WO2013172229A1 - 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 of a conductive pattern or the like that can be used for manufacturing an electromagnetic wave shield, an integrated circuit, an organic transistor, or the like.

In recent years, with increasing performance, size, and thickness of electronic devices, there has been a strong demand for higher density and thickness of electronic circuits and integrated circuits used therefor.

The conductive pattern that can be used for the electronic circuit, for example, is to apply (print) conductive ink containing a conductive material such as silver on the surface of the support by various printing methods, and to heat as necessary. Can be manufactured by.

However, even if the conductive ink is directly applied to the surface of various supports, the conductive ink is difficult to adhere to the surface of the support, and thus easily peels off, and finally the disconnection of an electronic circuit or the like obtained Etc. may be caused. In particular, since the support made of polyimide resin or polyethylene terephthalate resin is relatively flexible, it can be used for the production of a foldable flexible device. For this reason, they are easy to peel off when bent, and as a result, there is a case where the finally obtained electronic circuit or the like is disconnected.

As a method for solving the above problem, for example, there is a method of producing a conductive pattern by drawing a pattern by a predetermined method using a conductive ink on an ink receiving substrate provided with a latex layer on the support surface. It is known that an acrylic resin can be used as the latex layer (see Patent Document 1).

However, since the conductive pattern obtained by the above method may not be sufficient in terms of the adhesion between the ink receiving layer and the conductive ink, the conductive pattern obtained by peeling of the conductive substance contained in the conductive ink may be used. There was a case of causing a decline in sex.

Moreover, when manufacturing the said conductive pattern, normally the printed matter obtained by printing etc. using a conductive ink in order to contact the conductive substances contained in a conductive ink and to provide electroconductivity. Are often heated at a relatively high temperature.

However, since the ink receiving layer such as the latex layer described in Document 1 is easily deformed or deteriorated due to the influence of high heat received in the heating step, the adhesion at the interface between the ink receiving layer and the support is not easily affected. In some cases, the conductive pattern is lost (such as cracks). Further, when a plastic substrate is used as the support, the support is deformed due to the influence of the high heat, which may cause an increase in resistance value (decrease in conductivity) of the conductive pattern.

On the other hand, even if a conductive pattern is produced by using a conventionally known conductive ink and its receiving layer and heating at a relatively low temperature, the bonding between the conductive materials is insufficient, or the support In some cases, the adhesiveness between the adhesive layer and the receiving layer and the adhesiveness between the conductive layer and the receiving layer are not sufficiently exhibited, and as a result, a decrease in electrical conductivity is caused.

As described above, the industry has demanded a conductive pattern that does not cause a decrease in adhesion or conductivity.

JP 2009-49124 A

The problem to be solved by the present invention is that the conductive material has excellent adhesion so that it does not peel from the primer layer (X) with time, and has low resistance and excellent conductivity. Is to provide a pattern.

As a result of studying the above problems, the present inventors combined a fluid (a) having a specific composition and a specific primer (x) that forms a primer layer (X) capable of receiving the fluid (a). It has been found that the problem can be solved when used.

That is, the present invention applies a primer to a part or all of the surface of the support, and then applies the following general formula (I) to a part or all of the surface of the coating film (x) formed using the primer. The support obtained by applying the fluid (a) containing the polyhydric alcohol (a1) containing the diol (a1-1) having the structure represented by (2) and the conductive substance (a2) and then heating. A conductive pattern in which a body, a primer layer (X) formed by heating the coating film (x), and a layer (Y) containing the conductive substance (a2) are laminated, The conductive film (x) relates to a conductive pattern characterized in that it absorbs 20% by mass to 500% by mass with respect to the mass of the coated film (x) in an environment of 25 ° C. is there.

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

The conductive pattern of the present invention has excellent adhesion at a level that does not cause peeling of the conductive substance (a2) over time, and has excellent conductivity. For example, formation of an electronic circuit, Organic solar cells, electronic book terminals, organic EL, organic transistors, flexible printed circuit boards, non-contact IC cards and other layers constituting RFID, etc., formation of peripheral wiring, plasma display electromagnetic wave shielding wiring, integrated circuits, organic transistors It can be used in new fields such as manufacturing, generally referred to as the printed electronics field.

In the conductive pattern of the present invention, a primer is applied to a part or all of the surface of the support, and then a part or all of the surface of the coating film (x) formed using the primer is represented by the following general formula. Obtained by applying a fluid (a) containing a polyhydric alcohol (a1) containing a diol (a1-1) having the structure represented by (I) and a conductive substance (a2) and then heating. A conductive pattern in which a support, a primer layer (X) formed by heating the coating film (x), and a layer (Y) containing the conductive substance (a2) are laminated. The coating film (x) absorbs 20 mass% to 500 mass% of ethanol in an environment of 25 ° C. with respect to the mass of the coating film (x) before applying the fluid (a). It is characterized by being.

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

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

First, the primer layer (X) will be described.

The primer layer (X) is formed by heating a coating film (x) formed using a primer described later.

The primer layer (X) adheres the support to the conductive material (a2) such as silver contained in the fluid (a) such as conductive ink. Specifically, the coating film (x), which is a precursor of the primer layer (X) and is formed using a primer, is in contact with the fluid (a) when the fluid (a) contacts the surface. ) And the conductive material (a2) contained in the fluid (a) is supported on the surface of the coating film (x), whereby the support and the conductive material ( Adhesion with a2) is improved. After that, by heating or the like, a conductive pattern including a layer (Y) made of the conductive substance (a2) supported on the surface of the primer layer (X) is formed.

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

Although the primer layer (X) varies depending on the use of the conductive pattern of the present invention, etc., the viewpoint of maintaining the good flexibility when a support having a bendable level of flexibility is used. Therefore, the thickness is preferably approximately 0.01 μm to 300 μm, and more preferably 0.05 μm to 20 μm.

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

The layer (Y) is a layer composed of the conductive substance (a2) contained in the fluid (a), and has a role as a conductive layer or a plating nucleus layer. For example, if the layer (Y) is a conductive ink containing silver as the fluid (a), the layer (Y) is formed on a conductive layer or a plating nucleus layer composed of silver contained in the conductive ink. It corresponds to a printed image or pattern made of silver.

The layer (Y) is mainly composed of the conductive substance (a2), but other components contained in the fluid (a), for example, the diol (a1-1) represented by the general formula (I) The polyhydric alcohol (a1) etc. may remain in the layer (Y).

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

The width (line width) of the thin-line layer (pattern) is about 0.01 μm to 200 μm, preferably about 0.01 μm to 150 μm, from the viewpoint of increasing the density of the conductive pattern.

The layer (Y) preferably has a thickness of 0.01 μm to 100 μm in order to form a conductive pattern having low resistance and excellent conductivity. In addition, when the layer (Y) has a thin line shape, the thickness (height) is preferably in the range of 0.1 μm to 50 μm.

Next, the support which comprises the electroconductive pattern of this invention is demonstrated.
Examples of the support used in the present invention include acrylic resins such as polyimide resin, polyamideimide resin, polyamide resin, polyethylene terephthalate, polyethylene naphthalate, polycarbonate, acrylonitrile-butadiene-styrene (ABS), and poly (meth) methyl acrylate. , Support made of polyvinylidene fluoride, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, polycarbonate, polyethylene, polypropylene, polyurethane, cellulose nanofiber, silicon, ceramics, glass, etc., porous support made of them, steel plate and A support made of a metal such as copper can be used.

Further, as the support, for example, a synthetic fiber such as polyester fiber, polyamide fiber or aramid fiber; a natural fiber such as cotton or hemp can be used. The fibers may be processed in advance.

Among these, as the support, generally used as a support in forming a conductive pattern such as a circuit board, from polyimide resin, polyethylene terephthalate, polyethylene naphthalate, glass, cellulose nanofiber, etc. It is preferable to use a support.

In addition, when the support is used for applications that require flexibility, it is possible to use a material that is relatively flexible and capable of being bent. It is preferable for obtaining a final product. Specifically, it is preferable to use a film or sheet-like support formed by uniaxial 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 preferably has a thickness of about 1 μm to 2,000 μm from the viewpoint of reducing the weight and thickness of the conductive pattern and the final product in which it is used, and about 1 μm to 200 μm. More preferably, it is a thickness. When the laminate is required to be relatively flexible, it is preferable to use a laminate having a thickness of about 1 μm to 80 μm.

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

Next, the fluid (a) used for production of the conductive pattern of the present invention will be described.
The fluid (a) includes a polyhydric alcohol (a1) containing a diol (a1-1) having a structure represented by the following general formula (I), a conductive substance (a2), and a solvent if necessary. It contains an additive.

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

Specifically, the fluid (a) has a viscosity measured at about 23 ° C. with an E-type viscometer (TVE-22LT, manufactured by Toki Sangyo Co., Ltd.) of 0.1 mPa · s to 500,000 mPa · s. The liquid is preferably 0.5 mPa · s to 10,000 mPa · s, more preferably a liquid or viscous liquid.
When the fluid (a) is applied (printed) to a desired position by an inkjet printing method, an offset printing method, a gravure printing method, a flexographic printing method, or the like, which will be described later, it is approximately 5 mPa · s to 1,000 mPa · It is preferable to use a fluid adjusted to a viscosity in the range of s.

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

As the polyhydric alcohol (a1) containing the diol (a1-1) used in the fluid (a), the diol (a1-1) is essential, and other polyhydric alcohols are included as necessary. Can be used.

The diol (a1-1) can improve the temporal stability of the fluid (a). The diol (a1-1) improves the adhesion and conductivity of the conductive pattern of the present invention by using in combination with the coating film (x) that can form the primer layer (X). be able to. The diol (a1-1) can also improve the discharge stability of the fluid (a) when the fluid (a) is discharged by an ink jet method.

As the diol (a1-1), the compound represented by the general formula (I) is used. R in the general 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. And more preferably 1 to 3 alkyl groups.

As the diol (a1-1), the layer (Y) formed by the conductive material (a2) contained in the fluid (a) is at a level that does not cause peeling from the primer layer (X). 1 in which R in the general formula (I) is a hydrogen atom in order to obtain a conductive pattern having better adhesion, no cracks in the depicted conductive pattern, and even better conductivity 1,3-butylene glycol or isoprene glycol in which R is an alkyl group is preferably used.

The diol (a1-1) is preferably contained in the range of 5% by mass to 60% by mass and more preferably in the range of 15% by mass to 50% by mass with respect to the total amount of the fluid (a). Preferably, it is contained in the range of 20% by mass to 40% by mass in order to improve the discharge stability of the fluid (a) and form a wiring pattern having excellent conductivity.

As other polyhydric alcohols that can be used in combination with the diol (a1-1), conventionally known polyhydric alcohols can be used, such as 2-ethyl-1,3-hexanediol, ethylene glycol, and the like. Diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, 1,2-butanediol, 1,4-butanediol, 2,3-butanediol, glycerin and the like can be used.

As the conductive substance (a2), a transition metal or a compound thereof can be used. Among them, it is preferable to use an ionic transition metal, for example, it is preferable to use a transition metal such as copper, silver, gold, nickel, palladium, platinum, cobalt, and to use copper, silver, gold, or the like. Further, it is more preferable because a conductive pattern having a low electric resistance and strong against corrosion can be formed, and it is more preferable to use silver.

Further, when the fluid (a) is used as a plating nucleating agent, the conductive material (a2) is a metal particle composed of a transition metal as described above, and the surface is formed by an oxide or an organic substance of the transition metal. One or more types of coated ones can be used.

In addition, since the transition metal oxide is usually in an inactive (insulating) state, even if a fluid containing it is simply applied to the surface of the support, it may not exhibit conductivity. Many. Therefore, when the fluid containing the oxide is applied to the surface of the support, the transition metal is exposed and activated by treating the surface with a reducing agent such as dimethylaminoborane. It is possible to form a layer having conductivity.

Further, examples of the metal whose surface is coated with the organic substance include those in which a metal is contained in resin particles (organic substance) formed by an emulsion polymerization method or the like. Like the transition metal oxides, these are usually in an inactive (insulating) state. Therefore, even if a fluid containing the same is simply applied to the surface of the support, it exhibits conductivity. Often not. Therefore, when a fluid containing a metal surface-coated with the organic material is applied to the surface of the support, the transition metal is exposed by irradiating the surface with a laser or the like and removing the organic material. Thus, a layer having activity (conductivity) can be formed.

As the conductive substance (a2), a particulate material having an average particle diameter of about 1 nm to 100 nm is preferably used, and a material having an average particle diameter of 1 nm to 50 nm is preferably used. Compared to the case of using a conductive material having an average particle diameter of the order, it is more preferable because a fine conductive pattern can be formed and the resistance value after heating can be further reduced. The “average particle size” is a volume average value measured by a dynamic light scattering method after diluting the conductive substance (a2) with a dispersion good solvent. For this measurement, Nanotrac UPA-150 manufactured by Microtrac can be used.

The conductive substance (a2) is preferably contained in the range of 5% by mass to 90% by mass with respect to the total amount of the fluid (a) used in the present invention. More preferably, it is contained in the range of 10% by mass to 60% by mass, and particularly preferably in the range of 20% by mass to 40% by mass.

In addition, the fluid preferably contains a solvent from the viewpoint of improving ease of application and the like. As the solvent, an organic solvent or an aqueous medium can be used.

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

Examples of the alcohol include methanol, ethanol, n-propanol, isopropyl alcohol, n-butanol, isobutyl alcohol, sec-butanol, tert-butanol, heptanol, hexanol, octanol, nonanol, decanol, undecanol, dodecanol, tridecanol, tetradecanol, and tetradecanol. Nord, pentadecanol, stearyl alcohol, allyl alcohol, cyclohexanol, terpineol, terpineol, dihydroterpineol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl Ether, tetraethylene glycol monobutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, propylene glycol monopropyl ether, dipropylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monobutyl ether, tri Propylene glycol monobutyl ether or the like can be used.

In addition to the above-described fluid (a), the fluid (a) may be, if necessary, a ketone solvent such as acetone, cyclohexanone, methyl ethyl ketone, ethyl acetate, butyl acetate, 3-methoxybutyl acetate, 3-methoxy-3- Ester solvents such as methyl-butyl acetate, hydrocarbon solvents such as toluene, octane, nonane, decane, dodecane, tridecane, tetradecane, cyclooctane, xylene, mesitylene, ethylbenzene, dodecylbenzene, tetralin, trimethylbenzenecyclohexane, mineral spirit, solvent A solvent such as naphtha can also be used in combination.

The fluid (a) of the present invention can be produced, for example, by mixing the polyhydric alcohol (a1), the conductive substance (a2) and, if necessary, the solvent. Among them, by producing a composition containing the conductive substance (a2) and the solvent, and then mixing the composition and the polyhydric alcohol (a1) containing the diol (a1-1) It is more preferable to improve the dispersion stability of the conductive substance and prevent the occurrence of cracks in the layer (Y).

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

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

When mixing the dispersion and the polyhydric alcohol (a1), for example, an apparatus such as a mixer, a disper, a bead mill, or an ultrasonic homogenizer can be used.

In addition, the fluid (a) used in the present invention further improves the dispersion stability of the conductive substance (a2) in the solvent, and also on the surface of the coating film (x) of the fluid (a). In order to further improve the wettability and the like, a surfactant, an antifoaming agent, a rheology adjusting agent and the like may be contained.

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

Next, the primer used in manufacturing the conductive pattern of the present invention will be described.

The primer forms a coating film (x) that can carry the conductive substance (a2) contained in the fluid (a) and can form the conductive pattern layer (Y) of the present invention. is there.

As the primer, any primer can be used as long as it can form a coating film (x) capable of absorbing ethanol in an environment of 25 ° C. by 20 mass% to 500 mass% with respect to the mass of the coating film (x). Things can also be used.

As the primer capable of forming the coating film (x), those containing various resins and solvents can be used.

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

Examples of the resin include a urethane resin having a polycarbonate structure as the urethane resin (x1), a urethane resin having an aliphatic polyester structure, an acrylic resin having a structural unit derived from methyl methacrylate as the vinyl resin (x2), and The use of one or more resins (x-1) selected from the group consisting of urethane-acrylic composite resins as the urethane-vinyl composite resin (x3) results in a coating film (x ) Is preferable, and it is more preferable to use a urethane-acrylic composite resin.

As the primer, it is preferable to use a primer containing 10% by mass to 70% by mass of the resin with respect to the whole primer, in order to maintain ease of application and the like, and it contains 10% by mass to 50% by mass. It is more preferable to use one.

Also, as the solvent that can be used for the primer, various organic solvents and aqueous media can be used.

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

Examples of the organic solvent miscible with water include alcohols such as methanol, ethanol, n-propanol, isopropanol, ethyl carbitol, ethyl cellosolve, and butyl cellosolve; ketones such as acetone and methyl ethyl ketone; and polymers such as ethylene glycol, diethylene glycol, and propylene glycol. Examples include alkylene glycols; alkyl ethers of polyalkylene glycols; and lactams such as N-methyl-2-pyrrolidone.

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

As the primer, it is preferable to use a primer containing 25% by mass to 90% by mass of the solvent with respect to the whole primer, in order to maintain ease of application, etc., and it contains 50% by mass to 85% by mass. It is more preferable to use one.

When an aqueous medium is used as the solvent, it is preferable to use a resin having a hydrophilic group as the resin in order to impart good water dispersibility to the primer and improve its storage stability.

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

As the anionic group, for example, a carboxyl group, a carboxylate group, a sulfonic acid group, a sulfonate group, and the like can be used. Among them, a carboxylate group formed by neutralizing a part or all of them with a basic compound or the like. Alternatively, it is preferable to use a sulfonate group in order to impart good water dispersibility.

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

When the carboxylate group or sulfonate group is used as the anionic group, they are present in the range of 50 mmol / kg to 2,000 mmol / kg with respect to the whole resin, so that the resin has good water dispersion stability. It is preferable for maintaining the property.

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

Further, as the nonionic group, for example, polyoxyalkylene groups such as polyoxyethylene group, poly (oxyethylene-oxypropylene) group, and polyoxyethylene-polyoxypropylene group can be used. Among these, it is preferable to use a polyoxyalkylene group having an oxyethylene unit in order to further improve the hydrophilicity.

As the urethane resin (x1) that can be used as the resin contained in the primer, a urethane resin obtained by reacting a polyol, a polyisocyanate, and, if necessary, a chain extender can be used. Especially, it is preferable to use the urethane resin which has a polycarbonate structure, and the urethane resin which has an aliphatic polyester structure from a viewpoint of forming the coating film (x) provided with the absorptivity of the said predetermined | prescribed ethanol.

It is preferable that the polycarbonate structure and the aliphatic polyester structure are structures derived from a polyol used for producing the urethane resin. Specifically, the urethane resin having the polycarbonate structure can be produced by using a resin containing a polycarbonate polyol described later as the polyol. Moreover, the urethane resin which has the said aliphatic polyester structure can be manufactured by using what contains the aliphatic polyester polyol mentioned later as the said polyol.

As the polyol that can be used for the production of the urethane resin (x1), as described above, polycarbonate polyol, aliphatic polyester polyol, and the like can be used. Moreover, as said polyol, another polyol can be combined and used as needed.

In addition, as the polycarbonate polyol, for example, those obtained by reacting a carbonate with a polyol, or those obtained by reacting phosgene with bisphenol A or the like can be used.

As the carbonate ester, methyl carbonate, dimethyl carbonate, ethyl carbonate, diethyl carbonate, cyclocarbonate, diphenyl carbonate and the like can be used.

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

Examples of the aliphatic polyester polyol include an aliphatic polyester polyol obtained by esterification reaction of a low molecular weight polyol and a polycarboxylic acid; a ring-opening polymerization reaction of a cyclic ester compound such as ε-caprolactone or γ-butyrolactone. Aliphatic polyesters obtained as above; these copolyesters can be used.

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

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

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

Further, as a polyol that can be used in the production of the urethane resin (x1), other polyols can be used in combination with the above-described ones as necessary.

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

In the case of producing a urethane resin having a hydrophilic group as the urethane resin (x1), it is preferable to use a polyol having a hydrophilic group as the other polyol.

Examples of the polyol having a hydrophilic group include a polyol having a carboxyl group such as 2,2-dimethylolpropionic acid, 2,2′-dimethylolbutanoic acid, 2,2-dimethylolvaleric acid, and the like; 5-sulfoisophthalic acid Polyols having a sulfonic acid group such as sulfoterephthalic acid, 4-sulfophthalic acid, and 5 [4-sulfophenoxy] isophthalic acid can be used. In addition, as the polyol having a hydrophilic group, a polyester polyol having a hydrophilic group obtained by reacting the above-described polyol having a low molecular weight hydrophilic group with various polycarboxylic acids such as adipic acid is used. You can also

Examples of the polyisocyanate that can react with the polyol to form a urethane resin include 4,4′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate, carbodiimide-modified diphenylmethane diisocyanate, crude diphenylmethane diisocyanate, phenylene diisocyanate, tolylene diisocyanate, and naphthalene. Polyisocyanates having an aromatic structure such as diisocyanate; aliphatic polyisocyanates such as hexamethylene diisocyanate, lysine diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, or aliphatic cyclic structures Po It is possible to use the isocyanate.

Also, as a chain extender that can be used when producing the urethane resin, polyamine, hydrazine compounds, and other compounds having active hydrogen atoms can be used.

Examples of the polyamine include ethylenediamine, 1,2-propanediamine, 1,6-hexamethylenediamine, piperazine, 2,5-dimethylpiperazine, isophoronediamine, 4,4'-dicyclohexylmethanediamine, 3,3'- Diamines such as dimethyl-4,4′-dicyclohexylmethanediamine, 1,4-cyclohexanediamine; N-hydroxymethylaminoethylamine, N-hydroxyethylaminoethylamine, N-hydroxypropylaminopropylamine, N-ethylaminoethylamine, N -Methylaminopropylamine, diethylenetriamine, dipropylenetriamine, triethylenetetramine, etc. can be used, preferably ethylenediamine.

Examples of the hydrazine compound include hydrazine, N, N′-dimethylhydrazine, 1,6-hexamethylenebishydrazine, succinic acid dihydrazide, adipic acid dihydrazide, glutaric acid dihydrazide, sebacic acid dihydrazide, isophthalic acid dihydrazide, β-semicarbazide propion Acid hydrazide, 3-semicarbazide-propyl-carbazate, semicarbazide-3-semicarbazide methyl-3,5,5-trimethylcyclohexane can be used.

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

The chain extender is preferably used, for example, in such a range that the equivalent ratio between the amino group of the polyamine and the isocyanate group is 1.9 or less (equivalent ratio), and 0.3 to 1 (equivalent ratio) It is more preferable to use in the range.

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

In the reaction of the polyol with the polyisocyanate, sufficient attention is paid to sudden heat generation and foaming, and the polyol and the polyisocyanate are preferably reacted at a reaction temperature of 50 ° C. to 120 ° C., more preferably 80 ° C. to 100 ° C. Can be carried out by batch mixing or by sequentially supplying either one to the other by dropping or the like and reacting for about 1 to 15 hours.

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

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

The reaction between the polyisocyanate and the polyol is preferably performed, for example, in a range where the equivalent ratio of the isocyanate group of the polyisocyanate and the hydroxyl group of the polyol [isocyanate group / hydroxyl group] is 0.9 to 2.

When manufacturing the said urethane resin (x1), an organic solvent can also be used as a solvent as above-mentioned. Examples of the organic solvent include ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran and dioxane; acetic esters such as ethyl acetate and butyl acetate; nitriles such as acetonitrile; amides such as dimethylformamide and N-methylpyrrolidone. Can do.
The organic solvent is preferably removed by distillation or the like after the production of the urethane resin (x1). However, when the primer containing the urethane resin (x1) and the organic solvent is used, the organic solvent used when the urethane resin (x1) is produced is used as the primer solvent. May be.

As the urethane resin (x1), it is preferable to use a resin having a weight average molecular weight of 5,000 to 500,000 in order to form a conductive pattern having excellent adhesion and excellent conductivity. 20,000 to 100,000 are more preferable.

As the urethane resin (x1), those having various functional groups can be used as necessary. Examples of the functional group include crosslinkable functional groups such as an alkoxysilyl group, a silanol group, a hydroxyl group, and an amino group.

The crosslinkable functional group is suitable for forming a pattern (layer (Y)) having excellent durability by forming a crosslinked structure in the primer layer (X) carrying the fluid (a). is there.

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

Further, when the urethane resin (x1) is used in combination with a crosslinking agent (D) described later, one having a functional group capable of reacting with the functional group of the crosslinking agent (D) can be used. As the functional group, although depending on the selection of the crosslinking agent (D) to be used in combination, for example, when a crosslinking agent such as a blocked isocyanate compound is used, a hydroxyl group or an amino group can be used.

Also, as the vinyl resin (x2) that can be used for the resin contained in the primer, a monomer polymer 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, etc. can be used, and a structure derived from methyl methacrylate. It is preferable to use an acrylic resin having units.

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

As the acrylic resin, it is preferable to use an acrylic resin having a structural unit derived from methyl (meth) acrylate from the viewpoint of forming the coating film (x) having the predetermined ethanol absorption rate.

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

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

Among the above, methyl methacrylate is preferably used for forming a coating film (x) having a predetermined ethanol absorption rate, such as heat in a heating step or the like in producing a conductive pattern. Regardless of the influence, it is preferable to use the methyl methacrylate in order to provide excellent adhesion between the primer layer (X) and the support. Also, a fine line having a width of about 0.01 μm to 200 μm, preferably about 0.01 μm to 150 μm, which is required when forming a conductive pattern such as an electronic circuit, is printed without causing bleeding (thin line). The use of the methyl methacrylate is more preferable in order to enable improvement of the property.

Further, it is preferable to use (meth) acrylic acid alkyl ester having an alkyl group having 2 to 12 carbon atoms together with the methyl methacrylate, and acrylic acid having an alkyl group having 3 to 8 carbon atoms. It is more preferable to use an alkyl ester, and the use of n-butyl acrylate forms the coating film (x) having the predetermined ethanol absorption rate, and further improves the adhesion and conductivity. It is preferable for improvement. Moreover, it is preferable also when forming the electroconductive pattern excellent in fine-line property without the bleeding etc. of the said fluid (a).

The methyl (meth) acrylate is preferably 10% by mass to 70% by mass, more preferably 30% by mass to 65% by mass with respect to the total amount of the (meth) acrylic monomer mixture, and The acrylic acid alkyl ester having an alkyl group having 2 to 12 carbon atoms, preferably the acrylic acid alkyl ester having an alkyl group having 3 to 8 carbon atoms is the total amount of the (meth) acrylic monomer mixture. Is preferably 20% by mass to 80% by mass, and more preferably 35% by mass to 70% by mass.

Further, (meth) acrylic monomers that can be used for producing the acrylic resin include, in addition to those described above, acrylic acid, methacrylic acid, β-carboxyethyl (meth) acrylate, 2- (meth) Carboxyl groups such as acryloylpropionic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, itaconic acid half ester, maleic acid half ester, maleic anhydride, itaconic anhydride, β- (meth) acryloyloxyethyl hydrogen succinate, etc. The vinyl monomer can be used. The vinyl monomer having a carboxyl group may be neutralized with ammonia, potassium hydroxide or the like.

In addition, as the (meth) acrylic monomer, the acrylic resin includes at least one amide group selected from the group consisting of a methylolamide group and an alkoxymethylamide group, an amide group other than the above, a hydroxyl group, a glycidyl group, A vinyl monomer having a crosslinkable functional group from the viewpoint of introducing the crosslinkable functional group such as amino group, silyl group, aziridinyl group, isocyanate group, oxazoline group, cyclopentenyl group, allyl group, carbonyl group, acetoacetyl group, etc. The body can be used.

Examples of the vinyl monomer having one or more amide groups selected from the group consisting of a methylolamide group and an alkoxymethylamide group that can be used for the (meth) acrylic monomer having a crosslinkable functional group include N- Methylol (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-methoxyethoxymethyl (meth) acrylamide, N-ethoxymethyl (meth) acrylamide, N-propoxymethyl (meth) acrylamide, N-isopropoxymethyl (meta ) Acrylamide, Nn-butoxymethyl (meth) acrylamide, N-isobutoxymethyl (meth) acrylamide, N-pentoxymethyl (meth) acrylamide, N-ethoxymethyl-N-methoxymethyl (meth) acrylamide, N, N'-dimethylol (Meth) acrylamide, N-ethoxymethyl-N-propoxymethyl (meth) acrylamide, N, N′-dipropoxymethyl (meth) acrylamide, N-butoxymethyl-N-propoxymethyl (meth) acrylamide, N, N-di Butoxymethyl (meth) acrylamide, N-butoxymethyl-N-methoxymethyl (meth) acrylamide, N, N′-dipentoxymethyl (meth) acrylamide, N-methoxymethyl-N-pentoxymethyl (meth) acrylamide, etc. Can be used.

Among them, the use of Nn-butoxymethyl (meth) acrylamide and N-isobutoxymethyl (meth) acrylamide can provide a level of durability that can prevent peeling of the conductive material (a2) in the plating process. It is preferable when forming the electroconductive pattern provided with.

Examples of the (meth) acrylic monomer having a crosslinkable functional group include those other than those described above, for example, a vinyl monomer having an amide group such as (meth) acrylamide, 2-hydroxyethyl (meth) acrylate, (Meth) acrylic acid 2-hydroxypropyl, (meth) acrylic acid 2-hydroxybutyl, (meth) acrylic acid 4-hydroxybutyl, (meth) acrylic acid 6-hydroxyhexyl, (meth) acrylic acid (4-hydroxymethyl) Cyclohexyl) methyl, glycerol (meth) acrylate, polyethylene glycol (meth) acrylate, vinyl monomers having a hydroxyl group such as N-hydroxyethyl (meth) acrylamide: glycidyl (meth) acrylate, allyl (meth) acrylate Polymerizable monomers having a glycidyl group such as glycidyl ether; Polymerizable monomers having an amino group such as aminoethyl acrylate, dimethylaminoethyl (meth) acrylate, N-monoalkylaminoalkyl (meth) acrylate, N, N-dialkylaminoalkyl (meth) acrylate; Vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, γ- (meth) acryloxypropyltrimethoxysilane, γ- (meth) acryloxypropyltriethoxysilane, γ- ( (Meth) acryloxypropylmethyldimethoxysilane, γ- (meth) acryloxypropylmethyldiethoxysilane, γ- (meth) acryloxypropyltriisopropoxysilane, N-β- (N-vinylbenzylaminoethyl) -γ- Aminopropyltrimethoxysila And a polymerizable monomer having a silyl group of a hydrochloride thereof; a polymerizable monomer having an aziridinyl group such as 2-aziridinylethyl (meth) acrylate; (meth) acryloyl isocyanate, (meth) acryloyl isocyanate ethyl Polymerizable monomers having an (blocked) isocyanate group such as phenol and their methyl ethyl ketoxime adducts; polymerizable monomers having an oxazoline group such as 2-isopropenyl-2-oxazoline and 2-vinyl-2-oxazoline Polymers having a cyclopentenyl group such as (meth) acrylate dicyclopentenyl; Polymerizable monomers having an allyl group such as allyl (meth) acrylate; Acrolein, diacetone (meth) acrylamide, etc. A polymerizable monomer having a carbonyl group can be used.

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

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

In addition, among the (meth) acrylic monomers having the crosslinkable functional group, the (meth) acrylic monomer having a hydroxyl group and the (meth) acrylic monomer having an acid group are used as a crosslinking agent ( Depending on the type of D), etc., it is preferably used in a range of approximately 0.05% by mass to 50% by mass with respect to the total amount of the (meth) acrylic monomer mixture, preferably 0.05% by mass to 30%. It is preferably used in the range of mass%, more preferably 0.1 mass% to 10 mass%.

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

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

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

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

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

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

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

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

Further, as the zwitterionic surfactant, for example, alkyl (amido) betaine, alkyldimethylamine oxide and the like can be used.

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

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

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

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

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

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

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

Further, as the urethane-vinyl composite resin (x3), it is preferable to use a urethane-acrylic composite resin in which the vinyl polymer (x3-2) is an acrylic resin.

The composite resin particles preferably have an average particle diameter in the range of 5 nm to 100 nm from the viewpoint of maintaining good water dispersion stability. The average particle diameter here refers to an average particle diameter on a volume basis measured by a dynamic light scattering method, as will be described later in Examples.

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

As the urethane resin (x3-1) constituting the urethane-vinyl composite resin, the same resin as the urethane resin (x1) can be used. The urethane resin (x3-1) constituting the urethane-vinyl composite resin includes, for example, a urethane resin having a polyether structure and an aromatic polyester structure other than those exemplified as the urethane resin (x1). Urethane resin can also be used.

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

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

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

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

Further, when the urethane resin having the aromatic polyester structure is used, an aromatic polyester polyol can also be used as the polyol.

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

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

As the aromatic polycarboxylic acid, for example, terephthalic acid, isophthalic acid, phthalic acid, naphthalenedicarboxylic acid, and anhydrides or esterified products thereof can be used.

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

As the vinyl polymer (x3-2) constituting the urethane-vinyl composite resin, it is possible to use a polymer having a glass transition temperature of 10 ° C. to 70 ° C. It is preferable for forming (x) and improving the adhesion with the conductive substance (a2) contained in the fluid (a) and the conductivity of the resulting conductive pattern. The glass transition temperature of the vinyl polymer (x3-2) is a value determined by calculation mainly based on the composition of the vinyl monomer used for the production of the vinyl polymer (x3-2). is there. Specifically, the vinyl polymer (x3-2) having the predetermined glass transition temperature can be obtained by using a combination of the vinyl polymer (x3-2) described later.

Further, as the vinyl polymer (x3-2), a coating film (x) having the predetermined ethanol absorption rate is formed, and the conductive polymer (a2) contained in the fluid (a) is formed. In order to improve adhesion and conductivity of the resulting conductive pattern and to make the pattern thin, it is preferable to use one having a weight average molecular weight of 800,000 or more, and a weight average of 1,000,000 or more. It is more preferable to use one having a molecular weight.

The upper limit of the weight average molecular weight of the vinyl polymer (x3-2) is not particularly limited, but is preferably approximately 10 million or less, and preferably 5 million or less.

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

As the vinyl polymer (x3-2), the same polymer as the vinyl polymer (x2) can be used. Specifically, examples of the (meth) vinyl monomer that can be used for the production of the vinyl polymer (x3-2) include the vinyl monomers exemplified as those that can be used for the production of the vinyl resin (x2). Preferably, the same as the (meth) acrylic monomer can be used. Among these, as the vinyl polymer (x3-2), it is preferable to use the same acrylic resin having a structural unit derived from methyl methacrylate exemplified as usable for the vinyl resin (x2).

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

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

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

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

When the composite resin particles are produced, if the urethane resin (x3-1) has a high viscosity and is not excellent in workability, a normal organic material such as methyl ethyl ketone, N-methylpyrrolidone, acetone, dipropylene glycol dimethyl ether or the like is used. Solvents and reactive diluents can be used. In particular, it is possible to use a vinyl monomer such as a (meth) acrylic monomer that can be used in the production of the vinyl polymer (x3-2) as the reactive diluent. It is preferable for improving the production efficiency.

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

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

The primer may be a combination of the urethane resin (x1) and the vinyl resin (x2). When used in such a combination, the mass ratio of the urethane resin (x1) and the vinyl resin (x2) is in the range of [(x1) / (x2)] = 90/10 to 10/90. It is preferable to use in the range of 70/30 to 10/90.

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

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

The coating film (x) formed using the primer may have a crosslinked structure before the fluid (a) is applied (printed) on a part or all of the surface thereof, It is necessary to adjust the ethanol absorption rate to fall within the range of 20% by mass to 500% by mass.

In addition, the coating layer (x) does not have a crosslinked structure before the fluid (a) is applied (printed) to the surface thereof, and after the fluid (a) is applied, the primer layer You may form the primer layer which has a crosslinked structure as (X).

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

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

In addition, the crosslinkable functional group is heated to approximately 100 ° C. or higher, preferably 120 ° C. or higher to cause a crosslink reaction between the crosslinkable functional groups or a cross-linking agent (D) described later to form the crosslink structure. In particular, it is preferable to use one or more thermally crosslinkable functional groups selected from the group consisting of a methylolamide group and an alkoxymethylamide group.

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

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

After applying (printing) the fluid (a) to the coating film not having the crosslinked structure, the primer layer is heated at a temperature of 100 ° C. or higher, or by heating separately from the heating step. A primer layer having a crosslinked structure is formed as (X).

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

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

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

Examples of the crosslinking agent (D) include a metal chelate compound, a polyamine compound, an aziridine compound, a metal salt compound, and an isocyanate compound, which can react at a relatively low temperature of about 25 ° C. to less than 100 ° C. to form a crosslinked structure. Reacts at a relatively high temperature of about 100 ° C. or higher, such as one or more selected from the group consisting of a thermal crosslinking agent (d1-1), a melamine compound, an epoxy compound, an oxazoline compound, a carbodiimide compound, and a blocked isocyanate compound. A thermal crosslinking agent (d1-2) capable of forming a crosslinked structure and various photocrosslinking agents can be used.

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

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

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

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

In addition, as a polyamine compound that can be used for the thermal crosslinking agent (d1-1), for example, a tertiary amine such as triethylamine, triethylenediamine, dimethylethanolamine or the like can be used.

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

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

Examples of isocyanate compounds that can be used in the thermal crosslinking agent (d1-1) include tolylene diisocyanate, hydrogenated tolylene diisocyanate, triphenylmethane triisocyanate, methylene bis (4-phenylmethane) triisocyanate, isophorone diisocyanate, hexamethylene. Polyisocyanates such as diisocyanates and xylylene diisocyanates; isocyanurate-type polyisocyanate compounds obtained by using them; adducts composed of these with trimethylolpropane; and the like, the polyisocyanate compound and a polyol such as trimethylolpropane are reacted. Urethanes having a polyisocyanate group obtained in the above manner can be used. Among them, hexamethylene diisocyanate nurate, adduct of hexamethylene diisocyanate and trimethylolpropane, adduct of tolylene diisocyanate and trimethylol propane, adduct of xylylene diisocyanate and trimethylol propane, etc. are used. It is preferable.

Examples of the melamine compound that can be used in the thermal crosslinking agent (d1-2) include hexamethoxymethyl melamine, hexaethoxymethyl melamine, hexapropoxymethyl melamine, hexabutoxymethyl melamine, hexapentyloxymethyl melamine, and hexahexyloxy. Methylmelamine or a mixed etherified melamine obtained by combining these two types can be used. Of these, trimethoxymethyl melamine and hexamethoxymethyl melamine are preferably used. Examples of commercially available products include Becamine M-3, APM, J-101 (manufactured by DIC Corporation), and the like. The melamine compound can form a crosslinked structure by a self-crosslinking reaction.

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

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

Examples of the epoxy compound include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, and γ-glycidoxypropyl other than those described above. Methyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethylmethyldiethoxysilane Alternatively, a silane compound having a glycidyl group such as γ-glycidoxypropyltriisopropenyloxysilane can also be used.

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

In addition, as the oxazoline compound, for example, a polymer having an oxazoline group obtained by polymerizing a combination of the following addition polymerizable oxazoline and other monomers as necessary can be used.

Examples of the addition polymerizable oxazoline include 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, etc., alone or in combination Can do. Of these, the use of 2-isopropenyl-2-oxazoline is preferred because it is easily available industrially.

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

In addition, as the blocked isocyanate compound that can be used in the thermal crosslinking agent (d1-2), a part or all of the isocyanate groups of the isocyanate compound exemplified as the thermal crosslinking agent (d1-1) are formed by a blocking agent. What was sealed can be used.

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

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

When using the crosslinking agent (D), it is preferable to use a resin having a group capable of reacting with the crosslinking functional group of the crosslinking agent (D) as the resin contained in the primer. Specifically, it is preferable to use the (block) isocyanate compound, the melamine compound, the oxazoline compound, and the carbodiimide compound as a crosslinking agent and a resin having a hydroxyl group or a carboxyl group as the resin.

Although the crosslinking agent (D) varies depending on the type and the like, it is usually preferable to use in the range of 0.01% by mass to 60% by mass with respect to 100 parts by mass of the total resin contained in the primer. More preferably, it is used in the range of 1% by mass to 10% by mass, and in the range of 0.1% by mass to 5% by mass is excellent in adhesion and conductivity and excellent in the durability. It is preferable because a conductive pattern can be formed.

Moreover, it is preferable that the crosslinking agent (D) is added and used in advance before the primer of the present invention is applied or impregnated on the surface of the support.

Further, as the additive, various fillers such as inorganic particles can be used. However, the amount of the filler used in the primer of the present invention 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 additive used is not particularly limited as long as the effect of the present invention is not impaired, but is preferably in the range of 0.01% by mass to 40% by mass with respect to the total amount of solids in the primer. .

Next, the manufacturing method of the electroconductive pattern of this invention is demonstrated.
In the conductive pattern of the present invention, a primer is applied to part or all of the surface of the support, and then the fluid is applied to part or all of the surface of the coating film (x) formed using the primer. It can manufacture by heating after apply | coating a body (a).

First, a method for 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) forms the primer layer (X) by being heated after the fluid (a) is applied. The said coating film (x) can be formed by the method of apply | coating the said primer to the said support body, and removing the solvent contained in the said primer.

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

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

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

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

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

The above-mentioned problem is that the coating film (x) is a coating film capable of absorbing 20% by mass to 500% by mass with respect to the mass of the coating film (x) in an environment of 25 ° C. Indispensable to resolve.

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

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

Next, the mass of the coating film obtained above is measured.

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

Next, 30 seconds after the coating film was immersed in the ethanol, the coating film was taken out from the ethanol, and it was placed on a stack of three becots, on which three becots were stacked, Further, leave it on for 10 seconds with a weight of 500 g.

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

Next, the mass ratio obtained by dividing the mass of ethanol absorbed in the coating film after immersion by the mass of the coating film before immersion and multiplying by 100 was defined as the ethanol absorption rate.

Here, when the ethanol absorptivity is less than 20% by mass, specifically, when the fluid (a) is applied to a coating film of 10% by mass, the decrease in conductivity and adhesion May cause decreased sex. Specifically, since the solvent contained in the fluid (a) is not easily absorbed by the coating film (x), the adhesion between the coating film (x) and the conductive pattern may be deteriorated.

On the other hand, when the ethanol absorption rate exceeds 500 mass%, the conductivity may be deteriorated.

The ethanol absorptivity is preferably in the range of 20% by mass to 300% by mass and more preferably in the range of 20% by mass to 200% by mass from the viewpoint of imparting even better adhesion and conductivity. Is more preferable, and the range of 45% by mass to 190% by mass is more preferable.

In the present invention, it is not only necessary to use the coating film (x) having the predetermined absorption rate, but a pattern is formed using the predetermined fluid (a) on the coating film (x). The problem can be solved only by printing.

Note that the primer layer (X) constituting the conductive pattern does not necessarily have the predetermined absorption rate. It is essential to solve the above-mentioned problems that the coating film (x) before the heating and before the fluid (a) is applied has the predetermined absorption rate. .

The coating film (x) is appropriately dissolved by the solvent contained in the fluid (a) and absorbs the solvent, whereby a conductive substance (a2) such as a metal contained in the fluid (a). Therefore, it is possible to contribute to obtaining a conductive pattern without bleeding. Further, by using the coating film (x), it is possible to form a transparent primer layer as compared with a conventionally known porous type receiving layer.

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

Examples of the method for applying the fluid (a) to part or all of the surface of the coating film (x) include a reverse printing method such as a letterpress reverse printing method, an ink jet printing method, a screen printing method, and an offset printing method. Using a coating method, spin coating method, spray coating method, bar coating method, die coating method, slit coating method, roll coating method, dip coating method, etc., the conductive ink is directly or inverted on the receiving substrate. Examples include a printing method.

In particular, when the fluid (a) is applied (printed) in the form of a thin wire of about 0.01 μm to 100 μm, which is required when realizing high density electronic circuits, etc., an ink jet printing method is adopted. It is preferable to do.

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

From the viewpoint of imparting conductivity by applying (printing) the fluid (a), the conductive material (a2) such as metal contained in the fluid (a) is in close contact and joined. It is preferable to be heated.

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

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

Further, when a resin having 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 fluid (a) is applied by using the crosslinking agent (d1-2). When a crosslinked structure is to be formed in the primer layer (X) after (printing), the crosslinked structure is formed after coating (printing) by passing through the heating step. Thereby, durability of a conductive pattern can be improved to each step.

When the crosslinking reaction step and the heating step are carried out, the heating temperature varies depending on the type of the crosslinking agent (D) used, the combination of the crosslinkable functional groups, etc., but is generally in the range of 80 ° C. to 300 ° C. It is preferably 100 ° C to 300 ° C, particularly preferably 120 ° C to 300 ° C. When the support is relatively weak against heat, the upper limit of the temperature is preferably 150 ° C. or less, more preferably 120 ° C. or less.

On the surface of the conductive pattern obtained through the heating step, a conductive pattern is formed by a conductive material such as a metal contained in the fluid (a). Such conductive patterns include the formation of electronic circuits using silver ink or the like, organic solar cells, electronic book terminals, organic EL, organic transistors, flexible printed boards, formation of RFID, peripheral wiring formation, plasma display It can be made suitable also in the field of printed electronics such as wiring of an electromagnetic wave shield.

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

The electroless plating treatment step is included in the electroless plating solution by bringing the electroless plating solution into contact with the surface of a plating nucleus such as palladium or silver supported on the primer layer (X). In this step, a metal such as copper is deposited to form an electroless plating layer (coating) made of a metal coating.

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

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

In addition, as the electroless plating solution, if necessary, monocarboxylic acids such as acetic acid and formic acid; dicarboxylic acids such as malonic acid, succinic acid, adipic acid, maleic acid, fumaric acid; malic acid, lactic acid, glycolic acid Hydroxycarboxylic acids such as gluconic acid and citric acid; amino acids such as glycine, alanine, arginine, aspartic acid and glutamic acid; aminopolycarboxylic acids such as iminodiacetic acid, nitrilotriacetic acid, ethylenediaminediacetic acid, ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid The organic acid may contain a complexing agent such as an organic acid, a soluble salt of these organic acids (sodium salt, potassium salt, ammonium salt, etc.), an amine such as ethylenediamine, diethylenetriamine, and triethylenetetramine.

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

Further, the electrolytic plating treatment step is performed by bringing an electrolytic plating solution into contact with, for example, the surface of the primer layer (X) carrying the plating nucleus or the surface of the electroless plating layer (coating) formed by the electroless treatment. The surface of the primer layer (X) placed on the negative electrode or the electroless plating layer (coating) formed by the electroless treatment is obtained by energizing the electroplating solution. And forming an electrolytic plating film (metal film).

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

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

In the electroless plating process and the electrolytic plating process as described above, a strong acid or strong alkaline plating solution as described above is often used. Therefore, in the normal primer layer (X), the primer layer ( X) is often attacked to cause peeling of the primer layer (X) from the support.

On the other hand, after printing using the fluid (a) such as the plating nucleating agent, the primer layer with respect to the support is formed in the plating step for the primer layer (X) in which the crosslinked structure is formed. (X) does not cause peeling. In particular, even when the support is made of a polyimide resin or the like, the primer layer (X) is not peeled off, and therefore can be used very suitably for the production of the conductive pattern.

Such conductive patterns include, for example, formation of electronic circuits using silver ink, organic solar cells, electronic book terminals, organic EL, organic transistors, flexible printed circuit boards, layers constituting RFID, etc., peripheral wiring It can be suitably used for forming and forming a conductive pattern, more specifically, a circuit board in manufacturing an electromagnetic wave shield wiring of a plasma display.

Moreover, after apply | coating (printing) fluid (a), such as electroconductive ink or a plating nucleating agent among the electroconductive patterns obtained by the said method, a crosslinked structure is formed in the said primer layer (X). Even when the conductive pattern obtained through the plating treatment step has a level at which good conductivity can be maintained without causing peeling of the primer layer (X) from the support. Can be imparted with excellent durability, formation of circuit forming substrates used in electronic circuits, integrated circuits, etc. using silver ink, organic solar cells, electronic book terminals, organic EL, organic transistors, flexible printed boards Of various layers constituting RFID, formation of peripheral wiring, wiring for electromagnetic wave shield of plasma display, etc., it can be suitably used for applications requiring particularly durability.In particular, the conductive pattern subjected to the plating treatment can form a highly reliable wiring pattern capable of maintaining good conductivity without causing disconnection or the like over a long period of time. (CCL: Copper Clad Laminate) and can be used for applications such as flexible printed circuit board (FPC), automatic tape bonding (TAB), chip-on-film (COF), and printed wiring board (PWB).

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

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

Under stirring, a vinyl monomer mixture consisting of 60 parts by weight of methyl methacrylate, 3 parts by weight of methacrylic acid and 37 parts by weight of n-butyl acrylate and Aqualon KH-1025 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd .: 25 parts by mass of active ingredient) A part (5 parts by mass) of a monomer pre-emulsion obtained by mixing 4 parts by mass and 15 parts by mass of deionized water was added, followed by 0.1 parts by mass of potassium persulfate. The polymerization was carried out for 60 minutes while maintaining the temperature in the reaction vessel at 75 ° C.

Next, while maintaining the temperature in the reaction vessel at 75 ° C., the remaining monomer pre-emulsion (114 parts by mass) and 30 parts by mass of an aqueous solution of potassium persulfate (active ingredient 1% by mass) were separately added to each dropping funnel. Was added dropwise over 180 minutes. After completion of dropping, the mixture was stirred at the same temperature for 60 minutes.

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

Next, primer 1 was prepared by using deionized water so that the non-volatile content was 30% by mass and then filtering with a 200 mesh filter cloth.

[Preparation Example 2] Preparation of Primer 2 First, 543 parts by mass of polyethylene glycol-diglycidyl ether (epoxy equivalent 185 g / equivalent) was added to a four-necked flask equipped with a thermometer, a stirring device, a reflux condenser, and a dropping device. After charging, the inside of the flask was purged with nitrogen.
After heating using an oil bath until the temperature in the flask reached 70 ° C., 380 parts by mass of di-n-butylamine was added dropwise over 30 minutes using a dropping device. Reacted. After completion of the reaction, using an infrared spectrophotometer (FT / IR-460Plus, manufactured by JASCO Corporation), it was confirmed that the absorption peak near 842 cm ⁻¹ due to the epoxy group of the reaction product had disappeared. Polyol K having a tertiary amino group (amine equivalent 315 g / equivalent, hydroxyl equivalent 315 g / equivalent) was prepared.

Next, a polyester polyol P (several number) obtained by reacting neopentyl glycol, 1,4-butanediol and adipic acid in a four-necked flask equipped with a thermometer, a stirring device, a reflux condenser, and a dropping device. 1070 parts by mass and 770 parts by mass of ethyl acetate were added, and the temperature was raised to 70 ° C. with stirring. After stirring and mixing them, 281 parts by mass of dicyclohexylmethane diisocyanate and 0.2 parts by mass of stannous octylate were added and reacted at 70 ° C. for 2 hours.

After completion of the reaction, 84 parts by mass of the polyol K having a tertiary amino group obtained above was added and reacted for 4 hours, and as a component capable of forming a crosslinked structure, “aminosilane A1100” [manufactured by Nippon Unicar Co., Ltd., [γ-Aminopropyltriethoxysilane] 36 parts by mass was added and reacted for 1 hour to prepare a urethane prepolymer solution having a silyl group. Next, 38 parts by mass of N-aminoethylethanolamine was added to the urethane prepolymer solution, and a chain extension reaction was performed for 1 hour to obtain an organic solvent solution of a cationic urethane resin.

Next, 1710 parts by mass of ethyl acetate and 22 parts by mass of acetic acid were added and held at 45 ° C. for 1 hour, then cooled to 40 ° C., and 3850 parts by mass of ion-exchanged water was added to prepare an aqueous dispersion. did. Primer 2 having a non-volatile content of 30% by mass was prepared by subjecting this aqueous dispersion to distillation under reduced pressure.

[Preparation Example 3] Preparation of Primer 3 First, 1,4-cyclohexanedimethanol, neopentyl glycol and adipic acid were reacted in a nitrogen-substituted container equipped with a thermometer, a nitrogen gas inlet tube, and a stirrer. 100 parts by mass of the polyester polyol Q (hydroxyl group equivalent 1000 g / equivalent in the polyester polyol Q) thus obtained, 17.6 parts by mass of 2,2-dimethylolpropionic acid, 21.7 parts by mass of 1,4-cyclohexanedimethanol Then, by reacting 106.2 parts by mass of dicyclohexylmethane diisocyanate in 178 parts by mass of methyl ethyl ketone, an organic solvent solution of a urethane prepolymer having an isocyanate group at the terminal was obtained.

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

Next, 8.8 parts by mass of a 25% by mass ethylenediamine aqueous solution is added to the aqueous dispersion, and the polyurethane prepolymer is chain-extended by stirring and subjected to aging and desolvation, whereby a solid content concentration of 30% by mass is obtained. An aqueous dispersion of urethane resin (L-1) was obtained. The urethane resin (L-1) obtained here had an acid value of 30 and a weight average molecular weight of 53,000.

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

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

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

The temperature in the reaction vessel was cooled to 40 ° C., then deionized water was used so that the non-volatile content was 20% by mass, and then filtered with a 200 mesh filter cloth to prepare Primer 3.

[Preparation Example 4] Preparation of primer 4

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

A monomer mixture containing 50 parts by weight of methyl methacrylate, 45 parts by weight of n-butyl acrylate and 5 parts by weight of Nn-butoxymethylacrylamide, and ammonium persulfate in a reaction vessel heated to 80 ° C. with stirring. 20 parts by mass of an aqueous solution (non-volatile content: 0.5% by mass) was dropped from a separate dropping funnel over 120 minutes while maintaining the temperature in the reaction vessel at 80 ± 2 ° C. to polymerize.

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

The temperature in the reaction vessel was cooled to 40 ° C., and then deionized water was used so that the non-volatile content was 20% by mass, followed by filtration with a 200 mesh filter cloth to prepare Primer 4.

[Preparation Example 5] Preparation of primer 5

A reaction vessel equipped with a stirrer, reflux condenser, nitrogen inlet tube, thermometer, dropping funnel for dropping the monomer mixture, dropping funnel for dropping the polymerization catalyst, 140 parts by mass of deionized water, and the urethane resin (L- 333 parts by mass of the aqueous dispersion 1) was added, and the temperature was raised to 80 ° C. while blowing nitrogen.

A monomer mixture containing 50 parts by weight of methyl methacrylate, 45 parts by weight of n-butyl acrylate and 5 parts by weight of Nn-butoxymethylacrylamide, and ammonium persulfate in a reaction vessel heated to 80 ° C. with stirring. 20 parts by mass of an aqueous solution (non-volatile content: 0.5% by mass) was dropped from a separate dropping funnel over 120 minutes while maintaining the temperature in the reaction vessel at 80 ± 2 ° C. to polymerize.

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

The temperature in the reaction vessel was cooled to 40 ° C., and then deionized water was used so that the non-volatile content became 20% by mass, followed by filtering with a 200 mesh filter cloth to prepare Primer 5.

[Preparation Example 6] Preparation of Primer 6 First, 1,4-cyclohexanedimethanol, neopentyl glycol and adipic acid were reacted in a nitrogen-substituted container equipped with a thermometer, a nitrogen gas inlet tube, and a stirrer. 100 parts by mass of the obtained polyester polyol Q (hydroxyl group equivalent in the polyester polyol 1000 g / equivalent) 100 parts by mass, hydroxyl group equivalent 1000 g in the polyester polyol 1000 parts by mass, 2,2-dimethylolpropionic acid 17.6 parts by mass Part of 1,4-cyclohexane dimethanol 21.7 parts by mass, dicyclohexylmethane diisocyanate 106.2 parts by mass in methyl ethyl ketone 178 parts by mass, an organic solvent solution of urethane prepolymer having an isocyanate group at the terminal Got.

Next, 10 parts by mass of “aminosilane A1100” (manufactured by Nippon Unicar Co., Ltd., γ-aminopropyltriethoxysilane) was mixed with the organic solvent solution of the urethane prepolymer, and the urethane prepolymer and γ-aminopropyltriethoxysilane were mixed. By reacting with silane, an organic solvent solution of urethane resin was obtained.

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

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

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

In a reaction vessel heated to 80 ° C., with stirring, a monomer mixture containing 50 parts by weight of methyl methacrylate and 50 parts by weight of n-butyl acrylate and an aqueous ammonium persulfate solution (nonvolatile content 0.5% by weight) 20 A part by mass was dropped from a separate dropping funnel over 120 minutes while maintaining the temperature in the reaction vessel at 80 ± 2 ° C., and polymerization was performed.

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

The temperature in the reaction vessel was cooled to 40 ° C., and then deionized water was used so that the non-volatile content was 20% by mass, followed by filtration with a 200 mesh filter cloth to prepare primer 6.

[Preparation Example 7] Preparation of primer 7 for comparative example In a nitrogen-substituted container equipped with a thermometer, a nitrogen gas introduction tube, and a stirrer, ethylene glycol, 1,4-butanediol, isophthalic acid, terephthalic acid Polyester polyol S having an aromatic structure obtained by reacting (hydroxyl equivalent 840 g / equivalent) 64 parts by mass, 1,4-cyclohexanedimethanol 6 parts by mass, 2,2-dimethylolpropionic acid 7 parts by mass, and 47 parts by mass of dicyclohexylmethane diisocyanate was mixed with 80 parts by mass of methyl ethyl ketone, and reacted under conditions of a temperature of 80 ° C. in the reaction vessel to obtain an organic solvent solution of a urethane prepolymer having an isocyanate group at the terminal.

Next, after neutralizing a part or all of the carboxyl groups of the urethane prepolymer by mixing an organic solvent solution of the urethane prepolymer and 5 parts by mass of triethylamine, 264 parts by mass of water is further added and sufficient. The aqueous solution of urethane resin (L-3) having a nonvolatile content of 35% by mass and a pH of 8 is obtained by adding 7 parts by mass of a 20% by mass ethylenediamine aqueous solution and subjecting it to chain extension reaction. A comparative primer 7 comprising a liquid was obtained. The weight average molecular weight of the urethane resin (L-3) was 50,000.

After cooling the temperature in the reaction vessel to 40 ° C., using deionized water so that the non-volatile content becomes 20% by mass, and then filtering with a 200 mesh filter cloth, the primer 7 for comparative example is obtained. Prepared.

[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 in a nitrogen-substituted container equipped with a thermometer, a nitrogen gas introduction tube, and a stirrer, By reacting 17.6 parts by mass of 2-dimethylolpropionic acid, 21.7 parts by mass of 1,4-cyclohexanedimethanol, and 106.2 parts by mass of dicyclohexylmethane diisocyanate in 178 parts by mass of methyl ethyl ketone, isocyanate is terminated at the end. An organic solvent solution of a urethane prepolymer having a group was obtained.

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

Next, 8.8 parts by mass of a 25% by mass ethylenediamine aqueous solution is added to the aqueous dispersion, and the polyurethane prepolymer is chain-extended by stirring and subjected to aging and desolvation, whereby a solid content concentration of 30% by mass is obtained. An aqueous dispersion of urethane resin (L-4) was obtained. The urethane resin (L-4) obtained here had an acid value of 30 and a weight average molecular weight of 30,000.

A reaction vessel equipped with a stirrer, reflux condenser, nitrogen inlet tube, thermometer, dropping funnel for dropping the monomer mixture, dropping funnel for dropping the polymerization catalyst, 140 parts by mass of deionized water, and the urethane resin (L- 4) 333 parts by mass of the aqueous dispersion was added, and the temperature was raised to 80 ° C. while blowing nitrogen.

In a reaction vessel heated up to 80 ° C., a monomer mixture containing 100 parts by mass of ethyl acrylate and 20 parts by mass of an aqueous ammonium persulfate solution (non-volatile content 0.5% by mass) were stirred from a separate dropping funnel. While maintaining the temperature in the reaction vessel at 80 ± 2 ° C., polymerization was carried out dropwise over 120 minutes.

After the completion of dropping, the shell layer made of the urethane resin (L-4) and the core layer made of a vinyl polymer formed by polymerizing the monomer mixture by stirring for 60 minutes at the same temperature. An aqueous dispersion of urethane-acrylic composite resin constituted was obtained.

The temperature in the reaction vessel was cooled to 40 ° C., and then deionized water was used so that the non-volatile content was 20.0% by mass, followed by filtration with a 200 mesh filter cloth. 8 was prepared.

[Method for measuring ethanol absorption rate of coating film formed using primer]
The said ethanol absorption rate is a mass ratio of the ethanol which the said coating film absorbs with respect to the mass of the coating film obtained using the said primer.

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

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

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

Next, 30 seconds after the coating film was immersed in the ethanol, the coating film was taken out from the ethanol, and it was placed on a stack of three becots, on which three becots were stacked, Furthermore, it was left to stand for 10 seconds with a weight of 500 g placed thereon.

After 10 seconds, the mass of the coating film after the immersion was determined by measuring the mass of the coating film.

Next, the mass ratio obtained by dividing the mass of ethanol absorbed in the coating film after immersion by the mass of the coating film before immersion and multiplying by 100 was defined as the ethanol absorption rate.

[Preparation of fluid (a-1)]
By dispersing 30 parts by mass of silver particles having an average particle diameter of 30 nm in a mixed solvent consisting of 30 parts by mass of 1,3-butylene glycol, 37 parts by mass of ion-exchanged water and 3 parts by mass of glycerin, and filtering with a micropore filter, A fluid (a-1) which is a conductive ink was prepared.

[Preparation of fluid (a-2)]
By dispersing 30 parts by mass of silver particles having an average particle diameter of 30 nm in a mixed solvent consisting of 15 parts by mass of 1,3-butylene glycol, 40 parts by mass of ion-exchanged water, and 15 parts by mass of glycerin, and filtering through a micropore filter. Then, a fluid (a-2) which is a conductive ink was prepared.

[Preparation of fluid (a-3)]
By mixing and stirring 10 parts by mass of 1,3-butylene glycol, 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 size of 30 nm with a stirrer disperser, A fluid (a-3) was prepared.

[Preparation of fluid (a′-1)]
By dispersing 60 parts by mass of silver particles having an average particle diameter of 30 nm in a mixed solvent consisting of 37 parts by mass of ion-exchanged water and 3 parts by mass of glycerin and filtering with a micropore filter, a fluid (a ′ -1) was prepared.

Example 1 <Production of Conductive Pattern>
The primer 1 obtained above was placed on the entire surface of one side of a support made of a polyimide film (Kapton 200H manufactured by Toray DuPont Co., Ltd., thickness 50 μm) so that the thickness of the coating film after drying would be 3 μm. It was applied using a coater. Subsequently, the receiving base material (1) in which the coating film formed on the surface of the said support body was obtained by drying for 3 minutes at 70 degreeC using a hot air dryer.

The fluid (a-1) and the fluid (a-2) are applied to the surface of the coating film formed using the primer constituting the receiving substrate (1) obtained above, by an inkjet printer (Konica). Using a Minolta IJ Co., Ltd. inkjet testing machine EB100, evaluation printer head KM512L, discharge amount 42 pl), a rectangular area (area) of 3 cm in length and 1 cm in width was printed with a film thickness of 0.5 μm, respectively. Two types of conductive patterns were obtained by drying for 30 minutes at 120 ° C.

Further, on the surface of the coating film formed using the primer constituting the receiving substrate (1) obtained above, the fluid (a-3) is 3 cm long using a screen plate of a metal mesh 250. A conductive pattern was obtained by printing a rectangular range (area) 1 cm wide and printing at a film thickness of 1 μm and then drying at 120 ° C. for 30 minutes.

Example 2 <Production of Conductive Pattern>
Three types of conductive patterns were obtained in the same manner as in Example 1 except that primer 2 was used instead of primer 1. The primer layer constituting the conductive pattern and the coating film forming the primer layer had a crosslinked structure.

Example 3 <Production of Conductive Pattern>
Three types of conductive patterns were obtained in the same manner as in Example 1 except that primer 3 was used instead of primer 1.

Example 4 <Production of Conductive Pattern>
Three types of conductive patterns were obtained in the same manner as in Example 1 except that primer 4 was used instead of primer 1. The primer layer constituting the conductive pattern had a crosslinked structure formed after application of the fluid.

Example 5 <Production of Conductive Pattern>
Three types of conductive patterns were obtained in the same manner as in Example 1 except that primer 5 was used instead of primer 1. The primer layer constituting the conductive pattern had a crosslinked structure formed after application of the fluid.

Example 6 <Production of Conductive Pattern>
Three types of conductive patterns were obtained in the same manner as in Example 1 except that primer 6 was used instead of primer 1. The primer layer constituting the conductive pattern and the coating film forming the primer layer had a crosslinked structure.

Comparative Example 1 <Production of Conductive Pattern>
Three types of conductive patterns were obtained in the same manner as in Example 1 except that the primer 7 for comparative example was used instead of the primer 1.

Comparative Example 2 <Production of Conductive Pattern (2 ')>
Three types of conductive patterns were obtained in the same manner as in Example 1 except that the primer 8 for comparative example was used instead of the primer 1.

Comparative Example 3 <Production of Conductive Pattern>
One type of conductivity is obtained in the same manner as in Example 3 except that the fluid (a′-1) is used instead of the fluid (a-1) to the fluid (a-3). Got a pattern.

[Method for evaluating adhesion between primer layer and conductive layer]
A cellophane adhesive tape (manufactured by Nichiban Co., Ltd., CT405AP-24, 24 mm) was pressure-bonded to the surface of the conductive layer constituting the conductive pattern obtained by the above method, and then the cellophane adhesive tape was peeled off. The adhesive surface of the peeled cellophane adhesive tape was visually observed, and the adhesiveness was evaluated based on the presence or absence of the adhering matter.

On the adhesive surface of the peeled cellophane adhesive tape, “A” indicates that the conductive layer constituting the conductive pattern was not attached at all, and a small portion of the conductive layer was observed. “B” indicates that no disconnection occurs in the wire portion), and “C” indicates that the conductive layer in the range of about 30% to 50% of the entire conductive layer adheres to the adhesive surface and the disconnection occurs. “A conductive layer in a range of about 50% or more with respect to the entire area of the conductive layer adhered to the adhesive surface, and a disconnection was evaluated as“ D ”.

[Evaluation method of conductivity (resistance value)]
The volume resistivity of the surface of the layer made of a conductive material having a rectangular area of 3 cm in length and 1 cm in width formed on the surface of the conductive pattern obtained above was measured using a Loresta pointer meter (MCP-T610 manufactured by Mitsubishi Chemical Corporation). It measured using. What volume resistivity is less than 5 × ^{10 -6} Ω · cm "A", 5 × ^{10 -6} or 9 × ^{10 -6} Ω · less than cm "B what is sufficient available levels “C”, a level that is 9 × 10 ⁻⁶ or more and less than 5 × 10 ⁻⁵ Ω · cm and that can be used, and “C” that is 5 × 10 ⁻⁵ or more and less than 9 × 10 ⁻⁵ Ω · cm Was evaluated as “E” when it was “D”, 9 × 10 ⁻⁵ or more and difficult to use practically.

[Method for evaluating adhesion after electroless plating]
The conductive patterns obtained in Example 1 and Comparative Examples 1 to 3 were immersed in a catalyst bath (OPC-SALM / OPC-80 manufactured by Okuno Pharmaceutical Co., Ltd.) for 5 minutes and then washed with water.

Next, 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 then an electroless copper plating bath (Okuno Pharmaceutical Co., Ltd.) adjusted to 30 ° C. A plating layer having a thickness of 8 μm was formed by immersing in a company-made ATS ad-copper and washing with water.

Thereby, a plating structure made of a conductive pattern in which a plating film made of copper was formed on the surface on which the plating nucleus was carried was obtained.

After the cellophane adhesive tape (manufactured by Nichiban Co., Ltd., CT405AP-24, 24 mm) is pressure-bonded to the surface of the plating layer of the plating structure obtained above with the finger, the cellophane adhesive tape is applied to the surface of the plating structure. And peeled in the direction of 90 degrees. The adhesive surface of the peeled cellophane adhesive tape was visually observed, and the adhesiveness was evaluated based on the presence or absence of the adhering matter.

The adhesive surface of the peeled cellophane pressure-sensitive adhesive tape is “A” where no deposits are seen, and is supported by either the plating layer or the conductive layer in a range of less than about 5% of the adhesive tape application area. "B" peels off the body and adheres to the adhesive tape, and either the plating layer or the conductive layer peels off from the support within a range of about 5% to less than 50% of the adhesive tape application area. “C” indicates that the material adheres to the tape, and “D” indicates that either the plating layer or the conductive layer peels off from the support within a range of about 50% or more of the adhesive tape application area, and adheres to the adhesive tape. It was evaluated.

[Method for evaluating adhesion after electrolytic plating]
The surface (conductive layer) of the conductive pattern obtained in Example 1 and Comparative Examples 1 to 3 is set as a cathode, phosphorous copper is set as an anode, and current density is 2 A using an electroplating solution containing copper sulfate. By performing electroplating at / dm ² for 15 minutes, a copper plating layer having a thickness of 8 μm was laminated on the surface of the conductive layer. As the electroplating solution, copper sulfate 70 g / liter, sulfuric acid 200 g / liter, chloride ion 50 mg / liter, Top Lucina SF (brightener manufactured by Okuno Pharmaceutical Co., Ltd.) 5 g / liter was used.

By the above method, a plating structure in which a plating film made of copper was laminated on the surface of the plating film made of copper of the plating structure was obtained.

After the cellophane adhesive tape (manufactured by Nichiban Co., Ltd., CT405AP-24, 24 mm) is pressure-bonded to the plating film surface of the plating structure obtained above with a finger, the cellophane adhesive tape is applied to the surface of the plating structure. Peeled in the direction of 90 degrees. The adhesive surface of the peeled cellophane adhesive tape was visually observed, and the adhesiveness was evaluated based on the presence or absence of the adhering matter.

The adhesive surface of the peeled cellophane pressure-sensitive adhesive tape is “A” where no deposits are seen, and is supported by either the plating layer or the conductive layer in a range of less than about 5% of the adhesive tape application area. Either the plating layer or the conductive layer is peeled off from the support within the range of about 5% or more and less than 50% of the adhesive area of the “B” pressure-sensitive adhesive tape. “C” is attached to the adhesive, and “D” is attached to the adhesive tape when either the plating layer or the conductive layer is peeled off from the support in a range of about 50% or more of the adhesive tape sticking area. evaluated.

The conductive pattern described in Example 1 produced by printing on a receiving substrate provided with a primer layer having an ethanol absorption rate of 26% by mass using a fluid containing 1,3-butylene glycol is the primer layer Have good adhesion to the conductive layer and excellent conductivity.
The conductive pattern described in Example 2 produced by printing using a fluid containing 1,3-butylene glycol on a receiving substrate provided with a primer layer having an ethanol absorption rate of 28% by mass is the primer layer It was excellent in adhesion between the conductive layer and the conductive layer, and also excellent in conductivity.
The conductive patterns described in Examples 3 and 4 produced by printing using a fluid containing 1,3-butylene glycol on a receiving substrate having an ethanol absorption rate of 180% by mass and 174% by mass are primers It was particularly excellent in terms of adhesion between the layer and the conductive layer and conductivity.
The conductive patterns described in Examples 5 and 6 produced by printing using a fluid containing 1,3-butylene glycol on a receiving substrate having an ethanol absorption rate of 50% by mass and 21% by mass are the primers It was particularly excellent in terms of adhesion between the layer and the conductive layer, and the conductivity was also excellent.
On the other hand, the conductive pattern described in Comparative Example 1 produced by printing using a fluid containing 1,3-butylene glycol on a receiving substrate provided with a primer layer having an ethanol absorption rate of 1% by mass, In terms of adhesion between the primer layer and the conductive layer, it was not practically sufficient, and was insufficient in terms of conductivity.
The conductive pattern described in Comparative Example 2 produced by printing using a fluid containing 1,3-butylene glycol on a receiving substrate provided with a primer layer having an ethanol absorption rate of 550% by mass is the primer layer In terms of adhesion and conductivity between the conductive layer and the conductive layer, it was not practically sufficient.
The conductive material according to Comparative Example 3 produced by printing using a fluid (a′-1) containing no 1,3-butylene glycol on a receiving substrate provided with a primer layer having an ethanol absorption rate of 180% by mass. The nature pattern was not practically sufficient in terms of adhesion between the primer layer and the conductive layer and conductivity.

Claims (10)

1. A primer is applied to part or all of the surface of the support, and then the structure represented by the following general formula (I) is applied to part or all of the surface of the coating film (x) formed using the primer. A support obtained by applying a fluid (a) containing a polyhydric alcohol (a1) containing a diol (a1-1) and a conductive substance (a2) and then heating the coating, and the coating film (X) is a conductive pattern in which a primer layer (X) formed by heating and a layer (Y) containing the conductive substance (a2) are laminated, wherein the coating film (x) is A conductive pattern which absorbs 20% by mass to 500% by mass of ethanol in an environment of 25 ° C. with respect to the mass of the coating film (x).
   

   

   (R in the general formula (I) represents a hydrogen atom or an alkyl group.)
2. 30 seconds after the coating film (x) was immersed in ethanol under an environment of 25 ° C., the coating film (x) was 20% by mass with respect to the mass of the coating film (x) before immersion. The conductive pattern according to claim 1, which absorbs up to 500% by mass of ethanol.
3. The conductive pattern according to claim 1, wherein the diol (a1-1) represented by the general formula (I) is isoprene glycol or 1,3-butylene glycol.
4. The conductive pattern according to claim 1, wherein the diol (a1-1) is contained in the range of 10% by mass to 60% by mass with respect to the total amount of the fluid (a).
5. The coating film (x) is selected from the group consisting of a urethane resin having a polycarbonate structure, a urethane resin having an aliphatic polyester structure, a urethane-acrylic composite resin, and an acrylic resin having a structural unit derived from methyl methacrylate. The conductive pattern according to claim 1, wherein the conductive pattern is a layer containing at least one kind of resin (x-1).
6. The conductive pattern according to claim 1, wherein the primer layer (X) has a crosslinked structure.
7. The conductive pattern according to claim 6, wherein the crosslinkable functional group involved in the formation of the crosslinked structure is one or more thermally crosslinkable functional groups selected from the group consisting of a methylolamide group and an alkoxymethylamide group.
8. The electroconductive pattern of Claim 1 which has a plating layer (Z) further on the surface of the layer (Y) containing the said electroconductive substance.
9. A conductive circuit comprising the conductive pattern according to any one of claims 1 to 8.
10. By applying a primer to a part or all of the surface of the support and drying, 20 mass% or more ethanol in a 25 ° C. environment with respect to the mass of the coating film (x) formed using the primer. A coating film (x) that absorbs 500% by mass is formed, and then a diol (a1-1) having a structure represented by the following general formula (I) is applied to a part or all of the surface of the coating film (x). The support and the coating film (x) are heated, wherein the fluid (a) containing the polyhydric alcohol (a1) and the conductive substance (a2) is applied and then heated. The manufacturing method of the electroconductive pattern in which the primer layer (X) formed by this and the layer (Y) containing the said electroconductive substance (a2) were laminated | stacked.
    

    

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