheet 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-(meth)acryloyl propionic acid, crotonic acid, itaconic acid, and maleic acid can be used. Acid, fumaric acid, itaconic acid half ester, maleic acid half ester, maleic anhydride, itaconic anhydride, succinic acid β-(meth) propylene methoxy hydroxyethanol, etc. Vinyl monomer. The above vinyl monomer having a carboxyl group can be neutralized by ammonia, potassium hydroxide or the like.

Further, as the (meth)acrylic monomer, one or more kinds of guanamines selected from the group consisting of a hydroxymethyl guanamine group and an alkoxymethyl guanamine group are introduced into the acrylic resin. a group other than the above, amidino group, 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 carbonyl group or an ethyl oxime group, a vinyl monomer having a crosslinkable functional group can be used.

As the (meth)acrylic monomer having a crosslinkable functional group, one or more kinds of decylamine having a group selected from the group consisting of a hydroxymethyl guanamine group and an alkoxymethyl guanamine group As the vinyl monomer, for example, N-methylol (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-methoxyethoxymethyl (A) can be used. Acrylamide, N-ethoxymethyl (meth) acrylamide, N-propoxymethyl (meth) acrylamide, N-isopropoxymethyl (meth) propylene oxime Amine, 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-propyl Oxymethyl (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) acrylamide, N- Oxymethyl pentoxy -N- methyl (meth) acrylamide and the like.

In particular, it is preferable to use N-n-butoxy group in terms of forming a conductive pattern which is excellent in durability such as peeling of the conductive material (a2) in the plating step. Methyl (meth) acrylamide, N-isobutoxymethyl (meth) acrylamide.

As the (meth)acrylic monomer having a crosslinkable functional group, in addition to the above, for example, a vinyl monomer containing 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, (Methyl)acrylic acid (4-hydroxymethylcyclohexyl)methyl ester, (meth)acrylic acid glyceride, polyethylene glycol (meth) acrylate, N-hydroxyethyl (meth) acrylamide, etc. a vinyl monomer of a hydroxyl group: a glycidyl group-containing polymerizable monomer such as glycidyl (meth)acrylate or allyl glycidyl ether (meth)acrylate; aminoethyl (meth)acrylate; Amino group-containing polymerization such as dimethylaminoethyl acrylate, N-monoalkylaminoalkyl (meth) acrylate, N,N-dialkylaminoalkyl (meth) acrylate Monomer; vinyl trichloromethane, vinyl trimethoxy decane, vinyl triethoxy decane, vinyl tris (β-methoxyethoxy) decane, γ-(meth) propylene decyloxy C Trimethoxy decane, γ-(meth) propylene methoxy propyl triethoxy decane, γ-(meth) propylene methoxy propyl methyl dimethoxy decane, γ-(meth) propylene醯oxypropylmethyldiethoxydecane, γ-(meth)acryloxypropyltriisopropoxydecane, N-β-(N-vinylbenzylaminoethyl)-γ a polymerizable monomer containing a decyl group of aminopropyltrimethoxydecane and a hydrochloride thereof; an aziridine-containing polymerizable monomer such as 2-aziridineethyl (meth)acrylate; a polymerizable monomer containing (blocking) an isocyanate group, such as a methyl propylene decyl isocyanate, a (meth) propylene decyl isocyanate ethyl phenol, or a methyl ethyl ketone oxime addition product; -isopropenyl-2- Oxazoline, 2-vinyl-2- Oxazoline a polymerizable monomer having an oxazoline group; a polymerizable monomer containing a cyclopentenyl group such as dicyclopentenyl (meth)acrylate; or an allyl group-containing polymerizable monomer such as allyl (meth)acrylate; A carbonyl group-containing polymerizable monomer such as acrolein or diacetone (meth) acrylamide.

The (meth)acrylic monomer having a crosslinkable functional group may be in a range of from 0% by mass to 50% by mass based on the total amount of the (meth)acrylic monomer mixture. use. 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 above-mentioned (meth)acrylic acid group containing a mercapto group is introduced from the viewpoint of introducing a self-crosslinking reactive hydroxymethylguanamine group. The amount is preferably from 0.1% by mass to 50% by mass based on the total amount of the (meth)acrylic monomer mixture, and more preferably from 1% by mass to 30% by mass. Further, the (meth)acrylic monomer having a different mercapto group and the (meth)acrylic monomer having a hydroxyl group used in combination with the above-mentioned self-crosslinking reactive methylolamine group are preferably relatively The total amount of the above (meth)acrylic monomers is 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 containing an acid group is also used in combination. The type of the crosslinking agent (D) is preferably used in a range of approximately 0.05% by mass to 50% by mass based on the total amount of the (meth)acrylic monomer mixture, and more preferably 0.05% by mass. It is used in the range of ~30% by mass, and more preferably used in an amount of 0.1% by mass to 10% by mass.

Further, in the production of the acrylic resin, the (meth)acrylic monomer may be used in combination with vinyl acetate, vinyl propionate, vinyl butyrate or 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-halogenated styrene, 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-methylallylsulfonic acid, 2-sulfoethyl (meth)acrylate, 2-sulfopropyl (meth)acrylate, "ADEKA REASOAP PP-70, PPE-710" (Adeka has Limited to the company's manufacture) or such salt.

The acrylic resin can be produced by polymerizing a mixture of the above various vinyl monomers by a conventionally known method, and is preferably an emulsion polymerization method in terms of producing a conductive pattern having excellent adhesion and excellent electrical conductivity. .

As the emulsion polymerization method, for example, a method in which water, a (meth)acrylic monomer mixture, a polymerization initiator, and a chain transfer agent, an emulsifier or a dispersion stabilizer which are added as needed are supplied at a time, a method of mixing and polymerizing in a reaction vessel; dropping a (meth)acrylic monomer mixture into a reaction vessel and polymerizing the monomer; or premixing the (meth)acrylic monomer A pre-emulsion method in which a mixture, an emulsifier, etc., and water are added dropwise to a reaction vessel and polymerized.

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, for example, preferably about 30 to 90 ° C, and the reaction time is preferably, for example, 1 to 10 Hours or so.

Examples of the polymerization initiator include persulfate such as potassium persulfate, sodium persulfate, and ammonium persulfate, and organic peroxidation such as benzamidine peroxide, cumene hydroperoxide, and tert-butyl hydroperoxide. , hydrogen peroxide, etc., may be subjected to radical polymerization using only the peroxide, or by using the above-mentioned peroxide together with ascorbic acid, isoascorbic acid, sodium erythorbate, metal salt of formaldehyde sulfoxylate, sodium thiosulfate The redox polymerization initiator of a reducing agent such as sodium bisulfite or ferric chloride may also be polymerized, and 4,4'-azobis(4-cyanovaleric acid) or 2,2'-even may also be used. An azo-based initiator such as bis(2-amidinopropane) 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 above acrylic resin include an anionic surfactant, a nonionic surfactant, a cationic surfactant, and an amphoteric ionic surfactant.

Examples of the anionic surfactant include sulfates of higher alcohols and salts thereof, alkylbenzenesulfonates, polyoxyethylene alkylphenylsulfonates, and polyoxyethylene alkyls. a phenyl ether sulfonate, a sulfuric acid half ester of a polyoxyethylene alkyl ether, an alkyl diphenyl ether disulfonate, a dialkyl succinate sulfonate, or the like, as a nonionic surfactant, for example, A polyoxyethylene alkyl ether, a polyoxyethylene alkylphenyl ether, a polyoxyethylene diphenyl ether, a polyoxyethylene-polyoxypropylene block copolymer, an acetylene glycol type surfactant, etc. are used.

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 (decylamine) betaine, an alkyldimethylamine oxide or the like can be used.

As the emulsifier, in addition to the above surfactant, a fluorine-based surfactant, a polyoxynphthene surfactant, or a emulsifier containing a polymerizable unsaturated group in a molecule generally called a "reactive emulsifier" may be used. Agents, etc.

As the reactive emulsifier, for example, "Latemul S-180" (manufactured by Kao) and "Eleminol JS-2, RS-30" containing sulfonic acid groups and salts thereof can be used (Sanyo Chemical Industry Co., Ltd.) Manufactured, etc.; "Aqualon HS-10, HS-20, KH-1025" (manufactured by Daiichi Kogyo Co., Ltd.) and "ADEKA REASOAP SE-10, SE-20" (ADEKA (") (manufacturing), etc.; "New Frontier A-229E" (manufactured by Daiichi Kogyo Co., Ltd.) containing a phosphate group; "Aqualon RN-10, RN-20, RN-30, which contains a nonionic hydrophilic group, RN-50" (manufactured by First Industrial Pharmaceutical Co., Ltd.) and the like.

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

Further, as the urethane-ethylene composite resin (x3) which can be used as the resin contained in the primer, there are mentioned urethane resin (x3-1) and vinyl polymer (x3- 2) A composite resin particle is formed and dispersed in an aqueous medium.

Specifically, the above composite resin particles may be exemplified by the above vinyl polymer (x3-2). Some or all of it is contained in the resin particles formed by the above urethane resin (x3-1). It is preferred to form core-shell type composite resin particles containing the above-mentioned vinyl 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 core-shell type composite resin particles which do not require the use of a surfactant which can reduce electrical characteristics. Further, as the composite resin particles, it is preferred that the vinyl polymer (x3-2) is almost completely coated with the urethane resin (x3-1), but it is not essential, and the present invention is not impaired. The range of the effect may be that a part of the above vinyl polymer (x3-2) is present on the outermost side of the composite resin particles.

Further, when the vinyl polymer (x3-2) is more hydrophilic than the urethane resin (x3-1), the composite resin particles may be the above-mentioned urethane. A part or all of the ester resin (x3-1) is contained in the resin particles formed of the above 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, and preferably 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.

Further, from the viewpoint of maintaining good water dispersion stability, the composite resin particles preferably have an average particle diameter in the range of 5 nm to 100 nm. The average particle diameter herein is also described in the examples described later, and refers to the average particle diameter on a volume basis measured by a dynamic light scattering method.

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

As a urethane resin constituting the above urethane-ethylene composite resin (x3- 1) The same as the above urethane resin (x1) can be used. In addition, as the urethane resin (x3-1) constituting the urethane-ethylene 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 for the production of the above urethane resin (x3-1) can be used as exemplified as the user who can manufacture the above urethane resin (x1). The polyol, polyisocyanate, and chain extender are the same.

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

As the above initiator, for example, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butylene glycol, 1,4-butanediol, 1,6 can be used. - 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, an esterification reaction of a low molecular weight polyol with an aromatic polycarboxylic acid can be used.

The low molecular weight polyol which can be used for the production of the above-mentioned aromatic polyester polyol is used alone or in combination of two or more kinds thereof as follows: ethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol, 1,4-butanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, glycerin, trimethylolpropane, etc. Preferably, ethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol or 1,4-butanediol is mixed with 3-methyl-1,5-pentanediol or neopentyl glycol. Used in combination.

As the aromatic polycarboxylic acid, for example, terephthalic acid, isophthalic acid, phthalic acid, naphthalene dicarboxylic acid, or an acid anhydride or ester compound 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.

The vinyl polymer (x3-2) constituting the urethane-ethylene composite resin forms a coating film (x) having the specific ethanol absorptivity described above, and is improved in the fluid (a). In terms of the adhesion between the conductive material (a2) and the conductivity of the obtained conductive pattern, it is preferred to use a glass transition temperature of 10 ° C to 70 ° C. Further, the glass transition temperature of the above vinyl polymer (x3-2) is mainly determined based on the composition of the vinyl monomer used for the production of the vinyl 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 vinyl polymers (x3-2) described later.

Further, as the vinyl polymer (x3-2), the coating film (x) having the specific ethanol absorptivity is formed, and the adhesion to the conductive material (a2) contained in the fluid (a) is improved. In view of the conductivity of the 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 vinyl polymer (x3-2) is not particularly limited, but is preferably about 10,000,000 or less, more preferably 5,000,000 or less.

Further, the vinyl polymer (x3-2) may optionally contain various functional groups, 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, as the (meth)vinyl monomer which can be used for the production of the above vinyl polymer (x3-2), it can be used as a manufacturer which can be used for the above-mentioned vinyl resin (x2). The vinyl monomer is preferably the same as the (meth)acrylic monomer. In particular, the vinyl polymer (x3-2) is preferably the same as the acrylic resin having a structural unit derived from methyl methacrylate exemplified as the vinyl resin (x2).

The above urethane-ethylene composite resin (x3) can be produced, for example, by producing an amine group by reacting and dispersing the above polyisocyanate, a polyol, and optionally a chain extender. a step (V) of the aqueous dispersion of the acid ester resin (x3-1); and a step of polymerizing the (meth)acrylic monomer in the aqueous dispersion to produce a vinyl polymer (x3-2) ( W).

Specifically, the polyisocyanate is reacted with a polyhydric alcohol in the absence of a solvent or in the presence of an organic solvent or a reactive diluent such as a (meth)acrylic monomer, whereby an aminocarboxylic acid is obtained. The ester resin (x3-1) is then partially or completely neutralized with one or all of the hydrophilic groups contained in the urethane resin (x3-1), if necessary, using a basic compound or the like, and if necessary, The chain extender reacts and disperses it in an aqueous medium, thereby producing an aqueous dispersion of the urethane resin (x3-1).

Then, a vinyl monomer such as the above (meth)acrylic monomer is supplied to the aqueous dispersion of the urethane resin (x3-1) obtained above, and the above urethane resin (x3-1) The vinyl monomer is subjected to radical polymerization in the particles to produce a vinyl resin (x3-2). Further, when the urethane resin (x3-1) is produced in the presence of a vinyl monomer, it is supplied by polymerization after the production of the urethane resin (x3-1). A vinyl monomer such as the above (meth)acrylic monomer is subjected to radical polymerization by a starter or the like to produce a vinyl resin (x3-2).

Thereby, the composite resin particles partially or wholly contained in the above-mentioned urethane resin (x3-1) particles of the vinyl resin (x3-2) can produce a primer which is dispersed in an aqueous medium.

When the above-mentioned composite resin particles are produced, when the above urethane resin (x3-1) is high in viscosity and workability is poor, methyl ethyl ketone or N-methyl pyrrolidine can be used. A common organic solvent such as ketone, acetone or dipropylene glycol dimethyl ether, or a reactive diluent. In particular, as the above-mentioned reactive diluent, in terms of omitting the solvent removal step and improving the production efficiency of the primer, it is preferred to use (meth) which can be used for the production of the above vinyl polymer (x3-2). A vinyl monomer such as an acrylic monomer.

Further, as the resin which can be used for 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, a polyimine resin, or a fluorine can be used. Resin, etc.

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

The primer may be used in combination with the above urethane resin (x1) and the above vinyl resin (x2). In the case of using the combination, it is preferred that the mass ratio of the above urethane resin (x1) to the above vinyl resin (x2) is [(x1)/(x2)] = 90/10 to 10/90. The range is used, and it is more preferably used in the range of 70/30 to 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) carrying the fluid (a), and forms a pattern (layer (excellent) having excellent adhesion and conductivity without causing bleeding or the like. Y)) can be preferably used in this respect.

The coating film (x) formed using the above primer may have a crosslinked structure before or partially coating (printing) the fluid (a), but it is necessary to have an ethanol absorption rate of 20% by mass. Adjust in the range of ~500% by mass.

Further, the coating film (x) may have a crosslinked structure before coating (printing) the fluid (a) on the surface thereof, and may be formed as an undercoat layer (X) after applying the fluid (a). Cross-linking The undercoat layer.

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

In the case of using a resin containing the above alkoxyalkylene group and a stanol group, the above alkoxyalkylene group and stanol are hydrolyzed and condensed in an aqueous medium as a solvent of a primer to form a crosslinked structure. By applying a primer to form a crosslinked structure to the surface of the support and drying, etc., a coating film (x) forming a crosslinked structure is formed before the application of the fluid (a).

Further, the crosslinkable functional group may be used by heating to a temperature of substantially 100 ° C or higher, preferably 120 ° C or higher, or a crosslinkable functional group or a crosslinking agent (D) to be described later. In the case of the above-mentioned crosslinked structure, it is preferred to use one or more kinds of thermal crosslinks selected from the group consisting of a hydroxymethyl guanamine group and an alkoxymethyl guanamine group. Sex functional group.

Specific examples of the alkoxymethylguanamine group include a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, a butoxymethyl group, and the like, which are bonded to a nitrogen atom. The amine group, wherein, in terms of greatly improving the durability of the undercoat layer (X) and the adhesion to various supports, it is preferred to use a compound selected from the group consisting of hydroxymethyl guanamine and alkoxymethyl hydrazine. One or more of the group consisting of amine groups.

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

After coating (printing) the fluid (a) on the coating film having no crosslinked structure, the substrate is heated at a temperature of 100 ° C or higher by a heating step or heating different from the heating step. (X) to form an undercoat layer having a crosslinked structure.

As described above, after the fluid (a) is applied, it can be formed in a plating treatment step described later by forming a crosslinked structure in the undercoat layer (X) even if it is exposed to a strong alkali or In the case of a plating agent for a strongly acidic substance, there is no conductive pattern having particularly excellent durability in the case where the undercoat layer (X) is peeled off from the support. In addition, the above-mentioned "substantially no cross-linking structure" means that cross-linking is formed within about 5% of the functional group of the cross-linking structure, including the aspect in which the cross-linking structure is not formed at all. Structure.

The crosslinkable functional group is preferably present in a total amount of from 0.005 equivalents/kg to 1.5 equivalents/kg based on the total amount of the resin used for the primer.

Further, the primer may be added to a pH adjuster, a film forming aid, a leveling agent, or a thickening agent which is mainly composed of a crosslinking agent (D) as needed within a range not impairing the effects of the present invention. It is used by a known agent such as a agent, a water repellent, and an antifoaming agent.

The crosslinking agent (D) can be formed, for example, by reacting a metal chelate compound, a polyamine compound, an aziridine compound, a metal salt compound or an isocyanate compound at a relatively low temperature of from about 25 ° C to less than 100 ° C. The thermal crosslinking agent (d1-1) of the crosslinked structure is selected from the group consisting of a melamine compound, an epoxy 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 approximately 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 dried at a relatively low temperature by, for example, applying it to the surface of the support, followed by coating (printing) the above fluid, and heating to less than 100 ° C When the temperature is formed to form a crosslinked structure, it is possible to form a conductive pattern having particularly excellent durability which is not affected by long-term heat or external force and which can prevent the level of the conductive material from being deficient.

On the other hand, the undercoating agent containing the above-mentioned thermal crosslinking agent (d1-2) is produced by applying it to the surface of the support, for example, at a low temperature (normal temperature (25 ° C) to a temperature of substantially less than 100 ° C). The coating film (x) having no crosslinked structure is formed, and then the fluid (a) is applied, and then heated at a temperature of, for example, 150 ° C or higher, preferably 200 ° C or higher to form a crosslinked structure, thereby obtaining no A conductive pattern having particularly excellent durability, which is affected by long-term heat or external force, and does not cause peeling of a conductive material.

However, when a support containing a relatively heat-resistant polyethylene terephthalate or the like is used as the support, it is preferably 150 ° C or less, preferably 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 for the above thermal crosslinking agent (d1-1), for example, a polyvalent metal such as aluminum, iron, copper, zinc, tin, titanium, nickel, ruthenium, magnesium, vanadium, chromium, zirconium or the like can be used. The acetamidine acetone complex compound, the acetamidine acetate complex compound, and the like are preferably an aluminum acetonide acetone complex compound, that is, aluminum acetonate.

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

Further, as the aziridine compound which can be used for the above thermal crosslinking agent (d1-1), for example, 2,2-bishydroxymethylbutanol-tris[3-(1-aziridine)propionate can be used. ], 1,6-hexamethylene diethyluronium, diphenylmethane-bis-4,4'-N, N'-diethylethureate, 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, chlorine can be used. A water-soluble metal salt such as aluminum hexahydrate, titanium tetrachloride, tetraisopropyl titanate, titanium acetylacetonate or titanium lactate.

As the isocyanate compound which can be used for the above thermal crosslinking agent (d1-1), for example, toluene diisocyanate, hydrogenated toluene diisocyanate, triphenylmethane triisocyanate, methylene bis(4-phenylmethane) triisocyanate, or the like can be used. a polyisocyanate such as isophorone diisocyanate, hexamethylene diisocyanate or benzene dimethylene diisocyanate; an isocyanurate type polyisocyanate compound obtained by using the same; containing the same with trimethylolpropane An adduct such as a polyisocyanate group-containing urethane obtained by reacting the polyisocyanate compound with a polyhydric alcohol such as trimethylolpropane. Among them, it is preferred to use hexamethylene diisocyanate. An isocyanurate ester of an acid ester, an adduct of hexamethylene diisocyanate and trimethylolpropane, an adduct of toluene diisocyanate and trimethylolpropane, or benzodiamethylene diisocyanate An adduct with trimethylolpropane or the like.

Further, as the melamine compound which can be used for the above thermal crosslinking agent (d1-2), for example, hexamethoxymethyl melamine, hexaethoxymethyl melamine, hexapropoxymethyl melamine or hexabutoxymethyl can be used. A mixture of melamine, hexaethoxymethyl melamine, hexahexyloxymethyl melamine or a mixture of these two etherified melamines. Among them, trimethoxymethyl melamine and hexamethoxymethyl melamine are preferably used. As a commercial item, Beckamine M-3, APM, J-101 (made by DIC), 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 may be used in terms of promoting the self-crosslinking reaction. As a commercial item, Catalyst ACX, 376, etc. can be used. The total amount of the catalyst relative to the total amount of the melamine compound is preferably in the range of approximately 0.01% by mass to 10% by mass.

Further, as the epoxy compound which can be used for the above thermal crosslinking agent (d1-2), for example, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, hexanediol diglycidyl ether or cyclohexanediol can be used. Polyglycidyl ether of an aliphatic polyol such as diglycidyl ether, glycerol diglycidyl ether, glycerol triglycidyl ether, trimethylolpropane triglycidyl ether, pentaerythritol tetraglycidyl ether; polyethylene glycol diglycidyl ether Polyglycidyl ether of a polyalkylene glycol such as ether, polypropylene glycol diglycidyl ether or poly(1,4-butanediol) diglycidyl ether; 1,3-bis(N,N'-diglycidylglycerol) Polyglycidylamine such as arylamino)cyclohexane; polycarboxylic acid [oxalic acid, adipic acid, butane tricarboxylic acid, maleic acid, phthalic acid, terephthalic acid, isophthalic acid Polyglycidyl ester of formic acid, benzenetricarboxylic acid, etc.; bisphenol A epoxy such as condensate of bisphenol A and epichlorohydrin; ethylene oxide adduct of condensate of bisphenol A and epichlorohydrin Resin; phenolic novolak resin; various vinyl-based (co)polymers which contain an epoxy group in a branched chain. Among them, it is preferred to use 1,3-bis(N,N'-diglycidylaminoethyl)cyclohexane A polyglycidyl ether of an aliphatic polyol such as polyglycidylamine or glycerol diglycidyl ether.

Further, as the epoxy compound, for example, γ-glycidoxypropyltrimethoxydecane, γ-glycidoxypropyltriethoxydecane, or 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 glycidyl group-containing decane compound such as decane or the like.

Further, as the above-mentioned thermal crosslinking agent (d1-2) An oxazoline compound, for example, 2,2'-bis-(2- can be used 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 combined with other monomers as needed and polymerized to contain An oxazoline-based polymer.

Addition polymerization The oxazoline, for example, may be used alone or in combination of two or more kinds using 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. Among them, since it is industrially easy to obtain, it is preferred to use 2-isopropenyl-2- Oxazoline.

Further, as a carbodiimide compound which can be used for the above thermal crosslinking agent (d1-2), for example Poly[phenylphenylbis(dimethylmethylene)carbodiimide], poly(methyl-1,3-phenylene carbodiimide), or the like can be used. Commercial products can be used with Carbodilite V-01, V-02, V-03, V-04, V-05, V-06 (made by Nisshinbo Co., Ltd.), UCARLINK XL-29SE, XL-29MP (Union Carbide) ) Manufacturing) and so on.

Further, as the blocked isocyanate compound which can be used for the above-mentioned thermal crosslinking agent (d1-2), one or all of the isocyanate groups contained in the isocyanate compound exemplified as the above-mentioned thermal crosslinking agent (d1-1) can be used. End sealer.

As the above-mentioned blocking agent, for example, phenol, cresol, 2-hydroxypyridine, butyl cellosolve, propylene glycol monomethyl ether, benzyl alcohol, methanol, ethanol, n-butanol, isobutanol, dimethyl malonate, or the like can be used. Diethyl malonate, methyl 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, ethienediamine, polyethylenimine and the like.

As the blocked isocyanate compound, as a commercially available product of a water-dispersible type, Elastron BN-69 (manufactured by Daiichi Kogyo Co., Ltd.) or the like 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 containing 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, The oxazoline compound and the carbodiimide compound are used as a crosslinking agent, and a resin containing a hydroxyl group or a carboxyl group is used as the above resin.

Though the crosslinking agent (D) is different depending on the type and the like, it is usually used in an amount of 0.01% by mass to 60% by mass based on 100 parts by mass of the total mass of the resin contained in the primer. More preferably, it is used in the range of 0.1% by mass to 10% by mass, and it is preferable to form a conductive pattern which is excellent in adhesion and conductivity and excellent in durability. It is used in the range of 0.1% by mass to 5% by mass.

Further, it is preferred to use the above-mentioned crosslinking agent (D) in advance before applying or impregnating the primer of the present invention to 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 coated with a part or all of the surface of the support by applying a primer to a part or all of the surface of the coating film (x) formed by using the primer (hereinafter). a) is produced by heating.

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

The coating film (x) is formed by heating to form the undercoat layer (X) after the application of the fluid (a). The coating film (x) can be formed by a method in which the primer is applied to the support and the solvent contained in the primer is removed.

The undercoating agent which can form 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 method, a spin method, a spray method, a spin coating method, and an ink jet method. .

Moreover, as a method of removing the solvent contained in the primer, for example, it is usually a method of drying using a dryer to volatilize the solvent. The drying temperature is set to a temperature at which the solvent can be volatilized and has no adverse effect on the support. can.

From the viewpoint of imparting excellent adhesion and conductivity, the coating amount of the primer on the support is preferably such that the film thickness of the coating film (x) is in the range of 0.01 μm to 300 μm, more preferably The range of 0.05 μm to 20 μm.

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

In order to solve the above problems, 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 mass ratio of the ethanol absorbed by the coating film (x) to the mass of the coating film (x) [absorbance of ethanol] is a value obtained by measurement by the following method.

After the primer was applied onto the surface of the release paper by an applicator and dried, 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.

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

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

Then, 30 seconds after the coating film was immersed in the above ethanol, the coating film was taken out from the ethanol, and placed on three overlapping ultra-low dusting wipes, and three superslots were superposed thereon. A low-dusting wipe was placed, and a weight of 500 g was placed thereon, and left in this state for 10 seconds.

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

Then, the mass of the ethanol absorbed by the above-mentioned immersed coating film is divided by the mass of the coating film before the immersion, and multiplied by 100, whereby the mass ratio obtained thereby is taken as the absorption rate of the above ethanol.

Here, when the absorption rate of the above-mentioned ethanol is less than 20% by mass, specifically, when the fluid (a) or the like is applied to a coating film of 10% by mass, conductivity is caused. Reduced or reduced adhesion. Specifically, since the solvent contained in the fluid (a) is hard to be absorbed by the coating film (x), the adhesion between the coating film (x) and the conductive pattern is deteriorated.

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

The absorption rate of the 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, and further preferably from the viewpoint of imparting more excellent adhesion and conductivity. 45% by mass to 190% by mass.

Further, in the present invention, it is not necessary to use only the coating film (x) having the specific absorption rate described above, and the above problem can be solved by printing the pattern on the coating film (x) using the specific fluid (a).

Further, it is not necessary for the undercoat layer (X) constituting the conductive pattern to have the specific absorption ratio described above. In order to solve the above problems, the coating film (x) before the application of the fluid (a) before the heating must have the specific absorption rate described above.

The coating film (x) is prepared by appropriately dissolving and absorbing the solvent by the solvent contained in the fluid (a), and the conductive material (a2) such as a metal contained in the fluid (a) can be accurately obtained. The fixed swelling type receiving layer helps to obtain a conductive pattern without flaws.

Further, by using the above coating film (x), a base coat which is transparent as compared with the previously known porous type receiving layer can be formed.

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

The method of applying the fluid (a) partially or completely to one surface of the coating film (x), for example, an inkjet printing method or screen printing using a reverse printing method such as a letterpress reverse printing method. Method, lithography method, spin coating method, spray coating method, bar coating method, extrusion coating method, slit coating method, roll coating method, dip coating method, etc., on the above-mentioned receiving substrate, etc. A method of printing the above conductive ink directly or in reverse.

Among them, approximately 0.01 μm is required to achieve high density of electronic circuits and the like. When the fluid (a) is applied (printed) in a thin line shape of about ~100 μm, an inkjet printing method is preferably used.

As the above inkjet printing method, a person generally referred to as an inkjet printer can be used. Specific examples thereof include Konica Minolta EB100, XY100 (manufactured by Konica Minolta IJ Co., Ltd.), dimer ticks Materials Printer DMP-3000, dimer ticks Materials Printer DMP-2831 (manufactured by Fuji Film Co., Ltd.), and the like.

It is preferable to apply (print) the above-mentioned fluid (a) from the viewpoint of bonding the conductive material (a2) such as a metal contained in the fluid (a) and bonding them to impart conductivity. Heating is carried out.

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

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

Further, when a resin containing a crosslinkable functional group capable of undergoing a crosslinking reaction at a relatively high temperature is used as the resin contained in the primer, the above crosslinking agent (d1-2) is used. After coating (printing) the above fluid (a), in the case where a crosslinked structure is to be formed 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 remarkably improved.

In the case where the crosslinking reaction step and the heating step are carried out together, the heating temperature is different depending on the type of the crosslinking agent (D) or the like to be used, or a combination of crosslinkable functional groups, etc., preferably. It is approximately in the range of 80 ° C to 300 ° C, more preferably in the range of 100 ° C to 300 ° C, and particularly preferably in the range of 120 ° C to 300 ° C. Further, in the case where the support is relatively heat-resistant, the upper limit of the temperature is preferably 150 ° C or lower, more preferably 120 ° C or lower.

A conductive pattern is formed on the surface of the conductive pattern obtained by the heating step by a conductive substance such as a metal contained in the fluid (a). The conductive pattern can be preferably used for forming an electronic circuit such as silver ink, forming an organic solar cell, 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. In the field of printed electronic equipment such as wiring of electromagnetic wave masks for plasma displays.

Further, as the conductive pattern, a plating pattern which is made of a metal such as copper can be used in order to form a highly reliable wiring pattern which can maintain good electrical conductivity without causing disconnection or the like for a long period of time. . Specifically, as the conductive pattern, for example, a plating layer (Z) including a plating film having a coating film formed using part or all of the surface of the support may be used. Applying (printing) a plating nucleating agent as the fluid (a) to a part or all of the surface of the coating film (x), thereby carrying a plating core on the surface of the coating film (x), if necessary After the heating step or the like, the plating film is formed by performing electrolytic plating treatment, electroless plating treatment, or electroless plating treatment after the electroless plating treatment.

The electroless plating treatment step is performed by, for example, contacting a surface of a nucleator having palladium or silver supported on the undercoat layer (X) with an electroless plating solution to cause the electroless plating solution to be in the electroless plating solution. A step of depositing a metal such as copper to form an electroless plating layer (coating film) containing 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 following compounding agent: a monocarboxylic acid such as acetic acid or formic acid; malonic acid, succinic acid, adipic acid, maleic acid, and antibutene; Dicarboxylic acid such as diacid; malic acid, lactic acid, glycolic acid, gluconic acid, citric acid, etc. Hydroxycarboxylic acid; amino acid such as glycine, alanine, arginine, aspartic acid, glutamic acid; iminodiacetic acid, nitrogen triacetic acid, ethylenediamine diacetic acid, ethylenediaminetetraacetic acid An organic acid such as an amine-based polycarboxylic acid such as ethyltriamine pentaacetic acid; a soluble salt of such an organic acid (sodium salt, potassium salt, ammonium salt, etc.), ethylenediamine, diethylenediamine, and trisole An amine such as ethyltetramine is extended.

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

Further, the electrolytic plating treatment step is performed, for example, by the surface of the undercoat layer (X) carrying the plating core or the surface of the electroless plating layer (film) formed by the above electroless treatment and electrolytic plating. When the liquid is in contact with the liquid, the metal such as copper contained in the electrolytic plating solution is deposited on the undercoat layer (X) provided on the negative electrode or the electroless plating layer formed by the above electroless treatment ( The step of coating the surface of the film to form an electrolytic plating film (metal film).

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

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

In the above steps of the electroless plating treatment and the electrolytic plating treatment, the above-mentioned strong acid or strong alkaline plating solution is often used, and in the case of the above-mentioned undercoat layer (X), the above-mentioned The undercoat layer (X) is corroded to cause the undercoat layer (X) to be peeled off from the support.

On the other hand, after printing using the fluid (a) such as the plating nucleating agent, the undercoat layer (X) is formed in the plating treatment step in the case where the crosslinked structure is formed in the undercoat layer (X). Will not peel off from the support. Especially if the above support is a polyimide-containing resin Otherwise, the above-mentioned undercoat layer (X) is not peeled off, so that it can be excellently used for the production of the above-mentioned conductive pattern.

For example, the above-described conductive pattern can be preferably used for forming an electronic circuit such as silver ink, and constituting each layer of an organic solar cell, an electronic book terminal, an organic EL, an organic transistor, a flexible printed circuit board, an RFID, etc., and a peripheral wiring. The conductive pattern, more specifically, the formation of a circuit board, is formed when the wiring of the electromagnetic wave mask of the plasma display is formed.

Further, in the conductive pattern obtained by the above method, after the fluid (a) such as a conductive ink or a plating nucleating agent is applied (printed), a crosslinked structure is formed in the undercoat layer (X). When the conductive pattern is subjected to the plating treatment step, the undercoat layer (X) is not peeled off from the support or the like, and particularly excellent durability at a level capable of maintaining good conductivity can be imparted. Therefore, it can be preferably used for forming a substrate for circuit formation using an electronic circuit such as silver ink or an integrated circuit, and constituting an organic solar cell, an e-book terminal, an organic EL, an organic transistor, a flexible printed circuit board, and an RFID. In particular, the use of each layer, the formation of the peripheral wiring, the wiring of the electromagnetic wave shield of the plasma display, and the like is particularly required. In particular, the conductive pattern which has been subjected to the plating treatment described above does not cause disconnection or the like for a long period of time, and can form a highly reliable wiring pattern capable of maintaining good electrical conductivity. For example, it is generally called a copper clad laminate (CCL, Copper). Clad Laminate), for example, flexible printed circuit (FPC), Tape Automated Bonding (TAB), chip on film (COF), and printed wiring board (PWB, Printed wiring board) and other uses.

[Examples]

The invention will now be described in detail by way of examples.

[Preparation Example 1] Preparation of primer 1

Add 115 parts by mass of deionized water to a reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, a thermometer, and a dropping funnel, and use Latemul E-118B (Kao) The amount of the active ingredient (25% by mass) was 4 parts by mass, and the temperature was raised to 75 ° C while blowing nitrogen gas.

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, Aqualon KH-1025 (First Industrial Pharmaceutical Co., Ltd.) was added to the reaction vessel under stirring. Manufactured in the reaction container, a part (5 parts by mass) of a monomer pre-emulsion obtained by mixing 4 parts by mass of the active ingredient and 2 parts by mass of deionized water, followed by adding 0.1 parts by mass of potassium persulfate The polymerization was carried out in 60 minutes while maintaining the temperature at 75 °C.

Then, while maintaining the temperature in the reaction vessel at 75 ° C, the remaining monomer pre-emulsion (114 parts by mass) and the potassium persulfate aqueous solution (active ingredient 1% by mass) were added dropwise for 180 minutes using different dropping funnels. ) 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 ammonia water (effective component: 10% by mass) was used so that the pH of the aqueous dispersion in the reaction vessel became 8.5.

Then, deionized water was used so that the nonvolatile content was 30% by mass, and then filtered using 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 condenser, and a dropping device, and then the inside of the flask was purged with nitrogen. .

After heating in an oil bath until the temperature in the flask became 70 ° C, 380 parts by mass of di-n-butylamine was added dropwise thereto over 30 minutes using a dropping device, and after completion of the dropwise addition, the reaction was carried out at 70 ° C for 10 hours. After completion of the reaction, an infrared spectrophotometer (FT/IR-460Plus, manufactured by JASCO Corporation) was used to confirm that the absorption peak near 842 cm ^-1 by the epoxy group of the reaction product disappeared, and a tertiary amine was prepared. Base polyol K (amine equivalent 315 g / equivalent, hydroxyl equivalent 315 g / equivalent).

Then, with a thermometer, a stirring device, a reflux condenser, and a dropping device A 10,70 parts by mass of a polyester polyol P (number average molecular weight: 2,000) obtained by reacting neopentyl glycol, 1,4-butanediol, and adipic acid, and 770 parts by mass of ethyl acetate were added to the flask, and the mixture was stirred. Warm up to 70 ° C on one side. 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 above reaction, 84 parts by mass of the above-obtained polyol K having a tertiary amino group was added, and after reacting for 4 hours, "Aminosilane A1100" (manufactured by Nippon Unicar Co., Ltd.) as a component capable of forming a crosslinked structure was added. 36 parts by mass of γ-aminopropyltriethoxydecane] and reacted for 1 hour, thereby preparing a urethane prepolymer solution having a mercaptoalkyl group. Then, 38 parts by mass of N-aminoethylethanolamine was added to the above urethane prepolymer solution, and a chain extension reaction was carried out for 1 hour, whereby an organic solvent solution of a cationic urethane resin was obtained.

Then, 1710 parts by mass of ethyl acetate and 22 parts by mass of acetic acid were added, and after maintaining at 45 ° C for 1 hour, the mixture was cooled to 40 ° C, and 3850 parts by mass of ion-exchanged water was added to prepare an aqueous dispersion. This aqueous dispersion was subjected to distillation under reduced pressure to prepare a primer 2 having a nonvolatile content of 30% by mass.

[Preparation Example 3] Preparation of primer 3

First, a polyester polyol Q obtained by reacting 1,4-cyclohexanedimethanol, neopentyl glycol, and adipic acid in a nitrogen-substituted vessel equipped with a thermometer, a nitrogen gas introduction tube, and a stirrer (100 parts by weight of the hydroxyl group equivalent of the polyester polyol Q), 17.6 parts by mass of 2,2-dimethylolpropionic acid, 21.7 parts by mass of 1,4-cyclohexanedimethanol, and dicyclohexyl 106.2 parts by mass of methane diisocyanate was reacted in 178 parts by mass of methyl ethyl ketone to obtain an organic solvent solution of a urethane prepolymer having an isocyanate group at the end.

Then, by adding 13.3 parts by mass of triethylamine to the organic solvent solution of the above urethane prepolymer, a part or all of the carboxyl group contained in the above urethane prepolymer is neutralized, and then water is added. 380 parts by mass and well stirred, thereby obtaining an aqueous dispersion of the urethane prepolymer.

Then, by adding 8.8 parts by mass of a 25% by mass aqueous solution of ethylenediamine to the aqueous dispersion and stirring, the polyurethane prepolymer chain is elongated to cause aging and desolvation, thereby obtaining a solid content concentration. An aqueous dispersion of 30% by 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.

Then, 140 parts by mass of deionized water was added to a reaction vessel equipped with a stirrer, a reflux condenser, 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, and the above obtained 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.

While maintaining the temperature in the reaction vessel at 80±2° C., a funnel was added from a different drop over 120 minutes, and 50 parts by mass of methyl methacrylate was added dropwise to the reaction vessel heated to 80° C. under stirring. 50 parts by mass of the monomer mixture of the 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, a core layer comprising a shell layer containing the above urethane resin (L-1) and a vinyl polymer formed by polymerization of the above monomer mixture was obtained by stirring at the same temperature for 60 minutes. An aqueous dispersion of a urethane-acrylic composite resin.

The primer 3 was prepared by cooling the temperature in the reaction vessel to 40 ° C and then using deionized water so as to have a nonvolatile content of 20% by mass, followed by filtration through a 200 mesh filter cloth.

[Preparation Example 4] Preparation of primer 4

In a reaction vessel equipped with a stirrer, a reflux condenser, 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 added, and the amine group obtained above was added. 100 parts by mass of the aqueous dispersion of the formic acid ester resin (L-1) was heated to 80 ° C while blowing nitrogen gas.

While maintaining the temperature inside the reaction vessel at 80±2°C, it will be different after 120 minutes. The funnel was added dropwise, and 50 parts by mass of methyl methacrylate, 45 parts by mass of n-butyl acrylate, and 5 mass of N-n-butoxymethyl acrylamide were added dropwise to the reaction vessel heated to 80 ° C under stirring. The monomer mixture and the ammonium persulfate aqueous solution (nonvolatile content: 0.5% by mass) were 20 parts by mass and polymerized.

After the completion of the dropwise addition, a core layer comprising a shell layer containing the above urethane resin (L-1) and a vinyl polymer formed by polymerization of the above monomer mixture was obtained by stirring at the same temperature for 60 minutes. An aqueous dispersion of a urethane-acrylic composite resin.

The primer 4 was prepared by cooling the temperature in the reaction vessel to 40 ° C and then using deionized water so that the nonvolatile content was 20% by mass, followed by filtration through a 200 mesh filter cloth.

[Preparation Example 5] Preparation of primer 5

In a reaction vessel equipped with a stirrer, a reflux condenser, 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 added, and the amine group obtained above was added. 333 parts by mass of the aqueous dispersion of the formate resin (L-1) was heated to 80 ° C while blowing nitrogen gas.

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

After the completion of the dropwise addition, a core layer comprising a shell layer containing the above urethane resin (L-1) and a vinyl polymer formed by polymerization of the above monomer mixture was obtained by stirring at the same temperature for 60 minutes. An aqueous dispersion of a urethane-acrylic composite resin.

Cooling the temperature in the above reaction vessel to 40 ° C, followed by a non-volatile content of 20 After the deionized water was used in a mass % manner, the primer 5 was prepared by filtration through a 200 mesh filter cloth.

[Preparation Example 6] Preparation of Primer 6

First, a polyester polyol Q obtained by reacting 1,4-cyclohexanedimethanol, neopentyl glycol, and adipic acid in a nitrogen-substituted vessel equipped with a thermometer, a nitrogen gas introduction tube, and a stirrer (100 parts by weight of the hydroxyl group equivalent of the above polyester polyol) 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 to obtain an organic solvent solution of a urethane prepolymer having an isocyanate group at the end.

Then, 10 parts by mass of "Aminosilane A1100" [manufactured by Nippon Unicar Co., Ltd., γ-aminopropyltriethoxydecane] was mixed with the above organic solvent solution of the urethane prepolymer. The urethane prepolymer is reacted with γ-aminopropyltriethoxysilane to obtain an organic solvent solution of the urethane resin.

Then, 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 contained in the urethane resin is neutralized, and 380 parts by mass of water is further added. Stirring is sufficient 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, the chain of the urethane resin is elongated to cause aging and desolvation, whereby a solid content concentration of 30% by mass is obtained. An aqueous dispersion of the urethane resin (L-2). The urethane resin (L-2) obtained here had an acid value of 30 and a weight average molecular weight of 88,000.

Then, 140 parts by mass of deionized water was added to a reaction vessel equipped with a stirrer, a reflux condenser, 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, and the above obtained was obtained. 100 parts by mass of the aqueous dispersion of the urethane resin (L-2) was heated to 80 ° C while blowing nitrogen gas.

While maintaining the temperature in the reaction vessel at 80±2° C., a funnel was added from a different drop over 120 minutes, and 50 parts by mass of methyl methacrylate was added dropwise to the reaction vessel heated to 80° C. under stirring. 50 parts by mass of the monomer mixture of the 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, a core layer comprising a shell layer containing the above urethane resin (L-2) and a vinyl polymer formed by polymerization of the above monomer mixture was obtained by stirring at the same temperature for 60 minutes. An aqueous dispersion of a urethane-acrylic composite resin.

The primer 6 was prepared by cooling the temperature in the reaction vessel to 40 ° C and then using deionized water so that the nonvolatile content was 20% by mass, followed by filtration through a 200 mesh filter cloth.

[Preparation Example 7] Preparation of Primer 7 for Comparative Example

In a nitrogen-substituted vessel equipped with a thermometer, a nitrogen gas introduction tube, and a stirrer, ethylene glycol, 1,4-butanediol, isophthalic acid, and terephthalic acid are reacted to have an aromatic structure. 64 parts by mass of polyester polyol S (hydroxyl equivalent: 840 g/eq), 6 parts by mass of 1,4-cyclohexanedimethanol, 7 parts by mass of 2,2-dimethylolpropionic acid, and dicyclohexylmethane diisocyanate 47 parts by mass of the mixture was mixed with 80 parts by mass of methyl ethyl ketone, and reacted at a temperature of 80 ° C in the above reaction vessel, thereby obtaining an organic solvent of a urethane prepolymer having an isocyanate group at the end. Solution.

Then, by partially or partially neutralizing one or all of the carboxyl groups contained in the urethane prepolymer by mixing the organic solvent solution of the urethane prepolymer with 5 parts by mass of triethylamine, 264 parts by mass of water was added and stirred well, and 7 parts by mass of a 20% by mass aqueous solution of ethylenediamine was added to carry out a chain extension reaction, followed by distillation under reduced pressure, thereby obtaining an amine having a nonvolatile content of 35% by mass and a pH of 8. Primer 7 for comparison of aqueous dispersions of urethane resin (L-3). The above urethane resin (L-3) has 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 so that the nonvolatile content was 20% by mass, and then filtered through a 200 mesh filter cloth to prepare a primer 7 for a comparative example.

[Preparation Example 8] Preparation of Primer 8 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 an organic urethane prepolymer having an isocyanate group at the end was obtained. Solvent solution.

Then, by adding 13.3 parts by mass of triethylamine to the organic solvent solution of the above urethane prepolymer, a part or all of the carboxyl group contained in the above urethane prepolymer is neutralized, and then water is added. 380 parts by mass and well stirred, thereby obtaining an aqueous dispersion of the urethane prepolymer.

Then, by adding 8 parts by mass of a 25% by mass aqueous solution of ethylenediamine to the aqueous dispersion and stirring, the polyurethane prepolymer chain is elongated to cause aging and desolvation, thereby obtaining a solid matter. An aqueous dispersion of a urethane resin (L-4) having a component concentration of 30% by mass. The urethane resin (L-4) obtained here had an acid value of 30 and a weight average molecular weight of 30,000.

In a reaction vessel equipped with a stirrer, a reflux condenser, 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 added, and the amine group obtained above was added. 333 parts by mass of the aqueous dispersion of the formate resin (L-4) was heated to 80 ° C while blowing nitrogen gas.

While maintaining the temperature in the reaction vessel at 80±2° C., a funnel was added from a different drop over 120 minutes, and a monomer mixture containing 100 parts by mass of ethyl acrylate was added dropwise to the reaction vessel heated to 80° C. under stirring. 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, a core layer comprising a shell layer containing the above urethane resin (L-4) and a vinyl polymer formed by polymerization of the above monomer mixture was obtained by stirring at the same temperature for 60 minutes. An aqueous dispersion of a urethane-acrylic composite resin.

The temperature in the reaction vessel was cooled to 40 ° C, and then deionized water was used so that the nonvolatile content was 20.0% by mass, and then filtered by a 200 mesh filter cloth to prepare a primer 8 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 the ethanol absorbed by the coating film to the mass of the coating film obtained by using the primer.

After the primer was applied onto the surface of the release paper by an applicator and dried, 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.

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

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

Then, 30 seconds after the coating film was immersed in the above ethanol, the coating film was taken out from the ethanol, and placed on three overlapping ultra-low dusting wipes, and three super lows were superimposed thereon. The dust wipes were placed, and a weight of 500 g was placed thereon, and placed in this state for 10 seconds.

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

Then, the mass of the ethanol absorbed by the above-mentioned immersed coating film is divided by the mass of the coating film before the above immersion and multiplied by 100, whereby the mass ratio obtained thereby is taken as the absorption rate of the above ethanol.

[Preparation of fluid (a-1)]

30 parts by mass of silver particles having an average particle diameter of 30 nm are dispersed in a mixed solvent containing 30 parts by mass of 1,3-butanediol, 37 parts by mass of ion-exchanged water, and 3 parts by mass of glycerin, and micropores are used. The filter was filtered to prepare a fluid (a-1) as a conductive ink.

[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 1,3-butanediol, 40 parts by mass of ion-exchanged water, and 15 parts by mass of glycerin, and filtered by a micropore filter. This was prepared as a fluid (a-2) of a conductive ink.

[Preparation of fluid (a-3)]

10 parts by mass of 1,3-butanediol, 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 mixed and stirred by a stirring disperser, thereby preparing a fluid as a conductive ink ( A-3).

[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 fluid as a conductive ink (a' -1).

Example 1 <Production of Conductive Pattern>

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

An ink jet printer (inkjet tester EB100 manufactured by Konica Minolta IJ Co., Ltd., print head KM512L for evaluation, discharge amount 42 pl) was used to use the above primer for constituting the above-obtained substrate (1). On the surface of the formed coating film, the fluid (a-1) and the fluid (a-2) were printed to have a rectangular (length) area of 3 cm in length and 1 cm in width, respectively, at a film thickness of 0.5 μm, and then at 120 ° C. It was dried for 30 minutes, whereby two kinds of conductive patterns were obtained.

Moreover, the screen of the metal mesh 250 is used to form the receiving substrate (1) which is obtained as described above. The surface of the coating film formed by the primer is printed at a film thickness of 1 μm to a rectangular (length) area of 3 cm in length and 1 cm in width, and then dried at 120 ° C for 30 minutes. A conductive pattern is obtained.

Example 2 <Production of Conductive Pattern>

Three kinds of conductive patterns were obtained in the same manner as in Example 1 except that the primer 2 was used instead of the 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 in the same manner as in Example 1 except that the primer 3 was used instead of the primer 1.

Example 4 <Production of Conductive Pattern>

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

Example 5 <Production of Conductive Pattern>

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

Example 6 <Production of Conductive Pattern>

Three types of conductive patterns were obtained in the same manner as in Example 1 except that the primer 6 was used instead of the 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>

Three kinds of conductive patterns were obtained in the same manner as in Example 1 except that the primer 7 for the comparative example was used instead of the primer 1.

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

Three kinds of conductive patterns were obtained in the same manner as in Example 1 except that the primer 10 for the comparative example was used instead of the primer 1.

Comparative Example 3 <Production of Conductive Pattern>

One type of conductive pattern was obtained in the same manner as in Example 3 except that the above fluid (a'-1) was used instead of the above fluid (a-1) to fluid (a-3).

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

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

When the conductive layer constituting the conductive pattern was not adhered to the adhesive surface of the above-mentioned peeled transparent adhesive tape, it was evaluated as "A", and a very small portion of the conductive layer was observed, but no conductive pattern was formed (line portion). The disconnector is evaluated as "B", and the conductive layer in the range of about 30% to 50% of the entire area of the conductive layer is attached to the adhesive surface, and the disconnection is evaluated as "C", and the relative value is "C". When the conductive layer having a total area of the conductive layer of about 50% or more adhered to the adhesive surface and the disconnection occurred, it was evaluated as "D".

[Evaluation method of electrical conductivity (resistance value)]

The volume resistivity of the layer surface of the conductive material in the range of a rectangle having a length of 3 cm and a width of 1 cm formed on the surface of the conductive pattern obtained above was measured using a Loresta pointer meter (MCP-T610 manufactured by Mitsubishi Chemical Corporation). 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 are fully usable are evaluated as "B" will be rated as "C" for those who are 9 × 10 ^-6 or higher and less than 5 × 10 ^-5 Ω ‧ cm and are usable, and will be 5 × 10 ^-5 or more and less than 9 × 10 ^{When -5} Ω‧cm is evaluated as "D", it will be 9 × 10 ^-5 or more, and it is difficult for the actual user to evaluate it as "E".

[Table 1]

[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 adjustment to 30 ° C. An electroless copper plating bath (ATS ADDCOPPER manufactured by Okuno Pharmaceutical Co., Ltd.) was washed with water to form a plating layer having a thickness of 8 μm.

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

After pressing a transparent adhesive tape (manufactured by Nichiban Co., Ltd., CT405AP-24, 24 mm) onto the surface of the plating layer of the obtained plating structure, the transparent adhesive tape is faced to the surface of the plating structure. Stripped in the direction of 90 degrees. The adhesive surface of the peeled transparent adhesive tape was visually observed, and the above adhesion was evaluated based on the presence or absence of the attached matter.

The adherent on the adhesive surface of the peeled transparent adhesive tape is evaluated as "A", and the adhesion area with respect to the adhesive tape is about 5% or less in the plating layer or the conductive layer. Any one of the plating layer or the conductive layer in the range of about 5% or more and less than 50% of the adhesion area with respect to the adhesive tape is evaluated as "B" when the support is peeled off from the support and adhered to the adhesive tape. One of them is evaluated as "C" when it is peeled off from the support and adhered to the adhesive tape, and is peeled off from the support in any of the plating layer or the conductive layer in a range of about 50% or more with respect to the adhesion area of the adhesive tape. The one attached 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 on the surface of the above-mentioned conductive layer was used. As the plating solution, 70 g/L of copper sulfate, 200 g/L of sulfuric acid, 50 mg/L of chloride ion, and 5 g/L of Toplucina SF (gloss agent manufactured by Okuno Pharmaceutical Co., Ltd.) were used.

According to the above method, a plated structure containing a copper plating film is obtained on the surface layer of the copper-containing plating film of the plated structure.

After pressing a transparent adhesive tape (manufactured by Nichiban Co., Ltd., CT405AP-24, 24 mm) onto the surface of the plating film of the obtained plating structure, the transparent adhesive tape was turned toward The surface of the plated structure was peeled off at a 90 degree direction. The adhesive surface of the peeled transparent adhesive tape was visually observed, and the above adhesion was evaluated based on the presence or absence of the attached matter.

The adherent on the adhesive surface of the peeled transparent adhesive tape is evaluated as "A", and the adhesion area with respect to the adhesive tape is about 5% or less in the plating layer or the conductive layer. Any one of the plating layer or the conductive layer in the range of about 5% or more and less than 50% of the adhesion area with respect to the adhesive tape is evaluated as "B" when the support is peeled off from the support and adhered to the adhesive tape. One of them is evaluated as "C" when it is peeled off from the support and adhered to the adhesive tape, and is peeled off from the support in any of the plating layer or the conductive layer in a range of about 50% or more with respect to the adhesion area of the adhesive tape. The one attached to the adhesive tape was evaluated as "D".

The conductive pattern of Example 1 produced by printing on a receiving substrate having an undercoat layer having an ethanol absorption rate of 26% by mass using a fluid containing 1,3-butanediol has an undercoat layer and a conductive layer Good adhesion and excellent electrical conductivity.

The conductive pattern-based undercoat layer and the conductive layer of Example 2 produced by printing a fluid containing 1,3-butanediol on a receiving substrate having an undercoat layer having an ethanol absorption rate of 28% by mass. Excellent in adhesion and excellent in electrical conductivity.

The conductive patterns of Examples 3 and 4 produced by printing a fluid containing 1,3-butanediol on a receiving substrate having an ethanol absorptivity of 180% by mass and 174% by mass were applied to the undercoat layer and The conductive layer is particularly excellent in terms of adhesion and electrical conductivity.

The conductive patterns of Examples 5 and 6 produced by printing a fluid containing 1,3-butanediol on a receiving substrate having an ethanol absorption rate of 50% by mass and 21% by mass were attached to the bottom. The adhesion between the coating layer and the conductive layer is particularly excellent, and the conductivity is also excellent.

On the other hand, a conductive pattern of Comparative Example 1 produced by printing a fluid containing 1,3-butanediol on a receiving substrate having an undercoat layer having an ethanol absorption rate of 1% by mass was applied to the undercoat layer. The adhesion to the conductive layer is insufficient in practicality and insufficient in electrical conductivity.

The conductive pattern of Comparative Example 2 produced by printing a fluid containing 1,3-butanediol on a receiving substrate having an undercoat layer having an ethanol absorption rate of 550% by mass is applied to the undercoat layer and the conductive layer. Insufficient practicality in terms of adhesion and electrical conductivity.

The conductive pattern of Comparative Example 3 produced by printing on a receiving substrate having an undercoat layer having an ethanol absorption rate of 180% by mass using a fluid (a'-1) containing no 1,3-butanediol The adhesion between the undercoat layer and the conductive layer and the conductivity are not practical.

Claims (10)

A conductive pattern characterized in that a portion of the surface of the support is coated with a primer or a portion of the surface of the coating film (x) formed by using the primer; The cloth contains a fluid (a) comprising a polyol (a1) having a diol (a1-1) having a structure represented by the following formula (I) and a conductive material (a2), and is heated to obtain a support. The undercoat layer (X) formed by heating 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. Absorbing ethanol in an amount of 20% by mass to 500% by mass based on the mass of the coating film (x), (R in the formula (I) represents a hydrogen atom or an alkyl group). The conductive pattern of claim 1, wherein the coating film (x) absorbs the coating film before the immersion 30 seconds after the coating film (x) is immersed in the ethanol at 25 ° C ( x) The mass of the mass is 20% by mass to 500% by mass of ethanol. The conductive pattern of claim 1, wherein the diol (a1-1) represented by the above formula (I) is isoprene glycol or 1,3-butylene glycol. The conductive pattern of claim 1, wherein the diol (a1-1) is contained in a range of 10% by mass to 60% by mass based on the total amount of the fluid (a). 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. One or more of the group consisting of an acid ester-acrylic composite resin and an acrylic resin having a structural unit derived from methyl methacrylate A layer of resin (x-1). The conductive pattern of claim 1, wherein the undercoat layer (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. Thermally crosslinkable functional group. The conductive pattern of claim 1, which further has a plating layer (Z) on the surface of the layer (Y) containing the conductive material. A conductive circuit comprising the conductive pattern of any one of claims 1 to 8. A method for producing a conductive pattern, wherein the conductive pattern-supporting body, the undercoat layer (X) formed by heating the coating film (x), and the layer (Y) containing the conductive material (a2) are laminated. The manufacturing method is characterized in that the coating film is formed by partially or completely coating a primer on the surface of the support and drying, and is formed at 25 ° C to absorb the coating film (x) formed by using the primer. The coating film (x) having a mass of 20% by mass to 500% by mass of ethanol, and then coating part or all of the surface of the coating film (x) containing the compound represented by the following formula (I) The polyol (a1) of the structural diol (a1-1) and the fluid (a) of the above conductive substance (a2) are subsequently heated. (R in the formula (I) represents a hydrogen atom or an alkyl group).