JP5569662B1 - Laminate, conductive pattern and electrical circuit - Google Patents

Abstract

  The present invention includes a layer (I) comprising a support containing a specific polyimide resin, a resin layer (II) receiving a fluid containing a conductive substance (x), and the conductive substance (x). The present invention relates to a laminate, a conductive pattern, and an electric circuit having a conductive layer (III) to be formed. The laminate of the present invention has excellent adhesion between the support layer and the resin layer that receives the conductive substance, and maintains excellent adhesion even when exposed to a high temperature environment. Therefore, it can be used as a laminate such as a conductive pattern.

Description

  The present invention relates to a laminate such as a conductive pattern that can be used for manufacturing an electromagnetic wave shield, an integrated circuit, an organic transistor, or the like.

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

  As the conductive pattern usable for the electronic circuit, for example, a conductive material layer is formed by applying and baking a conductive ink containing a conductive material such as silver or a plating nucleating agent on the surface of a support. Then, a conductive pattern in which a plating layer is provided on the surface of the conductive material layer by plating the surface of the conductive material layer is known (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 is lost from the surface of the support over time and is formed by the conductive material. In some cases, the conductive pattern is disconnected or the conductivity is lowered (resistance value is increased).

  As a method for improving the adhesion between the support and the conductive material, for example, a pattern is drawn by a predetermined method using a conductive ink on an ink receiving substrate provided with a latex layer on the support surface. Thus, a method for producing a conductive pattern is known (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 from the surface of the support over time. In some cases, the layer and the conductive material are lost, causing disconnection of the conductive pattern formed by the conductive material or a decrease in conductivity.

  Further, the peeling of the ink receiving layer from the surface of the support is not sufficient in terms of heat resistance, for example, when it is heated to about 100 ° C. to 200 ° C. in the plating process, etc. In some cases, the pattern cannot be plated for the purpose of improving its strength.

JP 2005-286158 A JP 2009-49124 A

  The problem to be solved by the present invention is excellent in adhesion between the layer made of the support and the resin layer receiving the conductive material, and even when exposed to a high temperature environment, the excellent It is an object of the present invention to provide a laminate such as a conductive pattern having a level of heat resistance capable of maintaining adhesion.

  As a result of studying the above problems, the present inventors have found that the above problems can be solved by using a specific support.

  That is, the present invention provides a support comprising 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). (I1) or 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) A laminate comprising: a resin layer (II) that receives a fluid containing the conductive substance (x); and a conductive layer (III) formed by the conductive substance (x), The present invention relates to a conductive pattern and an electric circuit.

〔一般式（１）中のＲ^１〜Ｒ^８は、それぞれ独立して水素原子、水酸基、ハロゲン原子、アルキル基またはアリール基を表す。ｎは１〜１，０００の整数を表す。〕

[R ^{1 to} R ⁸ in General Formula (1) each independently represent a hydrogen atom, a hydroxyl group, a halogen atom , an alkyl group, or an aryl group. n represents an integer of 1 to 1,000. ]

〔一般式（２）中のＲ^９〜Ｒ^２２は、それぞれ独立して水素原子、水酸基、ハロゲン原子、アルキル基またはアリール基を表す。ｍは１〜１，０００の整数を表す。〕

[R ^{9 to} R ²² in General Formula (2) each independently represent a hydrogen atom, a hydroxyl group, a halogen atom , an alkyl group, or an aryl group. m represents an integer of 1 to 1,000. ]

  The laminate of the present invention can maintain excellent adhesion even when exposed to a high temperature environment, and as a result, can maintain excellent conductivity without causing disconnection or the like. And formation of electronic circuits, organic solar cells and electronic book terminals, organic EL, organic transistors, flexible printed circuit boards, non-contact IC cards, etc., forming each layer and peripheral wiring, wiring for plasma display electromagnetic shielding, It can be used in a new field generally referred to as a printed electronics field, such as the manufacture of integrated circuits and organic transistors.

  The laminate of the present invention includes 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 layer (I2) 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): ), A resin layer (II) for receiving a fluid containing the conductive substance (x), and a conductive layer (III) formed by the conductive substance (x), For example, it can be suitably used for conductive patterns, electrical circuits, and the like.

〔一般式（１）中のＲ^１〜Ｒ^８は、それぞれ独立して水素原子、水酸基、ハロゲン原子、アルキル基またはアリール基を表す。ｎは１〜１，０００の整数を表す。〕

[R ^{1 to} R ⁸ in General Formula (1) each independently represent a hydrogen atom, a hydroxyl group, a halogen atom , an alkyl group, or an aryl group. n represents an integer of 1 to 1,000. ]

〔一般式（２）中のＲ^９〜Ｒ^２２は、それぞれ独立して水素原子、水酸基、ハロゲン原子、アルキル基またはアリール基を表す。ｍは１〜１，０００の整数を表す。〕

[R ^{9 to} R ²² in General Formula (2) each independently represent a hydrogen atom, a hydroxyl group, a halogen atom , an alkyl group, or an aryl group. 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) that supports the laminate.

  The support includes 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). (I1) 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.

〔一般式（１）中のＲ^１〜Ｒ^８は、それぞれ独立して水素原子、水酸基、ハロゲン原子、アルキル基またはアリール基を表す。ｎは１〜１，０００の整数を表す。〕

[R ^{1 to} R ⁸ in General Formula (1) each independently represent a hydrogen atom, a hydroxyl group, a halogen atom , an alkyl group, or an aryl group. n represents an integer of 1 to 1,000. ]

〔一般式（２）中のＲ^９〜Ｒ^２２は、それぞれ独立して水素原子、水酸基、ハロゲン原子、アルキル基またはアリール基を表す。ｍは１〜１，０００の整数を表す。〕
前記支持体（Ｉ１）は、前記ポリイミド樹脂（ｉ−１）及びポリイミド樹脂（ｉ−２）を含有するものである。

[R ^{9 to} R ²² in General Formula (2) each independently represent a hydrogen atom, a hydroxyl group, a halogen atom , an alkyl group, or an aryl group. 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 , an alkyl group, or an aryl group . Before Symbol R ¹ to R ⁸ imparts excellent adhesion and heat resistance, a relatively inexpensive available that can, and is preferably a hydrogen atom.

  M in the general formula (1) is preferably an integer of 1 to 1,000, more preferably an integer of 3 to 50,0, still more preferably an integer of 50 to 500, An integer of 100 to 500 is particularly preferable.

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

  The polyimide resin (i-1) is prepared by reacting, for example, a polyamic acid by reacting a polyamine containing 4,4′-oxydianiline and the like with a tetracarboxylic acid dihydrate containing pyromellitic anhydride. It can manufacture by mixing with a catalyst etc. as needed, and heating etc. then.

  The reaction between the polyamine and the tetracarboxylic acid dihydrate can be performed by a conventionally known method.

  When the polyimide resin (i-1) is produced, a polyamine other than 4,4′-oxydianiline and a tetracarboxylic acid dihydrate other than pyromellitic anhydride may be used in combination. It is preferable to use 4,4′-oxydianiline and pyromellitic anhydride in a total range of 95% by mass to 100% by mass with respect to the total amount of raw materials used for the production of the polyimide resin (i-1).

  Moreover, the method of heating is mentioned as a method of manufacturing a polyimide resin (i-1) using the polyamic acid obtained above.

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

  As a method for producing the polyimide resin (i-1), specifically, 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 , an alkyl group, or an aryl group . Before Symbol R ⁹ to R ²² are, in order to impart excellent adhesion, is preferably a hydrogen atom.

  N in the general formula (2) is preferably an integer of 1 to 1,000, more preferably an integer of 3 to 500, further preferably an integer of 50 to 500, 100 to Particularly preferred is an integer of 500.

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

  The polyimide resin (i-2) includes, for example, a tetraamine containing polyamine containing 4,4′-oxydianiline and the like and biphenyl 3,4,3 ′, 4′-tetracarboxylic acid dihydrate. A polyamic acid can be produced by reacting with an acid dihydrate, then mixed with a catalyst or the like, if necessary, and heated.

  The reaction between the polyamine and the tetracarboxylic acid dihydrate can be performed by a conventionally known method.

  When the polyimide resin (i-2) is produced, a polyamine other than 4,4′-oxydianiline or a tetracarboxylic acid other than biphenyl 3,4,3 ′, 4′-tetracarboxylic acid dihydrate is used. Although acid dihydrate may be used in combination, 4,4′-oxydianiline and biphenyl 3,4,3 ′, relative to the total amount of raw materials used in the production of the polyimide resin (i-2) It is preferable to use 4′-tetracarboxylic acid dihydrate in a total range of 95% by mass to 100% by mass.

  Moreover, the method of heating is mentioned as a method of manufacturing a polyimide resin (i-2) using the polyamic acid obtained above.

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

  As a method for producing the polyimide resin (i-2), specifically, JOURNAL OF POLYMER SCIENCE: PART A-2 VOL. 6, 953-960 (1968).

  As said support body (I1) which comprises the said layer (I), the said polyimide resin (i-1) and the said polyimide resin (i-2) are [the said polyimide resin (i-1) / the said polyimide resin ( i-2)] = It is preferable to use those contained at a ratio of 5 to 95.

  Moreover, as a support body (I2) which comprises the layer (I) of the laminated body of this invention, the polyimide resin which combines the structure shown by the following general formula (1), and the structure shown by the following general formula (2) ( Supports containing i-3) can be used.

  As said polyimide resin (i-3), the 4, 4'- oxydianiline etc. which were illustrated as what can be used for manufacture of the said polyimide resin (i-1) or the said polyimide resin (i-2) are contained. A polyamic acid by reacting the polyamine with a tetracarboxylic acid dihydrate containing pyromellitic anhydride or biphenyl 3,4,3 ′, 4′-tetracarboxylic acid dihydrate, If necessary, it can be produced by mixing with a catalyst or the like and heating.

  The reaction between the polyamine and the tetracarboxylic acid dihydrate can be performed by a conventionally known method.

  In producing the polyimide resin (i-3), polyamines other than 4,4′-oxydianiline, pyromellitic anhydride and biphenyl 3,4,3 ′, 4′-tetracarboxylic acid dihydrate are used. Tetracarboxylic acid dihydrate other than the product may be used in combination, but pyromellitic anhydride and biphenyl 3,4,3 ′ are used with respect to the total amount of raw materials used for the production of the polyimide resin (i-3). , 4′-tetracarboxylic acid dihydrate is preferably used in the range of 95 mass% to 100 mass% in total.

  Moreover, the method of heating is mentioned as a method of manufacturing a polyimide resin (i-3) using the polyamic acid obtained above.

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

  As said support body (I1) and said support body (I2) other than said polyimide resin (i-1), said polyimide resin (i-2), and said polyimide resin (i-2), as needed. Those containing various additives can be used.

  As the additive, for example, using an inorganic filler such as silica or calcium phosphate improves the ease of transporting the support (I1) and the support (I2) made of a polyimide film, It is preferable for preventing blocking of the support (I1) and the support (I2).

  As said inorganic filler, when improving the smoothness of the surface of the said support body, in the range of 0.5 mass%-30 mass% with respect to the mass of the said support body (I1) or the said support body (I2). It is preferable to use it. Moreover, the average particle diameter of the inorganic filler is preferably 0.01 μm to 5 μm, and more preferably 0.01 μm to 0.5 μm. In addition, the said average particle diameter points out the value measured with the laser diffraction scattering type particle size distribution analyzer apparatus.

  As a method for producing the support (I1), for example, a polyamic acid that is a precursor of the polyimide resin (i-1) and a polyamic acid that is a precursor of the polyimide resin (i-2) are necessary. A film or sheet after filtering or defoaming a solution obtained by mixing a solvent as required and a mixture obtained by mixing additives such as the inorganic filler as necessary. The method of shape | molding in a shape and heating is mentioned.

  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 as necessary, and if necessary, Examples include a method in which a mixture obtained by mixing additives such as the inorganic filler is filtered or defoamed as necessary, and then formed into a film or a sheet and heated.

  Examples of the molding method include a method in which the mixture is extruded onto a drum using a T die or the like and cast.

  After the casting, for example, by removing the solvent by heating at a temperature of 80 ° C. to 150 ° C. for about 30 seconds to 90 seconds, the film or sheet-like molded product can be obtained.

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

  The layer (I) comprising the support (I1) or the support (I2) obtained by the above method is preferably about 1 μm to 5,000 μm in thickness, and about 1 μm to 300 μm in thickness. More preferably. When a relatively flexible material is required as the laminate, it is preferable to use a material having a thickness of about 1 μm to 200 μm.

Next, the resin layer (II) constituting the laminate of the present invention will be described.
The resin layer (II) is a layer capable of receiving a fluid containing a conductive substance (x) that forms a conductive layer (III) described later. The resin layer (II) quickly absorbs the solvent contained in the fluid when the fluid contacts, and supports the conductive substance (x) on the surface of the resin layer (II). Thereby, the adhesiveness and heat resistance between the layer (I) composed of the support (I1) or the support (I2), the resin layer (II), and the conductive layer (III) composed of the conductive substance (x). Can greatly improve

  The resin layer (II) may be provided on a part or all of the surface of the layer (I) composed of the support (I1) or the support (I2), or may be provided on one side or both sides thereof. . For example, the laminate includes a resin layer (II) on the entire surface of the layer (I) composed of the support (I1) or the support (I2), and is necessary among the resin layers (II). What has the said conductive layer (III) can also be used only for a part. Moreover, the laminated body in which the resin layer (II) is provided only on the portion where the conductive layer (III) is provided on the surface of the layer (I) comprising the support (I1) or the support (I2). Can also be used.

  Although the said resin layer (II) changes with uses etc. which the laminated body of this invention uses, it is preferable to set it normally as the thickness of the range of 10 nm-1000 micrometers. Moreover, since the adhesiveness between the layer (I) comprising the support (I1) or the support (I2) and the conductive layer (III) can be further improved, the thickness of the resin layer (II) is 10 nm. The range of ˜300 nm is more preferable, and the range of 10 nm to 100 nm is more preferable.

  As the resin layer (II), composite resin (II-1), melamine resin (II-2) composed of urethane resin and acrylic resin, urethane resin, vinyl resin, epoxy resin, imide resin, amide resin, phenol A resin layer formed using a resin, polyvinyl alcohol, polyvinyl pyrrolidone, or the like can be used. Among these, a layer formed using a composite resin (II-1) or a melamine resin (II-2) composed of a urethane resin and an acrylic resin has excellent adhesion and heat resistance. It is preferable when manufacturing a body.

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 substance (x) contained in a fluid such as conductive ink or plating nucleating agent. The conductive layer (III) corresponds to a layer composed of the silver contained in the plating nucleating agent, for example, when a plating nucleating agent containing silver is used as the fluid. It corresponds to a printed image or pattern that is configured.

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

  The conductive layer (III) may be provided on a part or all of the surface of the resin layer (II). For example, as the laminate, the conductive layer (III) may be provided only on a necessary portion of the surface of the resin layer (II). Specifically, the conductive layer (III) provided only in a necessary portion of the surface of the resin layer (II) includes a linear layer formed by drawing a line. A laminate having a linear layer as the conductive layer (III) is suitable for producing a conductive pattern, an electric circuit, or the like.

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

  As the conductive layer (III) constituting the laminate of the present invention, one 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 coating amount of the fluid containing the conductive substance (x) that can be used to form the conductive layer (III). When the conductive layer (III) has a thin line shape, the thickness (height) is preferably in the range of 10 nm to 1 μm.

  In addition, the surface of the conductive layer (III) has a part or all of the surface of the conductive layer (III) in order to improve adhesion with the plating layer (IV) that can be provided as necessary. It is preferably oxidized.

  Here, the oxidation means that the conductive substance (x) contained in the conductive layer (III) combines with oxygen to form an oxide, and the valence of the conductive substance (x) increases. Including cases.

  Therefore, as the oxidized surface of the conductive layer (III), for example, when silver is used as the conductive substance (x) included in the conductive layer (III), the surface containing silver oxide, The silver can be used as a surface made of a substance in which the silver is bonded to a hydroxyl group or the like and the valence thereof is increased from 0 to +1.

  The conductive layer (III) only needs to be oxidized on the surface in contact with the plating layer (IV). However, together with the surface, all of the conductive material contained in the conductive layer (III) is oxidized. May be.

  The oxidized surface of the conductive layer (III) preferably has a resistance value in a range of 0.1Ω / □ to 50Ω / □, and a range of 0.2Ω / □ to 30Ω / □. It is preferable when providing the outstanding adhesiveness with the said plating layer (IV).

  Moreover, the laminated body of this invention may have a plating layer (IV) as needed other than the said layer (I), the said resin layer (II), and the said conductive layer (III).

  The plating layer (IV) forms a highly reliable wiring pattern capable of maintaining good electrical conductivity without causing disconnection or the like over a long period of time when the laminate is used for a conductive pattern, for example. It is a layer provided for the purpose of doing.

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

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

Next, the manufacturing method of the laminated body of this invention is demonstrated.
In the laminate of the present invention, for example, the resin composition (R) is applied to part or all of the surface of the support (I1) or the support (I2) constituting the layer (I) and dried. The resin layer (II) is formed by applying a fluid containing the conductive substance (x) to a part or all of the surface of the resin layer (II), followed by baking, and then the conductive layer (III). Can be manufactured. In the case of providing the plating layer (IV), a laminate including the plating layer (IV) can be manufactured 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 all of the surface of the support (I1) or the support (I2), the resin composition (R) may be used as the support (I1) or the support (I1). It can apply | coat to one part or all part of the surface of a body (I2), and can form by removing solvents, such as an aqueous medium and an organic solvent, which are contained in the said resin composition (R).

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

  The surface of the support (I1) or the support (I2) to which the resin composition (R) is applied is optionally subjected to a plasma discharge treatment method such as a corona discharge treatment method or a dry treatment method such as an ultraviolet treatment method. The surface treatment may be performed by a wet treatment method using water, an acidic or alkaline chemical solution, an organic solvent, or the like.

  As a method for removing the solvent contained in the coating layer after coating the resin composition (R) on the surface of the support (I1) or the support (I2), for example, drying is performed using a dryer. A method of volatilizing the solvent is general. What is necessary is just to set as drying temperature as the temperature of the range which can volatilize the said solvent and does not have a bad influence on the said support body (I1) or a support body (I2).

The coating amount of the resin composition (R) on the support (I1) or the support (I2) is the support (I1) or support (I) from the viewpoint of imparting excellent adhesion and conductivity. is preferably in the range of 0.01g ^{/ m 2} ~60g ^/ m 2 of the area of the I2), wherein when considering the absorbent and manufacturing cost of the solvent contained in the fluid 0.1 g ^{/ m} 2 ~ 10 g / m ² is particularly preferred.

  As resin composition (R) which can be used for manufacture of the said resin layer (II), what contains various resin and a solvent can 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, an amide resin, a phenol resin, Polyvinyl alcohol, polyvinyl pyrrolidone, etc. can be used.

  As the resin, it is possible to use a composite resin (II-1) or a melamine resin (II-2) composed of a urethane resin and an acrylic resin, in particular, the support (I1) or the support (I2). This is preferable for further improving the adhesion between the layer (I) comprising the above and the conductive layer (III).

  As the resin composition (R), use of the resin composition (R) containing 10% by mass to 70% by mass of the resin with respect to the entire resin composition (R) maintains ease of application. It is preferable to use a material containing 10% by mass to 50% by mass.

  Moreover, as a solvent which can be used for 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, or the like can be used. Examples of the aqueous medium include water, organic solvents miscible with water, and mixtures thereof.

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

  Moreover, as resin used for the said resin composition (R), the resin which has a hydrophilic group is used from a viewpoint of improving the adhesiveness to various said support body (I1) or support body (I2) further. It is preferable. Examples of the hydrophilic group include an anionic group such as a carboxylate group and a sulfonate group formed by neutralizing a part or all of them with a basic compound or the like, a cationic group, and a nonionic group. It is preferably a group.

  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 methylolamide group, an alkoxymethylamide group, or a methylolamino group as necessary. . Therefore, the resin layer (II) may already have a crosslinked structure before the fluid is applied, and after the fluid is applied, for example, by heating in a baking step or the like. A crosslinked structure may be formed.

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

The composite resin particles, specifically, which is the acrylic resin and the composite resin particles of the core-shell type composed of a urethane resin having a hydrophilic group as the shell layer as the core layer. In particular, the composite resin particles of the core-shell-type, in forming the conductive pattern, need not name to use a surfactant which can reduce the electric characteristics. In addition, as the composite resin particles, it is preferable that the acrylic resin is almost completely covered with the urethane resin, but it is not essential, and a part of the acrylic resin is within a range not impairing the effects of the present invention. You may exist in the outermost part of the said composite resin particle. The urethane resin and the acrylic resin may form a covalent bond, but preferably does not form a bond.

  Moreover, it is preferable that the said composite resin particle is an average particle diameter of the range of 5 nm-100 nm from a viewpoint of maintaining favorable 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 composite resin (II-1) preferably includes the urethane resin and the acrylic resin in a range of [urethane resin / acrylic resin] = 90/10 to 10/90, and 70/30 to 10 / More preferably, it is included in the range of 90.

  As the urethane resin that can be used for the production of the composite resin (II-1), those obtained by reacting various polyols, polyisocyanates, and, if necessary, a chain extender can be used.

  As said polyol, polyether polyol, polyester polyol, polyester ether polyol, polycarbonate polyol etc. can be used, for example.

  Examples of the polyester polyol include a ring-opening polymerization reaction of a cyclic ester compound such as an aliphatic polyester polyol, an aromatic polyester polyol, or ε-caprolactone obtained by esterifying a low molecular weight polyol and a polycarboxylic acid. Polyester obtained, these copolyesters, etc. can be used.

  Examples of the low molecular weight polyol include ethylene glycol, propylene glycol, 1,6-hexanediol, neopentyl glycol, and the like.

  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 the like. An anhydride or ester-forming derivative of can be used.

  In addition, as the polyether polyol, for example, one obtained by addition polymerization of alkylene oxide using one or more compounds having two or more active hydrogen atoms as an initiator can be used.

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

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

  Moreover, as said polyester ether polyol, what reacted the polyether polyol which the said alkylene oxide added to the said initiator and polycarboxylic acid can be used, for example. As the initiator and the alkylene oxide, the same ones exemplified as those usable when the polyether polyol is produced can be used. Moreover, as said polycarboxylic acid, the thing similar to what was illustrated as what can be used when manufacturing the said polyester polyol can be used.

  Moreover, as said polycarbonate polyol, what is obtained by making carbonate ester and polyol react, for example, what is obtained by making phosgene, bisphenol A, etc. react 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- Heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 3-methyl-1,5-pentanediol, 2 -Ethyl-1,3-hexanediol, 2-methyl-1,3-pro Diol, 2-methyl-1,8-octanediol, 2-butyl-2-ethylpropanediol, 2-methyl-1,8-octanediol, neopentyl glycol, 1,4-cyclohexanediol, 1,4-cyclohexane Relatively low molecular weight dihydroxy compounds such as dimethanol, hydroquinone, resorcin, bisphenol-A, bisphenol-F, 4,4′-biphenol, polyether polyols such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, Polyester polyols such as hexamethylene adipate, polyhexamethylene succinate, and polycaprolactone can be used.

  Examples of the polyol include 2,2′-dimethylolpropionic acid, 2,2′-dimethylolbutanoic acid, 2,2′-dimethylolbutyric acid, 5 from the viewpoint of introducing a hydrophilic group into the urethane resin. -Sulfoisophthalic acid, sulfoterephthalic acid, 4-sulfophthalic acid, 5 [4-sulfophenoxy] isophthalic acid and the like can be used.

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

  In addition, as the chain extender, conventionally known ones such as ethylenediamine, piperazine, and isophoronediamine can be used.

  Moreover, as an acrylic resin which can be used for manufacture of the said composite resin (II-1), what is obtained by superposing | polymerizing various (meth) acrylic monomers including methyl (meth) acrylate should be used. Can do.

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

  Among the above, methyl methacrylate causes blurring of a thin 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. It is preferable to use it for printing without any problems (improving fine line properties).

  Moreover, it is preferable to use the (meth) acrylic acid alkyl ester which has a C2-C12 alkyl group with the said methyl methacrylate, Acrylic acid which has a C3-C8 alkyl group It is more preferable to use an alkyl ester, and it is preferable to use n-butyl acrylate in order to obtain a printed matter excellent in printability. In addition, even when a conductive ink is used, it is particularly preferable for forming a conductive pattern having no fine lines and no bleeding.

  As the (meth) acrylic monomer, the crosslinkable functional group such as one or more amide groups selected from the group consisting of a methylolamide group and an alkoxymethylamide group is introduced into the acrylic resin, and more A cross-linkable functional group-containing (meth) acrylic monomer can be used to further improve the adhesion and the like.

  As the crosslinkable functional group-containing (meth) acrylic monomer, Nn-butoxymethyl (meth) acrylamide or N-isobutoxymethyl (meth) acrylamide is used for conductivity excellent in thin-line property and adhesion. It is preferable when obtaining laminated bodies, such as a property pattern.

  The composite resin (II-1) is, for example, a step of producing an aqueous dispersion of a urethane resin by reacting the above-described polyol, polyisocyanate and, if necessary, a chain extender and dispersing in water, and It can be manufactured by polymerizing the (meth) acrylic monomer in the aqueous dispersion to produce an acrylic resin.

  Specifically, a urethane resin is obtained by reacting the polyisocyanate with a polyol in the absence of a solvent or an organic solvent or in the presence of a reactive diluent such as a (meth) acryl monomer, If necessary, neutralize part or all of the hydrophilic group of the urethane resin with a basic compound, and if necessary, further react with a chain extender and disperse it in an aqueous medium. Thus, an aqueous dispersion of urethane resin is produced.

  Next, the (meth) acrylic monomer is supplied into the urethane resin aqueous dispersion obtained above, and the acrylic resin is produced by radical polymerization of the (meth) acrylic monomer in the urethane resin particles. . In addition, when the urethane resin is produced in the presence of a (meth) acrylic monomer, the (meth) acrylic monomer is supplied by supplying a polymerization initiator or the like after the production of the urethane resin. Acrylic resin is produced by radical polymerization.

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

  Moreover, as said resin composition (R), what contains a urethane resin can be used.

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

  These urethane resins are reacted using the same polyol as described in the description of the composite resin (II-1) or a polyol such as a conventionally known polycarbonate polyol and the same polyisocyanate or chain extender as described above. The urethane resin obtained by making it can be used. In that case, the urethane resin provided with the said desired structure can be manufactured by selecting suitably the said polyether polyol, the conventionally known polycarbonate polyol, aliphatic polyester polyol, etc. as said polyol.

  Moreover, as a vinyl resin which can be used for the said resin composition (R), the vinyl monomer containing the (meth) acryl monomer described by description of the said composite resin (II-1), a styrene, etc. is used. A vinyl resin obtained by radical polymerization can be used.

  Moreover, as a resin composition (R) which can be used for formation of the said resin layer (II), what used the melamine resin (II-2) containing was equipped with the outstanding adhesiveness and heat resistance. It is preferable when manufacturing a laminated body.

  As said melamine resin (II-2), the methylolation thing obtained by making the amino compound which has triazine rings, such as a melamine and a benzoguanamine, and formaldehyde react, and an alkoxylation thing can be used, for example.

  As said methylolation thing, a methoxy methylolation melamine resin, a butylated methylolation melamine resin, etc. can be used, for example.

  Examples of the alkoxylated product include those in which part or all of the methylol group of the methylolated product is sealed with monoalcohol or the like, and examples thereof include alkoxylated melamine resins such as methoxymethylolated melamine resins.

  The alkoxylated melamine resin may be prepared by reacting the amino compound having the triazine ring such as melamine or benzoguanamine, the formaldehyde, and the monoalcohol in a batch, and the amino compound having the triazine ring in advance. A product obtained by reacting with the formaldehyde to obtain a methylolated melamine compound and then reacting with the monoalcohol may be used.

  Specific examples of the alkoxylated melamine resin include Becamine M-3 manufactured by DIC Corporation.

  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) is appropriately added with known additives such as a crosslinking agent, a pH adjuster, a film forming aid, a leveling agent, a thickener, a water repellent, and an antifoaming agent as necessary. , May be contained.

  The cross-linking agent may be a resin layer (II) that has already formed a cross-linked structure before the fluid is applied, or after the fluid is applied, for example, by heating in a baking step or the like. A resin layer (II) that can be formed can be formed.

  Examples of the crosslinking agent include a metal crosslinking compound, a polyamine compound, an aziridine compound, a metal salt compound, an isocyanate compound, and the like that can react at a relatively low temperature of 25 ° C. to less than 100 ° C. to form a crosslinked structure. , A melamine compound, an epoxy compound, an oxazoline compound, a carbodiimide compound, and a thermal crosslinking agent capable of forming a crosslinked structure by reacting at a relatively high temperature of 100 ° C. or higher such as one or more selected from the group consisting of blocked isocyanate compounds In addition, various photocrosslinking agents can be used.

  Although the said crosslinking agent changes with kinds etc., it is preferable to use normally in the range of 0.01 mass%-60 mass% with respect to 100 mass parts of total mass of resin contained in the said primer, 0.1 mass It is more preferable to use in the range of 10% by mass to 10% by mass, and it is preferable to use in the range of 0.1% by mass to 5% by mass with excellent adhesion and electrical conductivity and excellent durability. This is preferable because a pattern can be formed.

  As described above, the resin composition (R) is applied to the layer (I) by applying the resin composition (R) to a part or all of the surface of the support (I1) or the support (I2) by the method described above. What laminated | stacked the said resin layer (II) can be obtained.

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

  Examples of a method for applying the fluid on the surface of the resin layer (II) include, for example, an ink jet printing method, a reverse printing method, a screen printing method, an offset printing method, a spin coating method, a spray coating method, a bar coating method, and a die coating. Method, slit coat method, roll coat method, dip coat method and the like.

  In particular, when the conductive layer (III) having a thin line shape of about 0.01 μm to 100 μm, which is required when realizing high density of an electronic circuit or the like, is formed using the fluid, inkjet printing is performed. It is preferable to apply the fluid by a method such as a reversal printing method.

  As the ink jet printing method, what is generally called an ink jet printer can be used. Specific examples include Konica Minolta EB100 and 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. .

  Further, as the reverse printing method, a letterpress reverse printing method, an intaglio reverse printing method, and the like are known. The fluid corresponding to the non-image area is selectively transferred to the surface of the plate to form the pattern on the surface of the blanket or the like, and then the pattern is transferred to the support (I1) or The method of making it transfer on the surface of the layer (I) which consists of a support body (I2), or the surface of the said resin layer (II) is mentioned.

  The firing performed after the fluid is applied by the above method is intended to form the conductive layer (II) by closely contacting and joining the conductive materials (x) such as metals contained in the fluid. Do as. The firing is preferably performed in the range of 80 ° C. to 300 ° C. for about 2 minutes to 200 minutes. The firing may be performed in the air, but from the viewpoint of preventing oxidation of the metal, part or all of the firing step may be performed in a reducing atmosphere.

  The baking step can be performed using, for example, an oven, a hot air drying furnace, an infrared drying furnace, laser irradiation, photosintering (light baking), light pulse irradiation, microwave, or the like.

  The fluid used for forming the conductive layer (III) contains the conductive substance (x) and, if necessary, a solvent and an additive, and generally contains conductive ink and plating nucleating agent. The thing which can be used is mentioned.

  As the conductive substance (x), 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, etc., and to use copper, silver, gold, etc. However, it is more preferable because it can form a conductive pattern having a low electric resistance and strong against corrosion, and it is more preferable to use silver.

  In addition, when the fluid is used as a plating nucleating agent, the conductive material (x) is coated with a surface of a metal particle made of a transition metal as described above, an oxide of the transition metal, or an organic substance. 1 or more types can be used.

  The transition metal oxide is usually in an inactive (insulating) state. For example, the metal is exposed by treatment with a reducing agent such as dimethylaminoborane to impart activity (conductivity). It becomes possible.

  In addition, examples of the metal whose surface is coated with the organic substance include those in which a metal is contained in resin particles (organic substance) formed by an emulsion polymerization method or the like. These are usually in an inactive (insulating) state. However, for example, by removing the organic substance using a laser or the like, it becomes possible to expose the metal and impart activity (conductivity).

  As the conductive substance (x), it is preferable to use particles having an average particle diameter of about 1 nm to 100 nm, and it is preferable to use those having an average particle diameter of 1 nm to 50 nm. Compared to the case of using a conductive substance (x) having an average particle size of 1, 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 a dynamic light scattering method after diluting the conductive substance (x) with a good dispersion solvent. For this measurement, Nanotrac UPA-150 manufactured by Microtrac can be used.

  The conductive substance (x) is preferably used in a range of 5% by mass to 90% by mass with respect to the total amount of the fluid used in the present invention. It is more preferable to use in.

  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.

  Examples of the solvent include aqueous media such as distilled water, ion exchange water, pure water, and ultrapure water, and organic solvents such as alcohol, ether, ester, and ketone.

  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, tetra Decanol, 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 mono Butyl 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.

  For the fluid, for example, ethylene glycol, diethylene glycol, 1,3-butanediol, isoprene glycol, and the like can be used together with the conductive substance (x), the solvent, and the like.

  The fluid is a liquid or viscous liquid having a viscosity measured by a B-type viscometer at 25 ° C. of 0.1 mPa · s to 500,000 mPa · s, preferably 0.5 mPa · s to 10,000 mPa · s. Are preferably used. When the fluid is applied (printed) by a method such as the ink jet printing method or letterpress reverse printing, it is preferable to use a fluid having a viscosity in the range of 5 mPa · s to 20 mPa · s.

  Part or all of the surface of the conductive layer (III) formed by applying and firing the fluid may be subjected to an 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. For example, a vacuum plasma discharge such as a normal pressure plasma discharge treatment method such as a corona discharge treatment method, a glow discharge treatment method performed under vacuum or reduced pressure, and an arc discharge treatment method. This is a process performed by a processing method.

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

  Further, the atmospheric pressure plasma discharge treatment method is performed in an environment containing an inert gas together with the oxygen, and further excellent adhesion without imparting excessive irregularities on the surface of the conductive layer (III). Is preferable. Argon, nitrogen, or the like can be used as the inert gas.

  When processing by the said normal pressure plasma discharge processing method, the normal pressure plasma processing apparatus (AP-T01) etc. by Sekisui Chemical Co., Ltd. can be used, for example.

  When processing by the said normal pressure plasma discharge processing method, it is preferable to carry out in the range of 5 liters / minute-50 liters / minute as flow rates of gas, such as air. Moreover, as an output, it is preferable that it is the range of 50W-500W. Moreover, it is preferable that the processing time by plasma is in the range of 1 second to 500 seconds.

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

  When the treatment is performed by the corona discharge treatment method, the output is preferably performed in the range of 5W to 300W. The time for the corona discharge treatment is preferably in the range of 0.5 seconds to 600 seconds.

  The plasma discharge treatment such as the corona discharge treatment is preferably performed under such a condition that unevenness is not formed on the surface of the layer (II) 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 may be performed on the surface of the non-oxidized conductive layer (III).

  Examples of the plating 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 method of combining two or more of these plating methods. .

  The plating layer (IV) formed by the above plating method has excellent adhesion to the surface of the conductive layer (III). Especially, the plating layer (IV) formed by the electroplating method with respect to the surface of the said conductive layer (III) can express especially outstanding adhesiveness.

  As the dry plating process, a sputtering method, a vacuum deposition method, or the like can be used. In the sputtering method, an inert gas (mainly argon) is introduced in a vacuum, negative ions are applied to the plating layer (IV) forming material to generate a glow discharge, and then the inert gas atoms are introduced. Ionized, vigorously struck gas ions against the surface of the plating layer (IV) forming material at high speed, and ejects atoms and molecules constituting the plating layer (IV) forming material to adhere to the surface of the conductive layer (III) vigorously. In this way, the plating layer (III) is formed.

As the plating layer (IV) forming material, chromium (Cr), copper (Cu), titanium (Ti), silver (Ag), platinum (Pt), gold (Au), nickel-chromium (Ni-Cr), SUS, copper - zinc _{(Cu-Zn), ITO,} may be used _{SiO 2, TiO 2, Nb 2} O 5, ZnO or the like.

  When performing the plating process by the sputtering method, for example, a magnetron sputtering apparatus or the like can be used.

  In addition, the vacuum deposition method heats various metals and metal oxides, which are plating layer (IV) forming materials, in a vacuum, and melts, evaporates, and sublimates them to form the surface of the conductive layer (IV). In this method, the plating layer (IV) is formed by attaching the metal atoms and molecules.

Examples of a material for forming the plating layer (IV) that can be used in the vacuum deposition method include aluminum (Al), silver (Ag), gold (Au), titanium (Ti), nickel (Ni), and copper (Cu). Chrome (Cr), tin (Sn), indium (In), SiO ₂ , ZrO ₂ , Al ₂ O ₃ , TiO _2, or the like can be used.

  The electroless plating method usable as the plating method includes, for example, bringing the electroless plating solution into contact with a conductive material such as palladium or silver constituting the conductive layer (III). This is a method of forming an electroless plating layer (coating) made of a metal film by depositing a metal such as copper contained in an electroplating solution.

  As the electroless plating solution, for example, a material containing a conductive material 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 may be used. it can.

  Examples of the reducing agent that can be used include dimethylaminoborane, hypophosphorous acid, sodium hypophosphite, dimethylamine borane, hydrazine, formaldehyde, sodium borohydride, and phenols.

  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, iminodiacetic acid, arginine, aspartic acid and glutamic acid; aminopoly acids such as iminodiacetic acid, nitrilotriacetic acid, ethylenediaminediacetic acid, ethylenediaminetetraacetic acid It may contain complexing agents such as organic acids such as carboxylic acids, soluble salts of these organic acids (sodium salts, potassium salts, ammonium salts, etc.), amines such as ethylenediamine, diethylenetriamine, and triethylenetetramine. .

  The temperature of the electroless plating solution when using the electroless plating solution is preferably in the range of 20 ° C to 98 ° C.

  The electroplating process that can be used as the plating process is, for example, a conductive material constituting the conductive layer (III) or the surface of the electroless plating layer (coating) formed by the electroless process. In addition, the conductive material constituting the conductive layer (III) disposed on the negative electrode is made of a metal such as copper contained in the electroplating solution by passing an electric current in contact with the electroplating solution or the electroless treatment. This is a method of forming an electroplating film (metal film) by depositing on the surface of the electroless plating layer (film) formed by the above method.

  As said electroplating liquid, what contains metals, such as copper, nickel, chromium, cobalt, tin, those sulfides, sulfuric acid, etc., and an aqueous medium can be used. Specifically, those containing copper sulfate, sulfuric acid and an aqueous medium can be used.

  The temperature of the electroplating solution when using the electroplating solution is preferably in the range of 20 ° C to 98 ° C.

  In the electroplating method, workability is good without using a highly toxic substance. Therefore, it is preferable to form a layer made of copper by the electroplating method.

  The laminate obtained by the above method can be used as a conductive pattern. Specifically, formation of electronic circuits using silver ink or the like, formation of organic solar cells or electronic book terminals, organic EL, organic transistors, flexible printed circuit boards, layers constituting peripheral RFID, peripheral wiring, electromagnetic waves of plasma display It can be suitably used for forming a conductive pattern in manufacturing a shield wiring or the like, more specifically, a circuit board.

  When the laminate is used for a conductive pattern, a desired pattern can be obtained by applying a fluid that can form the conductive layer (III) to a position corresponding to a desired pattern shape to be formed and baking it. Can be produced.

  Moreover, the said conductive pattern can be manufactured by photolithographic etching methods, such as a subtractive method, a semiadditive method, and a full additive method, for example.

  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 is removed by subsequent development processing. In this method, a desired pattern is formed by dissolving and removing the plated layer (IV) and the conductive layer (III) of the formed portion with a chemical solution. As the chemical solution, a chemical solution containing copper chloride, iron chloride or the like can be used.

  The semi-additive method produces a laminate comprising the layer (I) comprising the support (I1) or the support (I2), the resin layer (II) and the conductive layer (III), If necessary, the surface of the conductive layer (III) is oxidized by plasma discharge treatment on the surface, and then a plating resist layer having a shape corresponding to a desired pattern is formed on the oxidized surface as necessary. Then, after forming a plating layer (IV) by an electroplating method or an electroless plating method, the plating resist layer and the conductive layer (III) in contact with the plating resist layer are dissolved and removed in a chemical solution, etc. This is a method of forming a pattern.

  In the full additive method, the resin layer (II) is provided on the layer (I) composed of the support (I1) or the support (I2), and the conductive layer (III) is formed by an ink jet method or a reverse printing method. After printing the pattern, if necessary, the surface of the conductive layer (III) is subjected to plasma discharge treatment to form a pattern. Then, the oxidized surface of the conductive layer (III) is electroplated or electrolessly formed. This is a method for forming a desired pattern by forming a plating layer (IV) by a plating method.

  Since the conductive pattern obtained by the above method can provide excellent durability at a level that can maintain good electrical conductivity without causing peeling between layers, an electron using silver ink or the like. Formation of circuit forming substrates used for circuits, integrated circuits, etc., formation of organic solar cells and electronic book terminals, organic EL, organic transistors, flexible printed circuit boards, RFID and other layers and peripheral wiring, plasma display electromagnetic waves Of shield wiring and the like, it can be suitably used for applications that require particularly durability. In particular, since the conductive pattern subjected to the plating treatment can form a highly reliable wiring pattern capable of maintaining good electrical conductivity without causing disconnection or the like over a long period of time, for example, a copper-clad laminate is generally used. (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 of Support (F-1)]
By preparing pyromellitic anhydride and 4,4′-oxydianiline in a molar ratio of 50/50 and polymerizing them in N, N ″ -dimethylacetamide, a nonvolatile content of 20% by mass was obtained. A polyamic acid solution (A-1) was obtained.

  Further, biphenyl 3,4,3 ′, 4′-tetracarboxylic acid dihydrate and 4,4′-oxydianiline are prepared in a molar ratio of 50/50, and these are prepared as N, N′-. By polymerizing with dimethylacetamide, a polyamic acid solution (A-2) having a nonvolatile content of 20% by mass was obtained.

  Next, the polyamic acid solution (A-1) and the polyamic acid solution (A-2) are combined into [the mass of polyamic acid contained in the polyamic acid solution (A-1)] / [the polyamic acid solution. The mixture was obtained by mixing so that the mass of the polyamic acid contained in (A-2) was 35/65 and mixing 0.2% by mass of silica particles having an average particle size of 0.3 μm.

  Thereafter, the mixture was filtered and defoamed, extruded from a T-die and cast on a drum.

  The cast material was dried at 100 ° C. for 60 seconds to produce a film containing the polyamic acid and the silica.

  After peeling the film from the drum, the film is dried at 250 ° C. for 60 seconds, then dried at 300 ° C. for 60 seconds, and then dried at 400 ° C. for 75 seconds to obtain a support (F-1) made of a polyimide film. It was. The thickness of the support was 40 μm.

[Preparation of Support (F-2)]
50/50 molar ratio of pyromellitic anhydride, 4,4′-oxydianiline, biphenyl 3,4,3 ′, 4′-tetracarboxylic acid dihydrate and 4,4′-oxydianiline The polyamic acid solution having a nonvolatile content of 20% by mass was prepared by polymerizing them in a ratio of / 100 and polymerizing them in N, N′-dimethylacetamide. Further, a mixture was obtained by mixing 0.2% by weight of silica particles having an average particle size of 0.3 μm.

  Thereafter, the mixture was filtered and defoamed, extruded from a T-die and cast on a drum.

  The cast material was dried at 100 ° C. for 60 seconds to produce a film containing the polyamic acid and the silica.

  After peeling the film from the drum, the film is dried at 250 ° C. for 60 seconds, then dried at 300 ° C. for 60 seconds, and then dried at 400 ° C. for 75 seconds to obtain a support (F-2) made of a polyimide film. It was. The thickness of the support was 39 μm.

[Preparation of Support (F-3)]
Instead of the polyamic acid solution (A-1) and the polyamic acid (A-2), biphenyl 3,4,3 ′, 4′-tetracarboxylic acid dihydrate and 1,4-diaminobenzene A support (F) made of a polyimide film in the same manner as the support (F-1), except that a polyamic acid obtained by polymerizing one prepared at a ratio of 50/50 is used. -3) was produced. The thickness of the support was 49 μm.

[Preparation of Support (F-4)]
Instead of the polyamic acid solution (A-1) and the polyamic acid (A-2), a polymer prepared by mixing pyrophosphoric anhydride and 4,4′-oxydianiline in a molar ratio of 50/50 was polymerized. Except that the polyamic acid thus obtained is used and 0.05 mass% of calcium phosphate having an average particle diameter of 1 μm is used instead of silica having an average particle diameter of 0.2 μm. The support body (F-4) which consists of a polyimide film was produced by the method similar to the preparation method of 1). The thickness of the support was 50 μm.

[Preparation of Resin Composition (R-1)]
Polyester polyol (polyester polyol obtained by reacting 1,4-cyclohexanedimethanol, neopentyl glycol and adipic acid) in a nitrogen-substituted container equipped with a thermometer, a nitrogen gas introduction tube, and a stirrer 100 parts by weight, 2,2-dimethylolpropionic acid 17.6 parts by weight, 1,4-cyclohexanedimethanol 21.7 parts by weight, dicyclohexylmethane diisocyanate 106.2 parts by weight in a mixed solvent of methyl ethyl ketone 178 parts by weight By making it react, the organic solvent solution of the urethane prepolymer which has an isocyanate group in the molecular terminal 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. Thus, an aqueous dispersion of urethane resin was obtained.

  Next, 8.8 parts by mass of a 25% by mass ethylenediamine aqueous solution is added to the aqueous dispersion, and the particulate polyurethane resin is chain-extended by stirring, followed by aging / desolving, thereby solid content concentration 30 An aqueous dispersion of mass% urethane resin (r-1) was obtained. The urethane resin (r-1) had 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 (r-1) 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 comprising 60 parts by mass of methyl methacrylate, 30 parts by mass of n-butyl acrylate, and 10 parts by mass of Nn-butoxymethylacrylamide, and ammonium persulfate 20 parts by mass of an aqueous solution (concentration: 0.5% by mass) was dropped and polymerized from a separate dropping funnel over 120 minutes while maintaining the temperature in the reaction vessel at 80 ± 2 ° C.

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

  The temperature in the reaction vessel is cooled to 40 ° C., then deionized water is used so that the non-volatile content becomes 20.0% by mass, and then filtered through a 200 mesh filter cloth to obtain a resin composition (R -1) was obtained.

[Preparation of resin composition (R-2)]
In a reaction flask equipped with a reflux condenser, a thermometer, and a stirrer, 600 parts by mass of formalin containing 37% by mass of formaldehyde and 7% by mass of methanol (formaldehyde content: 222 parts by mass (7.4 mol), methanol content: 42 200 parts by mass of water and 350 parts by mass (10.92 mol) of methanol were added to (parts by mass (1.31 mol)). After adding 25 mass% sodium hydroxide aqueous solution to this aqueous solution and adjusting to pH 10, melamine 310 mass parts (2.46 mol) was added, liquid temperature was raised to 85 degreeC, and it was made methylol (primary reaction) (reaction time). : 1 hour).

  Thereafter, formic acid was added to adjust the pH to 7, followed by cooling to 60 ° C. to carry out an etherification reaction (secondary reaction). A 25% by mass aqueous sodium hydroxide solution was added at a cloudiness temperature of 40 ° C. 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 ° C. (demethanol removal time: 4 hours) to obtain a resin composition (R-2) containing a melamine resin having a nonvolatile content of 80% by mass.

  In addition, the measuring method of the said cloudiness temperature is demonstrated below. 1 g of resin was sampled and mixed with 100 ml of hot water adjusted to the specified temperature. At that time, the highest temperature when the resin became cloudy without dissolving in hot water was defined as the cloudiness 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]
TEC-4AX (corona surface modification evaluation apparatus manufactured by Kasuga Electric Co., Ltd., gas: air (oxygen concentration of about 21% by mass), gap: 1.5 mm, output: 100 W is applied to the surface of the support (F-1). , Treatment time; 2 seconds).

  Thereafter, the resin composition (R-1) is applied to the surface of the support using a spin coater so that the dry film thickness becomes 0.1 μm, and then 80 ° C. using a hot air dryer. By drying for 5 minutes under the condition of ° C., a laminate in which the resin layer (II) was laminated on the surface of the layer (I) made of the support was obtained.

  Next, the conductive ink is applied to the surface of the resin layer (II) by a spin coating method, and then baked at 250 ° C. for 3 minutes, thereby forming the conductive layer (III) (thickness) formed of the silver. 0.1 μm) was produced. The surface resistance of the conductive layer (III) was measured by the method described later and found to be 2Ω / □.

  Next, the surface of the conductive layer (III) was subjected to TEC-4AX (corona surface modification evaluation apparatus manufactured by Kasuga Electric Co., Ltd., gas; air (oxygen concentration of about 21% by mass), gap; 1.5 mm, output; , Treatment time; 2 seconds). The surface resistance of the conductive layer (III) before the corona discharge treatment was 2Ω / □, but the surface resistance of the conductive layer (III) subjected to the corona discharge treatment increased to 5Ω / □. Moreover, when the surface was analyzed using the same X-ray photoelectron analyzer, a peak indicating that silver forming the conductive layer (III) was oxidized could be confirmed.

Next, the oxidized surface of the conductive layer (III) is set as a cathode, copper-containing copper is set as an anode, and electroplating is performed at a current density of 2 A / dm ² for 15 minutes using an electroplating solution containing copper sulfate. By performing, a copper plating layer having a thickness of 8 μm was laminated on the surface of the conductive layer (III). 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 laminate (L-1) in which the layer (I), the resin layer (II), the conductive layer (III), and the plating layer (IV) made of the support were laminated was obtained.

[Example 2]
Except for using the resin composition (R-2) in place of the resin composition (R-1), a layer (I) and a resin layer (II) comprising the support are prepared in the same manner as in Example 1. ), The conductive layer (III), and the plating layer (IV) were obtained to obtain a laminate (L-2).

[Example 3]
Instead of the support (F-1), the support (F-2) is used, and instead of the resin composition (R-1), a resin composition (R-1) and a resin composition ( R-2) and the layer (I) and the resin layer (II) comprising the support by the same method as in Example 1 except that a mixture containing 50/50 (solid content) is used. And the laminated body (L-3) which the said electroconductive layer (III) and the said plating layer (IV) laminated | stacked was obtained.

[Comparative Example 1]
Except for using the support (F-3) instead of the support (F-1), the layer (I) and the resin layer (II) comprising the support are formed in the same manner as in Example 1. A laminate (L′-1) in which the conductive layer (III) and the plating layer (IV) were laminated was obtained.

[Comparative Example 2]
Except for using the support (F-4) instead of the support (F-1), the layer (I) and the resin layer (II) comprising the support are formed in the same manner as in Example 1. Laminated body (L′-2) in which the conductive layer (III) and the plating layer (IV) are laminated.

<Adhesion; evaluation by peel test>
The peel strength of the laminate obtained above was measured by a method based on IPC-TM-650 and NUMBER 2.4.9. The lead width used for the measurement was 1 mm, and the peel angle was 90 °. The peel strength tends to show a higher value as the thickness of the plating layer increases, but the measurement of the peel strength in the present invention was performed based on the measurement value in the currently used plating layer of 8 μm. .

<Heat resistance; evaluation by peel test after heat test (temperature 150 ° C.)>
The laminate obtained above was dried for 168 hours using a dryer set at 150 ° C. Peel strength was measured by the same method as described in <Evaluation by peel test> except that the dried laminate was used.

<Moisture and heat resistance; evaluation by peel test after moisture and heat test (temperature 135 ° C. and humidity 85%)>
The laminate obtained above was placed in a HAST tester set at a temperature of 135 ° C. and a humidity of 85% for 168 hours. Peel strength was measured by the same method as described in <Evaluation by Peel Test>, except that the laminate after the wet heat test was used.

Claims (8)

A support (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), or 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), and a conductive substance ( A laminate having a resin layer (II) for receiving a fluid containing x) and a conductive layer (III) formed of the conductive substance (x).

[R ^{1 to} R ⁸ in General Formula (1) each independently represent a hydrogen atom, a hydroxyl group, a halogen atom , an alkyl group, or an aryl group. n represents an integer of 1 to 1,000. ]

[R ^{9 to} R ²² in General Formula (2) each independently represent a hydrogen atom, a hydroxyl group, a halogen atom , an alkyl group, or an aryl group. m represents an integer of 1 to 1,000. ]   The layered product according to claim 1, wherein the layer (I) comprising the support further contains silica fine particles having an average particle size of 0.01 µm to 1 µm. The resin layer (II) is a composite resin (II-1) composed of core-shell type composite resin particles composed of an acrylic resin as a core layer and a urethane resin as a shell layer , or a melamine resin (II- The laminate according to claim 1, which is 2).   The laminated body of Claim 1 which has plating layer (IV) in a part or all of the surface of the said conductive layer (III).   The laminate according to claim 4, wherein a part or all of the conductive layer (III) is composed of oxidized silver.   The laminate according to claim 4, wherein the plating layer (IV) is formed by an electrolytic copper plating method.   The electroconductive pattern which consists of a laminated body of any one of Claims 1-6.   The electric circuit which has a laminated body of any one of Claims 1-6.