KR101721966B1 - Laminate, electroconductive pattern, and electric circuit - Google Patents

Abstract

The present invention relates to a method for producing a polyimide resin which comprises a layer (I) comprising a support containing a specific polyimide resin, a resin layer (II) containing a fluid containing the conductive material (x) A conductive pattern (III), and a conductive pattern and an electric circuit. Since the laminate of the present invention has excellent adhesion between the layer made of the support and the resin layer containing the conductive material and can maintain excellent adhesion even when exposed under a high temperature environment, .

Description

LAMINATE, ELECTROCONDUCTIVE PATTERN, AND ELECTRIC CIRCUIT BACKGROUND OF THE INVENTION 1. Field of the Invention [0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a laminate such as an electromagnetic wave shield, a conductive pattern usable for manufacturing an integrated circuit, an organic transistor, and the like.

2. Description of the Related Art In recent years, there has been a strong demand for high density and thinness of electronic circuits and integrated circuits used for electronic devices with high performance, miniaturization and thinness.

Examples of the conductive pattern that can be used in the above electronic circuit include a conductive material layer formed by applying a conductive ink or a plating agent containing a conductive material such as silver to the surface of a support and firing to form a conductive material layer, There is known a conductive pattern in which a plating layer is provided on the surface of the conductive material layer by plating the surface of the layer (see, for example, Patent Document 1).

However, since the conductive pattern has insufficient adhesion between the support and the conductive material layer, the conductive material may be lost from the surface of the support over time, and the conductive pattern may be formed by the conductive material. (Increase of the resistance value) of the conductive layer.

As a method for improving the adhesion between the support and the conductive material, for example, a conductive ink is applied to an ink containing base material provided with a latex layer on the surface of the support, and a pattern is drawn by a predetermined method, (See Patent Document 2).

However, since the conductive pattern obtained by the above method may still not be sufficient in terms of adhesion between the support and the ink receiving layer, the ink receiving layer and the conductive material may be separated from the surface of the support over time Resulting in disconnection of the conductive pattern formed by the conductive material and deterioration of the conductivity.

In addition, the peeling of the ink receiving layer from the surface of the support is not sufficient in terms of isothermal resistance which occurs when the substrate is heated to, for example, about 100 ° C to 200 ° C in the plating process or the like. The plating treatment can not be carried out for the purpose of improving the strength and the like.

Patent Document 1: JP-A-2005-286158 Patent Document 2: JP-A-2009-49124

A problem to be solved by the present invention is to provide a resin composition which is excellent in adhesion between a layer composed of a support and a resin layer containing a conductive material and has a heat resistance at a level capable of maintaining excellent adhesion even when exposed under a high temperature environment And a conductive pattern provided with a conductive pattern.

The inventors of the present invention have conducted studies to examine the above problems, and as a result, they have found that the above problems can be solved by using a specific support.

That is, the present invention relates to a polyimide resin composition comprising a polyimide resin (i-1) having a structure represented by the following general formula (1) and a polyimide resin (i-2) (I) comprising a support (I1) or a support (I2) containing a polyimide resin (i-3) having a structure represented by the following formula (1) and a structure represented by the following formula , A resin layer (II) containing a fluid containing the conductive material (x), and a conductive layer (III) formed of the conductive material (x) Circuit.

[R ¹ to R ⁸ in the general formula (1) each independently represent a hydrogen atom, a halogen atom or an organic group. and n represents an integer of 1 to 1,000.

[R ⁹ to R ²² in the general formula (2) each independently represent a hydrogen atom, a halogen atom or an organic group. and m represents an integer of 1 to 1,000.

The laminate of the present invention can maintain excellent adhesiveness even when exposed under a high temperature environment, and as a result, can maintain excellent conductivity without causing disconnection or the like. Therefore, for example, formation of a conductive pattern or an electronic circuit, Such as the formation of layers or peripheral wirings constituting RFID such as a battery, an electronic book terminal, an organic EL, an organic transistor, a flexible printed board, a noncontact IC card and the like, wiring of an electromagnetic wave shield of a plasma display, And can be used in a new field generally referred to as the field of printed electronics.

The laminate of the present invention comprises a polyimide resin (i-1) having a structure represented by the following general formula (1) and a polyimide resin (i-2) having a structure represented by the following general formula (2) (I2) containing a polyimide resin (i-3) having a structure represented by the following general formula (1) and a structure represented by the following general formula (2) And a conductive layer (III) formed of the conductive material (x), wherein the conductive layer (I) comprises a conductive material (x) It can be suitably used for a pattern or an electric circuit.

[R ¹ to R ⁸ in the general formula (1) each independently represent a hydrogen atom, a halogen atom or an organic group. and n represents an integer of 1 to 1,000.

[R ⁹ to R ²² in the general formula (2) each independently represent a hydrogen atom, a halogen atom or an organic group. and m represents an integer of 1 to 1,000.

First, the layer (I) constituting the laminate of the present invention will be described.

The layer (I) constituting the laminate of the present invention is a layer constituted by the support (I1) or the support (I2) for supporting the laminate.

As the support, a support containing a polyimide resin (i-1) having a structure represented by the following general formula (1) and a polyimide resin (i-2) having a structure represented by the following general formula (2) Or a support (I2) containing a polyimide resin (i-3) having a structure represented by the following general formula (1) and a structure represented by the following general formula (2) is used.

[R ¹ to R ⁸ in the general formula (1) each independently represent a hydrogen atom, a halogen atom or an organic group. and n represents an integer of 1 to 1,000.

[R ⁹ to R ²² in the general formula (2) each independently represent a hydrogen atom, a halogen atom or an organic group. and m represents an integer of 1 to 1,000.

The support (I1) contains the polyimide resin (i-1) and the polyimide resin (i-2).

The polyimide resin (i-1) has a structure represented by the general formula (1).

R ¹ to R ⁸ in the general formula (1) are each independently a hydrogen atom, a hydroxyl group, a halogen atom or an organic group. Specific examples of the organic group include an alkyl group and an aryl group. The above R ¹ to R ⁸ are preferably hydrogen atoms since they give excellent adhesion and heat resistance and can be obtained at relatively low cost.

M in the general formula (1) is preferably an integer of 1 to 1,000, more preferably an integer of 3 to 500, still more preferably an integer of 50 to 500, particularly preferably an integer of 100 to 500.

As the polyimide resin (i-1), it is preferable that the molecular terminal structure is an amino group.

The polyimide resin (i-1) can be produced, for example, by reacting a polyamine containing 4,4'-oxydianiline and the like with a tetracarboxylic acid dihydrate containing anhydrous pyromellitic acid to prepare a polyamic acid , Followed by mixing with a catalyst or the like, if necessary, followed by heating or the like.

The reaction of the polyamine and the tetracarboxylic acid dihydrate can be carried out by a conventionally known method.

In producing the polyimide resin (i-1), a polyamine other than 4,4'-oxydianiline or a tetracarboxylic acid dihydrate other than anhydrous pyromellitic acid may be used in combination, but the polyimide resin (i-1) ), It is preferable to use 4,4'-oxydianiline and anhydrous pyromellitic acid in a total amount of 95 mass% to 100 mass% with respect to the total amount of raw materials used in the production of

As a method for producing the polyimide resin (i-1) using the polyamic acid obtained above, a method of heating may be mentioned.

The heating can be performed preferably at 150 ° C or higher, more preferably 200 ° C to 300 ° C.

Specific examples of the method for producing the polyimide resin (i-1) include the methods described in JOURNAL OF POLYMER SCIENCE: PART A-2 VOL.6, 953-960 (1968).

The polyimide resin (i-2) constituting the support (I1) has a structure represented by the general formula (2).

R ⁹ to R ²² in the general formula (2) are each independently a hydrogen atom, a hydroxyl group, a halogen atom or an organic group. Specific examples of the organic group include an alkyl group and an aryl group. It is preferable that R ⁹ to R ²² are hydrogen atoms in order to give good adhesion.

N in the general formula (2) is preferably an integer of 1 to 1,000, more preferably an integer of 3 to 500, still more preferably an integer of 50 to 500, and particularly preferably an integer of 100 to 500.

As the polyimide resin (i-2), it is preferable that the molecular terminal structure is an amino group.

The polyimide resin (i-2) can be produced, for example, by reacting a polyamine containing 4,4'-oxydianiline or the like with a tetra (meth) acrylate containing biphenyl 3,4,3 ', 4'-tetracarboxylic acid dihydrate By reacting a carboxylic acid dihydrate to prepare a polyamic acid, and then, if necessary, mixing with a catalyst or the like, followed by heating or the like.

The reaction of the polyamine and the tetracarboxylic acid dihydrate can be carried out by a conventionally known method.

In the production of the polyimide resin (i-2), a polyamine other than 4,4'-oxydianiline or a tetracarboxylic acid dihydrate other than biphenyl 3,4,3 ', 4'-tetracarboxylic acid dihydrate However, it is preferable to use 4,4'-oxydianiline and biphenyl 3,4,3 ', 4'-tetracarboxylic acid dihydrate as the starting materials for the polyimide resin (i-2) It is preferably used in a total amount of 95 mass% to 100 mass%.

As a method for producing the polyimide resin (i-2) using the polyamic acid thus obtained, a method of heating may be mentioned.

The heating can be performed preferably at 150 ° C or higher, more preferably 200 ° C to 300 ° C.

Specific examples of the method for producing the polyimide resin (i-2) include the methods described in JOURNAL OF POLYMER SCIENCE: PART A-2 VOL.6, 953-960 (1968).

As the support (I1) constituting the layer (I), the polyimide resin (i-1) and the polyimide resin (i-2) (i-2)] = 5 to 95, is preferably used.

The support (I2) constituting the layer (I) of the layered product of the present invention may be a polyimide resin having a combination of a structure represented by the following formula (1) and a structure represented by the following formula (2) i-3) may be used.

Examples of the polyimide resin (i-3) include 4,4'-oxydianiline and the like, which are exemplified as usable for the production of the polyimide resin (i-1) and the polyimide resin (i-2) And a tetracarboxylic acid dihydrate containing anhydride pyromellitic acid or biphenyl 3,4,3 ', 4'-tetracarboxylic acid dihydrate is reacted with a polyamic acid to prepare a polyamic acid, Mixing, heating, and the like.

The reaction of the polyamine and the tetracarboxylic acid dihydrate can be carried out by a conventionally known method.

In the production of the polyimide resin (i-3), polyamines other than 4,4'-oxydianiline, pyromellitic anhydride and biphenyl 3,4,3 ', 4'-tetracarboxylic acid dihydrate Tetracarboxylic acid dihydrate may be used in combination. However, it is preferable to use tetracarboxylic dihydrate and biphenyl 3,4,3 ', 4'-tetracarboxylic acid dihydrate (i-3) relative to the total amount of raw materials used for the production of the polyimide resin In a total amount of 95 mass% to 100 mass%.

As a method for producing the polyimide resin (i-3) using the polyamic acid obtained above, a method of heating may be mentioned.

The heating can be performed preferably at 150 ° C or higher, more preferably 200 ° C to 300 ° C.

As the support (I1) and the support (I2), various additives may be added as necessary in addition to the polyimide resin (i-1), the polyimide resin (i-2) and the polyimide resin (i- May be used.

The use of an inorganic filler such as silica or calcium phosphate improves the ease of conveyance of the support I1 made of a polyimide film and the support I2, Or to prevent blocking of the support (I2).

The inorganic filler is preferably used in a range of 0.5% by mass to 30% by mass with respect to the mass of the support (I1) or the support (I2) in order to enhance the smoothness of the surface of the support. The average particle diameter of the inorganic filler is preferably 0.01 탆 to 5 탆, more preferably 0.01 탆 to 0.5 탆. The average particle diameter refers to a value measured by a laser diffraction scattering type particle size distribution meter.

Examples of the method for producing the support (I1) include a method in which a polyamic acid which is a precursor of the polyimide resin (i-1), a polyamic acid which is a precursor of the polyimide resin (i-2) A method in which a mixture obtained by mixing a solution obtained by mixing a solvent and an additive such as an inorganic filler as necessary is filtered or defoamed if necessary and then molded into a film or a sheet and heated.

As a method for producing the support (I2), a solution obtained by mixing a polyamic acid which is a precursor of the polyimide resin (i-3) and a solvent if necessary, and, if necessary, additives such as the inorganic filler And then, if necessary, filtering or degassing the mixture, forming the mixture into a film or sheet, and heating the mixture.

Examples of the molding method include a method of extruding the mixture into a drum shape using a T-die or the like to make it flexible.

After the above-mentioned softening, the film or sheet-like molded article can be obtained by removing the solvent by heating at a temperature of, for example, 80 to 150 DEG C for 30 seconds to 90 seconds.

By heating the molded article at a temperature of, for example, 200 DEG C to 450 DEG C for 30 seconds to 200 seconds, a support containing a polyimide resin can be produced.

The layer (I) comprising the support (I1) or the support (I2) obtained by the above method preferably has a thickness of about 1 탆 to 5,000 탆 and more preferably about 1 탆 to 300 탆. When a relatively flexible laminate is required, it is preferable to use a laminate having a thickness of about 1 mu m to 200 mu m.

Next, the resin layer (II) constituting the laminate of the present invention will be described.

The resin layer (II) is a layer which can accommodate a fluid containing a conductive substance (x) forming a conductive layer (III) described below. The resin layer (II) quickly absorbs the solvent contained in the fluid when the fluid contacts, and also carries the conductive substance (x) on the surface of the resin layer (II). This makes it possible to remarkably improve the adhesion and heat resistance between the layer (I) comprising the support (I1) or the support (I2) and the resin layer (II) and the conductive layer (III) composed of the conductive material .

The resin layer (II) may be provided on a part or all of the surface of the layer (I) comprising the support (I1) or the support (I2), or may be provided on one side or both sides thereof. For example, as the laminate, it is preferable that the resin layer (II) is provided on the entire surface of the layer (I) comprising the support (I1) or the support (I2) And a conductive layer (III) can be used. A laminate in which the resin layer (II) is provided only on the surface of the layer (I) comprising the support (I1) or the support (I2) where the conductive layer (III) is provided can also be used.

The resin layer (II) differs depending on the intended use of the laminate of the present invention, but is usually preferably in the range of 10 nm to 1000 μm. The adhesion between the layer (I) composed of the support (I1) or the support (I2) and the conductive layer (III) can be further improved and the thickness of the resin layer (II) is preferably 10 nm to 300 nm More preferably in the range of 10 nm to 100 nm.

Examples of the resin layer (II) include a composite resin (II-1), a melamine resin (II-2), a urethane resin, a vinyl resin, an epoxy resin, an imide resin, an amide resin, A resin layer formed by using a resin, polyvinyl alcohol, polyvinylpyrrolidone or the like can be used. Among them, a layer formed using a composite resin (II-1) or a melamine resin (II-2) composed of a urethane resin and an acrylic resin is preferable for producing a laminate having excellent adhesion and heat resistance .

Next, the conductive layer (III) constituting the laminate of the present invention will be described.

The conductive layer (III) is a layer composed of a conductive material (x) contained in a fluid such as a conductive ink or a plating nucleating agent. The conductive layer (III), for example, corresponds to a layer constituted of the silver contained in the plating nucleating agent when a plating nucleating agent containing silver is used as the fluid, and the printing It is equivalent to pattern or pattern.

The conductive layer (III) is preferably composed of the conductive material (x), and it is preferable that the conductive layer (III) is made of silver. The conductive layer (III) is mainly composed of the conductive material as described above, but a solvent or an additive contained in the fluid may remain in the conductive layer (III).

The conductive layer (III) may be provided on part or all of the surface of the resin layer (II). For example, as the above-mentioned laminate, the conductive layer (III) may be provided only on a necessary portion of the surface of the resin layer (II). Specifically, as the conductive layer (III) provided only in a necessary portion of the surface of the resin layer (II), a linear layer formed by line drawing is exemplified. The layered product having a linear layer as the conductive layer (III) is favorable when a conductive pattern, an electric circuit or the like is produced.

It is preferable that the width (line width) of the above-mentioned line-like layer is about 0.01 mu m to 200 mu m, preferably about 0.01 mu m to 150 mu m, in order to achieve high density of the conductive pattern.

As the conductive layer (III) constituting the laminate of the present invention, those having a thickness in the range of 10 nm to 10 μm can be used. The thickness of the conductive layer (III) can be adjusted by controlling the application amount of a fluid containing the conductive substance (x) and the like usable for forming the conductive layer (III). When the conductive layer (III) is of fine wire shape, its thickness (height) is preferably in the range of 10 nm to 1 탆.

It is preferable that the surface of the conductive layer (III) is formed so that part or all of the surface of the conductive layer (III) is oxidized to improve the adhesion with the plating layer (IV) desirable.

Here, the oxidation refers to the fact that the conductive substance (x) contained in the conductive layer (III) forms an oxide by binding with oxygen, and includes the case where the valence of the conductive substance (x) increases .

Therefore, as the oxidized surface of the conductive layer (III), for example, when silver is used as the conductive substance (x) contained in the conductive layer (III), the surface containing silver oxide, And the surface is made of a material whose valence increases from 0 to +1.

The surface of the conductive layer (III) that is in contact with the plating layer (IV) may be oxidized, but the conductive material contained in the conductive layer (III) may be entirely oxidized together with the surface.

The oxidized surface of the conductive layer (III) preferably has a resistance value in the range of 0.1 Ω / □ to 50 Ω / □ and is in the range of 0.2 Ω / □ to 30 Ω / □. And the like.

The laminate of the present invention may have a plating layer (IV), if necessary, in addition to the layer (I), the resin layer (II) and the conductive layer (III).

The plating layer (IV) is provided for the purpose of forming a highly reliable wiring pattern capable of maintaining good conductivity without causing disconnection or the like for a long period of time, for example, when the laminate is used for a conductive pattern or the like Lt; / RTI >

The plating layer (IV) is preferably a layer made of a metal such as copper, nickel, chromium, cobalt or tin, and more preferably a plated layer made of copper.

The plating layer (IV) may have a thickness in the range of 1 탆 to 50 탆. The thickness of the plating layer (IV) can be adjusted by controlling the processing time, the current density, the amount of the plating additive used, and the like in the plating process at the time of forming the plating layer (IV).

Next, a method of manufacturing the laminate of the present invention will be described.

The laminate of the present invention can be obtained by, for example, applying and drying a resin composition (R) to a part or all of the surface of the support (I1) or the support (I2) constituting the layer (I) (II), and then applying and firing a fluid containing a conductive material (x) on a part or the whole of the surface of the resin layer (II) to form the conductive layer (III) . In the case of providing the plating layer (IV), a laminate including the plating layer (IV) can be produced by plating a part or all of the surface of the conductive layer (III).

As a method for forming the resin layer (II) on a part or the whole of the surface of the support (I1) or the support (I2), the resin composition (R) is preferably applied to the surface of the support (I1) Or the like, and removing the solvent such as an aqueous medium or an organic solvent contained in the resin composition (R).

Examples of the method of applying the resin composition (R) to the surface of the support (I1) or the support (I2) include a gravure coating method, a coating method, a screen method, a roller method, a rotary method, .

The surface of the support (I1) or the support (I2) to which the resin composition (R) is applied may be subjected to a surface treatment such as a plasma treatment method such as a corona discharge treatment method or a dry treatment method such as an ultraviolet ray treatment method, Or may be surface-treated by a wet treatment method using an organic solvent or the like.

As a method for applying the resin composition (R) to the surface of the support (I1) or the support (I2) and then removing the solvent contained in the coating layer, it is dried using, for example, a drier, Is generally volatilized. The drying temperature may be set to a temperature which can volatilize the solvent and does not adversely affect the support (I1) or the support (I2).

The amount of the resin composition (R) applied on the support (I1) or the support (I2) is preferably 0.01 g / m < 2 > to the area of the support (I1) or the support (I2) M < 2 > to 60 g / m < 2 >, and from 0.1 g / m < 2 > to 10 g / m < 2 >

As the resin composition (R) usable in the production of the resin layer (II), a resin containing various resins and a solvent may be used.

Examples of the resin include a composite resin (II-1) composed of a urethane resin and an acrylic resin, a melamine resin (II-2), a urethane resin, an acrylic resin, an epoxy resin, an imide resin, Resin, polyvinyl alcohol, polyvinyl pyrrolidone, and the like can be used.

As the resin, it is preferable to use a composite resin (II-1) or a melamine resin (II-2) composed of a urethane resin and an acrylic resin, (I) and the conductive layer (III).

As the resin composition (R), it is preferable to use the resin composition (R) containing 10% by mass to 70% by mass of the resin for the entire resin composition (R) More preferably 50 mass% or less.

As the solvent usable in the resin composition (R), 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 that are miscible with water, and mixtures thereof.

Examples of the organic solvent to be mixed with water include alcohols such as methanol, ethanol, n- and isopropanol, ethyl carbitol, ethyl cellosolve and butyl cellosolve; Ketones such as acetone and methyl ethyl ketone; Polyalkylene glycols such as ethylene glycol, diethylene glycol and propylene glycol; Alkyl ethers of polyalkylene glycols; N-methyl-2-pyrrolidone and the like.

As the resin used for the resin composition (R), it is preferable to use a resin having a hydrophilic group from the viewpoint of further improving the adhesion to the various supports (I1) or (I2). Examples of the hydrophilic group include anionic groups such as carboxylate groups and sulfonate groups formed by neutralization with a basic compound or the like in part or whole, cationic groups and nonionic groups, and preferably anionic groups.

The resin may have a crosslinkable functional group such as an alkoxysilyl group, a silanol group, a hydroxyl group, an amino group, a methylol group, a methylol amide group, an alkoxymethyl amide group and a methylol amino group, if necessary. Therefore, the resin layer (II) may have already formed a crosslinked structure before the fluid is applied, or after the fluid has been applied, for example, by heating in a firing step or the like, .

Examples of the composite resin (II-1) usable in the resin composition (R) include those in which the urethane resin and the acrylic resin form composite resin particles and can be dispersed in an aqueous medium.

Specifically, the composite resin particle may be one in which a part or all of the acrylic resin is contained in the resin particle formed by the urethane resin. At this time, the acrylic resin may be dispersed in a plurality of particles in the urethane resin particle, and the core-shell type composite resin particle composed of the acrylic resin as the core layer and the urethane resin having the hydrophilic group as the shell layer . Particularly, when forming the conductive pattern, it is preferable to use the above-mentioned core-shell type composite resin particles in which it is not necessary to use a surfactant capable of lowering the above characteristics. As the composite resin particle, it is preferable that the acrylic resin is almost completely covered with the urethane resin. However, it is not essential, and a part of the acrylic resin is contained in the composite resin Or may be present at the outermost part of the particle. The urethane resin and the acrylic resin may form a covalent bond, but preferably do not form a bond.

The composite resin particle is preferably 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 referred to herein refers to an average particle diameter on a volume basis measured by a dynamic light scattering method, which is also described in the following Examples.

As the composite resin (II-1), it is preferable that the urethane resin and the acrylic resin contain [urethane resin / acrylic resin] in the range of 90/10 to 10/90, preferably 70/30 to 10/90 More preferably in the range

As the urethane resin usable in the production of the composite resin (II-1), there can be used those obtained by reacting various polyols and polyisocyanates and, if necessary, chain extenders and the like.

As the polyol, for example, a polyether polyol, a polyester polyol, a polyester ether polyol, a polycarbonate polyol and the like can be used.

Examples of the polyester polyols include aliphatic polyester polyols obtained by esterifying a low molecular weight polyol and polycarboxylic acid, aromatic polyester polyols, polyester obtained by ring-opening polymerization reaction of cyclic ester compounds such as? -Caprolactone , And copolyesters of these may be used.

As the low molecular weight polyol, for example, ethylene glycol, propylene glycol, 1,6-hexanediol, neopentyl glycol and the like can be used.

Examples of the polycarboxylic acid include aliphatic polycarboxylic acids such as succinic acid, adipic acid, sebacic acid and dodecanedicarboxylic acid; aromatic polycarboxylic acids such as terephthalic acid, isophthalic acid and phthalic acid; and anhydrides or ester- Derivatives and the like can be used.

As the polyether polyol, for example, one obtained by subjecting one or more compounds having two or more active hydrogen atoms as an initiator to addition polymerization of an alkylene oxide may 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, etc., and bisphenol A, bisphenol F, bisphenol B, and bisphenol AD.

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

As the polyester ether polyol, there can be used, for example, a polyether polyol to which the alkylene oxide is added as the initiator and a polycarboxylic acid reacted with the polyether polyol. As the initiator and the alkylene oxide, those exemplified as those which can be used in the production of the polyether polyol may be used. As the polycarboxylic acid, the same ones as those which can be used in the production of the polyester polyol can be used.

As the polycarbonate polyol, for example, those obtained by reacting a carbonic ester with a polyol, or those obtained by reacting phosgene with bisphenol A or the like can be used.

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

Examples of the polyol which can be reacted with the carbonic ester include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, dipropylene glycol, Butanediol, 1,5-pentanediol, 1,5-hexanediol, 2,5-hexanediol, 1,6-hexanediol, 1,7- Heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, Ethyl-1,3-hexanediol, 2-methyl-1,3-propanediol, 2-methyl-1,8-octanediol, Cyclohexanediol, 1,4-cyclohexanedimethanol, hydroquinone, resorcin, bisphenol-A, bisphenol-F, and 4,4'-biphenol A low molecular weight dihydroxy compound, a polyol such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol Thermal or polyol, polyhexamethylene adipate can be used sulfates, polyhexamethylene succinate, polyester polyol such as polycaprolactone and the like.

As the polyol, from the viewpoint of introducing a hydrophilic group into the urethane resin, there may be mentioned, for example, 2,2'-dimethylolpropionic acid, 2,2'-dimethylolbutanoic acid, 2,2'- Sulfoisophthalic acid, phosiphthalic acid, sulfoterephthalic acid, 4-sulfophthalic acid, and 5 [4-sulfophenoxy] isophthalic acid.

Examples of the polyisocyanate include aromatic polyisocyanates such as 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate and tolylene diisocyanate, and aromatic polyisocyanates such as hexamethylene diisocyanate, cyclohexane diisocyanate, Aliphatic polyisocyanates such as diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, xylylene diisocyanate and tetramethyl xylylene diisocyanate, and polyisocyanates containing aliphatic cyclic structure can be used. Among them, it is preferable to use a polyisocyanate containing an aliphatic cyclic structure.

As the above-described make-up agent, for example, ethylenediamine, piperazine, isophoronediamine and the like known in the art can be used.

As the acrylic resin usable for the production of the composite resin (II-1), those obtained by polymerizing various (meth) acrylic monomers including methyl (meth) acrylate can be used.

Examples of the (meth) acrylic monomers include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, (Meth) acrylic acid alkyl esters such as 2-ethylhexyl (meth) acrylate, hexyl (meth) acrylate and cyclohexyl (meth) acrylate.

Among the above-mentioned, methyl methacrylate has a tendency to cause a thin line composed of a width of about 0.01 to 200 mu m, preferably about 0.01 to 150 mu m, which is required when forming a conductive pattern such as an electronic circuit, It is preferable to use it in order to enable printing (improvement in thin line) without printing.

In addition, it is preferable to use (meth) acrylic acid alkyl ester having an alkyl group of 2 to 12 carbon atoms together with the methyl methacrylate, and to use an alkyl acrylate having an alkyl group of 3 to 8 carbon atoms , And it is more preferable to use n-butyl acrylate in order to obtain a printed matter having excellent printability. In addition, even when a conductive ink is used, it is particularly preferable to form a conductive pattern having no smearing and excellent in thinning property.

As the (meth) acrylic monomer, it is preferable to introduce the crosslinkable functional group such as one or more amide groups selected from the group consisting of a methylol amide group and an alkoxymethyl amide group into the acrylic resin to further improve adhesion and the like (Meth) acrylic monomer containing a crosslinkable functional group can be used for the purpose of the present invention.

As the (meth) acrylic monomer having a crosslinkable functional group, it is preferable to use Nn-butoxymethyl (meth) acrylamide or N-isobutoxymethyl (meth) acrylamide as a layered product such as a conductive pattern excellent in thin- .

The composite resin (II-1) can be obtained by, for example, a step of reacting the above-mentioned polyol and polyisocyanate and, optionally, a chain extender to cause water oxidation to produce an urethane resin aqueous dispersion, And then polymerizing the (meth) acrylic monomer to prepare an acrylic resin.

Specifically, a urethane resin is obtained by reacting the polyisocyanate with a polyol under a solventless or organic solvent or in the presence of a reactive diluent such as a (meth) acrylic monomer, and then a part of the hydrophilic group of the urethane resin or The whole is neutralized with a basic compound or the like as occasion demands, and if necessary, is further reacted with a chain extender and dispersed in an aqueous medium to prepare an urethane resin aqueous dispersion.

Next, the (meth) acrylic monomer is supplied into the urethane resin aqueous dispersion obtained as described above, and the (meth) acrylic monomer is subjected to radical polymerization in the urethane resin particle to prepare an acrylic resin. When the urethane resin is produced in the presence of a (meth) acrylic monomer, an acrylic resin is prepared by radical polymerization of the (meth) acrylic monomer by supplying a polymerization initiator or the like after the production of the urethane resin .

Thereby, the resin composition (R) in which the composite resin particles in which a part or the whole of the acrylic resin is contained in the urethane resin particles is dispersed in an aqueous medium can be produced.

As the resin composition (R), those containing a urethane resin can be used.

As the urethane resin, for example, a urethane resin having a polyether structure or a urethane resin having a polycarbonate structure or a urethane resin having a polyester structure can be used.

These urethane resins can be produced by reacting a polyol such as the one described in the description of the composite resin (II-1) or a conventionally known polycarbonate polyol with a polyisocyanate or a chain extender, Resin can be used. At this time, a urethane resin having the desired structure can be prepared by appropriately selecting the polyether polyol, the conventionally known polycarbonate polyol, aliphatic polyester polyol, or the like as the polyol.

Examples of the vinyl resin which can be used for the resin composition (R) include a vinyl resin obtained by radical polymerization of a (meth) acrylic monomer described in the description of the composite resin (II-1) or a vinyl monomer containing styrene or the like Can be used.

As the resin composition (R) usable for the formation of the resin layer (II), it is preferable to use a composition containing a melamine resin (II-2) in order to produce a laminate having excellent adhesion and heat resistance Do.

As the melamine resin (II-2), for example, a methylol compound or an alkoxide compound obtained by reacting an amino compound having a triazine ring such as melamine or benzoguanamine with formaldehyde can be used.

As the methylolide, for example, methoxymethylolmelamine resin, butylated methylolmelamine resin and the like can be used.

Examples of the alkoxides include those in which a part or all of the methylol group in the methylolide is encapsulated with a monoalcohol or the like. For example, an alkoxylated melamine resin such as methoxymethylol melamine resin, .

The alkoxylated melamine resin may be reacted by charging the amino compound having the triazine ring, such as melamine or benzoguanamine, with the formaldehyde and the monoalcohol in a lump, and reacting the amino compound having the triazine ring in advance , The formaldehyde may be reacted to obtain a methylolated melamine compound, and then the monohydric alcohol may be reacted.

As the alkoxylated melamine resin, betamycin M-3 manufactured by DIC Corporation may be used.

The number average molecular weight of the melamine resin (II-2) is preferably 100 to 10,000, more preferably 300 to 2,000.

The resin composition (R) may contain, if necessary, a known additive such as a pH adjuster, a film forming aid, a leveling agent, a thickener, a water repellent agent, and a defoaming agent as well as a crosslinking agent.

The cross-linking agent may be a resin layer (II) which has already formed a cross-linking structure before the fluid is applied, or a cross-linking structure after heating, for example, in a firing step after the fluid has been applied (II) can be formed.

Examples of the crosslinking agent include a heat crosslinking agent capable of forming a crosslinking structure at a relatively low temperature of less than 25 ° C to 100 ° C such as a metal chelate compound, a polyamine compound, an aziridine compound, a metal salt compound, an isocyanate compound, At least one kind selected from the group consisting of a melamine compound, an epoxy compound, an oxazoline compound, a carbodiimide compound, and a block isocyanate compound and the like, which can form a crosslinked structure at a relatively high temperature of 100 DEG C or higher Various photo-crosslinking agents can be used.

The crosslinking agent varies depending on the type and the like, but is preferably used in a range of 0.01% by mass to 60% by mass relative to 100% by mass of the total mass of the resin contained in the primer, more preferably in a range of 0.1% by mass to 10% , And more preferably 0.1% by mass to 5% by mass, because it is possible to form a conductive pattern having excellent adhesion and conductivity and excellent durability.

As described above, by applying the resin composition (R) to part or all of the surface of the support (I1) or the support (I2) by the above-mentioned method, the resin layer (II) ) Can be obtained.

Next, a method of forming the conductive layer (III) by applying and firing a fluid containing a conductive material (x) on a part or the whole of the surface of the resin layer (II) will be described.

Examples of the method of applying the fluid on the surface of the resin layer (II) include inkjet printing, reversal printing, screen printing, offset printing, spin coating, spray coating, A coating method, a slit coating method, a roll coating method, and a dip coating method.

Among them, in the case of forming the conductive layer (III) in fine lines of about 0.01 탆 to about 100 탆 required for realizing high density of an electronic circuit or the like by using the above-mentioned fluid, inkjet printing, It is preferable to apply the above-mentioned fluid.

As the inkjet printing method, an inkjet printer can be generally used. Concretely, there are listed Konica Minolta EB100, XY100 (manufactured by Konica Minolta IJ Kogyo Co., Ltd.), Dymatic Material Printer DMP-3000, Dymatic Material Printer DMP-2831 (manufactured by Fuji Film Co., Ltd.) .

As the reversal printing method, there are known known methods such as a convex plate reverse printing method and a concave plate reversal printing method. For example, the liquid is applied to the surface of various blanket, the plate is brought into contact with the plate projecting from the non- The pattern is formed on the surface of the blanket or the like by selectively transferring the corresponding fluid to the surface of the plate, and then the pattern is transferred to the layer (I) comprising the support (I1) or the support (I2) To the surface of the resin layer (II) or the surface of the resin layer (II).

The firing performed after the fluid is applied by the above method is carried out for the purpose of forming the conductive layer (II) by adhering and bonding conductive substances (x) such as metals contained in the fluid. The firing is preferably performed at a temperature in the range of 80 ° C to 300 ° C for about 2 minutes to 200 minutes. The firing may be performed in the atmosphere, but a part or all of the firing step may be performed in a reducing atmosphere from the viewpoint of preventing oxidation of the metal.

The firing step may be carried out using, for example, an oven, a hot air drying furnace, an infrared drying furnace, laser irradiation, photo sintering (photopolymerization), optical pulse irradiation, microwave or the like.

As the fluid used for forming the conductive layer (III), those containing the conductive material (x) and, if necessary, a solvent or an additive, can be used generally as conductive inks or plating nucleating agents.

As the conductive material (x), a transition metal or a compound thereof may be used. Among them, it is preferable to use an ionic transition metal. For example, a transition metal such as copper, silver, gold, nickel, palladium, platinum or cobalt is preferably used. Is more preferable because it can form a conductive pattern which is low in electric resistance and resistant to corrosion, and it is more preferable to use silver.

When the above-mentioned fluid is used for the plating nucleating agent, the above-mentioned conductive material (x) may be one kind of metal particles composed of the transition metal as described above, those coated with an oxide of the transition metal or an organic substance, Or more.

The oxide of the transition metal is usually in an inert (insulated) state. However, by treating the oxide with a reducing agent such as dimethylaminoborane, the metal can be exposed to impart activity (conductivity).

Examples of the metal surface-coated with the organic material include metal particles embedded in resin particles (organic material) formed by the emulsion polymerization method or the like. These are normally in an inert (insulated) state. However, by removing the organic substances by using a laser or the like, for example, it becomes possible to expose the metal to impart the activity (conductivity).

As the conductive material (x), it is preferable to use a particulate material having an average particle size of about 1 nm to 100 nm, and it is preferable that the material having an average particle size of 1 nm to 50 nm is a conductive material having an average particle size of micrometer order x is used, a fine conductive pattern can be formed, and the resistance value after firing can be further reduced, which is more preferable. The " average particle size " is a volume average value measured by dynamic light scattering method in which the conductive substance (x) is diluted with a positive dispersion solvent (good solvent). For this measurement, a nano-track UPA-150 manufactured by Microtrac Inc. can be used.

The conductive material (x) is preferably used in an amount of 5% by mass to 90% by mass, more preferably 10% by mass to 60% by mass, based on the total amount of the fluid used in the present invention Is more preferable.

Further, it is preferable that the above-mentioned fluid contains a solvent from the viewpoint of improving easiness of application and the like. As the solvent, an organic solvent or an aqueous medium can be used.

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

Examples of the alcohol include alcohols such as methanol, ethanol, n-propanol, isopropyl alcohol, n-butanol, isobutyl alcohol, sec-butanol, tert-butanol, heptanol, hexanol, , Stearyl alcohol, allyl alcohol, cyclohexanol, terpineol, terpineol, dihydroterpineol, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene 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 mono Methyl ether, tripropylene glycol monomethyl ether, propylene glycol monopropyl ether, dipropylene glycol monopropyl ether, propylene glycol mo N-butyl ether, dipropylene glycol monobutyl ether, and tripropylene glycol monobutyl ether.

The fluid may be, for example, ethylene glycol, diethylene glycol, 1,3-butanediol, isoprene glycol or the like together with the conductive material (x) or solvent.

As the fluid, it is preferable to use a liquid or viscous liquid having a viscosity measured at 25 캜 by a B-type viscometer of 0.1 mPa s to 500,000 mPa,, preferably 0.5 mPa s to 10,000 mPa 것을 Do. When the fluid is applied (printed) by the ink jet printing method or the convex inverted printing method, it is preferable that the viscosity is in the range of 5 mPa · s to 20 mPa · s.

Some or all of the surface of the conductive layer (III) formed by applying and firing the fluid may be subjected to oxidation treatment. Specifically, the surface of the conductive layer (III) may be subjected to plasma discharge treatment such as corona treatment.

The plasma discharge treatment is not particularly limited and is a treatment which is carried out by, for example, an atmospheric plasma discharge treatment method such as a corona discharge treatment method or a vacuum plasma discharge treatment method such as a glow discharge treatment method and an arc discharge treatment method performed under vacuum or reduced pressure .

The atmospheric plasma discharge treatment is a plasma discharge treatment in an atmosphere having an oxygen concentration of about 0.1% by mass to 25% by mass. In the present invention, it is particularly preferable to employ a corona discharge treatment method in which the plasma discharge treatment is preferably performed in a range of 10 mass% to 22 mass%, more preferably in the air (oxygen concentration is about 21 mass%), Is preferable.

Further, the atmospheric-pressure plasma discharge treatment method is carried out under an environment containing an inert gas together with the above-mentioned oxygen, so that the surface of the conductive layer (III) is not provided with excessive irregularities, desirable. As the inert gas, argon or nitrogen may be used.

For example, an atmospheric pressure plasma treatment apparatus (AP-T01) manufactured by Sekisui Chemical Co., Ltd. can be used for the treatment by the above-mentioned atmospheric plasma discharge treatment method.

It is preferable that the treatment is carried out in the range of 5 liters / minute to 50 liters / minute as the flow rate of gas such as air when the treatment is carried out by the above-mentioned atmospheric plasma discharge treatment method. The output is preferably in the range of 50W to 500W. In addition, it is preferable that the time to be treated by the plasma is in the range of 1 second to 500 seconds.

Specifically, as the atmospheric pressure plasma discharge treatment method, it is preferable to adopt the corona discharge treatment method. When the corona discharge treatment method is employed, for example, a corona surface modification evaluation apparatus (TEC-4AX) manufactured by Kasuga Chemical Co., Ltd. can be used.

When the treatment is carried out by the corona discharge treatment method, it is preferable to perform the discharge in the range of 5W to 300W. The time for corona discharge treatment is preferably in the range of 0.5 seconds to 600 seconds.

It is preferable that the plasma discharge treatment such as the corona discharge treatment is performed under such a condition that the surface of the layer (II) is not formed with unevenness by such treatment.

The surface of the conductive layer (III) formed by the above method is preferably plated. The plating treatment may be performed on the oxidized surface of the conductive layer (III) or on the surface of the conductive layer (III) which is not oxidized.

Examples of the plating treatment method include a dry plating method such as a sputtering method and a vacuum deposition method, a wet plating method such as an electroless plating method and an electroplating method, or a combination of two or more of these plating methods.

The plating layer (IV) formed by the plating treatment method on the surface of the conductive layer (III) has excellent adhesion. Among them, the plating layer (IV) formed by the electroplating method on the surface of the conductive layer (III) can exert excellent excellent adhesion.

As the dry plating treatment process, a sputtering method, a vacuum deposition method, or the like can be used. In the sputtering method, an inert gas (principally argon) is introduced in vacuum to generate glow discharge by applying (-) ions to the material for forming the plating layer (IV), and subsequently ionizing the inert gas atoms, The gas ions are intensely struck on the surface of the plating layer (IV) forming material and the atoms or molecules constituting the plating layer (IV) forming material are splashed and adhered to the surface of the conductive layer (III) .

As the material for forming the plating layer (IV), a metal such as Cr, Cu, Ti, Ag, Pt, Au, Ni-Cr, SUS, copper-zinc can be used (Cu-Zn), ITO, SiO 2, TiO 2, Nb 2 O 5, ZnO and the like.

When performing the plating treatment by the above-described sputtering method, for example, a magnetron sputtering apparatus or the like can be used.

The vacuum deposition method is a method in which various metals or metal oxides as a material for forming a plating layer (IV) are heated in a vacuum, and they are melted, evaporated and sublimated, and the metal atoms or molecules To form a plating layer (IV).

Examples of the material for forming the plating layer (IV) usable in the vacuum deposition method include aluminum (Al), silver (Ag), gold (Au), titanium (Ti), nickel (Ni) (Cr), tin can be used (Sn), indium _{(In), SiO 2, ZrO} 2, Al 2 O 3, TiO 2 or the like.

The electroless plating process that can be used as the plating process can be performed by, for example, bringing an electroless plating solution into contact with a conductive material such as palladium or silver constituting the conductive layer (III) And depositing a metal such as copper to form an electroless plating layer (coating film) composed of a metal coating.

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

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

Examples of the electroless plating solution include monocarboxylic acids such as acetic acid and formic acid; Dicarboxylic acids such as malonic acid, succinic acid, adipic acid, maleic acid, and fumaric acid; Hydroxycarboxylic acids such as malic acid, lactic acid, glycolic acid, gluconic acid and citric acid; Amino acids such as glycine, alanine, iminodiacetic acid, arginine, aspartic acid, and glutamic acid; Aminopolycarboxylic acids such as iminodiacetic acid, nitrilotriacetic acid, ethylenediaminetriacetic acid, ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid, and soluble salts (sodium salt, potassium salt, ammonium salt, etc.) of these organic acids ), And complexing agents such as amines such as ethylenediamine, diethylenetriamine, and triethylenetetramine.

When the electroless plating solution is used, the temperature of the electroless plating solution is preferably in the range of 20 占 폚 to 98 占 폚.

The above-mentioned plating treatment method that can be used as the plating treatment method is a method in which the surface of an electrically conductive material constituting the conductive layer (III) or an electroless plating layer (coating film) formed by the electroless plating treatment, A metal such as copper contained in the electroplating solution is allowed to react with a conductive material constituting the conductive layer (III) provided on the negative electrode or an electroless plating layer (coating film) formed by the electroless treatment, To form an electroplated film (metal film).

As the electroplating solution, those containing a metal such as copper, nickel, chromium, cobalt, and tin, a sulfide thereof, sulfuric acid, etc., and an aqueous medium may be used. Concretely, it is possible to use those containing copper sulfate, sulfuric acid and an aqueous medium.

When the electroplating solution is used, the temperature of the electroplating solution preferably ranges from 20 캜 to 98 캜.

As the electroplating treatment method, it is preferable to form a layer made of copper by an electroplating method because a high toxicity material is not used and workability is good.

The laminate obtained by the above method can be used as a conductive pattern. Specifically, the formation of electronic circuits using silver ink or the like, the formation of layers or peripheral wirings constituting an organic solar battery, an electronic book terminal, an organic EL, an organic transistor, a flexible printed board, an RFID or the like, And the like, more specifically, it can be used suitably for forming a circuit board.

When the laminate is used for a conductive pattern, a fluid capable of forming the conductive layer (III) is applied and fired at a position corresponding to a desired pattern shape to be formed, A conductive pattern can be produced.

The conductive pattern can be produced by a photolithography method such as a subtractive method, a semi-additive method or a pull additive method.

In the subtractive method, an etching resist layer having a shape corresponding to a desired pattern shape is formed on the plating layer (IV) constituting the laminate of the present invention manufactured in advance, and the resist And the plating layer (IV) and the conductive layer (III) in the removed portion are dissolved and removed with a chemical solution to form a desired pattern. As the chemical liquid, a chemical liquid containing copper chloride, iron chloride, or the like can be used.

The semi-additive method is a method of producing a laminate comprising the layer (I) comprising the support (I1) or the support (I2), the resin layer (II) and the conductive layer (III) The surface of the conductive layer (III) is oxidized by plasma discharge to form a plating resist layer having a shape corresponding to a desired pattern on the oxidized surface, and then a plating resist layer After the plating layer IV is formed by a solution plating method, the plating resist layer and the conductive layer (III) in contact with the plating resist layer are dissolved in a chemical solution or the like and removed to form a desired pattern.

The pull-add method is a method in which a resin layer (II) is provided on a layer (I) comprising the support (I1) or the support (I2) A pattern is formed on the oxidized surface of the conductive layer III by electroplating or electroless plating to form a pattern on the surface of the conductive layer III, IV) to form a desired pattern.

The conductive pattern obtained by the above method can be provided with remarkably excellent durability at a level at which good conductivity can be maintained without causing peeling or the like between the respective layers, The formation of a substrate, the formation of layers or peripheral wirings constituting an organic solar battery, an electronic book terminal, an organic EL, an organic transistor, a flexible printed board, an RFID, etc., wiring of electromagnetic shields of a plasma display, It can be used for personal use. 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 over a long period of time. Therefore, for example, a copper-clad laminate (CCL) Clad Laminate), and can be used for applications such as flexible printed circuit boards (FPC), tape automatic bonding (TAB), chip-on-film (COF), and printed wiring board (PWB).

[Example]

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

[Preparation of Support (F-1)] [

Anhydrous pyromellitic acid and 4,4'-oxydianiline were prepared at a molar ratio of 50/50 and polymerized in N, N "-dimethylacetamide to obtain a polyamic acid solution with a nonvolatile content of 20 mass% (A-1).

Further, biphenyl 3,4,3 ', 4'-tetracarboxylic acid dihydrate and 4,4'-oxydianiline were prepared in a molar ratio of 50/50, and they were dissolved in N, N'-dimethylacetamide By polymerization, a polyamic acid solution (A-2) having a nonvolatile content of 20 mass% was obtained.

Next, the polyamic acid solution (A-1) and the polyamic acid solution (A-2) were mixed so that the mass of the polyamic acid contained in the polyamic acid solution (A- -2)) = 35/65, and 0.2 mass% of silica particles having an average particle diameter of 0.3 占 퐉 was mixed to obtain a mixture.

Thereafter, the mixture was subjected to filtration and defoaming, and the mixture was extruded from a T-die to be poured into a drum shape.

The flexible one was dried at 100 DEG C for 60 seconds to produce a film containing the polyamic acid and the silica.

The film was peeled off from the drum, dried at 250 캜 for 60 seconds, then dried at 300 캜 for 60 seconds, and then dried at 400 캜 for 75 seconds to obtain a support (F-1) composed of a polyimide film . The thickness of the support was 40 탆.

[Preparation of support (F-2)] [

Oxydianiline, biphenyl 3,4,3 ', 4'-tetracarboxylic acid dihydrate and 4,4'-oxydianiline in a molar ratio of 50/50/100 , And these were polymerized in N, N'-dimethylacetamide to obtain a polyamic acid solution having a nonvolatile content of 20 mass%. Further, a mixture was obtained by mixing 0.2 wt% of silica particles having an average particle diameter of 0.3 mu m.

Thereafter, the mixture was subjected to filtration and defoaming, and the mixture was extruded from a T-die to be poured into a drum shape.

The flexible one was dried at 100 DEG C for 60 seconds to produce a film containing the polyamic acid and the silica.

The film was peeled off from the drum, then dried at 250 캜 for 60 seconds, then dried at 300 캜 for 60 seconds, and then dried at 400 캜 for 75 seconds to obtain a support (F-2) composed of a polyimide film . The film thickness of the support was 39 탆.

[Preparation of Support (F-3)] [

Except that the biphenyl 3,4,3 ', 4'-tetracarboxylic acid dihydrate and 1,4-diaminobenzene were used in a molar ratio of 50/1, instead of the polyamic acid solution (A-1) and the polyamic acid (A- (F-3) made of a polyimide film was produced in the same manner as in the production of the above support (F-1), except that the polyamic acid obtained by polymerizing the polyamic acid prepared in the ratio of 50% The film thickness of the support was 49 탆.

[Preparation of Support (F-4)] [

A polyamic acid obtained by polymerizing an anhydrous pyrophosphoric acid and 4,4'-oxydianiline in a ratio of 50/50 by mole in place of the polyamic acid solution (A-1) and the polyamic acid (A-2) (F-1) was prepared in the same manner as in the production of the above-mentioned support (F-1), except that 0.05 mass% of calcium phosphate having an average particle diameter of 1 탆 was used instead of the above- To prepare a support (F-4). The thickness of the support was 50 탆.

[Preparation of Resin Composition (R-1)] [

100 parts by mass of a polyester polyol (a polyester polyol obtained by reacting 1,4-cyclohexanedimethanol with neopentyl glycol and adipic acid) in a nitrogen-purged container equipped with a thermometer, a nitrogen gas introducing tube and a stirrer, 17.6 parts by mass of 2,2-dimethylolpropionic acid, 21.7 parts by mass of 1,4-cyclohexanedimethanol and 106.2 parts by mass of dicyclohexylmethane diisocyanate were reacted in a mixed solvent of methyl ethyl ketone and 178 parts by mass, An organic solvent solution of a urethane prepolymer having an isocyanate group was obtained.

Then, 13.3 parts by mass of triethylamine was added to the organic solvent solution of the urethane resin to neutralize part or all of the carboxyl groups contained in the urethane resin, add 380 parts by mass of water, and sufficiently stir to obtain urethane resin Of an aqueous dispersion.

Subsequently, 8.8 parts by mass of an aqueous solution of 25% by mass of ethylenediamine was added to the aqueous dispersion, and the mixture was agitated to make the particulate polyurethane resin to be brightened. Subsequently, the polyurethane resin was aged and degreased, To obtain an aqueous dispersion of Resin (r-1). The weight average molecular weight of the urethane resin (r-1) was 53,000.

Next, 140 parts by mass of deionized water was added to a reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, a thermometer, a dropping funnel for dropping a monomer mixture, and a dropping funnel for dropping polymerization catalyst, Of 100 parts by mass of water dispersed therein, and the temperature was raised to 80 DEG C while blowing nitrogen therein.

A monomer mixture consisting of 60 parts by mass of methyl methacrylate, 30 parts by mass of n-butyl acrylate, and 10 parts by mass of Nn-butoxymethylacrylamide was mixed with an aqueous ammonium persulfate solution (concentration: 0.5 mass%) was added dropwise from each dropping funnel over 120 minutes while maintaining the temperature in the reaction vessel at 80 占 占 폚.

After completion of the dropwise addition, the mixture was stirred at the same temperature for 60 minutes to obtain an aqueous dispersion composed of the shell layer of the urethane resin (r-1) and the core layer of the vinyl polymer.

The temperature in the reaction vessel was cooled to 40 캜, and then deionized water was used so that the nonvolatile content became 20.0% by mass, followed by filtration with a 200-mesh filter cloth to obtain a resin composition (R-1).

[Preparation of Resin Composition (R-2)] [

(Formaldehyde content: 222 parts by mass (7.4 mol), methanol content: 42 parts by mass) containing 37% by mass of formaldehyde and 7% by mass of methanol was added to a reaction flask equipped with a reflux condenser, a thermometer and a stirrer (1.31 mol)), 200 parts by mass of water and 350 parts by mass (10.92 mol) of methanol were added. To this aqueous solution, a 25 mass% sodium hydroxide aqueous solution was added and the pH was adjusted to 10. Thereafter, 310 parts by mass (2.46 mol) of melamine was added and the temperature was elevated to 85 캜 to perform methylolization (primary reaction) time).

Thereafter, formic acid was added to adjust the pH to 7, and then the mixture was cooled to 60 占 폚 and subjected to an etherification reaction (secondary reaction). At a clouding temperature of 40 캜, an aqueous solution of 25 mass% sodium hydroxide was added to adjust the pH to 9, and the etherification reaction was stopped (reaction time: 1 hour). The remaining methanol was removed under reduced pressure at a temperature of 50 占 폚 (demethanol time: 4 hours) to obtain a resin composition (R-2) containing a melamine resin having a nonvolatile content of 80% by mass.

The method of measuring the cloudiness temperature will be described below. 1 g of the resin was sampled, and this resin was mixed with 100 ml of hot water adjusted to a specified temperature. At that time, the highest temperature at which the resin did not dissolve in the hot water but became opaque was the opacity temperature.

[Preparation of conductive ink]

Conductive ink 1 was prepared by dispersing silver particles having an average particle diameter of 30 nm in a mixed solvent of 45 parts by mass of ethylene glycol and 55 parts by mass of ion-exchanged water.

[Example 1]

The surface of the support (F-1) was measured with a TEC-4AX (Corona Surface Modification Evaluation Apparatus, Gas: air (oxygen concentration: about 21 mass%), gap: 1.5 mm, output: 100 W , Processing time: 2 seconds) was used for corona discharge treatment.

Thereafter, the resin composition (R-1) was applied on the surface of the support so as to have a dry film thickness of 0.1 mu m using a spin coater. Subsequently, using a hot air drier, 5 Minute drying to obtain a layered product in which the resin layer (II) was laminated on the surface of the layer (I) comprising the support.

Subsequently, the conductive ink (III) (thickness: 0.1 mu m) formed by the silver was applied to the surface of the resin layer (II) by applying the conductive ink by spin coating method and then firing at 250 DEG C for 3 minutes. . When the surface resistance of the conductive layer (III) was measured by a method described later, it was 2? / ?.

Subsequently, the surface of the conductive layer (III) was treated with TEC-4AX (corona surface modification evaluation device, gas: oxygen (concentration of about 21 mass%), gap: 1.5 mm, output; 100 W, treatment time: 2 seconds) was used for corona discharge treatment. The surface resistance of the conductive layer (III) before the corona discharge treatment was 2? / ?, but the surface resistance of the conductive layer (III) subjected to the corona discharge treatment increased to 5? / ?. Further, when the surface of the conductive layer (III) was analyzed using the X-ray photoelectron spectroscopic analyzer as described above, a peak indicating that silver forming the conductive layer (III) was oxidized was confirmed.

Subsequently, the oxidized surface of the conductive layer (III) was set as a cathode, phosphorus-containing copper was set as an anode, and electroplating was carried out for 15 minutes at a current density of 2 A / dm ² using an electroplating solution containing copper sulfate A copper plating layer having a thickness of 8 占 퐉 was laminated on the surface of the conductive layer (III). As the electroplating solution, 70 g / liter of copper sulfate, 200 g / liter of sulfuric acid, 50 mg / liter of chlorine ion, and 5 g / liter of Toppuruni SF (a polisher of Okuno Seiyaku Kogyo K.K.) were used.

By the above method, a laminate (L-1) in which the layer (I) comprising the support, the resin layer (II), the conductive layer (III) and the plating layer (IV) were laminated was obtained.

[Example 2]

(I) composed of the support, the resin layer (II), and the conductive layer (II) were obtained in the same manner as in Example 1 except that the resin composition (R-2) was used in place of the resin composition To obtain a layered product (L-2) in which the layer (III) and the plated layer (IV) were laminated.

[Example 3]

The resin composition (R-1) and the resin composition (R-2) were mixed in a ratio of 50/1, instead of the above-mentioned support (F- (II) composed of the support, the resin layer (II), the conductive layer (III), and the plating layer (II) were formed in the same manner as in Example 1, (L-3) laminated with the layer (IV).

[Comparative Example 1]

(I), the resin layer (II), and the conductive layer (II) were formed in the same manner as in Example 1, except that the support (F-3) was used in place of the support III) and the plated layer (IV) were laminated to obtain a laminate (L'-1).

[Comparative Example 2]

(I) composed of the support, the resin layer (II), and the conductive layer (II) were formed in the same manner as in Example 1 except that the support (F-4) was used in place of the support III) and the plated layer (IV) were laminated.

≪ Adhesion property; Evaluation by peeling test>

The peeling strength of the laminate thus obtained was measured by the method according to IPC-TM-650, NUMBER 2.4.9. The lead width used for the measurement was 1 mm, and the angle of the filling was 90 °. The peeling strength tends to show a higher value as the thickness of the plating layer becomes thicker. The peeling strength in the present invention was measured based on the measurement value at 8 mu m of the plating layer which is currently in general use.

<Heat resistance; Evaluation by peeling test after heat resistance test (temperature: 150 캜)>

The thus obtained laminate was dried for 168 hours using a dryer set at 150 캜. The peeling strength was measured in the same manner as described in < Evaluation by Peeling Test > except that the above-mentioned dried layered product was used.

<Humidity Resistance; Evaluation by peeling test after anti-wet heat test (at a temperature of 135 ° C and a humidity of 85%)>

The laminate thus obtained was placed in a HAST tester set at a temperature of 135 ° C and a humidity of 85% for 168 hours. The peeling strength was measured in the same manner as described in < Evaluation by Peeling Test > except that the laminate after the above-mentioned moisture resistance heat test was used.

[Table 1]

Claims (8)

(I1) containing a polyimide resin (i-1) having a structure represented by the following general formula (1) and a polyimide resin (i-2) having a structure represented by the following general formula (2) , A layer (I) comprising a support (I2) containing a polyimide resin (i-3) having a structure represented by the following general formula (1) and a structure represented by the following general formula (2) x), and a conductive layer (III) formed of the conductive material (x). The laminate according to claim 1, wherein the resin layer (II)

[R ¹ to R ⁸ in the general formula (1) each independently represent a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group or an aryl group. and n represents an integer of 1 to 1,000.

[R ⁹ to R ²² in the general formula (2) each independently represent a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group or an aryl group. and m represents an integer of 1 to 1,000. The method according to claim 1,
Wherein the layer (I) comprising the support further contains silica fine particles having an average particle diameter of 0.01 to 1 占 퐉. The method according to claim 1,
(II-1) comprising a core-shell type composite resin particle composed of an acrylic resin as a core layer and a urethane resin having a hydrophilic group as a shell layer, or a melamine resin (II-2) ). The method according to claim 1,
And a plating layer (IV) on a part or the whole of the surface of the conductive layer (III). 5. The method of claim 4,
And a part or the whole of the conductive layer (III) is constituted by oxidized silver. 5. The method of claim 4,
Wherein the plating layer (IV) is formed by an electrolytic copper plating method. A conductive pattern comprising the laminate according to any one of claims 1 to 6. An electric circuit having the laminate according to any one of claims 1 to 6.