JP6327442B2 - Method for producing conductive material and conductive material - Google Patents

Description

  The present invention relates to a method for producing a conductive material that can be suitably used as a laminated substrate for a printed wiring board. Moreover, this invention relates to the electroconductive material manufactured using the said manufacturing method.

  The laminated substrate for printed wiring boards is a material having a structure in which a low dielectric constant material and a conductive thin layer are laminated. Conventionally, for example, a laminate with flexible copper (FCCL) is a method in which a heat-resistant polymer film and a copper foil are bonded using an epoxy resin adhesive, or a resin solution is coated on the copper foil surface. It has been manufactured using a method such as drying.

  In recent years, there has been a demand for higher density and higher performance of printed wiring boards due to the downsizing and speeding up of electronic devices. To meet this demand, a conductive layer (copper foil) with a smooth surface and a sufficiently thin surface is required. There is a need for printed wiring boards having layers.

  However, the method using an epoxy resin adhesive has the disadvantages of low heat resistance and inferior insulation reliability. Moreover, in the manufacturing method using the copper foil, since the manufacturing is performed while pulling out the copper foil wound in a roll shape, it is difficult to handle, so the copper foil cannot be made sufficiently thin, In addition, in order to improve the adhesion with the polymer film, it is necessary to roughen the surface of the copper foil, and the printed wiring board has a high density and high performance, that is, a high frequency (GHz band), a high The request for suppressing transmission loss in the transmission speed (several tens of Gbps) region has not been sufficiently met.

  In response to the demand for higher performance of printed wiring boards, for example, a copper thin film substrate in which a copper thin layer is laminated on a polymer film regardless of bonding of a copper foil with an adhesive is disclosed (for example, patents). Reference 1). This copper thin film substrate manufacturing method uses a sputtering method to provide a copper thin film layer as a first layer on the surface of a heat-resistant insulating substrate, and form a copper thick film layer by electroplating on the first layer. Is.

  Since the copper thin film substrate described in Patent Document 1 can reduce the thickness of the copper foil layer, it responds to the demand for higher density and higher performance of the printed wiring board, but a method called sputtering that requires vacuum equipment. Since it is used, there are problems that the process is complicated and expensive, and the size of the base material is limited due to equipment.

  Therefore, as a method for producing a laminated substrate for a printed wiring board that does not require vacuum equipment for production, and does not use bonding of copper foil with an adhesive, the conductive layer (copper foil layer) can be made sufficiently thin. A metal conductive layer is formed by coating metal fine particles on an insulating base material, followed by heating and baking, and a conductive copper foil layer having a necessary thickness is obtained by plating on the metal conductive layer. A method is disclosed (for example, see Patent Documents 2 to 3).

  In Patent Document 2, (1) a dispersion containing metal thin film precursor fine particles having a primary particle size of 200 nm or less, which are fused to each other by heat treatment, is applied onto an insulating substrate, and the metal thin film is formed by heat treatment. There is disclosed a method of manufacturing a laminated substrate including a step of forming and forming a conductive layer, and (2) a step of performing electroplating on the metal thin film to form a metal film.

  Further, in Patent Document 3, a first conductive layer on an insulating substrate and a second conductive layer formed thereon are provided, and the first conductive layer includes a metal particle of 1-500 nm. A printed wiring board substrate characterized in that it is configured as a coating layer of a conductive ink, and the second conductive layer is configured as a plating layer, and a method for manufacturing the same.

  These methods are excellent in that a conductive film layer having an appropriate thickness can be obtained without using vacuum equipment by forming a conductive metal layer on an insulating substrate and performing electroplating. However, in order to perform electrolytic plating, it is necessary to form a conductive metal film having high in-plane uniformity and sufficient conductivity. However, the surface of an insulating substrate usually used for a conductive material is not necessarily excellent in coating properties, and often a fine “drop” can be generated by repelling a coating dispersion or ink. , Uneven coating may occur. If there is such “missing” or “unevenness”, it is difficult to form a uniform conductive layer having sufficient conductivity, and in the subsequent plating process, plating defects and plating film thickness become non-uniform. Practical issues remain.

The conductivity of the conductive layer thus formed is, for example, described in Patent Document 2 as a volume resistance value required for a metal thin film used for this purpose, 1 × 10 ⁻⁴ Ωcm or less, more preferably 1 × 10 ⁻⁵ Ωcm or less is recommended. In order to form a conductive layer exhibiting such a low resistivity, it is necessary to visually check or use a general optical microscope for reasons such as “missing” on the insulating base material (the coating liquid “repells” on the base material). An area where the coating material is not present on the base material with a level that can be confirmed) and the coating is applied without any "unevenness", and the conductive ink or metal film precursor fine particle dispersion applied. The dispersant and other organic substances contained therein must be volatilized and decomposed by heating to be removed from the coating layer, and the particles must be in a sufficiently fused state.

  However, when a conductive film is formed by heating and baking a coating film on which a dispersion of these fine metal particles and metal thin film precursor particles is applied, it is difficult to completely fill the voids between the particles, It becomes a metal thin film leaving voids. In addition, although the particle shape in the film changes due to fusion and particle growth, and the particles are partially connected, a phenomenon in which the coating density decreases as a whole is often observed. As a result, sufficient electrical conductivity is not exhibited and plating cannot be performed, or even if it can be performed, it takes a very long time. Also, electroplating failure due to the occurrence of a partial non-conductive portion, plating nonuniformity There were problems such as happening. In addition, the metal thin film having a partially low coating density and a large number of voids as described above has a problem that the void portion becomes a starting point of breakage and the conductive layer is peeled off from the insulating base material.

  As a countermeasure against this problem, in Patent Document 3, filling the voids in the first conductive layer formed on the insulator base material by electroless metal plating causes the elimination of poor conduction and the cause of peeling. Although it has been proposed to reduce the starting point of fracture, the voids in the conductive film fused by heating and firing often exist as isolated spaces inside the film, and the chemical solution does not penetrate, so electroless There may be voids after plating, which is not a sufficient solution.

  In addition, palladium is usually used as a catalyst for electroless plating. However, when expensive palladium is used as the catalyst metal, the cost of the electroless plating treatment process is increased, and it is formed by heating and firing. If the voids in the conductive layer are filled by electroless plating using a palladium catalyst, the palladium is randomly taken into the conductive layer, and the subsequent removal of the palladium in the etching process does not sufficiently remove the circuit board characteristics. There were problems such as causing it to drop.

  Therefore, as an inexpensive electroless plating catalyst that does not use palladium, for example, a method using a silver salt as a catalyst is provided (see, for example, Patent Document 4). In this method, an aqueous solution containing a silver salt and a surfactant is added with 2 to 4 times moles of a reducing agent with respect to the silver salt to form a silver hydrosol, which is brought into contact with the object to be plated, In this method, electroless plating is performed by applying a silver colloid. However, this method has a drawback that a large amount of reducing agent is required, the production cost is high, the stability of the formed silver hydrosol is low, and aggregation precipitation is likely to occur. Further, in the method disclosed in this document, fiber compositions such as paper and nonwoven fabric, glass, ceramics, and plastics are exemplified as objects to be plated. However, paper and cloth are practically used as objects to be plated. Only "porous materials" such as are used, and the catalyst is applied by utilizing the fact that the catalyst "hangs" in the porous structure of the object to be plated. When applying a uniform catalyst, it is difficult to apply the method disclosed in Patent Document 4.

  Moreover, silver salt 0.01-100 mmol / L, anionic surfactant 0.01-0.5 wt. %, And a catalyst solution for electroless plating containing 0.1 to 0.8 moles of a reducing agent with respect to the silver salt (see, for example, Patent Document 5). On the other hand, it is said that the catalyst solution is 0.1 to 0.8-fold mol, a small amount of the reducing agent compared with Patent Document 4, and has good stability.

  In the methods described in Patent Documents 4 and 5, the object to be plated is immersed in a dilute dispersion of silver colloid, and the silver colloid is mainly removed by electrostatic interaction between the silver colloid and the surface of the object to be plated. It is attached to the surface and used as a catalyst for electroless plating, and the amount of silver colloid attached is controlled by the immersion time, but the concentration of the catalyst attached on the object to be plated is not sufficient, Application to a large area substrate such as a laminated substrate for a printed wiring board is difficult in practice because it requires a long time in a large immersion tank. In addition, in such a method of natural adsorption in a liquid, the adsorptivity of silver colloid to the object to be plated is low, so that the catalytic substance is removed from the object to be plated during the water washing process or electroless plating after the silver colloid catalyst is applied. (Silver colloid) easily drops off, plating deposition becomes uneven, and decomposition of the plating bath occurs due to contamination of the plating solution. Although these documents also mention the possibility of applying a silver colloid on the object to be plated to give a catalyst, the low concentration of silver colloid as disclosed is sufficient on the object to be plated by application. A large amount of silver colloid cannot be applied, and uniform plating cannot be performed on the object to be plated. Also, when the disclosed silver colloid is concentrated, agglomeration occurs and coating film formation cannot be performed. There was a problem.

JP-A-9-136378 JP 2006-305914 A JP 2010-272837 A JP-A 64-068478 JP-A-10-030188

  The present invention has been made in view of the above-described problems of the prior art, and the problem to be solved by the present invention is not to use copper foil bonding with an adhesive, but to use an appropriate thickness without using vacuum equipment. Another object of the present invention is to provide a method for producing a conductive material having a conductive layer. More specifically, a resin layer having a specific chemical structure is formed on the substrate to ensure coating uniformity on the resin layer, and the layer containing the coated metal fine particles is non-uniform. There is no need to convert to a conductive film, and there is no concern about deterioration of properties due to the palladium catalyst, and the conductive layer is formed on the insulator substrate with sufficient adhesion strength by a simpler and more reliable method. An object of the present invention is to provide a method for producing a conductive material which is laminated. Furthermore, this invention aims at providing the electroconductive material which can be used suitably as a laminated base material for printed wiring boards manufactured using the said manufacturing method.

  As a result of intensive studies to solve the above problems, the present inventors have formed a resin layer on various insulating substrates, thereby protecting gold, silver, copper, A non-conductive layer containing metal fine particles containing platinum can be easily obtained by a coating method, and the non-conductive layer exhibits excellent electroless plating catalytic activity and has high adhesion. It discovered that it functions as a scaffold of the induced plating film, and came to complete this invention.

That is, the present invention
(1) A step of applying a resin layer forming composition (b) on the insulating substrate (A) to form a resin layer (B),
(2) A group consisting of gold, silver, copper and platinum whose surface is protected with a compound (c1) having a nitrogen atom, sulfur atom, phosphorus atom or oxygen atom on the resin layer (B) obtained in (1) A step of applying a dispersion (C) containing 0.5% by mass or more of one or more metal fine particles (c2) selected from the above, and forming a nonconductive layer (D) having a resistance value of 10 ⁷ Ω or more ,
(3) performing electroless plating on the substrate having the nonconductive layer (D) obtained in (2) to form a conductive layer (E);
A method for producing a conductive material comprising:
The resin layer forming composition (b)
A method for producing a conductive material, which is a composition for forming a resin layer containing a urethane resin (b1), a vinyl polymer (b2), and an aqueous medium (b3), and a conductive material obtained by this method The manufacturing method of the laminated base material for printed wiring boards using a conductive material is provided.

  According to the present invention, a high-performance conductive material, a printed wiring board substrate, and a printed wiring board that can be used in the high-density mounting field can be manufactured at low cost without the need for vacuum equipment.

It is a schematic diagram showing the one form cross section of the base material which formed the resin layer (B) on the insulating base material (A). It is a schematic diagram showing the one form cross section of the base material which formed the nonelectroconductive layer (D) on the base material of FIG. It is a schematic diagram showing the one form cross section of the base material which formed the nonelectroconductive layer (D) on the base material of FIG. It is a schematic diagram showing one form cross section of the electroconductive material which formed the electroconductive layer (E) on the base material of FIG. 2 by electroless plating. Schematic diagram showing one mode cross section of a conductive material in which a conductive layer (E) is formed by electroless plating on the substrate of FIG. FIG. 5 is a schematic diagram showing a cross-section of a conductive material in which a conductive layer (F) is formed by electroplating on the conductive layer (E) in FIG. 4 and a laminated substrate for a printed wiring board. FIG. 6 is a schematic view illustrating a cross-section of a conductive material in which a conductive layer (F) is formed by electroplating on the conductive layer (E) in FIG. 5 and a laminated substrate for a printed wiring board. In Example 2, it is an electron micrograph of the film | membrane surface after baking the silver particle film formed on the resin layer produced on the polyimide film at 150 degreeC for 30 minutes. In Example 2 in which black and white binarization was performed to calculate the surface coverage, an electron microscope of the film surface after baking the silver particle film formed on the resin layer produced on the polyimide film at 150 ° C. for 30 minutes It is a photograph (black and white binarization of the electron micrograph of FIG. 8). In Example 1, it is the external appearance photograph (A) of the surface which formed the nonelectroconductive layer on the resin layer, and the external appearance photograph (B) of the surface which apply | coated the silver fine particle on the polyimide in the comparative example 1. The shadow in the upper right part of the photograph (A) is a shadow at the time of photography. In Example 30, it is an electron micrograph of the film | membrane surface after baking the silver particle film formed on the resin layer produced on the polyimide film at 270 degreeC for 30 minutes. In Example 2 in which black and white binarization was performed to calculate the surface coverage, an electron microscope of the film surface after baking the silver particle film formed on the resin layer produced on the polyimide film at 270 ° C. for 30 minutes It is a photograph (black and white binarization of the electron micrograph of FIG. 11). In the comparative example 6, it is the external appearance photograph of the surface which apply | coated the dispersion liquid (c) -3 to the resin layer (b) -4 surface formed on the polyimide.

The present invention is described in detail below.
<Insulating base material (A)>
As the insulating substrate (A) used in the present invention, for example, polyimide resin, polyethylene terephthalate, polyethylene naphthalate, polyester resin such as liquid crystal polymer, polyester amide resin, cycloolefin polymer, paper phenol, paper epoxy, glass epoxy, Materials such as ABS resin, glass, and ceramics can be suitably used, and any form of a flexible material, a rigid material, and a rigid flexible material can be used. These insulating base materials (A) can be used as a thin film and as a sheet or plate as a thick one.

The polyimide and polyester resin films can be used for flexible substrates. Examples of the polyimide resin include Kapton (Toray DuPont), Upilex (Ube Industries), Apical (Kaneka), Pomilan (Arakawa Chemical), etc. The film can be suitably used. Further, as the polyester resin, a Bexter series (Kuraray) of liquid crystal polymer can be suitably used. In addition, these films may be used in a state of being cut into a certain size, or may be used in a continuous film state.
These insulating base materials (A) used in the present invention may have through holes for connecting the front and back surfaces. The through hole can be formed by a known and common method such as a drill, a puncher, or a laser.

  The insulating base material (A) used in the present invention has an insulating base material (A) and a resin layer (B), and a non-conductive layer (D) formed in a later step, and adhesion to the plating film. In order to improve the surface treatment, a surface treatment may be performed before applying the metal fine particle dispersion (C) described later. As a surface treatment method of the insulating base material (A), various methods may be appropriately selected. For example, physical methods such as UV treatment, ozone treatment, corona treatment, and plasma treatment can be suitably used. . Moreover, when the insulating base material (A) is a polyimide resin, a chemical method of treating the base surface of the polyimide resin with an alkaline aqueous solution may be used. When the insulating substrate (A) is a polyester resin, the surface of the polyester resin is preferably subjected to UV treatment, corona treatment, ozone treatment, or plasma treatment. These surface treatment methods may be performed independently or a plurality of methods may be performed in succession.

<Resin layer forming composition (b)>
The resin layer forming composition (b) used in the present invention is a resin layer forming composition containing a urethane resin (b1), a vinyl polymer (b2), and an aqueous medium (b3). Furthermore, other additives can be contained as required.

  By using the said urethane resin (b1), a softness | flexibility can be provided to a resin layer (B) and the followability to an insulating base material (A) can be ensured. As a urethane resin (b1), what is obtained by making polyisocyanate, a polyol, and a chain extender react as needed can be used normally or synthesized. In particular, adhesion to the insulating base material (A) and durability from the plating treatment in the electroless plating step performed in the subsequent step (base material due to the influence of a plating agent made of a strong alkali or strong acid substance) Is not a peeling from the resin), and is preferably a urethane resin having an aliphatic cyclic structure of 2,000 mmol / kg to 5,500 mmol / kg with respect to the total amount of the urethane resin (b1), particularly 3,000 mmol. It is possible to use a resin having an aliphatic cyclic structure of / kg to 5,000 mmol / kg, such as adhesion of resin to the insulating substrate (A), in particular, the insulating substrate ( It is more preferable in preventing the resin layer (B) from peeling off from A) and improving durability.

  Examples of the aliphatic cyclic structure include a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a propylcyclohexyl group, a tricyclo [5,2,1,0,2,6] decyl group, and a bicyclo [4]. , 3,0] -nonyl group, tricyclo [5,3,1,1] dodecyl group, propyltricyclo [5,3,1,1] dodecyl group, norbornene group, isobornyl group, dicyclopentanyl group, adamantyl Examples thereof include a cyclohexyl group, a norbornene group, an isobornyl group, and an adamantyl group.

  The aliphatic cyclic structure as described above is a polyisocyanate or aliphatic ring having an aliphatic cyclic structure as the polyisocyanate (b1-1) or polyol (b1-2) used in the production of the urethane resin (b1). By using a polyol having a formula structure, it can be introduced into the urethane resin (b1). Among them, it is preferable to use a urethane resin having an aliphatic cyclic structure derived from a polyol having an aliphatic cyclic structure, and a polyisocyanate having an aliphatic cyclic structure and a fat derived from a polyol having an aliphatic cyclic structure. It is particularly preferable to use a urethane resin having an alicyclic structure in order to greatly improve the adhesion of the resin layer (B) to the various insulating substrates (A).

  Moreover, as said urethane resin (b1), it is preferable to use what has a hydrophilic group from a viewpoint of providing the favorable water dispersion stability in an aqueous medium (b3).

  As said hydrophilic group, an anionic group, a cationic group, and a nonionic group can be used, for example, It is more preferable to use an anionic group.

  As the anionic group, for example, a carboxyl group, a carboxylate group, a sulfonic acid group, a sulfonate group and the like can be used. Among them, a carboxylate group partially or wholly neutralized with a basic compound or the like It is preferable to use a sulfonate group in order to impart good water dispersibility.

  Examples of basic compounds that can be used for neutralizing the anionic group include organic amines such as ammonia, triethylamine, pyridine, morpholine, alkanolamines such as monoethanolamine, sodium, potassium, lithium, and calcium. Although a metal base compound is mentioned, since the said metal salt compound may inhibit electroconductivity etc., it is preferable to use the said organic amine and alkanolamine.

  When the carboxylate group or sulfonate group is used as the anionic group, they are preferably present in the range of 5 mmol / kg to 4,000 mmol / kg with respect to the entire urethane resin (b1), and 50 mmol / kg. It is more preferable to exist in the range of ˜2,000 mmol / kg in order to maintain good water dispersion stability of the urethane resin (b1) particles.

Moreover, as said cationic group, a tertiary amino group etc. can be used, for example.
Examples of the acid that can be used when neutralizing part or all of the tertiary amino group include organic acids such as acetic acid, propionic acid, lactic acid, and maleic acid, sulfonic acid, methanesulfonic acid, and the like. Organic sulfonic acids and inorganic acids such as hydrochloric acid, sulfuric acid, orthophosphoric acid and orthophosphorous acid may be used alone or in combination of two or more. Chlorine, sulfur, and the like may interfere with electrical conductivity, and therefore, it is preferable to use acetic acid, propionic acid, lactic acid, maleic acid, and the like.

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

  The urethane resin (b1) can be produced by reacting a polyisocyanate (b1-1), a polyol (b1-2) and a chain extender as necessary.

  Examples of the polyisocyanate (b1-1) include aromatics such as 4,4′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate, carbodiimide-modified diphenylmethane diisocyanate, crude diphenylmethane diisocyanate, phenylene diisocyanate, tolylene diisocyanate, and naphthalene diisocyanate. Polyisocyanates containing structures, aliphatic polyisocyanates such as hexamethylene diisocyanate, lysine diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, and polyisocyanates having an aliphatic cyclic structure Use Can. Among these, it is preferable to use a polyisocyanate having an aliphatic cyclic structure.

  The polyol (b1-2) capable of reacting with the polyisocyanate (b1-1) is preferably a polyol having a hydrophilic group, and if necessary, a polyol having an aliphatic cyclic structure and other polyols Can be used in combination.

  Examples of the polyol having a hydrophilic group include carboxyls such as 2,2′-dimethylolpropionic acid, 2,2′-dimethylolbutanoic acid, 2,2′-dimethylolbutyric acid, and 2,2′-dimethylolvaleric acid. Group-containing polyols and polyols having a sulfonic acid group such as 5-sulfoisophthalic acid, sulfoterephthalic acid, 4-sulfophthalic acid, and 5 [4-sulfophenoxy] isophthalic acid can be used. Examples of the polyol having a hydrophilic group include a polyester polyol having a hydrophilic group obtained by reacting the above-described polyol having a low molecular weight hydrophilic group with various polycarboxylic acids such as adipic acid. It can also be used.

  The hydrophilic group is preferably present in the range of 5 mmol / kg to 4,000 mmol / kg with respect to the total amount of the polyol (b1-2) used in the production of the urethane resin (b1). More preferably, it is used in the range of 2,000 mmol / kg.

  Moreover, it is preferable to use the polyol which has an aliphatic cyclic structure as said polyol (b1-2) from a viewpoint of introduce | transducing an aliphatic cyclic structure into the said urethane resin (b1).

  Examples of the polyol having an aliphatic cyclic structure include 1,4-cyclohexanedimethanol, cyclobutanediol, cyclopentanediol, 1,4-cyclohexanediol, cycloheptanediol, cyclooctanediol, cyclohexanedimethanol, tricyclo [5 , 2,1,0,2,6] decandimethanol, bicyclo [4,3,0] -nonanediol, dicyclohexanediol, tricyclo [5,3,1,1] dodecanediol, bicyclo [4,3, 0] nonanedimethanol, tricyclo [5,3,1,1] dodecanediethanol, spiro [3,4] octanediol, butylcyclohexanediol, 1,1'-bicyclohexylidenediol, cyclohexanetriol, hydrogenated bisphenol- A, 1,3- Such Daman Tan diols, can be used polyols having aliphatic cyclic structure of relatively low molecular weight. In addition, the molecular weight of the polyol having the aliphatic cyclic structure is based on the formula weight.

  As the polyol having an aliphatic cyclic structure, in addition to those described above, those obtained by reacting a polycarboxylic acid having an aliphatic cyclic structure with an aliphatic polyol can be used.

  Examples of the polycarboxylic acid having an aliphatic cyclic structure include 1,3-cyclopentanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, and these An anhydride or an ester-forming derivative of the compound can be used, and in particular, a polycarboxylic acid having an aliphatic cyclic structure such as 1,2-cyclohexanedicarboxylic acid or 1,4-cyclohexanedicarboxylic acid can be used. preferable.

  Examples of the polyol that can be used for the esterification reaction with the polycarboxylic acid having an aliphatic cyclic structure include 1,6-hexanediol, ethylene glycol, diethylene glycol, triethylene glycol, and 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, neopentyl glycol, 3-methyl-1,5-pentanediol, 2-methyl-1,3- It may be used aliphatic polyols such as propanediol. The aliphatic polyol may be used in combination with an esterification reaction between the polyol having the aliphatic cyclic structure and the polycarboxylic acid.

  As the polyol having an aliphatic cyclic structure, for example, a polycarbonate polyol having an aliphatic cyclic structure can be used. As the polycarbonate polyol having an aliphatic cyclic structure, for example, those obtained by reacting the polyol having a low molecular weight aliphatic cyclic structure with dimethyl carbonate, phosgene or the like can be used.

  As the polycarbonate polyol having an aliphatic cyclic structure, it is preferable to use a polycarbonate polyol having an aliphatic cyclic structure having a number average molecular weight of 800 to 3,000, and a number average molecular weight of 800 to 2,000. It is more preferable to use what has.

  As the polyol having an aliphatic cyclic structure, for example, a polyether polyol having an aliphatic cyclic structure can be used. Examples of the polyether polyol having an aliphatic cyclic structure include those obtained by addition polymerization of an alkylene oxide such as ethylene oxide and propylene oxide using, for example, the above-described polyol having a low molecular weight aliphatic cyclic structure as an initiator. Can be used.

  Moreover, as said polyol (b1-2), another polyol other than the above-mentioned polyol can be used as needed. As said other polyol, polyester polyol other than what was mentioned above, polyether polyol, polycarbonate polyol, etc. can be used, for example.

  Examples of the polyester polyol include ring-opening polymerization of aliphatic polyester polyol and aromatic polyester polyol obtained by esterification reaction of low molecular weight polyol and polycarboxylic acid, and cyclic ester compounds such as ε-caprolactone and γ-butyrolactone. Polyester obtained by reaction, copolymerized polyester thereof, or the like can be used.

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

  Examples of the polycarboxylic acid include succinic acid, adipic acid, sebacic acid, dodecanedicarboxylic acid, azelaic acid, terephthalic acid, isophthalic acid, phthalic acid, naphthalenedicarboxylic acid, and anhydrides or ester-forming derivatives thereof. It is preferable to use an aliphatic polycarboxylic acid such as adipic acid. When the polyester polyol containing the aromatic cyclic structure is used, an aromatic polycarboxylic acid such as terephthalic acid, isophthalic acid, phthalic acid, or naphthalenedicarboxylic acid can be used as the polycarboxylic acid. .

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

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

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

  Examples of the polycarbonate polyol that can be used for the other polyols include those obtained by reacting a carbonate with a polyol, and those obtained by reacting phosgene with bisphenol A or the like.

  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 capable of reacting with the carbonate ester include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, dipropylene glycol, 1,4-butanediol, 1,3- Butanediol, 1,2-butanediol, 2,3-butanediol, 1,5-pentanediol, 1,5-hexanediol, 2,5-hexanediol, 1,6-hexanediol, 1,7-heptane Diol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 3-methyl-1,5-pentanediol, 2- Ethyl-1,3-hexanediol, 2-methyl-1,3-propa Diol, 2-methyl-1,8-octanediol, 2-butyl-2-ethylpropanediol, 2-methyl-1,8-octanediol, neopentyl glycol, hydroquinone, resorcin, bisphenol-A, bisphenol-F, Relatively low molecular weight dihydroxy compounds such as 4,4′-biphenol, polyether polyols such as polyethylene glycol, polypropylene glycol and polytetramethylene glycol, and polyesters such as polyhexamethylene adipate, polyhexamethylene succinate and polycaprolactone Polyols and the like can be used.

  As the polyester polyol, polyether polyol, and polycarbonate polyol, those having a number average molecular weight of 500 to 4,000 are preferably used from the viewpoint of ease of mixing with the matrix resin, and the like. More preferably, 500 is used.

  Examples of the other polyol include, in addition to the polyester polyol, polyether polyol, and polycarbonate polyol, for example, ethylene glycol, 1,2-propanediol, 1,3-butanediol, and 1,4-butanediol. , 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, neopentyl glycol, diethylene glycol, dipropylene glycol, glycerin, trimethylolpropane, dimethylolpropionic acid, etc. Hydrophilic group-containing polyols, acrylic polyols with hydroxyl groups introduced into acrylic copolymers, polybutadiene polyols that are butadiene copolymers containing hydroxyl groups in the molecule, hydrogenated polybutadiene polyols, ethylene It can be appropriately used partially saponified products of vinyl acetate copolymers.

  Moreover, as a chain extender which can be used when manufacturing the said urethane resin (b1), a polyamine, another active hydrogen atom containing compound, etc. can be used.

  Examples of the polyamine include ethylenediamine, 1,2-propanediamine, 1,6-hexamethylenediamine, piperazine, 2,5-dimethylpiperazine, isophoronediamine, 4,4′-dicyclohexylmethanediamine, and 3,3′-. Diamines such as dimethyl-4,4′-dicyclohexylmethanediamine, 1,4-cyclohexanediamine; N-hydroxymethylaminoethylamine, N-hydroxyethylaminoethylamine, N-hydroxypropylaminopropylamine, N-ethylaminoethylamine, N-methylaminopropylamine; diethylenetriamine, dipropylenetriamine, triethylenetetramine; hydrazine, N, N′-dimethylhydrazine, 1,6-hexamethylenebishydrazine; Razide, adipic acid dihydrazide, glutaric acid dihydrazide, sebacic acid dihydrazide, isophthalic acid dihydrazide; β-semicarbazide propionic acid hydrazide, 3-semicarbazide-propyl-carbazate, semicarbazide-3-semicarbazide methyl-3,5 5-Trimethylcyclohexane can be used, and ethylenediamine is preferably used.

  Examples of the other active hydrogen-containing compound include ethylene glycol, diethylene recall, triethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, hexamethylene glycol, and sucrose. , Glycols such as methylene glycol, glycerin, sorbitol; phenols such as bisphenol A, 4,4′-dihydroxydiphenyl, 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxydiphenyl sulfone, hydrogenated bisphenol A, hydroquinone , And water can be used.

  The chain extender is preferably used, for example, in a range where the equivalent ratio of the amino group and excess isocyanate group of the polyamine is 1.9 or less (equivalent ratio), 0.3 to 1.0 (equivalent It is more preferable to use it in the range of the ratio.

  The urethane resin (b1) is, for example, in the absence of a solvent or in the presence of an organic solvent, the polyisocyanate (b1-1), the polyol (b1-2), and, if necessary, the chain extender. It can be produced by reacting in a known manner.

  The reaction between the polyisocyanate (b1-1) and the polyol (b1-2) is preferably in the range of 50 ° C. to 120 ° C., more preferably 80 ° C. At a reaction temperature of -100 ° C., the polyisocyanate (b1-1) and the polyol (b1-2) are sequentially mixed, or one of them is sequentially supplied to the other by a method such as dropping, and approximately 1 hour. The reaction can be carried out for about 15 hours.

  The aqueous dispersion of the urethane resin (b1) is obtained by reacting the polyisocyanate (b1-1), the polyol (b1-2), and, if necessary, a chain extender by the method described above. The resin (b1) is produced, and if necessary, after neutralizing a part or all of the hydrophilic groups such as an anionic group of the urethane resin (b1) and then mixing with the aqueous medium (b3). The urethane resin (b1) aqueous dispersion in which the urethane resin (b1) is dispersed or partially dissolved in the aqueous medium (b3) can be obtained.

  Specifically, the urethane prepolymer (b1 ′) having an isocyanate group at the terminal is produced by reacting the polyisocyanate (b1-1) and the polyol (b1-2) by the above-described method, and is necessary. According to the above, after neutralizing a part or all of the hydrophilic group such as anionic group of the urethane prepolymer (b1 ′), it is mixed with the aqueous medium (b3), and the chain extension is performed as necessary. By extending the chain using an agent, an aqueous dispersion of urethane resin (b1) in which the urethane resin (b1) is dispersed or dissolved in the aqueous medium (b3) can be obtained.

  The reaction between the polyisocyanate (b1-1) and the polyol (b1-2) is, for example, an isocyanate group [X] of the polyisocyanate (b1-1) and a hydroxyl group of the polyol (b1-2) [Y. ] The equivalent ratio [isocyanate group [X] / hydroxyl group [Y]] is preferably in the range of 0.90 to 2.0.

  When the urethane resin (b1) is produced, an organic solvent can be used as a solvent. Examples of the organic solvent include ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran and dioxane; acetic esters such as ethyl acetate and butyl acetate; nitriles such as acetonitrile; amides such as dimethylformamide and N-methylpyrrolidone. Can be used alone or in combination of two or more. The organic solvent is preferably removed by distillation or the like after the production of composite resin particles with the urethane resin (b1) or the vinyl polymer (b2) described later.

  As the urethane resin (b1) obtained by the above method, from the adhesiveness with the insulating substrate (A) and the coating properties on the resin layer (B) of the dispersion of fine metal particles (C) described later, Those having a weight average molecular weight of 5,000 to 500,000 are preferably used, and those having a weight average molecular weight of 20,000 to 100,000 are more preferably used.

  The urethane resin (b1) obtained by the above method may have various functional groups as necessary. Examples of the functional group include crosslinks such as alkoxysilyl groups, silanol groups, hydroxyl groups, and amino groups. Sex functional group.

  The alkoxysilyl group or silanol group can be introduced into the polyurethane (b1) by using γ-aminopropyltriethoxysilane or the like when the urethane resin (b1) is produced.

  On the other hand, as the crosslinkable functional group, one that forms a crosslink structure by reacting with the crosslinkable functional groups or the crosslinker (b4) described later by heating to approximately 100 ° C or higher, preferably 120 ° C or higher. be able to.

  Specifically, when a urethane resin having a functional group capable of undergoing a crosslinking reaction by heating to approximately 100 ° C. or higher, preferably 120 ° C. or higher is used, the resin layer forming composition (b) including the same The resin layer (B) obtained by applying to the surface of the insulating substrate (A), non-heat drying and the like does not substantially form a crosslinked structure. After applying a dispersion (C) of metal fine particles, which will be described later, on this resin layer (B), a crosslinking reaction can be caused by heating or the like to form a crosslinked structure inside the resin layer (B). . Thereby, even if it is a case where it exposes to the plating chemical | medical agent which consists of a strong alkali or a strong acidic substance in the metal-plating process mentioned later, a resin layer (B) does not peel from an insulating base material (A), and is remarkable. Excellent durability.

  The functional group capable of undergoing a cross-linking reaction by heating to 100 ° C. or higher, preferably 120 ° C. or higher, depends on the selection of the cross-linking agent (b4) used in combination, but for example, a cross-linking agent such as a blocked isocyanate compound is used. In some cases, a hydroxyl group or an amino group can be used.

  It is preferable that the said crosslinkable functional group is contained in the range of 0.005 equivalent / kg-1.5 equivalent / kg in total with respect to the whole quantity of the said urethane resin (b1).

  Further, one or more metal fine particles (c2) selected from the group consisting of gold, silver, copper and platinum protected with a compound (c1) having a nitrogen atom, sulfur atom, phosphorus atom or oxygen atom, which will be described later, are reduced to 0. In the step of applying the dispersion (C) containing 5% by mass or more and drying it, when the crosslinkable functional group is present in the resin layer (B), the functional group in the compound (c1) The group and the functional group in the resin layer (B) can be crosslinked. With such a combination, the adhesion between the resin layer (B) and the non-conductive layer (D) described later can be further improved, and in the subsequent electroless plating step, the metal fine particles (c2 ) Is more preferable because it can further prevent peeling and the like.

  Next, the vinyl polymer (b2) constituting the resin layer forming composition (b) used in the present invention will be described.

  In the vinyl polymer (b2), a dispersion (C) of metal fine particles (c2) described later is excellent on the resin layer (B) formed on the insulating base (A). Is important to show.

  As the vinyl polymer (b2), use of a polymer having a glass transition temperature of 10 ° C. to 70 ° C. is a coating property of a dispersion liquid (C) of metal fine particles (c2) described later, that is, “missing”. There is no unevenness and it is preferable for imparting uniform coatability. In addition, the glass transition temperature of the said vinyl polymer (b2) is a value determined by calculation mainly based on the composition of the vinyl monomer used for manufacture of this vinyl polymer (b2). Specifically, the vinyl polymer having the predetermined glass transition temperature can be obtained by using a combination of vinyl monomers described later.

  In addition, when the resin layer (B) is formed, the resin layer-forming composition (b) has a good film-forming property, and the film-like insulating substrate (A) has a resin layer-forming composition. The film-like substrate on which the resin layer (B) is formed by applying (b) is wound up in a roll shape, or the resin layer forming composition (b) is applied on the insulating substrate (A). When the base material on which the resin layer (B) is formed is stacked, the resin layer (B) and the back side of the stacked upper insulating base material (A) do not cause sticking over time. From the viewpoint of providing a level of blocking resistance, it is preferable to use a glass transition temperature of 10 ° C to 40 ° C.

  Further, as the vinyl polymer (b2), a resin layer (B) that gives excellent coating properties to the dispersion liquid (C) of metal fine particles (c2) described later is used as the insulating base material (A). When forming above, it is preferable to use what has a weight average molecular weight of 800,000 or more, and it is more preferable to use what has a weight average molecular weight of 1 million or more. In the present invention, “good coating property” means that when the dispersion liquid (C) of the metal fine particles (c2) is applied, occurrence of “missing” and unevenness is suppressed, and a good non-conductive layer (D ) Is formed.

  Although it does not specifically limit as an upper limit of the weight average molecular weight of the said vinyl polymer (b2), It is preferable that it is generally 10 million or less, and it is preferable that it is 5 million or less.

  The vinyl polymer (b2) may have various functional groups as necessary. Examples of the functional group include an amide group, a hydroxyl group, a glycidyl group, an amino group, a silyl group, and an aziridinyl group. , Crosslinkable functional groups such as isocyanate group, oxazoline group, cyclopentenyl group, allyl group, carboxyl group, and acetoacetyl group.

  The crosslinkable functional group undergoes a crosslinking reaction by heating or the like to form a crosslinked structure in the resin layer (B). As a result, even when a solvent such as a plating agent or a cleaning agent adheres, the resin layer (B) can be prevented from being dissolved or peeled off. Furthermore, in the case of a combination having reactivity with the compound (c1) protecting the metal fine particles (c2) in the dispersion (C), the metal fine particles (c2) are stably deposited on the resin layer (B). It is also possible to hold it in a preferable manner.

  As the crosslinkable functional group, for example, it is preferable to use one that can form a crosslinked structure by heating to approximately 100 ° C. or higher, preferably 120 ° C. or higher, specifically, methylol. It is preferable to use one or more thermally crosslinkable functional groups selected from the group consisting of amide groups and alkoxymethylamide groups.

  Specific examples of the alkoxymethylamide group include an amide group formed by bonding a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, a butoxymethyl group, or the like to a nitrogen atom.

  Moreover, as said crosslinkable functional group, when using the crosslinking agent (b4) mentioned later, it is preferable to use a hydroxyl group, a carboxyl group, etc., for example. Moreover, when the conditions at the time of forming a resin layer (B) can fully be controlled, an amino group can also be used.

  As the vinyl polymer (b2), among those described above, it is possible to use one having at least one selected from the group consisting of a methylolamide group and an alkoxymethylamide group. In view of greatly improving the adhesion to the various insulating substrates (A), it is particularly preferable.

  As the vinyl polymer (b2), various types can be used. For example, those obtained by radical polymerization of conventionally known vinyl monomers can be used.

  Examples of vinyl monomers that can be used in the production of the vinyl polymer (b2) include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, and (meth) acrylic acid. i-butyl, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, (Meth) acrylic such as dodecyl (meth) acrylate, stearyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate Acid esters; (meth) acrylic acid 2,2,2-trifluoroethyl, (meth) acrylic acid 2,2,3,3 (Meth) acrylic such as pentafluoropropyl, perfluorocyclohexyl (meth) acrylate, 2,2,3,3, -tetrafluoropropyl (meth) acrylate, β- (perfluorooctyl) ethyl (meth) acrylate Acid alkyl esters can be used.

  Among the above, methyl methacrylate, in particular, has excellent adhesion between the resin layer (B) and the insulating substrate (A), and excellent moisture and heat resistance, regardless of the influence of heat in the baking process or the like. It is preferable also in providing.

  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 the use of n-butyl acrylate does not cause “missing” or unevenness with respect to the dispersion liquid (C) of metal fine particles, which will be described later. From the viewpoint of securing

  Moreover, as a vinyl monomer which can be used when manufacturing the vinyl polymer (b2), in addition to the above-mentioned ones, acrylic acid, methacrylic acid, (meth) acrylic acid β-carboxyethyl, 2- (meth) Carboxyl groups such as acryloylpropionic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, itaconic acid half ester, maleic acid half ester, maleic anhydride, itaconic anhydride, β- (meth) acryloyloxyethyl hydrogen succinate, etc. The vinyl monomer can be used. The vinyl monomer having a carboxyl group may be neutralized with ammonia, potassium hydroxide, or the like.

  Examples of the other vinyl monomer include one or more amide groups selected from the group consisting of a methylolamide group and an alkoxymethylamide group, an amide group other than the above, and a hydroxyl group in the vinyl polymer (b2). From the viewpoint of introducing the crosslinkable functional group such as glycidyl group, amino group, silyl group, aziridinyl group, isocyanate group, oxazoline group, cyclopentenyl group, allyl group, carbonyl group, acetoacetyl group, etc. The vinyl monomer can be used.

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

  Among these, the use of Nn-butoxymethyl (meth) acrylamide and N-isobutoxymethyl (meth) acrylamide causes “missing” and unevenness with respect to the dispersion liquid (C) of metal fine particles described later. This is preferable from the viewpoint of ensuring excellent coating properties.

  Examples of the vinyl monomer having a crosslinkable functional group include those other than those described above, such as amide group-containing vinyl monomers such as (meth) acrylamide, 2-hydroxyethyl (meth) acrylate, and (meth) acrylic. 2-hydroxypropyl acid, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, (4-hydroxymethylcyclohexyl) methyl (meth) acrylate, Vinyl monomers having a hydroxyl group such as glycerol (meth) acrylate, polyethylene glycol (meth) acrylate, N-hydroxyethyl (meth) acrylamide: glycidyl (meth) acrylate, allyl glycidyl ether (meth) acrylate, etc. Polymerizable monomer having a glycidyl group; amino (meth) acrylate Polymerizable monomers having an amino group such as ethyl, dimethylaminoethyl (meth) acrylate, N-monoalkylaminoalkyl (meth) acrylate, N, N-dialkylaminoalkyl (meth) acrylate; vinyltrichlorosilane , Vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, γ- (meth) acryloxypropyltrimethoxysilane, γ- (meth) acryloxypropyltriethoxysilane, γ- (meth) acryl Roxypropylmethyldimethoxysilane, γ- (meth) acryloxypropylmethyldiethoxysilane, γ- (meth) acryloxypropyltriisopropoxysilane, N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltri Methoxysilane and its hydrochloride A polymerizable monomer having a silyl group; a polymerizable monomer having an aziridinyl group such as 2-aziridinylethyl (meth) acrylate; a phenol or methylethylketo of (meth) acryloyl isocyanate, (meth) acryloyl isocyanate ethyl Polymerizable monomers having isocyanate groups and / or blocked isocyanate groups such as oxime adducts; polymerizable monomers having oxazoline groups such as 2-isopropenyl-2-oxazoline and 2-vinyl-2-oxazoline; Polymerizable monomers having a cyclopentenyl group such as (meth) acrylate dicyclopentenyl; Polymerizable monomers having an allyl group such as allyl (meth) acrylate; Carbonyl groups such as acrolein and diacetone (meth) acrylamide A polymerizable monomer having .

  In addition to the above-mentioned vinyl monomers, the vinyl monomers include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl versatate, methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, amyl vinyl ether, hexyl vinyl ether, ( (Meth) acrylonitrile, styrene, α-methylstyrene, vinyltoluene, vinylanisole, α-halostyrene, vinylnaphthalene, divinylstyrene, isoprene, chloroprene, butadiene, ethylene, tetrafluoroethylene, vinylidene fluoride, N-vinylpyrrolidone, polyethylene Glycol mono (meth) acrylate, glycerol mono (meth) acrylate, vinyl sulfonic acid, styrene sulfonic acid, allyl sulfonic acid, 2-methyl Ruallylsulfonic acid, 2-sulfoethyl (meth) acrylate, 2-sulfopropyl (meth) acrylate, “Adekaria soap PP-70, PPE-710” (manufactured by Asahi Denka Kogyo Co., Ltd.) or the like Can be used.

  As described above, as the vinyl monomer having a crosslinkable functional group, N-butoxymethyl (meth) acrylamide and N-isobutoxymethyl (meth) acrylamide capable of undergoing a self-crosslinking reaction by heating or the like are used alone or in combination. And (meth) acrylamide, hydroxyl group-containing vinyl monomers such as (meth) acrylic acid 2-hydroxyethyl and (meth) acrylic acid 4-hydroxybutyl are preferably used in combination.

  Moreover, when using the crosslinking agent (b4) mentioned later, when introducing the functional group which can become a crosslinking point with a crosslinking agent (b4), for example, a hydroxyl group, (meth) acrylic acid 2-hydroxyethyl, (meta It is more preferable to use 2-hydroxypropyl acrylate and 4-hydroxybutyl (meth) acrylate. The use of the vinyl monomer having a hydroxyl group is preferable when an isocyanate crosslinking agent is used as the crosslinking agent (b4) described later.

  The vinyl monomer having a crosslinkable functional group can be used in the range of 0% by mass to 50% by mass with respect to the total amount of the vinyl monomer mixture. In addition, when the crosslinking agent (b4) undergoes a self-crosslinking reaction, or when the crosslinking agent (b4) reacts with a crosslinkable functional group that the urethane resin (b1) can have, the crosslinkable functional group. It is not necessary to use a vinyl monomer having

  Among the vinyl monomers having the crosslinkable functional group, the vinyl monomer having the amide group is based on the total amount of the vinyl monomer mixture when introducing a self-crosslinking reactive methylolamide group or the like. It is preferably used in the range of 0.1% by mass to 50% by mass, and more preferably in the range of 1% by mass to 30% by mass. The vinyl monomer having another amide group used in combination with the self-crosslinking reactive methylolamide group or the vinyl monomer having a hydroxyl group is 0.1% based on the total amount of the vinyl monomer. It is preferable to use in the range of mass% to 30 mass%, and it is more preferable to use in the range of 1 mass% to 20 mass%.

  Of the vinyl monomers having a crosslinkable functional group, the vinyl monomer having a hydroxyl group depends on the type of the crosslinking agent (b4) used in combination, but the total amount of the vinyl monomer mixture. In general, it is preferably used in the range of 0.05% by mass to 50% by mass, preferably in the range of 0.05% by mass to 30% by mass, and 0.1% by mass to 10% by mass. More preferably it is used.

  The (meth) acrylic acid alkyl ester is preferably used in the range of 30% by mass to 95% by mass with respect to the total amount of the vinyl monomer mixture used for the production of the vinyl polymer (b2). In particular, methyl (meth) acrylate is preferably used in the range of 10% by mass to 70% by mass, more preferably 30% by mass to 65% by mass, based on the total amount of the vinyl monomer mixture, and An acrylic acid alkyl ester having an alkyl group having 2 to 12 carbon atoms, preferably an acrylic acid alkyl ester having an alkyl group having 3 to 8 carbon atoms, more preferably butyl (meth) acrylate is 10 It is used in the range of mass% to 50 mass%.

  The vinyl polymer (b2) can be produced by polymerizing a mixture of various vinyl monomers as described above by a conventionally known method. With respect to the above, it is preferable to apply an emulsion polymerization method as a means for obtaining a high molecular weight polymer capable of forming a resin layer that imparts excellent coating properties without causing “missing” or unevenness.

  As the emulsion polymerization method, for example, water, a vinyl monomer mixture, a polymerization initiator, and, if necessary, a chain transfer agent, an emulsifier, a dispersion stabilizer, and the like are collectively supplied and mixed in a reaction vessel. A polymerization method, a monomer dropping method in which a vinyl monomer mixture is dropped into a reaction vessel and polymerization, or a vinyl monomer mixture, an emulsifier, etc. and water mixed in advance are dropped into the reaction vessel for polymerization. A pre-emulsion method or the like can be applied.

  The temperature during the emulsion polymerization varies depending on the type of vinyl monomer and polymerization initiator used, but is preferably about 30 ° C. to 90 ° C., for example, and the polymerization time is preferably about 1 hour to 10 hours, for example.

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

  Examples of the emulsifier that can be used for the production of the vinyl polymer (b2) include anionic surfactants, nonionic surfactants, cationic surfactants, and zwitterionic surfactants.

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

  Moreover, as said cationic surfactant, alkyl ammonium salt etc. can be used, for example.

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

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

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

  Moreover, as an aqueous medium used for manufacture of the said vinyl polymer (b2), the thing similar to what was illustrated as an aqueous medium (b3) mentioned later can be used.

  Moreover, as a chain transfer agent which can be used for manufacture of the said vinyl polymer (b2), a lauryl mercaptan etc. can be used and it is 0 mass%-1.0 mass with respect to the whole quantity of the said vinyl monomer mixture. % Is preferable, and the range of 0% by mass to 0.5% by mass is more preferable.

  The resin composition for forming a receiving layer in which the urethane resin (b1) and the vinyl polymer (b2) are independently present in the aqueous medium (b3) is, for example, an aqueous dispersion of the urethane resin (b1) obtained above. It can manufacture by mixing a body and the aqueous dispersion of the said vinyl polymer (b2).

  The urethane resin (b1) and the vinyl polymer (b2) contained in the resin-forming composition (b) may be present independently in the aqueous medium (b3). You may exist in the state which formed the composite resin particle.

  Specifically, the composite resin particles refer to those in which part or all of the vinyl polymer (b2) is contained in the resin particles formed by the urethane resin (b1). At that time, the vinyl polymer (b2) may be dispersed in a plurality of particles in the urethane resin (b1) particles, and the vinyl polymer (b2) as a core layer and a shell layer The core-shell type composite resin particle comprised from the urethane resin (b1) which has the said hydrophilic group as may be formed. The core-shell type composite resin particles can be particularly preferably used because it is not necessary to use a surfactant capable of lowering electrical characteristics. In addition, as the composite resin particles, it is preferable that the vinyl polymer (b2) is almost completely covered with the urethane resin (b1), but it is not essential, and in a range not impairing the effect of the present invention, A part of the vinyl polymer (b2) may be present on the outermost part of the composite resin particle.

  Further, as the composite resin particles, when the vinyl polymer (b2) is more hydrophilic than the urethane resin (b1), the resin formed by the vinyl polymer (b2). A part or all of the urethane resin (b1) may be present in the particles to form composite resin particles.

  The urethane resin (b1) and the vinyl polymer (b2) may form a covalent bond, but preferably do 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. Here, the average particle diameter refers to an average particle diameter based on volume measured by a dynamic light scattering method.

  The resin layer forming composition (B) used in the present invention comprises the urethane resin (b1) and the vinyl polymer (b2), [urethane resin (b1) / vinyl polymer (b2)] = 90/10. It is preferable to include in the range of 10/90, and it is more preferable to include in the range of 70/30 to 10/90.

  Moreover, the composition (b) for resin layer formation containing the composite resin particle formed with the said urethane resin (b1) and the said vinyl polymer (b2) can be manufactured with the following method, for example.

  For example, as described above, the composite resin particles may be obtained by reacting the polyisocyanate (b1-1), the polyol (b1-2), and a chain extender as necessary, and dispersing in water to form a urethane resin (b1). ) And a step of polymerizing the vinyl monomer in the aqueous dispersion to produce a vinyl polymer (b2).

  Specifically, urethane is obtained by reacting the polyisocyanate (b1-1) and the polyol (b1-2) in the absence of a solvent or in an organic solvent or in the presence of a reactive diluent such as a vinyl monomer. Resin (b1) is obtained, and then part or all of the hydrophilic group of the urethane resin (b1) is neutralized with a basic compound, if necessary, and further, if necessary, chain extension An aqueous dispersion of the urethane resin (b1) is produced by reacting with an agent and dispersing it in an aqueous medium.

  Next, the vinyl monomer is supplied into the aqueous dispersion of the urethane resin (b1) obtained above, and the vinyl monomer is radically polymerized in the urethane resin (b1) particles to give a vinyl polymer (b2). ).

  Thereby, the resin layer forming composition (b) in which the composite resin particles in which the vinyl polymer (b2) is contained in the urethane resin (b1) particles is dispersed in the aqueous medium (b3) can be produced. .

  When the composite resin particles are produced, if the urethane resin (b1) has high viscosity and is not excellent in workability, a normal organic solvent such as methyl ethyl ketone, N-methylpyrrolidone, acetone, dipropylene glycol dimethyl ether, Reactive diluents can be used. In particular, the use of a vinyl monomer or the like that can be used for the production of the vinyl polymer (b2) as the reactive diluent results in the production efficiency of the resin layer forming composition (b) by omitting the solvent removal step. It is preferable for improving the above.

  Examples of the urethane resin (b1) and the vinyl polymer (b2) obtained by the reaction or the like, or the aqueous medium (b3) in which the composite resin particles can be dispersed or dissolved include water, an organic solvent miscible with water, and These mixtures are mentioned. Examples of organic solvents miscible with water include alcohols such as methanol, n- and isopropanol; ketones such as acetone and methyl ethyl ketone; polyalkylene glycols such as ethylene glycol, diethylene glycol and propylene glycol; alkyl ethers of polyalkylene glycols And lactams such as N-methyl-2-pyrrolidone, and the like. In the present invention, only water may be used, a mixture of water and an organic solvent miscible with water may be used, or only an organic solvent miscible with water may be used. From the viewpoint of safety and load on the environment, water alone or a mixture of water and an organic solvent miscible with water is preferable, and only water is particularly preferable.

  The aqueous medium (b3) is preferably contained in an amount of 50% by mass to 90% by mass and more preferably 65% by mass to 85% by mass with respect to the total amount of the resin layer forming composition (b). .

  Further, as the resin layer forming composition (b), in a dispersion (C) of metal fine particles (c2) described later, a solvent for dispersing the metal fine particles (c2) is water, water and a water-soluble organic solvent. In the case of any one of the mixed solvents, a water-soluble resin can be used in combination for the purpose of improving the coating property.

  Examples of the water-soluble resin include polyvinyl alcohol, polyvinyl pyrrolidone, polyvinyl acetal, polyalkylene oxide, starch, methylcellulose, hydroxycellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, carboxymethylcellulose and other cellulose derivatives, polyethyleneimine, polyamide, various Quaternary ammonium base-containing water-soluble resins, modified products thereof, and the like can be used. Among these, it is preferable to use polyvinyl alcohol.

  Further, the resin layer forming composition (b) is within a range that does not impair the effects of the present invention, and includes a crosslinking agent (b4), a pH adjuster, a film forming aid, a leveling agent, and a thickener as necessary. Water repellents, antifoaming agents and the like may be added as appropriate.

  Examples of the crosslinking agent (b4) include heat that can form a crosslinked structure by reacting at a relatively low temperature of approximately 25 ° C. to less than 100 ° C. such as a metal chelate compound, a polyamine compound, an aziridine compound, a metal salt compound, and an isocyanate compound. It reacts at a relatively high temperature of approximately 100 ° C. or higher, such as one or more selected from the group consisting of a crosslinking agent (b4-1), a melamine compound, an epoxy compound, an oxazoline compound, a carbodiimide compound, and a blocked isocyanate compound. A thermal crosslinking agent (b4-2) capable of forming a crosslinked structure and various photocrosslinking agents can be used.

  If it is the resin layer forming composition (b) containing the thermal crosslinking agent (b4-1), for example, it is applied to the surface of the insulating substrate (A) and heated to a temperature of less than 100 ° C. By forming a cross-linked structure, even when used in a high-temperature and high-humidity environment, it does not cause dissolution or whitening of the resin layer (B) over time, peeling from the insulating substrate (A), or the like. Regardless of the level of moist heat resistance and long-term effects of heat and external force, it is possible to prevent the loss of the non-conductive layer (D) and conductive layer (E) formed on the resin layer in the subsequent process. An excellent conductive material can be formed.

  Further, the resin layer forming composition (b) containing the thermal crosslinking agent (b4-1) is applied to the surface of the insulating substrate (A), dried at a relatively low temperature, and then the metal fine particles (c2) After applying the dispersion liquid (C), it is heated to a temperature of less than 100 ° C. to form a crosslinked structure, so that even when used in a high temperature and high humidity environment, the resin layer (B) over time Non-conductive layer (D) formed on the resin layer regardless of the heat and moisture resistance at a level that does not cause dissolution, whitening, peeling from the insulating substrate (A), and the influence of heat and external force over a long period of time. ) And a conductive material excellent in durability without the loss of the conductive layer (E) formed in a later step.

  On the other hand, if it is the resin layer forming composition (b) containing the thermal crosslinking agent (b4-2), for example, it is applied to the surface of the insulating substrate (A), and it is at room temperature (25 ° C.) to about less than 100 ° C. Is dried at a low temperature to produce a receiving substrate that does not form a crosslinked structure, and then, after applying a dispersion (C) of metal fine particles (c2), for example, 100 ° C. or higher, preferably 120 ° C. or higher. Even when used in a high-temperature and high-humidity environment, the resin layer (B) is dissolved and whitened over time, and the insulating substrate (A) A non-conductive layer (D) and a conductive layer (E) formed on the resin layer (B) in a later step regardless of the effects of moisture and heat resistance at a level that does not cause peeling and the like, and heat and external force over a long period of time. ) To obtain a conductive material with excellent durability that does not cause peeling It can be.

  Examples of the metal chelate compound that can be used for the thermal crosslinking agent (b4-1) include acetylacetone of polyvalent metals such as aluminum, iron, copper, zinc, tin, titanium, nickel, antimony, magnesium, vanadium, chromium, and zirconium. Coordination compounds, acetoacetate coordination compounds and the like can be used, and it is preferable to use acetylacetone aluminum which is an acetylacetone coordination compound of aluminum.

  Moreover, as a polyamine compound which can be used for the said thermal crosslinking agent (b4-1), tertiary amines, such as a triethylamine, a triethylenediamine, a dimethylethanolamine, can also be used, for example.

  Examples of the aziridine compound that can be used in the thermal crosslinking agent (b4-1) include 2,2-bishydroxymethylbutanol-tris [3- (1-aziridinyl) propionate], 1,6-hexamethylenediethylene urea. Diphenylmethane-bis-4,4′-N, N′-diethyleneurea and the like can be used.

  Examples of the metal salt compound that can be used as the crosslinking agent (b4-1) include aluminum sulfate, aluminum alum, aluminum sulfite, aluminum thiosulfate, polyaluminum chloride, aluminum nitrate nonahydrate, and aluminum chloride hexahydrate. Water-soluble metal salts such as aluminum-containing compounds such as titanium tetrachloride, tetraisopropyl titanate, titanium acetylacetonate, and titanium lactate can be used.

  Examples of isocyanate compounds that can be used in the thermal crosslinking agent (b4-1) include tolylene diisocyanate, hydrogenated tolylene diisocyanate, triphenylmethane triisocyanate, methylene bis (4-phenylmethane) triisocyanate, isophorone diisocyanate, hexamethylene. A polyisocyanate such as diisocyanate and xylylene diisocyanate, an isocyanurate type polyisocyanate compound obtained by using them, an adduct comprising them and trimethylolpropane, the polyisocyanate compound and a polyol such as trimethylolpropane. Polyisocyanate group-containing urethane obtained by reacting can be used. Among them, hexamethylene diisocyanate nurate, adduct of hexamethylene diisocyanate and trimethylolpropane, adduct of tolylene diisocyanate and trimethylolpropane, adduct of xylylene diisocyanate and trimethylolpropane, etc. are used. It is preferable.

  Examples of the melamine compound that can be used in the thermal crosslinking agent (b4-2) include hexamethoxymethyl melamine, hexaethoxymethyl melamine, hexapropoxymethyl melamine, hexabutoxymethyl melamine, hexapentyloxymethyl melamine, and hexahexyl. Oxymethyl melamine or a mixed etherified melamine obtained by combining these two types can be used. Of these, trimethoxymethyl melamine and hexamethoxymethyl melamine are preferably used. As a commercial item, becamine M-3, APM, J-101 (made by DIC Corporation) etc. can be used. The melamine compound can form a crosslinked structure by a self-crosslinking reaction.

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

  Examples of the epoxy compound that can be used for the thermal crosslinking agent (b4-2) include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, hexamethylene glycol diglycidyl ether, cyclohexanediol diglycidyl ether, and glycerin diglycidyl ether. , Polyglycidyl ethers of aliphatic polyhydric alcohols such as glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, pentaerythritol tetraglycidyl ether; polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, polytetramethylene glycol diglycidyl ether Polyglycidyl ethers of polyalkylene glycols such as 1,3-bis (N, N -Polyglycidylamines such as diglycidylaminoethyl) cyclohexane; polyglycidyl esters of polycarboxylic acids [succinic acid, adipic acid, butanetricarboxylic acid, maleic acid, phthalic acid, terephthalic acid, isophthalic acid, benzenetricarboxylic acid, etc.] Bisphenol A-based epoxy resins such as condensates of bisphenol A and epichlorohydrin, ethylene oxide adducts of condensates of bisphenol A and epichlorohydrin, phenol novolac resins, various vinyl (co) polymers having an epoxy group in the side chain, etc. Can be used. Among these, it is preferable to use polyglycidylamines such as 1,3-bis (N, N′-diglycidylaminoethyl) cyclohexane and polyglycidyl ethers of aliphatic polyhydric alcohols such as glycerin diglycidyl ether.

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

  Examples of the oxazoline compound that can be used for the thermal crosslinking agent (b4-2) include 2,2′-bis- (2-oxazoline), 2,2′-methylene-bis- (2-oxazoline), 2 , 2'-ethylene-bis- (2-oxazoline), 2,2'-trimethylene-bis- (2-oxazoline), 2,2'-tetramethylene-bis- (2-oxazoline), 2,2'- Hexamethylene-bis- (2-oxazoline), 2,2′-octamethylene-bis- (2-oxazoline), 2,2′-ethylene-bis- (4,4′-dimethyl-2-oxazoline), 2 , 2'-p-phenylene-bis- (2-oxazoline), 2,2'-m-phenylene-bis- (2-oxazoline), 2,2'-m-phenylene-bis- (4,4'- Dimethyl-2-oxazo Emissions), bis - (2-oxazolinyl sulfonyl cyclohexane) sulfide, bis - (2-oxazolinyl sulfonyl norbornane) can be used sulfides.

  In addition, as the oxazoline compound, for example, an oxazoline group-containing polymer obtained by combining and polymerizing the following addition polymerizable oxazoline and, if necessary, other monomers can also be used.

  Examples of the addition polymerizable oxazoline include 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, and 2-isopropenyl-2-oxazoline. , 2-isopropenyl-4-methyl-2-oxazoline, 2-isopropenyl-5-methyl-2-oxazoline, 2-isopropenyl-5-ethyl-2-oxazoline, etc., alone or in combination. Can do. Among them, it is preferable to use 2-isopropenyl-2-oxazoline because it is easily available industrially.

  Moreover, as a carbodiimide compound which can be used for the thermal crosslinking agent (b4-2), for example, poly [phenylenebis (dimethylmethylene) carbodiimide], poly (methyl-1,3-phenylenecarbodiimide) and the like can be used. . Commercially available products include “Carbodilite V-01”, “V-02”, “V-03”, “V-04”, “V-05”, “V-06” (manufactured by Nisshinbo Co., Ltd.), UCARLINK XL- 29SE, XL-29MP (manufactured by Union Carbide Co., Ltd.) or the like can be used.

  Moreover, as a block isocyanate compound which can be used for the said thermal crosslinking agent (b4-2), a part or all of the isocyanate group which the isocyanate compound illustrated as the said thermal crosslinking agent (b4-1) has by a blocking agent is used. What was sealed can be used.

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

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

  When using the said crosslinking agent (b4), it is preferable to use what has a group which can react with the crosslinkable functional group which the said crosslinking agent (b4) has as said vinyl polymer (b2). Specifically, the (block) isocyanate compound, melamine compound, oxazoline compound, and carbodiimide compound are used as a crosslinking agent (b4), and a vinyl polymer having a hydroxyl group or a carboxyl group is used as the vinyl polymer (b2). It is preferable to do.

  Although the said crosslinking agent (b4) changes with kinds etc., normally with respect to the total mass of the said urethane resin (b1) and the said vinyl polymer (b2), or further the total mass of the said composite resin particle 100 mass parts. Is preferably used in the range of 0.01% by mass to 60% by mass, more preferably in the range of 0.1% by mass to 10% by mass, and in the range of 0.1% by mass to 5% by mass. The use improves the adhesion between the resin layer (B) and the insulating substrate (A), and the applicability of the dispersion liquid (C) of the metal fine particles (c2) on the resin layer (B). From the viewpoint of securing

  The crosslinking agent (b4) is preferably added and used in advance before the resin layer forming composition (b) is applied to the surface of the insulating substrate (A).

  Further, as the resin layer forming composition (b), in addition to the additives described above, solvent-soluble or solvent-dispersible thermosetting resins such as phenol resins, urea resins, melamine resins, polyester resins, polyamides A resin, a urethane resin, or the like can be mixed and used.

  Moreover, as said additive, various fillers, such as an inorganic particle, can also be used. However, in the present invention, as the resin composition for forming a resin layer, the amount of filler used is preferably as small as possible, and is 5% by mass or less based on the total amount of the resin layer forming composition (b). More preferred.

  Although the usage-amount of the said additive will not be specifically limited if it is a range which does not impair the effect of this invention, 0.01 mass%-40 mass with respect to the total amount of solid content in the composition for resin layer formation (b). % Is preferable.

  The resin layer (B) formed by using the resin layer forming composition (b) is composed of the urethane resin (b1), vinyl polymer (b2) and composite resin particles constituting the metal fine particles (described later). The metal fine particles (c2) contained in the dispersion liquid (C) of the metal fine particles (c2) are appropriately dissolved in the solvent contained in the dispersion liquid (C2) of c2) and absorb the solvent, so that the resin layer (B) Since it is a swelling type that can be efficiently fixed on the surface, it is possible to obtain a non-conductive layer (D) having no “missing” or unevenness. Further, the resin layer forming composition (b) used in the present invention can form a transparent resin layer as compared with a conventionally known porous ink receiving layer for coating.

The method for applying the resin layer forming composition (b) to the surface of the insulating substrate (A) is not particularly limited as long as the resin layer (B) is properly formed, and as necessary. Various printing / coating methods may be appropriately selected depending on the shape, size, degree of flexibility, etc. of the insulating base material (A) to be used. Specifically, gravure method, offset method, letterpress method, letterpress Inversion method, screen method, micro contact method, reverse method, air doctor coater method, blade coater method, air knife coater method, squeeze coater method, impregnation coater method, transfer roll coater method, kiss coater method, cast coater method, spray coater method, Examples include an inkjet method, a die method, a spin coater method, a bar coater method, and a dip coat method.
In addition, as a method of applying the resin layer forming composition (b) on both surfaces of the film, sheet or plate-like insulating substrate (A), the resin layer (B) is appropriately formed on both surfaces. As long as there is no particular limitation, the above-described various printing / coating methods may be selected as appropriate, and both sides may be formed simultaneously, or one side may be coated and the other side coated. good.
When the insulating base material (A) in the form of a film, sheet or plate has a through hole connecting the front and back, the method for forming the resin layer (B) on the inner wall surface of the through hole is not particularly limited, If the resin layer forming composition (b) is applied using the various printing / coating techniques, the resin layer forming composition (b) penetrates into the inner wall surface of the through hole. The resin layer (B) can be suitably formed.

  Moreover, in this invention, the resin layer (B) may be formed in the whole surface of an insulating base material (A), and may be suitably formed in pattern shape according to the objective. As a method for obtaining such a patterned resin layer (B), if the patterned resin layer (B) is directly formed on the substrate (A) using any of the various coating methods described above, good. In this way, when the patterned resin layer (B) is formed, the wettability of the insulating product substrate (A) and the resin layer (B) when the metal fine particle dispersion (C) described later is applied. It is also possible to form the nonconductive layer (D) made of metal fine particles only on the resin layer (B).

  Moreover, the method of drying the coating film after coating the resin layer forming composition (b) on the insulating substrate (A) is not particularly limited, but the insulating base material (A) However, in the case of a single-wafer film, sheet, or plate, in addition to natural drying at a coating place, it can be carried out in a dryer such as an air blower or a constant temperature dryer. Further, when the insulating substrate (A) is a roll sheet, the roll sheet is continuously moved in an installed non-heated or heated space following the printing / coating step, thereby drying. It can be carried out.

  The drying temperature is within a range in which the aqueous medium (b3) constituting the resin layer forming composition (b) can be volatilized and does not adversely affect the insulating base material (A) as a support. What is necessary is just to set to temperature. Specifically, when the thermal crosslinking agent (b4-1) is used, it is preferably dried at a temperature of about 25 ° C. to less than 100 ° C. When the thermal crosslinking agent (b4-2) is used. Is approximately 100 ° C or higher, preferably about 120 ° C to 300 ° C. On the other hand, when using the thermal cross-linking agent (b4-2) and applying a dispersion (C) of metal fine particles (c2) to be described later to form a cross-linked structure, normal temperature (25 ° C.) It is preferable to dry at a relatively low temperature of about -100 ° C. and adjust so as not to form a crosslinked structure before printing.

  The layer thickness of the resin layer (B) formed on the surface of the insulating substrate (A) may be adjusted depending on the type and thickness of the substrate, and a dispersion (C) of metal fine particles (c2) described later. In consideration of the amount of solvent contained therein, and from the viewpoint of maintaining various properties of the insulating base (A), the film thickness after drying is desirably 5 μm or less, more preferably 2 μm or less. It is preferable. Furthermore, when the insulating substrate (A) is a film-like substrate having a thickness of 50 μm or less, it is preferably 1 μm or less, more preferably 500 nm. In the case of using it for the production of a high-speed, high-frequency compatible conductive material, it is preferable that the thickness be 100 nm or less.

<Dispersion liquid (C) of metal fine particles (c2)>
The metal fine particles (c2) contained in the dispersion (C) applied to form the nonconductive layer (D) in the present invention are resin layers (C) formed on the insulating base (A). B) above, which functions as a catalyst for electroless plating, and particles of gold, silver, copper, platinum, and alloys of these metals, core-shell type particles such as gold-silver core shell, gold -Copper core shell, silver-copper core shell particles, anisotropic composite particles of these metal particles, and the like. In the present invention, only one kind of the metal fine particles (c2) may be used, or a mixture of a plurality of kinds may be used. From the viewpoint of industrial availability and cost, it is preferable to use silver and copper particles as the metal species. Moreover, even if an oxide film or a sulfide film exists on the surface of the metal fine particles (c2), it does not matter as long as it functions as an electroless plating catalyst.

  The shape of the metal fine particles (c2) is not particularly limited as long as it can be applied on the resin layer (B) formed on the insulating substrate (A) and a stable dispersion (C) is obtained. , Spherical, lens-shaped, polyhedral, flat-plate, rod-shaped, wire-shaped or the like, various kinds of fine metal particles alone or a mixture of plural kinds can be appropriately selected and used depending on the purpose. .

  The size of the metal fine particles (c2) is observed by observing the particle shape with an electron microscope. When the observed shape is a circle or a polyhedron, the diameter is preferably 1 to 200 nm. From the viewpoint of dispersibility and stability of the metal fine particles (c2) in C), it is more preferable to use those having a particle size of 2 to 100 nm. Furthermore, it is especially preferable that it is a metal fine particle of 5-50 nm from a viewpoint which can form a denser and more uniform conductive layer (E) efficiently by electroless plating.

  When the observation image of the metal fine particles (c2) in the electron microscope has a shape symmetric with respect to the minor axis and the major axis, such as a lens shape, a rod shape, or a wire shape, the minor axis is 1 to 200 nm, more preferably 2-100 nm, more preferably 5-50 nm. The particle size distribution of the metal fine particles (c2) dispersed in the dispersion liquid (C) may be monodispersed or may be a mixture of particles having a particle size in the above preferred particle size range. good.

  The dispersion liquid (C) used in the present invention is obtained by dispersing the metal fine particles (c2) in various dispersion media, and the metal fine particles (c2) aggregate, fuse and precipitate in the dispersion medium. Therefore, since it is necessary to maintain long-term dispersion stability, the surface of the metal fine particles (c2) is protected by an organic compound protective agent. Moreover, the said metal microparticle (c2) apply | coats the dispersion liquid (C) on the resin layer (B) formed on the said insulating base material (A), and becomes a nonelectroconductive layer (D). This functions as a catalyst for electroless plating, but since the plating process is performed in a liquid, it is necessary that the nonconductive layer (D) does not peel from the substrate in the plating process liquid, The protective agent for the metal fine particles (c2) has a function of improving the adhesion between the resin layer (B) formed on the insulating base material (A) and the non-conductive layer (D). preferable.

  From such a viewpoint, in the present invention, it is essential to use and disperse the compound (c1) having a nitrogen atom, sulfur atom, phosphorus atom or oxygen atom as the compound (c1) for protecting the metal fine particles (c2). It can select suitably according to the intended purpose of the dispersion liquid (C) of metal microparticles (c2), such as a metal microparticle, the kind of dispersion solvent to be used, and the resin layer (B) which apply | coats a metal microparticle. These specific atoms may be contained alone in the compound (c1), but from the viewpoint of efficiently expressing the above-mentioned functions, they may have two or more different atoms in one molecule. preferable.

In order to include such a hetero atom in the compound (c1) used as the protective agent, for example, an amino group (—NH ₂ ), a carboxy group (—COOH), a hydroxy group (—OH), a thiol group (— SH), phosphate group (H ₂ PO ₄ −), quaternary ammonium group (—NRR′R ″ ₄ ⁺ ), quaternary phosphonium group, cyano group (—CN), ether group (—O—), thioether group (-S-), a disulfide group (-S-S-), etc. These functional groups may be contained alone or in a plurality of types in one molecule. Moreover, even if it uses a single compound (c1) as a protective agent, you may use multiple types of the compound (c1) which has such a functional group simultaneously.

  Specific examples of the compound (c1) include low-molecular weight compounds such as 2-dimethylaminoethanol, 2-diethylaminoethanol, 2-dimethylaminoisopropanol, 3-diethylamino-1-propanol, 2-dimethylamino-2- Methyl-1-propanol, 2-methylaminoethanol, 4-dimethylamino-1-butanol, formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid , Dodecanoic acid, tetradecanoic acid, oleic acid, linoleic acid, linolenic acid, stearic acid, oxalic acid, tartaric acid, phthalic acid, methacrylic acid, citric acid, acrylic acid, benzoic acid, cholic acid, ethylenediamine, propylamine, butylamine, trimethylamine , Pentylami , Hexylamine, heptylamine, octylamine, nonylamine, decylamine, undecylamine, dodecylamine, tridecylamine, tetradecylamine, pentadecylamine, hexadecylamine, trioctylamine, dodecyldimethylamine, butylethanolamineamine, Examples include thiocholine bromide, allyl thiol, octane thiol, decane thiol, dodecane thiol, L-cysteine, sodium sulfosuccinate, sodium dodecylbenzene sulfonate, and the like.

In addition, examples of the high molecular weight compound include polymer units such as polyvinyl alcohol, polyvinyl pyrrolidone, polyethylene glycol, polyethylene glycol-polypropylene glycol copolymer, polyethyleneimine, polypropyleneimine, polypyrrole, poly (meth) acrylate, and polystyrene. A polymer having one kind or plural kinds in a molecule can be suitably used. When these kinds of polymer units are used, each polymer unit can be directly or amide bond, ester bond, ether group ( Those bonded through —O— or a thioether group (—S—) can be used. Furthermore, some of the terminals of these polymers are an amino group (—NH ₂ ), a carboxy group (—COOH), a carboxylic acid ester (—COOR: R is selected from methyl, ethyl, propyl), a hydroxy group (— OH), a thiol group (—SH), or the like, and a phosphate group represented by —OP (O) (OH) ₂ or —SR (R is carbon An alkyl group having 1 to 18 carbon atoms, a phenyl group optionally having a substituent on the benzene ring, or a hydroxy group, an alkoxy group having 1 to 18 carbon atoms, an aralkyloxy group having 1 to 18 carbon atoms, and a benzene ring A phenyloxy group, a carboxy group, a carboxy group salt, a monovalent or polyvalent alkylcarbonyloxy group having 1 to 18 carbon atoms, and a monovalent or polyvalent group having 1 to 18 carbon atoms, which may have a substituent. Price Alkoxyalkyl is an alkyl group having 1 to 8 carbon atoms having one or more functional groups selected from the group consisting of a carbonyl group.) Can be suitably used those having a functional group represented by. These polymers can be used alone or as a mixture of two or more thereof.

  Among these, the dispersion stability of the dispersion liquid (C), the film forming property of the nonconductive layer (D) on the resin layer (B) formed on the insulating substrate (A), and the viewpoint of adhesion From the above, the compound (c1) preferably has a number average molecular weight in the range of 1,000 to 50,000, and the structure thereof is a compound having a polyethyleneimine block and a polyethylene glycol block (P1). A (meth) acrylic polymer (P2) and an organic compound (P3) having a specific structure containing a thioether group (sulfide bond) can be particularly preferably used.

  The compound (P1) having a polyethyleneimine block and a polyethyleneglycol block can be obtained by, for example, deriving a terminal hydroxyl group of a commercially available polyethylene glycol as an active group and chemically bonding this to a commercially available polyethyleneimine. A compound in which polyethylene glycol having a number average molecular weight of 500 to 5,000 is bonded to an amino group in polyethyleneimine having a number average molecular weight of 500 to 50,000 can be particularly preferably used. The compound (P1) used in the present invention only needs to have a specific structure of a polyethyleneimine block and a polyethylene glycol block, and may be one into which another structure is further introduced.

The (meth) acrylic polymer (P2) that can be suitably used in the present invention includes a (meth) acrylate macromonomer having a polyethylene glycol chain, and -OP (O) (OH) ₂ . (Meth) acrylate monomer having a phosphate ester residue represented by polymerization in the presence of a chain transfer agent having a functional group represented by -SR (R is the same as above) (meta) ) Acrylic polymers can be mentioned (for example, refer to Japanese Patent No. 4697356).

Further, the organic compound (P3) having a specific structure containing a thioether group (sulfide bond) that can be suitably used in the present invention includes the following general formula (1).
^{_{X- (OCH 2 CHR 1) n}} -O-CH 2 -CH (OH) -CH 2 -S-Z (1)
Wherein (1), X is an alkyl group of _C ¹ _{~C 8,} ^R 1 is a hydrogen atom or a methyl radical, n is an integer indicating the number of repetitions of 2 to 100, ^{R 1} is repeated independently for each unit may be different even in the same, Z is an alkyl group of _C 2 _{-C 12,} an allyl group, an aryl group, an arylalkyl ^{group, -R 2 -OH, -R 2 -NHR} 3 , or ^-R 2 -COR ⁴ (where, ^{R 2} is an alkylene chain of _C 2 _{~C 4,} ^{R 3} is a hydrogen _atom, an acyl group of C 2 -C _4, alkoxycarbonyl group C 2 -C _4, Or a C ₁ -C ₄ alkyl group or a C ₁ -C ₈ alkoxy group which may have a substituent on the aromatic ring, and R ⁴ is a hydroxy group, C ₁ -C ₄ It is alkyl or alkoxy group _C 1 -C ₈ ) Is a group represented by. ]
A thioether-containing organic compound (P3) represented by the formula can be suitably used (see, for example, Japanese Patent No. 4784847).

  The compound (c1) used in the present invention may be added during the production of the metal fine particles (c2), or may be added after the metal fine particles (c2) are produced. In the dispersion liquid (C), as the solvent for dispersing the metal fine particles (c2), the metal fine particles (c2) can be stably dispersed. In the state where the metal fine particles (c2) are dispersed, the insulation is performed. The solvent is not particularly limited as long as it has good wettability to the resin layer (B) formed on the conductive substrate (A) and can form a liquid film on the resin layer (B). Any of water, a mixed solvent of water and a water-soluble organic solvent, and an organic solvent not containing water may be used.

  Examples of the water-soluble solvent that can be mixed with water include alcohols such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, tert-butyl alcohol, acetone, -Ketones such as butanone, polyhydric alcohols such as ethylene glycol and glycerin and other esters, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, propylene glycol methyl ether acetate, butyl diethylene glycol acetate Glycol ethers such as, etc., and these solvents can be used alone or in combination. Kill.

  In the dispersion (C), the organic solvent in which the metal fine particles (c2) are dispersed is a water-soluble solvent that can be mixed with the water, for example, methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol. , Alcohols such as n-butyl alcohol, isobutyl alcohol and tert-butyl alcohol, ketones such as acetone and 2-butanone, polyhydric alcohols such as ethylene glycol and glycerin and other esters, ethylene glycol monoethyl ether, ethylene Glycol ethers such as glycol dimethyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, propylene glycol methyl ether acetate, butyl diethylene glycol acetate, etc. You can gel alone these solvents, or a plurality of a mixture may be used without mixing with water. In this case, water may be contained a little due to moisture absorption or the like, but since it is not intended to be mixed with water, it is treated as an organic solvent not containing water in the present invention.

  In the dispersion (C), the organic solvent in which the metal fine particles (c2) are dispersed is an organic solvent that is not mixed with water, for example, hexane, heptane, octane, nonane, decane, undecane, dodecane, tridecane, tetradecane, Long-chain alkanes such as pentadecane, hexadecane, octadecane, nonadecane, eicosane, and trimethylpentane, cyclic alkanes such as cyclohexane, cyclobutane, and cyclooctane, aromatic hydrocarbons such as benzene, toluene, xylene, trimethylbenzene, and dodecylbenzene, hexanol, Examples thereof include alcohols such as heptanol, octanol, decanol, cyclohexanol, and terpineol. These solvents may be used singly or as a mixture thereof.

  There is no restriction | limiting in particular as a manufacturing method of the dispersion liquid (C) used by this invention, It can manufacture using various methods, For example, using vapor phase methods, such as the evaporation method in a low vacuum gas, The produced metal fine particles may be dispersed in a solvent, or the metal compound may be reduced in a liquid phase to directly prepare a dispersion of metal fine particles. In both the gas phase and the liquid phase method, it is possible to change the solvent composition of the dispersion at the time of production and the dispersion at the time of coating by exchanging the solvent or adding a solvent as necessary. Among the gas phase and liquid phase methods, the liquid phase method can be particularly suitably used because of the stability of the dispersion and the simplicity of the production process.

  As a method for producing the dispersion liquid (C) by the liquid phase method, a method of reducing the metal compound in the presence of the compound (c1) in the liquid phase can be suitably used, and Japanese Patent Application Laid-Open No. 2008-037884. It can be produced by using the methods described in JP-A-2008-037949, JP-A-2008-03818, and JP-A-2010-007124. For example, after the compound (P1) having the polyethyleneimine block and the polyethylene glycol block is dissolved or dispersed in an aqueous medium, a metal compound is added to the compound, and a complexing agent is used in combination as necessary to achieve uniform dispersion. By mixing the reducing agent simultaneously with the complex or simultaneously with the complexing agent, the reduced metal becomes nanoparticles (fine particles having a size on the order of nanometers) and at the same time protected with the compound (P1). A dispersion (C) of metal fine particles can be obtained.

  Moreover, as a manufacturing method of the dispersion liquid (C) by the liquid phase method used by this invention, for example, in the presence of the method described in patent 4697356, the said (meth) acrylic-type polymer (P2) protective agent. A method of reducing a metal compound can be suitably used.

  Moreover, as a manufacturing method of the dispersion liquid (C) by the liquid phase method used by this invention, a metal compound is reduce | restored in presence of the organic compound (P3) protective agent of the specific structure containing the said thioether group (sulfide bond). The method can be suitably used, and in the presence of the thioether-containing organic compound (P3), a metal fine particle dispersion (C) is obtained through a step of mixing a metal compound with a solvent and a step of reducing the metal compound. Can be obtained.

  Further, one form of the metal fine particles (c2) used in the present invention is a core-shell type particle of silver core-copper shell. As a method for producing the dispersion liquid (C) of the metal fine particles, silver nanoparticles are used. And a step of mixing the thioether-containing organic compound (P3), copper oxide (I) and / or copper oxide (II) and a solvent, and reducing the copper oxide using a reducing agent to form silver nanoparticles. Through a step of generating a copper shell around the core, a dispersion (C) of core-shell particles of a silver core-copper shell can be obtained. As the silver nanoparticles used in this method, commercially available silver nanoparticles may be used, or silver nanoparticles obtained by using the above-described method for producing a dispersion of metal fine particles may be used.

  In the present invention, the aqueous dispersion of fine metal particles obtained by these methods is used as it is, or an excess complexing agent, a reducing agent, or a counter ion contained in a silver compound used as a raw material is subjected to ultrafiltration. That has undergone a purification process in which various purification methods such as a method, precipitation method, centrifugal separation, vacuum distillation, vacuum drying, etc. are carried out alone or in combination of two or more, and the concentration (nonvolatile content) and dispersion medium are further changed. Etc. may be used.

  Examples of the metal compound that can be used in the method for producing the dispersion liquid (C) of the metal fine particles (c2) in the liquid phase method include the elements that form the metal fine particles (c2) used in the present invention, that is, gold Silver, copper and platinum salts and oxides can be used, but from the viewpoint of solubility, acetates, nitrates, sulfates, chlorides, acetylacetonates and the like are preferable examples. Of these, nitrate or acetate is preferred. However, even if it is an insoluble compound, it can be used as a complexing agent such as ammonia, amine compounds, hydrazines, hydroxylamines, etc. Insoluble compounds such as can also be used.

For example, when the metal element is gold or a platinum group, tetrachloroauric acid, tetrachloroplatinic acid, or the like can be used. When the metal species is copper, Cu (OAc) ₂ , Cu (NO ₃ ) ₂ , CuCl ₂ , Cu (HCOO) ₂ , Cu (CH ₃ COO) ₂ , Cu (CH ₃ CH ₂ COO) ₂ , CuCO ₃ , CuSO ₄ , C ₅ H ₇ CuO ₂ , and a basic salt obtained by heating a carboxylate, such as Cu (OAc) ₂ .CuO, can be used in the same manner. When the metal species is silver, silver nitrate, silver oxide, silver acetate, silver chloride, silver sulfide and the like can be used. However, when handled as an aqueous solution, silver nitrate is preferable in terms of its solubility.

  The concentration of the metal fine particles (c2) in the dispersion (C) used in the present invention is such that the dispersion (C) is applied onto the resin layer (B) formed on the insulating substrate (A). From the viewpoint of making it necessary to form the nonconductive layer (D), it is necessary to contain the metal fine particles (c2) at 0.5 mass% or more in the dispersion (C). is there. That is, if it is too dilute, the distribution of the metal fine particles (c2) on the resin layer (B) becomes too sparse to form a film, and it may be difficult to form the nonconductive layer (D). on the other hand. If it is too thick, the number of laminated metal fine particles (c2) applied on the non-conductive layer (D) will be too large, and it will become a conductive layer by firing and function as a scaffold for the plating film showing strong adhesion. Sometimes things can't be fully demonstrated. From such a viewpoint, the concentration of the metal fine particles in the dispersion (C) used in the present invention is essential to be 0.5% by mass or more, preferably 20% by weight or less, and more preferably. Is preferably 0.7 to 15 wt%, and more preferably 1 to 10 wt% from the viewpoint of coating film formability.

  In the dispersion (C) used in the present invention, various surface tension adjusting agents and leveling agents can be added and used as needed mainly for the purpose of improving the coating film forming property. The amount of these surface tension adjusting agent and leveling agent added is preferably 2.0% by mass or less, particularly preferably 0.5% by mass or less of the active ingredient, with respect to the dispersion.

<Application of dispersion liquid (C)>
In the present invention, as a method of applying the dispersion (C) on the resin layer (B) formed on the insulating substrate (A), the non-conductive layer (D) is satisfactorily formed. As long as there is no particular limitation, various printing / coating methods may be appropriately selected depending on the shape, size, degree of flexibility, etc. of the insulating base material (A) to be used. Offset method, letterpress method, letterpress inversion method, screen method, microcontact method, reverse method, air doctor coater method, blade coater method, air knife coater method, squeeze coater method, impregnation coater method, transfer roll coater method, kiss coater method, cast Examples thereof include a coater method, a spray coater method, an ink jet method, a die method, a spin coater method, a bar coater method, and a dip coat method.
As a method for applying the dispersion liquid (C) on the resin layer (B) formed on both surfaces of the film, sheet or plate-like insulating base material (A), a non-conductive layer (D) is used. There is no particular limitation as long as it is formed satisfactorily, and the above-described various printing / coating methods may be appropriately selected. Both sides may be formed at the same time. After one side is applied, the other side is applied. May be performed.
When the insulating substrate (A) in the form of a film, sheet or plate has a through hole for connecting the front and back, a non-conductive layer (D) on the inner wall surface of the through hole in which the resin layer (B) is formed There is no particular limitation on the method for forming the dispersion, and if the dispersion (C) is applied using the above-described various printing / coating techniques, the dispersion (C) penetrates into the through holes. The non-conductive layer (D) can be suitably formed on the inner wall surface of the through hole in which the resin layer (B) is formed.

  After the dispersion liquid (C) of the metal fine particles (c2) is applied on the resin layer (B), the coating film is dried to form the nonconductive layer (D). The coating film may be dried at room temperature or may be heat-dried. At this time, as described above, the heating may be performed so that the crosslinking reaction occurs in the resin layer (B), or the crosslinking reactive group in the resin layer (B), the compound (c1), and It may be intended to cause this reaction. Further, the air may be blown at the time of drying, or it may not be specially blown. For blowing air, hot air may be blown or only at room temperature. Moreover, drying may be performed in air | atmosphere, replacement | exchange atmosphere, such as nitrogen and argon, or airflow may be performed, and you may carry out in a vacuum. Moreover, you may carry out in hydrogen atmosphere below an explosion lower limit density | concentration.

  When the insulating substrate (A) is a single-wafer film, sheet, or plate, in addition to natural drying at the coating place, the coating film is dried in a dryer such as an air blower or a constant temperature dryer. It can be carried out. Further, when the insulating substrate (A) is a roll sheet, the roll sheet is continuously moved in an installed non-heated or heated space following the printing / coating step, thereby drying. It can be carried out.

<Non-conductive layer (D)>
In the present invention, the non-conductive layer (D) formed by applying a dispersion (C) of metal fine particles (c2) on the resin layer (B) formed on the insulating substrate (A) is When the metal fine particles (c2) protected by the compound (c1) are arranged almost uniformly on the resin layer (B), and there is partial contact between the metal fine particles (c2). There is also a layer that does not exhibit conductivity. In the present invention, the layer in which the metal fine particles (c2) are uniformly arranged does not exhibit conductivity, that is, is non-conductive, a level at which the resistance value of the film cannot be measured using a low resistivity meter. For example, in the Loresta series resistivity meter manufactured by Mitsubishi Chemical Analytech Co., Ltd., the overrange (the resistance of the layer measured by the four-terminal method is 9.999 × 10 ⁷ Ω or more) or over What is necessary is just to confirm the display of the load (the constant current cannot be measured even when a voltage of 90 V is applied between the terminals).

  The non-conductive layer (D) formed on the resin layer (B) used in the present invention may be subjected to a heat treatment before electroless plating in a subsequent step as appropriate. By heat treatment, the adhesion between the non-conductive layer (D) and the resin layer (B) can be improved, and in the resin layer (B) or between the resin layer (B) and the compound (c1). Crosslinking reaction proceeds. Moreover, when using a printed wiring board, for example, it may go through a high-temperature process such as soldering. In the base material, the compound (c1) which is a protective agent, a surface conditioning agent added if necessary, a leveling agent, When the dispersion solvent or the like rapidly volatilizes or decomposes and vaporizes in the high temperature process, it becomes a problem. Therefore, it is recommended to remove such components by performing a heat treatment in advance during production.

  The heat treatment may be performed by treating the substrate on which the non-conductive layer (D) is formed on the resin layer (B) by various heating methods, such as an electric furnace, a muffle furnace, a vacuum furnace, an atmosphere furnace, light One or a plurality of heating devices such as an irradiation heating device, an infrared heating device, a microwave heating device, and an electron beam heating device can be used. Moreover, heat processing can be performed in air | atmosphere, a vacuum, nitrogen atmosphere, argon atmosphere, and hydrogen atmosphere below an explosion lower limit density | concentration as needed. Further, when the insulating substrate (A) is a sheet film, sheet or plate, it may be carried out in a vessel of the heat treatment apparatus, and when it is in the form of a roll sheet, electric heating or light heating is performed. Infrared heating or microwave heating can be performed by continuously moving the sheet into the space.

  In the present invention, the heat treatment of the nonconductive layer (D) may be performed simultaneously with the drying after the dispersion (C) is applied on the resin layer (B), or the drying and the heat treatment are separately performed. You can go. Further, the heat treatment of the non-conductive layer (D) forms a crosslinked structure in the resin layer (B), or the crosslinked structure between the crosslinkable functional group in the resin layer (B) and the compound (c1). The heat treatment for forming the resin layer (B) may be performed, or may be performed separately from the heat treatment for forming the crosslinked structure of the resin layer (B).

  In the present invention, the heat treatment temperature and heat treatment time of the nonconductive layer (D) may be appropriately selected according to the purpose of use and the heat resistant temperature of the material of the insulating base material (A) to be used, and there is no particular limitation. However, if the insulating substrate (A) is a polyimide resin, it is 400 ° C. or less, preferably 300 ° C. or less, polyethylene terephthalate is 150 ° C. or less, polyethylene naphthalate is 200 ° C. or less, liquid crystal polymer is 380 ° C. or less, paper It is preferable to perform heat treatment at 130 ° C. or lower for phenol and paper epoxy, 150 ° C. or lower for glass epoxy, and 100 ° C. or lower for ABS resin.

  Moreover, what is necessary is just to use the conditions suitable for the crosslinked structure formation of the said resin layer (B), when heat-processing a nonelectroconductive layer (D) simultaneously with crosslinked structure formation of the said resin layer (B).

  As described above, the heat treatment of the nonconductive layer (D) on the resin layer (B) formed on the insulating substrate (A), which is performed in the present invention, is performed with the metal fine particles (c2) and the resin layer. The purpose is to improve the adhesion of (B) and to remove components that volatilize and decompose and vaporize in a high-temperature process, and the metal fine particles (c2) are brought into close contact with each other and fused to express conductivity. Is characterized by maintaining non-conductivity after heat treatment.

  In the non-conductive layer (D) on the resin layer (B) formed on the insulating base material (A) used in the present invention, the metal fine particles (c2) are arranged on the resin layer (B). If the number of stacked metal fine particles (c2) in the thickness direction is too large, a large number of joints where the metal fine particles (c2) are fused to each other are formed by the heat treatment, and the entire film is uneven. Therefore, it is easy to form a conductive film. Since the conductive film having such a non-uniform fusion structure includes a large number of voids in the film, the film is inferior in mechanical strength, and the film inferior in mechanical strength becomes the resin layer (B) and the subsequent plating step. In other words, the plating film may be easily peeled off from the substrate. In addition, when electroless plating is performed using a film having such a non-uniform fusion structure, the inside of the fusion structure and the lower part of the fusion structure can be sufficiently filled with the plating metal even though the voids above the film can be filled. It is difficult to fill and it is difficult to improve the mechanical strength of the film. From such a viewpoint, the number of stacked metal fine particles (c2) disposed on the resin layer (B) is preferably 5 or less, and more preferably 3 or less. The number of metal fine particles (c2) stacked on the resin layer (B) is determined by measuring the film thickness of the nonconductive layer (D) using a confocal microscope, an interference microscope, a surface shape measuring device, or the like, This can be confirmed by observing the surface and cross section of the conductive layer (D).

  Further, the non-conductive layer (D) formed on the resin layer (B) used in the present invention is formed by coating the resin layer (B) with the metal fine particles (c2). It functions as a plating catalyst, a plating seed, and a scaffold layer in a subsequent plating step. If the surface coverage by the metal fine particles (c2) on the surface of the resin layer (B) is too low, the distance between the deposited metal crystals is too far away and the crystals do not adhere to each other. Is difficult. On the other hand, when the coverage of the surface of the resin layer (B) with the metal fine particles (c2) becomes high and the number of metal fine particles (c2) stacked on the surface increases, the heat treatment causes bonding between the metal fine particles (c2). A non-uniform fusion structure with many voids is formed to form a conductive film. When a conductive film having such a non-uniform fusion structure is formed, a large number of independent voids are formed inside the film as described above, so that the mechanical strength is inferior and plating formed in a later step The metal film cannot maintain a practical peel strength. If the surface coverage by the metal fine particles (c2) is appropriate, the connection between the deposited plated metal crystals is good and a film is easily formed, and the plated metal sufficiently penetrates into the gaps between the metal fine particles (c2). An anchor effect occurs and peel strength is improved. From such a viewpoint, the surface coverage by the metal fine particles (c2) on the surface of the resin layer (B) is preferably 55% or more and 95% or less (area ratio). From the viewpoint of maintaining the peel strength from the insulating substrate, it is more preferably 70% or more and 90% or less.

  In the present invention, the surface coverage by the metal fine particles (c2) on the resin layer (B) is determined by observing the surface of the non-conductive layer (D) using a high-resolution scanning electron microscope (SEM). It can be evaluated by calculating the occupation ratio of the metal fine particle (c2) image on the observation image. From the size of the metal fine particles (c2) used in the present invention, it is recommended to use an observation magnification of about 50,000 times for the evaluation of the surface coverage.

  In the present invention, the nonconductive layer (D) formed on the resin layer (B) may be formed on the entire surface or may be formed on a part of the surface. A patterned non-conductive layer (D) may be formed.

  As a method for obtaining such a patterned non-conductive layer (D), the patterned non-conductive layer (D) is directly formed on the resin layer (B) using any of the various coating methods described above. The circuit pattern may be patterned before the electroless plating process which is the third step. Examples of the patterning method include a method of inducing an ablation phenomenon by laser irradiation to remove unnecessary portions. As a laser used for this purpose, a laser having any wavelength of a UV laser, a visible light laser, a near infrared laser, and an infrared laser may be used. In addition, as described above, when the patterned resin layer (B) is formed, spontaneously due to the difference in wettability between the insulating substrate (A) and the resin layer (B). In some cases, the metal fine particles (c2) are selectively present only on the resin layer (B) to form the patterned non-conductive layer (D).

<Electroless plating process>
In the step (3) of the present invention, the conductive layer (E) is formed on the base material provided with the nonconductive layer (D) on the resin layer (B) obtained through the steps (1) and (2). The non-conductive layer (D) formed on the resin layer (B) is used as a catalyst layer and a seed layer for electroless plating, and is performed by electroless plating.

  The electroless plating process is preferably performed through a cleaner process, a water washing process, a catalyst activation process, and a water washing process. Although there is no restriction | limiting in particular in the kind of plating metal, It is preferable to perform electroless copper plating from electroconductivity and industrial utilization. In this electroless copper plating, a bath may be used with the composition of the electroless copper plating solution described in the literature, or a commercially available electroless plating reagent may be used. Commercially available electroless plating reagents are sold for various uses such as thickening, thinning, selective deposition, etc., and may be appropriately selected according to the purpose. For example, OIC Copper manufactured by Okuno Pharmaceutical Co., Ltd. An OPC copper or the like can be used particularly preferably.

  The conductive layer (E) formed by electroless plating in the step (3) of the present invention is not particularly limited, but preferably has a surface resistivity of 1000Ω / □ or less, and is further electroplated by the step (4). In the case of carrying out the above, the surface resistivity is preferably 10Ω / □ or less. Considering the efficiency of forming the metal conductive layer (F) by electroplating in the step (4), it is more preferably 1Ω / □ or less. The thickness of the conductive layer (E) formed by electroless plating is preferably 1500 nm or less from the viewpoint of manufacturing work efficiency.

<Electroplating process>
In the present invention, a conductive material having a conductive layer (E) on the surface can be obtained by the above-described electroless plating step, but the conductivity is further increased or the thickness of the conductive layer is increased. For this purpose, electroplating may be further performed as step (4). There are no particular restrictions on the metal species formed by electroplating at this time, but from the viewpoint of conductivity and stability, copper, nickel, gold, etc. are preferable, particularly from the viewpoint of low resistance and industrial applicability. Copper is preferred.

  The electroplating process is not particularly limited, and various electroplating methods may be used. For example, the conductive layer (E) surface obtained in the process (3) is degreased and / or the oxide layer is removed. Then, a plating layer can be formed by immersing in a plating solution and energizing.

  The thickness of the metal conductive layer (F) obtained by electroplating is not particularly limited and may be appropriately selected depending on the purpose of use. The conductive layer (E) formed by electroless plating in step (3) In addition, the thickness is preferably 200 nm or more and 30 μm or less, and more preferably 400 nm or more and 20 μm or less from the viewpoint of conductivity and circuit patternability during use.

  The conductive material produced through the above three steps forms a resin layer (B) on the insulating substrate (A), and a nonconductive layer (D) made of metal fine particles (c2) thereon. Furthermore, the conductive layer (E) is laminated thereon, and the conductive material obtained from the four steps is a resin layer (B) on the insulating base material (A). And a non-conductive layer (D) made of metal fine particles (c2) is formed thereon, and a conductive layer (E) and a metal conductive layer (F) are laminated thereon. is there. In the conductive material of the present invention, the metal species of the metal fine particles (c2) and the conductive layer (E) formed thereon, or all of the metal species forming the conductive layer (E) and the metal conductive layer (F) May be the same metal or different metal species. For example, in one form of the conductive material of the present invention, the nonconductive layer (D) on the resin layer (B) formed on the insulating base (A) is made of silver fine particles, The formed conductive layer (E) is made of copper. As another form, the non-conductive layer (D) on the resin layer (B) formed on the insulating substrate (A) is made of copper fine particles, and the conductive layer (E ) And metal conductivity (F) can also be made of copper. Furthermore, as another form, the non-conductive layer (D) on the resin layer (B) formed on the insulating substrate (A) is composed of core-shell particles having silver as a core and copper as a shell. And the conductive layer (E) and metal conductive layer (F) formed thereon are made of copper.

  In the conductive material of the present invention, the non-conductive layer (D) composed of the metal fine particles (c2) on the resin layer (B) formed on the insulating base (A) is the conductive layer (E). ) Is formed, the voids between the metal fine particles (c2) are filled by the formation of the conductive layer (F), so that a substantially independent non-conductive layer (D) on the resin layer (B) is formed. Does not have to exist.

  The schematic diagram about the structure of the electroconductive material of this invention was shown in FIGS. Such a conductive material can be suitably used as a laminated base material for a printed wiring board that particularly requires fine wire processing because of its excellent adhesion between the insulating base material (A) and the conductive layer.

  EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. Unless otherwise specified, “%” represents “mass%”.

The equipment used in the present invention is as follows.
¹ H-NMR: manufactured by JEOL Ltd., AL300, 300 Hz
TEM observation: JEM-2200FS, manufactured by JEOL Ltd.
SEM observation: Hitachi, ultra-high resolution field emission scanning electron microscope S-800, or Keyence Corporation, VE-9800
TGA measurement: SII Nano Technology Co., Ltd., TG / DTA6300
Plasmon absorption spectrum: manufactured by Hitachi, Ltd., UV-3500
Dynamic light scattering particle size measuring device: FPAR-1000, manufactured by Otsuka Electronics Co., Ltd.
Surface resistance measurement: Mitsubishi Chemical Corporation, low resistivity meter Loresta EP (4-terminal method)
Surface coverage measurement: Surface coverage by metal fine particles on the surface of the base material is applied to the dispersion using Hitachi, super high resolution field emission scanning electron microscope S-800, and the surface after drying is multiplied by 50,000 times. After the observation image was binarized into a black and white image, the area occupied by the metal fine particles relative to the entire area of the image surface was calculated.
Peel strength test: Tensilon universal testing machine manufactured by A & D Co., Ltd. RTC-1210A: The plating film was peeled from the substrate in a 1 cm strip shape, and the peel strength was measured by determining the tensile strength in the 180 ° C. direction.

[Production of Resin Layer Forming Composition (b)]
(Manufacture of urethane resin (b1))
Synthesis Example 1 Production of Urethane Resin (b1-a) Polyester polyol (1,4-cyclohexanedimethanol, neopentyl glycol, and adipic acid in a nitrogen-substituted container equipped with a thermometer, a nitrogen gas inlet tube, and a stirrer Polyester polyol obtained by reacting with the above, the aliphatic cyclic structure content in the polyester polyol is 1426 mmol / kg, hydroxyl group equivalent 1000 g / equivalent) 100 parts by mass, 2,2-dimethylolpropionic acid 17.6 Urethane prepolymer having an isocyanate group at the molecular end by reacting in mass solvent, 21.7 parts by mass of 1,4-cyclohexanedimethanol and 106.2 parts by mass of dicyclohexylmethane diisocyanate in a mixed solvent of 178 parts by mass of methyl ethyl ketone An organic solvent solution 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 a urethane resin having an aliphatic cyclic structure and a carboxyl group 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 (b1-a) was obtained. The urethane resin (b1-a) obtained here had an acid value of 30, an aliphatic cyclic structure content calculated from the raw material ratio of 4452 mmol / kg, and a weight average molecular weight of 53,000.

Synthesis Example 2 Production of Urethane Resin (b1-b) In a nitrogen-substituted container equipped with a thermometer, a nitrogen gas introduction tube, and a stirrer, 100 parts by mass of polyester polyol (neopentyl glycol and 1,6-hexanediol and Polyester polyol obtained by reacting with adipic acid, hydroxyl group equivalent 1000 g / equivalent), 2,2-dimethylolpropionic acid 12.6 parts by mass, 1,4-cyclohexanedimethanol 5.5 parts by mass, dicyclohexylmethane diisocyanate By reacting 58.2 parts by mass in a mixed solvent of 124 parts by mass of methyl ethyl ketone, an organic solvent solution of a urethane prepolymer having an isocyanate group at the molecular end was obtained.

  Next, by adding 9.5 parts by mass of triethylamine to the organic solvent solution of the urethane resin, part or all of the carboxyl groups of the urethane resin is neutralized, and further 277 parts by mass of water is added and sufficiently stirred. An aqueous dispersion of urethane resin having an aliphatic cyclic structure and a carboxyl group was obtained.

  Next, 4.8 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 and desolvation, whereby a solid content concentration of 30 is obtained. An aqueous dispersion of mass% urethane resin (b1-b) was obtained. The urethane resin (b1-b) obtained here had an acid value of 30, an aliphatic cyclic structure content calculated from the raw material ratio of 2714 mmol / kg, and a weight average molecular weight of 51,000.

Synthesis Example 3 Production of Urethane Resin (b1-c) 100 parts by mass of polyester polyol (1,4-cyclohexanedimethanol and neopentyl glycol) in a nitrogen-substituted container equipped with a thermometer, a nitrogen gas inlet tube, and a stirrer Polyol obtained by reacting adipic acid with adipic acid, aliphatic cyclic structure content in the polyester polyol: 1426 mmol / kg, hydroxyl group equivalent 1000 g / equivalent), 2,2-dimethylolpropionic acid 17.6 mass Part, 1,4-cyclohexane dimethanol 21.7 parts by mass, dicyclohexylmethane diisocyanate 106.2 parts by mass in a mixed solvent with methyl ethyl ketone 178 parts by mass, urethane prepolymer having an isocyanate group at the molecular terminal An organic solvent solution was obtained.

  Next, 10 parts by mass of γ-aminopropyltriethoxysilane is mixed with the organic solvent solution of the urethane prepolymer, and the urethane prepolymer and γ-aminopropyltriethoxysilane are reacted to form an aliphatic cyclic structure. An organic solvent solution of a urethane resin having a carboxyl group and a hydrolyzable silyl group or silanol group 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. 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 (b1-c) was obtained. The urethane resin (b1-c) obtained here had an acid value of 30, an aliphatic cyclic structure content calculated from the raw material ratio of 4307 mmol / kg, and a weight average molecular weight of 88,000.

Synthesis Example 4 Production of Urethane Resin (b1-d) In a nitrogen-substituted container equipped with a thermometer, a nitrogen gas introduction tube, and a stirrer, 100 parts by mass of a polyether polyol (“PTMG2000” manufactured by Mitsubishi Chemical Corporation, hydroxyl group) Equivalent of 1000 g / equivalent), 17.4 parts by mass of 2,2-dimethylolpropionic acid, 34.2 parts by mass of 1,4-cyclohexanedimethanol, 109.3 parts by mass of dicyclohexylmethane diisocyanate, and 31.5 parts by mass of isophorone diisocyanate. Was reacted in a mixed solvent of 178 parts by mass of methyl ethyl ketone to obtain an organic solvent solution of a urethane prepolymer having an isocyanate group at the molecular end.

  Next, 12.5 parts by mass of γ-aminopropyltriethoxysilane is mixed with the organic solvent solution of the urethane prepolymer, and the urethane prepolymer and γ-aminopropyltriethoxysilane are reacted to form an aliphatic ring. An organic solvent solution of a urethane resin having a formula structure, a carboxyl group, and a hydrolyzable silyl group or silanol group was obtained.

  Next, 13.1 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 488 parts by mass of water is further added and sufficiently stirred. An aqueous dispersion of urethane resin was obtained.

  Next, 17 parts by mass of a 25% by mass aqueous ethylenediamine solution is added to the aqueous dispersion, and the resulting polyurethane resin is chain-extended by stirring, followed by aging and desolvation, thereby solid content concentration of 30% by mass. An aqueous dispersion of urethane resin (b1-d) was obtained. The urethane resin (b1-d) obtained here had an acid value of 25, an aliphatic cyclic structure content calculated from the raw material ratio of 3921 mmol / kg, and a weight average molecular weight of 99000.

Synthesis Example 5 Production of Urethane Resin (b1-e) Polycarbonate polyol (1,4-cyclohexanedimethanol and carbonate ester were reacted in a nitrogen-substituted container equipped with a thermometer, a nitrogen gas inlet tube, and a stirrer. Polycarbonate diol containing an aliphatic cyclic structure obtained in this manner, the aliphatic cyclic structure content in the polycarbonate polyol is 3000 mmol / kg, hydroxyl group equivalent 1000 g / equivalent) is 100 parts by mass, 2,2-dimethylolpropionic acid By reacting 9.7 parts by mass, 5.5 parts by mass of 1,4-cyclohexanedimethanol, and 51.4 parts by mass of dicyclohexylmethane diisocyanate in a mixed solvent of 111 parts by mass of methyl ethyl ketone, the molecular terminal has an isocyanate group. Obtained organic solvent solution of urethane prepolymer

  Next, 7.3 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 355 parts by mass of water is further added and sufficiently stirred. Thus, an aqueous dispersion of a urethane resin having an aliphatic cyclic structure and a carboxyl group was obtained.

  Next, 4.3 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, so that the solid content concentration is 30. An aqueous dispersion of mass% urethane resin (b1-e) was obtained. The urethane resin (b1-e) obtained here had an acid value of 24, an aliphatic cyclic structure content calculated from the raw material ratio of 4356 mmol / kg, and a weight average molecular weight of 61,000.

Synthesis Example 6 Production of Vinyl Polymer (b2-a) 115 parts by mass of deionized water, Latemul E-118B (Kao Corporation) in a reaction vessel equipped with a stirrer, reflux condenser, nitrogen inlet tube, thermometer, and dropping funnel (Product: 25% by mass of active ingredient) 4 parts by mass was added, and the temperature was raised to 75 ° C. while blowing nitrogen.

  Under stirring, a vinyl monomer mixture comprising 60.0 parts by mass of methyl methacrylate, 38.0 parts by mass of n-butyl acrylate, and 2.0 parts by mass of methacrylic acid in a reaction vessel, and Aqualon KH-1025 ( Daiichi Kogyo Seiyaku Co., Ltd .: active ingredient 25% by mass) Add a part (5 parts by mass) of the monomer pre-emulsion obtained by mixing 4 parts by mass and 15 parts by mass of deionized water. 0.1 parts by mass of potassium sulfate was added, and polymerization was performed for 60 minutes while maintaining the temperature in the reaction vessel at 75 ° C.

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

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

  Next, deionized water was used so that the non-volatile content was 20.0% by mass, followed by filtration with a 200 mesh filter cloth to obtain an aqueous dispersion of vinyl polymer (b2-a).

Synthesis Example 7 Preparation of Resin Layer Forming Composition (b) -1 Aqueous dispersion of urethane resin (b1-a) obtained in Synthesis Example 1 and water of vinyl polymer (b2-a) obtained in Synthesis Example 6 The dispersion was mixed with an aqueous dispersion of urethane resin (b1-a): an aqueous dispersion of vinyl polymer (b2-a) = 100: 350 (solid content mass ratio 30:70), and the non-volatile content was 20 mass. After using deionized water so that it becomes%, the resin layer forming composition (b) -1 used by this invention was obtained by filtering with a 200 mesh filter cloth.

Synthesis Example 8 Preparation of Resin Layer Forming Composition (b) -2 In a reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen inlet, a thermometer, a dropping funnel for dropping a monomer mixture, and a dropping funnel for dropping a polymerization catalyst 140 parts by mass of deionized water and 100 parts by mass of an aqueous dispersion of the urethane resin (b1-a) obtained in Synthesis Example 1 were added, and the temperature was raised to 80 ° C. while blowing nitrogen. 60.0 parts by mass of methyl methacrylate and 40.0 parts by mass of n-butyl acrylate to obtain a vinyl polymer (b2-a) constituting the core layer with stirring in a reaction vessel heated to 80 ° C. A monomer mixture consisting of 20 parts by mass of an aqueous ammonium persulfate solution (concentration: 0.5% by mass) was dropped from a separate dropping funnel over 120 minutes while maintaining the temperature in the reaction vessel at 80 ± 2 ° C. for polymerization. .

  After completion of dropping, the composite resin particles are constituted by a shell layer made of the urethane resin (b1-a) and a core layer made of the vinyl polymer (b2-a) by stirring at the same temperature for 60 minutes. An aqueous dispersion was obtained.

  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. A resin layer forming composition (b) -2 was obtained.

Synthesis Examples 9 to 11 Preparation of Resin Layer Forming Compositions (b) -3 to 5 The types of urethane resins were changed to (b1-a) to (b1-c) described in Table 1 below, respectively, and vinyl polymers The composition for forming a resin layer having a nonvolatile content of 20% by mass is the same as the method described in Synthesis Example 8 except that the composition of the vinyl monomer used in the production of each is changed to the composition described in Table 1 below. Products (b) -3 to 5 were prepared.

Synthesis Example 12 Preparation of Resin Layer Forming Composition (b) -6 200 parts by mass of Resin Layer Forming Composition (b) -2 obtained in Synthesis Example 8 and a melamine compound [Beckamine M-3 (DIC) Co., Ltd.)] By mixing 3.0 parts by mass and deionized water, a resin layer forming composition (b) -6 having a nonvolatile content of 20% by mass was obtained.

Synthesis Example 13-17 Preparation of Resin Layer Forming Compositions (b) -7 to (b) -11 The types of urethane resins were changed to (b1-a) to (b1-e) described in Table 2 below, respectively. In the same manner as described in Synthesis Example 10 except that the composition of the vinyl monomer used in the production of the vinyl polymer is changed to the compositions described in Tables 1 and 2 below, the nonvolatile content is 20% by mass. The resin compositions for forming a receiving layer (b) -7 to (b) -11 were prepared.

Explanation of Abbreviations in Tables 1 and 2 MMA: Methyl methacrylate BA: n-butyl acrylate NBMAM: Nn-butoxymethylacrylamide HEMA; 2-hydroxyethyl methacrylate 4HBA; 4-hydroxybutyl acrylate MAA: methacrylic acid cross-linking Agent 1: Melamine compound (DIC Corporation Becamine M-3, Trimethoxymethyl Melamine)

[Method for specifying content of aliphatic cyclic structure]
The total mass of all raw materials such as polyol and polyisocyanate used in the production of the urethane resin and the compound having an aliphatic cyclic structure used in the production of the urethane resin (a polyol or an aliphatic ring having an aliphatic cyclic structure) Calculation was based on the amount of the aliphatic cyclic structure possessed by the polyisocyanate having the formula structure.

[Method for judging formation of crosslinked structure in resin layer]
Whether or not a crosslinked structure is formed in the resin layer is determined by “drying at normal temperature (23 ° C.) and then heating at 70 ° C. and gel fraction of the resin layer formed” and heating at 150 ° C. The determination was made based on the “gel fraction of the formed resin layer”. That is, the gel fraction of the resin layer obtained by heating at 150 ° C. was 25% by mass compared with the gel fraction (uncrosslinked state) of the resin layer obtained by drying at room temperature and then heating at 70 ° C. From the above, it was judged that a crosslinked structure was formed by high-temperature heating.
The gel fraction of the resin layer formed by drying at normal temperature (23 ° C.) and then heating at 70 ° C. was calculated by the following method.

  The composition for forming a resin layer is poured onto a polypropylene film surrounded by cardboard so that the film thickness after drying becomes 100 μm, dried under conditions of a temperature of 23 ° C. and a humidity of 65% for 24 hours, and then at 70 ° C. A resin layer was formed by heat treatment for 3 minutes. The obtained resin layer was peeled from the polypropylene film and cut into a size of 3 cm in length and 3 cm in width was used as a test piece. After measuring the mass (X) of the test piece 1, the test piece 1 was immersed in 50 ml of methyl ethyl ketone adjusted to 25 ° C. for 24 hours.

  By the immersion, the residue (insoluble matter) of the test piece 1 that did not dissolve in methyl ethyl ketone was filtered through a 300-mesh wire mesh.

  The mass (Y) of the residue obtained above was dried at 108 ° C. for 1 hour and measured.

  Subsequently, the gel fraction was calculated based on the formula of [(Y) / (X)] × 100 using the values of the masses (X) and (Y).

  The “gel fraction of the resin layer formed by heating at 150 ° C.” was calculated by the following method.

  The composition for forming a resin layer is poured onto a polypropylene film surrounded by cardboard so that the film thickness after drying becomes 100 μm, dried for 24 hours under conditions of a temperature of 23 ° C. and a humidity of 65%, and then at 150 ° C. A resin layer was formed by heating and drying for 30 minutes. The obtained resin layer was peeled from the polypropylene film and cut into a size of 3 cm in length and 3 cm in width to make a test piece 2. After measuring the mass (X ′) of the test piece 2, the test piece 2 was immersed in 50 ml of methyl ethyl ketone adjusted to 25 ° C. for 24 hours.

  By the immersion, the residue (insoluble matter) of the test piece 2 that did not dissolve in methyl ethyl ketone was filtered through a 300-mesh wire mesh.

  The mass (Y ′) of the residue obtained above was dried at 108 ° C. for 1 hour and measured.

  Next, using the mass (X ′) and (Y ′) values, the gel fraction was calculated based on the formula [(Y ′) / (X ′)] × 100.

[Production of metal fine particle dispersion]
<Synthesis of Compound (P1) Having Polyethyleneimine Block and Polyethylene Glycol Block>
Synthesis Example 18 [Synthesis of Polyethylene Glycol (PEG) -Branched Polyethyleneimine (PEI) Compound (P1-1)]
18-1 [Synthesis of Tosylated Polyethylene Glycol]
A solution of 150 ml of chloroform mixed with 150 g [30 mmol] of one-end methoxylated polyethylene glycol (hereinafter referred to as “PEGM” [number average molecular weight (Mn) 5000] (manufactured by Aldrich)] and 24 g (300 mmol) of pyridine, and 29 g (150 mmol) of tosyl chloride ) And 30 ml of chloroform were mixed uniformly.

While stirring a mixed solution of PEGM and pyridine at 20 ° C., a toluene solution of tosyl chloride was added dropwise thereto. After completion of the dropping, the reaction was carried out at 40 ° C. for 2 hours. After completion of the reaction, the reaction mixture was diluted with 150 ml of chloroform, washed with 250 ml (340 mmol) of 5% aqueous HCl, and then washed with saturated brine and water. The obtained chloroform solution was dried over sodium sulfate, and then the solvent was distilled off with an evaporator and further dried. The yield was 100%. Each peak was assigned by ¹ H-NMR spectrum (2.4 ppm: methyl group in tosyl group, 3.3 ppm: methyl group at PEGM terminal, 3.6 ppm: EG chain of PEG, 7.3-7.8 ppm) : Benzene ring in tosyl group) and tosylated polyethylene glycol.

18-2 [Synthesis of compound having PEG-branched PEI structure]
23.2 g (4.5 mmol) of the tosylated polyethylene glycol obtained in 18-1 above and 15.0 g (1.5 mmol) of branched polyethyleneimine (manufactured by Nippon Shokubai Co., Ltd., Epomin SP200) were added to dimethylacetamide (hereinafter, (DMA) After dissolving in 180 ml, 0.12 g of potassium carbonate was added and reacted at 100 ° C. for 6 hours in a nitrogen atmosphere. After completion of the reaction, the solid residue was removed, and a mixed solvent of 150 ml of ethyl acetate and 450 ml of hexane was added to obtain a precipitate. The precipitate was dissolved in 100 ml of chloroform and reprecipitated again by adding a mixed solvent of 150 ml of ethyl acetate and 450 ml of hexane. This was filtered and dried under reduced pressure. Each peak is assigned by ¹ H-NMR spectrum (2.3 to 2.7 ppm: ethylene of branched PEI, 3.3 ppm: methyl group at PEG end, 3.6 ppm: EG chain of PEG), PEG-branched PEI It was confirmed that the compound was a compound having a structure (P1-1). The yield was 99%.

Synthesis Example 19 [Synthesis of Compound (P1-2) Having PEG-Branched PEI-Bisphenol A Type Epoxy Resin Structure]
19-1 [Modification of epoxy resin]
Bisphenol A type epoxy resin EPICLON AM-040-P (manufactured by DIC Corporation) 37.4 g (20 mmol) and 4-phenylphenol 2.72 g (16 mmol) were dissolved in DMA 100 ml, and then 65% ethyl acetate triphenylphosphonium ethanol solution 0 .52 ml was added and reacted at 120 ° C. for 6 hours under a nitrogen atmosphere. After allowing to cool, the solution was dropped into a large amount of water, and the resulting precipitate was further washed with a large amount of water. The reprecipitation purified product was filtered and dried under reduced pressure to obtain a modified bisphenol A type epoxy resin. The yield of the obtained product was 100%.

^{As a result of 1} H-NMR measurement and considering the integration ratio of epoxy groups, 0.95 epoxy rings remain in one molecule of the bisphenol A type epoxy resin, and the resulting modified epoxy resin has a single bisphenol A skeleton. It was confirmed to be a functional epoxy resin.

19-2 [Synthesis of PEG-Branched PEI-Bisphenol A Type Epoxy Resin Compound (P1-2)]
A bisphenol A type monofunctional compound obtained by modifying the above epoxy resin in a solution of 20 g (0.8 mmol) of the compound (P1-1) having a PEG-branched PEI structure obtained in Synthesis Example 18 in 150 ml of methanol. A solution prepared by dissolving 4.9 g (2.4 mmol) of a functional epoxy resin in 50 ml of acetone was dropped in a nitrogen atmosphere, and the reaction was carried out by stirring at 50 ° C. for 2 hours. After completion of the reaction, the solvent was distilled off under reduced pressure and further dried under reduced pressure to obtain a compound (P1-2) having a PEG-branched PEI-bisphenol A type epoxy resin structure. The yield was 100%.

<Synthesis of (meth) acrylic polymer (P2)>
Synthesis Example 20 [Synthesis of (meth) acrylic polymer (P2-1) containing methoxycarbonylethylthio group and phosphate ester residue]
A four-necked flask equipped with a thermometer, a stirrer, and a reflux condenser was charged with 32 parts of methyl ethyl ketone (hereinafter, MEK) and 32 parts of ethanol, and the temperature was raised to 80 ° C. with stirring in a nitrogen stream. Next, a mixture comprising 20 parts of phosphooxyethyl methacrylate, 80 parts of methoxypolyethylene glycol methacrylate (molecular weight 1,000), 4.1 parts of methyl mercaptopropionate, 80 parts of MEK, and a polymerization initiator “2,2′-azobis ( 2,4-dimethylvaleronitrile) [Wako Pure Chemicals Co., Ltd. product V-65] 0.5 parts and MEK 5 parts each was added dropwise over 2 hours. (Registered trademark) O ”(manufactured by NOF Corporation) 0.3 part was added twice and stirred at 80 ° C. for 12 hours. Water was added to the obtained resin solution for phase inversion emulsification, and after desolvation under reduced pressure, water was added to adjust the concentration, whereby an aqueous solution of a (meth) acrylic polymer having a nonvolatile content of 76.8% was obtained. . The weight average molecular weight of the resin measured by gel permeation chromatography was 4,300 in terms of polystyrene, and the acid value was 97.5 mgKOH / g.

Synthesis Example 21 [Synthesis of (meth) acrylic polymer (P2-2) containing 2- (2-ethylhexyloxycarbonyl) ethylthio group and phosphate residue]
In place of 4.1 parts of methyl mercaptopropionate in Synthesis Example 20, 11.2 parts of mercaptopropionate 2-ethylhexyl was used, and the others were operated in the same manner as in Synthesis Example 20, and (meth) having a nonvolatile content of 73.2% An aqueous solution of an acrylic polymer (P2-2) was obtained. The polymer had a weight average molecular weight of 4,100 and an acid value of 98.1 mgKOH / g.

<Synthesis of an organic compound (P3) containing a thioether group (sulfide bond)>
Synthesis Example 22
[Polyethylene glycol methyl glycidyl ether (molecular weight of polyethylene glycol chain 2000)]

To 1000 g of dehydrated toluene, potassium t-butoxide (100.8 g, 0.8983 mol) was added and stirred. To this mixture was added a toluene (2000 g) solution of polyethylene glycol monomethyl ether (molecular weight 2000, 600 g) at room temperature. It was added dropwise over time. After stirring for 2 hours at room temperature, the temperature was raised to 40 ° C. and stirring was continued for 2 hours. Epichlorohydrin (168 g, 1.82 mol) was added dropwise to the mixture at the same temperature, and the mixture was stirred at 40 ° C. for 5.5 hours. The reaction mixture was filtered, and the filtrate was concentrated. The residue obtained was dissolved again by adding chloroform, and this was washed 5 times with water. The chloroform layer was decolorized by adding dry alumina, the alumina was filtered, and the filtrate was concentrated. The concentrated residue was purified by reprecipitation with toluene / n-hexane, and the resulting solid was collected and dried under reduced pressure to obtain 507.0 g of the title compound (yield 82%).

¹ H-NMR (deuterated chloroform): δ = 3.9-3.4 (m, polyethylene glycol chain, etc.), 3.43 (dd, 1H, J = 6.0, 5.7 Hz, -oxirane ring adjacent methylene One of hydrogen), 3.38 (s, 3H, PEG terminal methoxy group), 3.16 (m, 1H, oxirane ring methine hydrogen), 2.79 (m, 1H, oxirane ring terminal methylene hydrogen), 2.61 (m, 1H, oxirane ring terminal methylene hydrogen).

[Methyl-3- (3- (methoxy (polyethoxy) ethoxy) -2-hydroxyprolsulfanyl) propionate (addition compound of methyl 3-mercaptopropionate to polyethylene glycol methyl glycidyl ether (molecular weight of polyethylene glycol chain 2000)) Synthesis]

Polyethylene glycol methyl glycidyl ether (molecular weight of methoxypolyethylene glycol 2000, 1.00 g) obtained above was added to methyl 3-mercaptopropionate (221 mg, 1.84 mmol) and 1 mol / L tetrabutylammonium fluoride / tetrahydrofuran solution ( 100 μL, 0.10 mmol) was added, the temperature was raised, and the mixture was stirred at 70 to 75 ° C. for 1 hour. After cooling, 20 mL of water and 20 mL of ethyl acetate were added to this mixture and stirred well, followed by liquid separation for standing. Thereafter, the aqueous layer was further washed twice with ethyl acetate (20 mL). When sodium sulfate was added to the aqueous layer, an oily substance was precipitated, and this was extracted with methylene chloride (20 mL × 3 times). The methylene chloride layer was collected, dried over anhydrous sodium sulfate, and then concentrated to dryness to obtain 0.94 g of the organic compound (P3-1) containing the title thioether (yield about 89%). ^{From 1} H-NMR, the purity required no special purification.

¹ H-NMR (deuterated chloroform): δ = 3.9-3.4 (m, polyethylene glycol chain, etc.), 3.70 (s, 3H, ester methyl group), 3.38 (s, 3H, PEG end Methoxy group), 2.84 (t, 2H, J = 7.2 Hz, thiol compound side S adjacent methylene group), 2.70 (dd, 1H, J = 5.4, 13.5 Hz, polyether compound side S Adjacent methylene group), 2.64 (t, 2H, J = 7.2 Hz, ester carbonyl group α-position methylene hydrogen), 2.62 (dd, 1H, J = 7.5, 13.5 Hz, polyether compound side S adjacent methylene group), 2.34 (br, 1H, OH).

Synthesis Example 23
[Synthesis of ethyl 3- (methoxy (polyethoxy) ethoxy) -2-hydroxypropylsulfanyl acetate (addition compound of ethyl mercaptoacetate to polyethylene glycol methyl glycidyl ether (molecular weight of polyethylene glycol chain 2000))]

When methyl mercaptoacetate (174 mg, 1.45 mmol) was used instead of methyl 3-mercaptopropionate (221 mg, 1.84 mmol) of Synthesis Example 22, and the same procedure was performed as in Synthesis Example 13, 1.04 g of the title thioether An organic compound (P3-2) was obtained (yield: about 98%).

¹ H-NMR (deuterated chloroform): δ = 4.19 (q, 2H, J = 6.9 Hz, ethyl ester O adjacent methylene hydrogen), 3.9-3.4 (m, polyethylene glycol chain, etc.), 3 .38 (s, 3H, PEG terminal methoxy group), 3.30 (s, 2H, —SCH ₂ CO—), 2.82 (dd, 1H, J = 5.1, 13.8 Hz, polyether compound side S adjacent methylene group), 2.64 (dd, 1H, J = 7.5, 13.8 Hz, polyether compound side S adjacent methylene group), 2.58 (br, 1H, OH), 1.29 (t 3H, J = 6.9 Hz, ethyl ester methyl hydrogen).

<Production of dispersion (C) of metal fine particles (c2)>
Synthesis Example 24
10.0 g of silver oxide was added to 138.8 g of an aqueous solution containing 0.592 g of the compound (P1-1) obtained in Synthesis Example 18, and the mixture was stirred at 25 ° C. for 30 minutes. Subsequently, when 46.0 g of dimethylethanolamine was gradually added with stirring, the reaction solution turned black-red and slightly exothermic, but was left as it was and stirred at 25 ° C. for 30 minutes. Thereafter, 15.2 g of a 10% ascorbic acid aqueous solution was gradually added with stirring. While maintaining the temperature, stirring was continued for another 20 hours to obtain a black-red dispersion.

  A mixed solvent of 200 ml of isopropyl alcohol and 200 ml of hexane was added to the dispersion obtained after completion of the reaction and stirred for 2 minutes, followed by centrifugal concentration at 3000 rpm for 5 minutes. After removing the supernatant, a mixed solvent of 50 ml of isopropyl alcohol and 50 ml of hexane was added to the precipitate and stirred for 2 minutes, followed by centrifugal concentration at 3000 rpm for 5 minutes. After removing the supernatant, 20 g of water was further added to the precipitate and stirred for 2 minutes, and the organic solvent was removed under reduced pressure to obtain an aqueous dispersion of silver particles (C-1).

  The obtained dispersion (C-1) was sampled, and a peak of a plasmon absorption spectrum was observed at 400 nm by measuring a visible absorption spectrum of a 10-fold diluted solution, thereby confirming the formation of silver nanoparticles. Moreover, spherical silver nanoparticles (average particle diameter: 17.5 nm) were confirmed by TEM observation. As a result of measuring the silver content in the solid using TG-DTA, it was 97.2%. From this, it can be estimated that the content of the compound (P1-1) in the nonvolatile content in the dispersion obtained by the present synthesis method is 2.8%.

Synthesis Example 25
A solution (1) obtained by dissolving 20 mg (ethyleneimine unit: 0.15 mmol) of the compound (P1-2) obtained in Synthesis Example 19 in 2.39 g of water and 0.16 g (0.97 mmol) of silver nitrate in water 1. A solution (2) dissolved in 30 g and a solution (3) in which 0.12 g (0.48 mmol) of sodium citrate was dissolved in 0.25 g of water were prepared. While stirring at 25 ° C., solution (2) was added to solution (1), followed by solution (3). The dispersion gradually changed to dark brown. After stirring for 7 days, it was purified by dialysis to obtain an aqueous dispersion (C-2).

  One part of the obtained aqueous dispersion (C-2) was sampled, and a peak of a plasmon absorption spectrum was observed at 400 nm by measurement of a visible absorption spectrum of a 10-fold diluted solution, confirming the formation of silver nanoparticles. Moreover, it confirmed that it was 20 nm or less silver nanoparticle from TEM observation.

  After the solvent of the obtained aqueous dispersion (C-2) was distilled off, the silver content was measured by TGA measurement. As a result, it was 83%. The obtained aqueous dispersion was confirmed to be excellent in storage stability without aggregation or precipitation even after 2 months.

Synthesis Example 26
Reduction consisting of 463 g (4.41 mol) of 85% N, N-diethylhydroxylamine, the (meth) acrylic polymer (P2-1, corresponding to 23.0 g of non-volatiles) obtained in Synthesis Example 20, and 1250 g of water An agent solution was prepared. Separately, the (meth) acrylic polymer (P2-1) obtained in Synthesis Example 20 corresponding to 11.5 g of nonvolatiles was dissolved in 333 g of water, and 500 g (2.94 mol) of silver nitrate was dissolved in 833 g of water. The solution was added and stirred well. The reducing agent solution was added dropwise to this mixture at room temperature (25 ° C.) over 2 hours. The obtained reaction mixture was filtered with a membrane filter (pore diameter 0.45 micrometer), and the filtrate was a hollow fiber type ultrafiltration module (MOLSEP module FB-02, manufactured by Daisen Membrane Systems Co., Ltd., molecular weight cut off 150,000). ) It was circulated through and purified by adding water in an amount corresponding to the amount of filtrate flowing out as needed. After confirming that the electric conductivity of the filtrate was 100 μS / cm or less, water injection was stopped and the filtrate was concentrated. When the concentrate was recovered, a silver nanoparticle dispersion having a nonvolatile content of 36.7% (dispersion medium is water: C-3) was obtained (742.9 g). The average particle diameter of the silver particles by dynamic light scattering was estimated to be 39 nm, and 10-40 nm from the TEM image. When the silver content in the nonvolatile material was measured by thermogravimetric analysis, it was 94.8 w / w% (yield 81%).

Synthesis Example 27
A reduction consisting of 5.56 g (53.0 mmol) of 85% N, N-diethylhydroxylamine, the (meth) acrylic polymer obtained in Synthesis Example 21 (equivalent to 106 mg of P2-2, non-volatile), and 15 g of water. An agent solution was prepared. Separately, the (meth) acrylic polymer (P2-2) obtained in Synthesis Example 21 corresponding to 106 mg of the nonvolatile material was dissolved in 5 g of water, and 6.00 g (35.3 mmol) of silver nitrate was dissolved in 10 g of water. The solution was added and stirred well. The reducing agent solution was added dropwise to this mixture at room temperature (25 ° C.) over 2 hours. The obtained reaction mixture was filtered with a membrane filter (pore diameter 0.45 micrometer), and the filtrate was a hollow fiber type ultrafiltration module (MOLSEP module HIT-1 type, manufactured by Daisen Membrane Systems Co., Ltd., molecular weight cut off 150,000). ) It was circulated through and purified by adding water in an amount corresponding to the amount of filtrate flowing out as needed. After confirming that the electric conductivity of the filtrate was 100 μS / cm or less, water injection was stopped and the filtrate was concentrated. When the concentrate was recovered, an aqueous dispersion (C-4) of silver nanoparticles having a nonvolatile content of about 30% was obtained. The particle size of the silver nanoparticles was estimated to be 10-40 nm from the TEM image.

Synthesis Example 28
The (meth) acrylic polymer (P2-1, 2.00 g in terms of solid content) obtained in Synthesis Example 20 was dissolved in 40 mL of water, and 10.0 g (50.09 mmol) of copper acetate hydrate was added to water. What was dissolved in 500 mL was added. An 80% aqueous hydrazine solution (about 160 mmol) was added dropwise over about 2 hours so that foaming occurred gently, and the mixture was further stirred for 1 hour at room temperature until the foaming stopped, to obtain a reddish brown solution.

  This was passed through an ultrafiltration module (Daisen Membrane Systems Co., Ltd., molecular weight cut off 150,000, 1 unit), and purified water deaerated by nitrogen bubbling until about 1 L of exudate was produced from the ultrafiltration unit. For purification. When the supply of deaerated water was stopped and concentrated, 15 g of an aqueous dispersion (C-5) was obtained (solid content: about 20 w / w%). When one drop of this dispersion was dissolved in ethanol (50 mL) and an ultraviolet-visible absorption spectrum was measured, absorption derived from plasmon resonance was observed near 600 nm, confirming the formation of copper nanoparticles. The particle size of the copper nanoparticles was estimated to be 30-80 nm from the TEM image.

Synthesis Example 29
To a mixture consisting of copper (II) acetate monohydrate (3.00 g, 15.0 mmol), the thioether-containing organic compound (P3-1, 0.451 g) obtained in Synthesis Example 22 and ethylene glycol (10 mL), The mixture was heated while blowing nitrogen at a flow rate of 50 mL / min, and deaerated by aeration and stirring at 125 ° C. for 2 hours. The mixture was returned to room temperature, and a solution of hydrazine hydrate (1.50 g, 30.0 mmol) diluted with 7 mL of water was slowly added dropwise using a syringe pump. At this time, caution was required because foaming was vigorously caused by the generation of nitrogen accompanying the initial reduction reaction. About 1/4 amount was dripped slowly over 2 hours, and the dripping of one end was stopped here. After stirring for 2 hours and confirming that foaming subsided, the remaining amount was further dropped over 1 hour. The resulting brown solution was heated to 60 ° C. and further stirred for 2 hours to complete the reduction reaction. At this time, a small amount of reddish brown reaction solution was collected over time, diluted with degassed purified water added with 0.1% hydrazine hydrate, and an ultraviolet-visible absorption spectrum was immediately obtained. A peak was observed at 570 to 580 nm. Observed. This is an absorption derived from the plasmon resonance absorption exhibited by the nano-sized reduced copper, and this confirmed the formation of nano-copper particles.

(Preparation of aqueous dispersion)
Subsequently, this reaction mixture is circulated in a hollow fiber type ultrafiltration membrane module (HIT-1-FUS1582, 145 cm ² , molecular weight cut off 150,000) manufactured by Daisen Membrane Systems Co., Ltd. While adding 0.1% hydrazine hydrate aqueous solution, it was circulated until the filtrate from the ultrafiltration module was about 500 mL and purified. When the supply of the 0.1% hydrazine hydrate aqueous solution was stopped and the solution was directly concentrated by ultrafiltration, 2.85 g of an aqueous dispersion (C-6) of a complex of an organic compound and nanocopper particles was obtained. . The non-volatile content in the dispersion was 16% and the metal content in the non-volatile was 95%. When the obtained copper particles were observed with an electron microscope, they were found to be fine particles of about 20 to 60 nm. At this time, the average particle diameter measured by the dynamic light scattering method was 108 nm. Wide-angle X-ray diffraction of the dispersion confirmed that it was reduced copper.

Synthesis Example 30
A dispersion (C-7) was prepared in the same manner as in Synthesis Example 29 except that the thioether-containing organic compound (P3-2) of Synthesis Example 23 was used instead of the thioether-containing organic compound (P3-1) of Synthesis Example 22. ) Was prepared. When a part of the reaction mixture was taken and an ultraviolet-visible absorption spectrum was measured, it was confirmed that an absorption maximum derived from the surface plasmon resonance of the nanocopper particles was observed between 570 and 600 nm.

Synthesis Example 31
Copper (I) oxide (5.4 g, 37.5 mmol), the thioether-containing organic compound (P3-1, 2.254 g) obtained in Synthesis Example 22, and the silver nanoparticle dispersion obtained in Synthesis Example 26 ( C-3, particle size 10-40 nm, silver 3.0 milligram atom, water solvent), ethanol 80 ml and water 20 ml were heated to 40 ° C. while blowing nitrogen at a flow rate of 50 mL / min. To this mixture was further added hydrazine monohydrate (7.5 g, 150 mmol). The reduction reaction was terminated by stirring for 2 hours while maintaining at 40 ° C.

Subsequently, this reaction mixture was circulated in a hollow fiber type ultrafiltration membrane module (HIT-1-FUS1582, 145 cm ² , molecular weight cut off 150,000) manufactured by Daisen Membrane Systems Co., Ltd., and nitrogen bubbling was performed. A 1% aqueous hydrazine solution was added while adding the same amount as the leached filtrate, and the filtrate from the ultrafiltration module was circulated until the volume became approximately 500 mL for purification. The supply of the 0.1% hydrazine aqueous solution was stopped and concentrated to obtain 27.9 g of a silver core copper shell nanoparticle dispersion (C-8). The non-volatile content in the dispersion was 15%, and the metal content in the non-volatile was 95%. When the obtained particles were observed with an electron microscope, they were found to be fine particles of about 40 to 80 nm. Further, from the wide-angle X-ray diffraction of the dispersion, it was confirmed that it was a mixture of silver and reduced copper. Moreover, it turned out that it is a silver core copper shell particle | grain from the TEM photograph and the TEM-EDS measurement. Further, when a small amount of the obtained reddish brown solution was collected and diluted with ethylene glycol to obtain an ultraviolet-visible absorption spectrum, a peak of plasmon resonance absorption at 565 to 580 nm indicated by nano-sized reduced copper was observed. In addition, even when an ultraviolet-visible absorption spectrum was obtained for an ethylene glycol diluted solution after 1 hour, the peak of plasmon resonance absorption did not decrease, indicating that the oxidation resistance was good.

Synthesis Examples 32-34
A silver core copper shell nanoparticle dispersion (C-9 to 11) was produced in the same manner as in Synthesis Example 31, except that the mixture of 80 ml of ethanol and 20 ml of water was changed to the mixed solvent shown in the following table in Synthesis Example 31. When the obtained particles were observed with an electron microscope, they were found to be fine particles of about 40 to 80 nm. Further, from the wide-angle X-ray diffraction of the dispersion, it was confirmed that it was a mixture of silver and reduced copper.

Comparative Synthesis Example 1
Based on Example 1 of Patent Document 4, 50 μmol of silver nitrate (I) was dissolved in 94 ml of pure water, and while vigorously stirring this solution, 1 ml of an aqueous solution containing 10 mg of stearylmethylammonium chloride and 200 μmol of sodium borohydride As a result, 5 ml of an aqueous solution containing was sequentially injected, and the liquid color changed to yellowish brown transparent, and 100 ml of silver hydrosol was obtained.

Comparative Synthesis Example 2
Based on Example 2 of Patent Document 5, 10 mmol of silver sulfate was dissolved in 800 ml of pure water, and 100 ml of an aqueous solution containing 500 mg of polyoxyethylene stearyl ether phosphoric acid was added to this solution with stirring so as to be uniform. Next, 50 ml of an aqueous solution containing 5 mmol of dimethylamine borane was added to this solution with vigorous stirring so as to be uniform. When the solution color suddenly changed to reddish brown, 50 ml of an aqueous solution containing 0.02 mmol of palladium nitrate was added. As a result, 1000 ml of a uniform reddish brown transparent silver fine particle dispersion was obtained.

Example 1
(Formation of resin layer on insulating substrate)
The resin layer forming composition (b) -1 obtained in Synthesis Example 7 was applied onto a polyimide film (Kapton EN150-C, 38 μm thickness, manufactured by Toray DuPont) so that the dry film thickness was 100 nm (bar The resin layer (B) was formed on the polyimide film by drying at 70 ° C. for 3 minutes using a hot air dryer, and this film was further heat-treated at 150 ° C. for 30 minutes.

(Formation of non-conductive layer on resin layer)
Ethanol is added to the aqueous dispersion of silver particles prepared in Synthesis Example 24 to obtain a silver particle dispersion of silver concentration 3%, water / ethanol (1/1 (w / w)), and 0.1% KF- 351A (Shin-Etsu Silicone) was added. Using this dispersion, No. 0 K101 bar (wet film thickness 4 μm), K-control coater (K101, manufactured by RK Print Coat Instruments) speed scale 4 (coating speed 10.66 m / min.) Then, coating (bar coating) was performed on the resin layer formed on the polyimide film. After the film was dried at room temperature, the surface of the film was observed with a scanning electron microscope. The coverage of the polyimide surface with silver particles was about 90%. When the resistance of the silver coating film surface was measured, it was impossible to measure due to the resistance of 10 ⁷ Ω or more, and it was confirmed that the film made of silver particles formed on the resin layer was a non-conductive film.

(Electroless copper plating process)
The film in which silver particles were coated on the resin layer was used as a test piece for plating, and electroless plating was performed using an electroless plating reagent manufactured by Okuno Pharmaceutical Co., Ltd. The process of electroless copper plating was performed through the steps of degreasing, washing with water, activation, washing with water, electroless plating, and washing with water. The washing was performed with running water for 2 minutes.
1. Degreasing: Using a degreasing agent (ICP cleaner SC, manufactured by Okuno Pharmaceutical Co., Ltd.), it was immersed in a treatment liquid at 40 ° C. for 5 minutes.
2. Activation: It was immersed in a sulfuric acid aqueous solution (about 6%) at 25 ° C. for 2 minutes.
3. Electroless plating: Using an electroless copper plating solution (OIC Copper, manufactured by Okuno Pharmaceutical Co., Ltd.), it was immersed in a plating solution having a pH of 12.5 at 55 ° C. for 20 minutes.

  In the test piece taken out from the electroless copper plating solution, the entire surface of the silver particle coated side became light red, and it was confirmed that the electroless plating of copper proceeded well. The test piece was baked at 100 ° C. for 60 minutes after washing with water and air drying. The surface resistance value of the copper film formed by electroless plating is 0.04Ω / □, and the conductive film has a copper conductive layer on a resin layer formed on a 38 μm-thick polyimide film as an insulating substrate. The material was able to be produced. As a result of the tape peeling test using the cellophane tape (manufactured by Nichiban), the copper conductive layer thus formed was not peeled off and had good adhesion.

Example 2
(Formation of resin layer on insulating substrate)
A resin layer was formed on the polyimide film in the same manner as in Example 1 except that heat treatment at 150 ° C. for 30 minutes was not performed.

(Formation of non-conductive layer on resin layer)
In the same manner as in Example 1, a dispersion having a silver concentration of 3% was applied (bar coating) on a resin layer formed on the polyimide film and not subjected to heat treatment. After the film was dried at 150 ° C. for 30 minutes, the surface of the film was observed with a scanning electron microscope. The coverage of the polyimide surface with silver particles was about 90%. When the resistance of the silver coating film surface was measured, it was impossible to measure due to the resistance of 10 ⁷ Ω or more, and it was confirmed that the film made of silver particles formed on the resin layer was a non-conductive film.

(Electroless copper plating process)
When electroless copper plating was performed in the same manner as in Example 1, the surface resistance value of the copper film formed by electroless plating was 0.04Ω / □, and a 38 μm thick polyimide as an insulating substrate. A conductive material having a copper conductive layer on the resin layer formed on the film could be produced. The copper conductive layer thus formed also had good adhesion by a cellophane tape (manufactured by Nichiban) peel test.

Examples 3 and 4
In Examples 1 and 2, the silver particle dispersion used was changed from the silver particle aqueous dispersion (C-1) prepared in Synthesis Example 24 to the water dispersion (C-2) obtained in Synthesis Example 25. Except for the change, the electroless copper plating was carried out in the same manner as in Example 1 except that the nonconductive layer of silver particles was coated on the resin layer formed on the polyimide film. In any of the examples, a good copper plating film was formed, and a copper conductive layer having a surface resistivity of about 0.04Ω / □ was formed on the polyimide film on which the resin layer was formed. A conductive material could be produced.

(Electroless copper plating process)
When electroless copper plating was performed in the same manner as in Example 1, the surface resistance value of the copper film formed by electroless plating was 0.04Ω / □, and a 38 μm thick polyimide as an insulating substrate. A conductive material having a copper conductive layer on the resin layer formed on the film could be produced. The copper conductive layer thus formed also had good adhesion by a cellophane tape (manufactured by Nichiban) peel test.

Comparative Example 1
(Formation of non-conductive layer on film)
In Example 1, except that the resin layer was not formed on the polyimide, a dispersion liquid having a silver concentration of 3% was applied on the polyimide in the same manner as in Example 1. As a result, the coating film of the silver fine particles was uneven in coating. In addition, a spotted pattern was observed on the surface, and the color development was different between the center and both ends of the film surface. Although the film center part was a nonelectroconductive layer, the electroconductive part was partially formed in the film edge part.

(Electroless copper plating process)
When electroless copper plating treatment was performed in the same manner as in Example 1, a phenomenon in which a partially deposited plating film was missing and peeled off at the film edge was observed.

Comparative Example 2
In the same manner as in Example 1 , a resin layer was formed on the polyimide film in the same manner as in Example 1 . This film was immersed in the silver particle dispersion prepared in Comparative Synthesis Example 10 for 10 minutes to adsorb the silver colloid on the surface of the resin layer , dried at room temperature, and then baked at 180 ° C. for 30 minutes. When the surface of this film was observed with a scanning electron microscope, the coverage of the polyimide surface with silver particles was 10%.

(Electroless copper plating process)
When this test piece was subjected to an electroless plating step in the same manner as in Example 1, the copper deposition in the electroless copper plating step was a spot-like non-uniform deposition and was about 40% of the total surface area.

Comparative Example 3
Water was removed from the silver hydrosol prepared in Comparative Synthesis Example 1 with an evaporator and concentrated to 0.5%. At this time, the silver colloid had already aggregated and was not a uniform dispersion. When this concentrated solution was applied on a polyimide film having a resin layer formed in the same manner as in Example 1, a uniform coating film could not be obtained. Thereafter, an electroless plating process was attempted in the same manner as in Example 1. However, non-glossy and uneven copper plating deposition occurred in about 30% of the total area.

Comparative Example 4
In the same manner as in Example 1 , a resin layer was formed on the polyimide film. The polyimide film formed with the resin layer in the silver particle dispersion prepared in Comparative Synthesis Example 2 is immersed for 10 minutes to adsorb the silver colloid on the surface of the resin layer, and the film is dried at room temperature. Baked for 30 minutes. When the surface of this film was observed with a scanning electron microscope, the coverage of the polyimide surface with silver particles was 15%.

(Electroless copper plating process)
When this film was subjected to an electroless plating step in the same manner as in Example 1, the copper deposition in the electroless copper plating step was a patchy uneven deposition and was about 40% of the total surface area.

Comparative Example 5
Water was removed from the silver particle dispersion prepared in Comparative Synthesis Example 2 with an evaporator and concentrated to 1%. At this time, the silver colloid had already aggregated and was not a uniform dispersion. When this concentrated solution was applied on the polyimide film having the resin layer formed in the same manner as in Example 1, a uniform coating film could not be obtained.

  The silver colloid adsorption polyimide film was subjected to an electroless plating process in the same manner as in Example 1. As a result, copper deposition was a spot-like non-uniform deposition and was about 50% of the total surface area.

Example 5
(Formation of resin layer on insulating substrate)
The resin layer was formed on the polyimide film in the same manner as in Example 1 except that the resin layer forming composition (b) -1 was changed to the resin layer forming composition (b) -4 obtained in Synthesis Example 10. (B) was formed, and this film was further heat-treated at 150 ° C. for 30 minutes to form a crosslinked structure in the resin layer (B).

(Formation of non-conductive layer on resin layer)
On the resin layer formed on the polyimide film thus obtained, a dispersion having a silver concentration of 3% was applied (bar coating) in the same manner as in Example 1 . When the surface of this film was observed with a scanning electron microscope, the coverage of the polyimide surface with silver particles was 80%. When the resistance on the surface of the silver coating film was measured, it was impossible to measure because the resistance was 10 ⁷ Ω or more in any case, and it was confirmed that the film made of silver particles formed on the resin layer was a non-conductive film. did.

(Electroless copper plating process)
When electroless copper plating was performed in the same manner as in Example 1, a good copper plating film was formed, and the surface resistivity was about 0.04Ω / □ on the polyimide film on which the resin layer was formed. A conductive material having a conductive layer was prepared. The copper conductive layer thus formed also had good adhesion by a cellophane tape (manufactured by Nichiban) peel test.

Example 6
(Formation of resin layer on insulating substrate)
The resin layer was formed on the polyimide film in the same manner as in Example 2 except that the resin layer forming composition (b) -1 was changed to the resin layer forming composition (b) -4 obtained in Synthesis Example 10. (B) was formed.

(Formation of non-conductive layer on resin layer)
In the same manner as in Example 1, a dispersion having a silver concentration of 3% was applied (bar coating) on a resin layer formed on the polyimide film and not subjected to heat treatment. After the film was dried at 150 ° C. for 30 minutes, the surface of the film was observed with a scanning electron microscope. The coverage of the polyimide surface with silver particles was about 85%. When the resistance of the silver coating film surface was measured, it was impossible to measure due to the resistance of 10 ⁷ Ω or more, and it was confirmed that the film made of silver particles formed on the resin layer was a non-conductive film.

(Electroless copper plating process)
When electroless copper plating treatment was performed in the same manner as in Example 1, a good copper plating film was formed in any test piece, and the surface resistivity was about 0 on the polyimide film on which the resin layer was formed. A conductive material having a copper conductive layer of approximately .04Ω / □ could be produced. The copper conductive layer thus formed also had good adhesion by a cellophane tape (manufactured by Nichiban) peel test.

Examples 7 and 8
In Examples 5 and 6, the silver particle dispersion used was changed from the silver particle aqueous dispersion (C-1) prepared in Synthesis Example 24 to the water dispersion (C-2) obtained in Synthesis Example 25. Except for the change, electroless copper plating was carried out in the same manner as in Example 1 except that the non-conductive layer of silver particles was coated on the resin layer formed on the polyimide film. In any of the examples, a good copper plating film was formed, and a copper conductive layer having a surface resistivity of about 0.04Ω / □ was formed on the polyimide film on which the resin layer was formed. A conductive material could be produced. The copper conductive layer thus formed also had good adhesion by a cellophane tape (manufactured by Nichiban) peel test.

Examples 9-17
(Formation of resin layer on insulating substrate)
In the same manner as in Example 1, except that the resin layer forming composition (b) -1 was changed to the resin layer forming compositions (b) -2 to 11 shown in Table 7 below, crosslinking was performed on the polyimide. A resin layer having a structure was formed. As can be seen from Table 3, in the resin compositions of (b) -4 to 6 and 8 to 11 obtained in Synthesis Examples 10 to 12 and 14 to 17, the resin layer has a crosslinked structure by heat treatment at 150 ° C. Been formed.

(Formation of non-conductive layer on resin layer)
On the resin layer formed on the polyimide film thus obtained, a dispersion having a silver concentration of 3% was applied (bar coating) in the same manner as in Example 1 . When the surface of this film was observed with a scanning electron microscope, the coverage of the polyimide surface with silver particles was about 80-90%. When the resistance on the surface of the silver coating film was measured, it was impossible to measure because the resistance was 10 ⁷ Ω or more in any case, and it was confirmed that the film made of silver particles formed on the resin layer was a non-conductive film. did.

(Electroless copper plating process)
When the electroless copper plating treatment was performed on each test piece described in Table 7 in the same manner as in Example 1, a good copper plating film was formed and a resin layer was formed in any test piece. A conductive material having a copper conductive layer with a surface resistivity of about 0.04Ω / □ could be fabricated on the polyimide film. The copper conductive layer thus formed also had good adhesion by a cellophane tape (manufactured by Nichiban) peel test.

Examples 18-26
(Formation of resin layer on insulating substrate)
Resin layer forming composition (b) -1 was changed to a resin layer forming composition (b) -2 to 11 obtained in Synthesis Examples 8 to 17 in the same manner as in Example 2 except that A resin layer was formed.

(Formation of non-conductive layer on resin layer)
On the resin layer formed on the polyimide film thus obtained, a dispersion having a silver concentration of 3% was applied (bar coating) in the same manner as in Example 2, and then the film was heated at 150 ° C. Dry for 30 minutes. As can be seen from Table 3, in the resin compositions of (b) -4 to 6 and 8 to 11 obtained in Synthesis Examples 10 to 12 and 14 to 17, the resin layer has a crosslinked structure by heat treatment at 150 ° C. It is formed. When the surface of this film was observed with a scanning electron microscope, the coverage of the polyimide surface with silver particles was about 80-90%. When the resistance on the surface of the silver coating film was measured, it was impossible to measure because the resistance was 10 ⁷ Ω or more in any case, and it was confirmed that the film made of silver particles formed on the resin layer was a non-conductive film. did.

(Electroless copper plating process)
When the electroless copper plating process was performed on each test piece described in Table 8 in the same manner as in Example 1, a good copper plating film was formed and a resin layer was formed in any test piece. A conductive material having a copper conductive layer with a surface resistivity of about 0.04Ω / □ could be fabricated on the polyimide film. The copper conductive layer thus formed also had good adhesion by a cellophane tape (manufactured by Nichiban) peel test.

Examples 27-30
(Formation of resin layer on insulating substrate)
The resin layer forming composition (b) -1 was changed to the resin layer forming composition (b) -10 obtained in Synthesis Example 16, and the dispersion used was changed to (C-2). In the same manner as in Example 2, a resin layer was formed on polyimide.

(Formation of non-conductive layer on resin layer)
In the same manner as in Example 1, a dispersion having a silver concentration of 3% was applied (bar coating) on the resin layer formed on the polyimide film and not subjected to heat treatment. This film was dried at a temperature shown in Table 9 for 30 minutes to form a crosslinked structure in the resin layer. After drying, when the surface of this film was observed with a scanning electron microscope, the coverage of the polyimide surface with silver particles was about 70-90% as shown in the table below. When the resistance of the silver coating film surface was measured, it was impossible to measure due to the resistance of 10 ⁷ Ω or more, and it was confirmed that the film made of silver particles formed on the resin layer was a non-conductive film.

(Electroless copper plating process)
When the electroless copper plating treatment was performed on each test piece described in Table 9 in the same manner as in Example 1, a good copper plating film was formed and a resin layer was formed in any test piece. A conductive material having a copper conductive layer with a surface resistivity of about 0.04Ω / □ could be fabricated on the polyimide film. The copper conductive layer thus formed also had good adhesion by a cellophane tape (manufactured by Nichiban) peel test.

Examples 31-42
(Formation of resin layer on insulating substrate)
In the same manner as in Examples 1 and 5, a resin layer shown in Table 10 was formed on polyimide.

(Formation of non-conductive layer on resin layer)
3% metal fine particle dispersion was applied onto the resin layer in the same manner as in Example 1 except that the metal fine particle dispersion was changed from (C-1) to the dispersion shown in Table 10. )did. When the surface of this film was observed with a scanning electron microscope, the coverage of the polyimide surface with particles was about 80 to 90%. When the resistance of the silver coating film surface was measured, it was impossible to measure due to the resistance of 10 ⁷ Ω or more, and it was confirmed that the film made of silver particles formed on the resin layer was a non-conductive film.

(Electroless copper plating process)
When the electroless copper plating treatment was performed on each test piece described in Table 10 in the same manner as in Example 1, a good copper plating film was formed and a resin layer was formed in any test piece. A conductive material having a copper conductive layer with a surface resistivity of about 0.04Ω / □ could be fabricated on the polyimide film. The copper conductive layer thus formed also had good adhesion by a cellophane tape (manufactured by Nichiban) peel test.

Comparative Example 6
(Formation of non-conductive layer on film)
In Examples 31 to 36, a dispersion of metal fine particles was applied on the polyimide film in the same manner as in Examples 31 to 36 except that no resin layer was formed on the polyimide film. As a result, repelling of the dispersion occurred, and a patch pattern was formed on the coated surface.

(Electroless copper plating process)
When electroless copper plating treatment was performed in the same manner as in Example 1, a plating film was not deposited in a region where metal fine particles were not present, and a phenomenon in which the plating deposition portion peeled during the plating treatment was observed. It was.

Examples 43-54
(Formation of resin layer on insulating substrate)
In the same manner as in Examples 2 and 6, the resin layer shown in Table 11 below was formed on polyimide.

(Formation of non-conductive layer on resin layer)
A 3% metal fine particle dispersion was applied onto the resin layer in the same manner as in Examples 2 and 6 except that the metal fine particle dispersion was changed from (C-1) to the dispersion shown in Table 11. Bar coating), followed by drying at 150 ° C. for 30 minutes. When the surface of this film was observed with a scanning electron microscope, the coverage of the polyimide surface with particles was about%. When the resistance of the silver coating film surface was measured, it was impossible to measure due to the resistance of 10 ⁷ Ω or more, and it was confirmed that the film made of silver particles formed on the resin layer was a non-conductive film.

(Electroless copper plating process)
When the electroless copper plating treatment was performed on each test piece described in Table 11 in the same manner as in Example 1, a good copper plating film was formed and a resin layer was formed in any test piece. A conductive material having a copper conductive layer with a surface resistivity of about 0.04Ω / □ could be fabricated on the polyimide film. The copper conductive layer thus formed also had good adhesion by a cellophane tape (manufactured by Nichiban) peel test.

Examples 55-62
On the resin layer formed on the polyimide film obtained in Examples 1 to 8, electroplating (copper sulfate) was performed using a conductive material having a copper conductive layer. Copper sulfate plating was performed by passing through the processes of degreasing, water washing, acid washing, water washing, copper sulfate plating, water washing, rust prevention treatment, and water washing based on a conventional method.
1. Degreasing: Using a degreasing agent (DP320 cleaner, manufactured by Okuno Pharmaceutical Co., Ltd.), it was immersed in a treatment liquid at 45 ° C. for 5 minutes.
2. Pickling: It was immersed in a sulfuric acid aqueous solution (about 5%) at 25 ° C. for 1 minute.
3. Copper sulfate plating: A copper sulfate plating solution to which Top Lucina SF-M (Okuno Pharmaceutical Co., Ltd.) was added was used for immersion for 29 minutes at 23 ° C. and 2.5 A / dm ² .
4). Rust prevention treatment: A rust inhibitor (Top Rinse CU-5, manufactured by Okuno Pharmaceutical Co., Ltd.) was used and immersed for 1 minute at 25 ° C.

  All of the 8 types of test pieces did not cause peeling in the electroplating process and exhibited good chemical resistance. The electroplated test piece was washed with water, wiped off moisture, dried with hot air, and baked at 120 ° C. for 60 minutes. The average film thickness of the copper layer formed on the polyimide film after electroplating is about 15-16 μm, and a conductive material having a conductive layer of about 16 μm thickness on the 38 μm-thick polyimide film via a resin layer. We were able to make it. The peel strength of the formed copper was about 7 to 9 N / cm, indicating good adhesion strength.

Examples 63-71
In Example 55, instead of using the conductive material obtained in Example 1, electroplating was performed in the same manner as in Example 55, using the conductive material obtained in Examples 18 to 26 shown in Table 12 below. Went. The copper layer formed on the resin layer has an average film thickness of 15 to 16 μm, and a conductive material having a conductive layer of about 16 μm thickness on a 38 μm-thick polyimide film can be produced via the resin layer. did it. The peel strength of the copper formed on the polyimide film via the resin layer was about 7 to 10 N / cm, indicating good adhesion strength.

Examples 72-83
In Example 55, instead of using the conductive material obtained in Example 1, using the conductive material obtained in Examples 43 to 54 shown in Table 13 below, Plating was performed. The copper layer formed on the resin layer has an average film thickness of 15 to 16 μm, and a conductive material having a conductive layer of about 16 μm thickness on a 38 μm-thick polyimide film can be produced via the resin layer. did it. The peel strength of the copper formed on the polyimide film via the resin layer was about 7 to 10 N / cm, indicating good adhesion strength.

Examples 84-89
(Formation of resin layer on insulating substrate)
In the same manner as in Examples 2 and 6, the resin layer shown in Table 14 below was formed on polyimide.

(Formation of non-conductive layer on resin layer)
3% metal fine particles on the resin layer in the same manner as in Examples 2 and 6, except that the dispersion of metal fine particles was changed from (C-1) to a dispersion having a different solvent composition shown in Table 14. After applying the dispersion (bar coating), drying was performed at 150 ° C. for 30 minutes. When the surface of this film was observed with a scanning electron microscope, the coverage of the polyimide surface with particles was about 70-90%. When the resistance of the silver coating film surface was measured, it was impossible to measure due to the resistance of 10 ⁷ Ω or more, and it was confirmed that the film made of silver particles formed on the resin layer was a non-conductive film.

(Electroless copper plating process)
When the electroless copper plating treatment was performed on each of the test pieces described in Table 14 in the same manner as in Example 1, a good copper plating film was formed and a resin layer was formed in any of the test pieces. A conductive material having a copper conductive layer with a surface resistivity of about 0.04Ω / □ could be fabricated on the polyimide film. The copper conductive layer thus formed also had good adhesion by a cellophane tape (manufactured by Nichiban) peel test.

(Electroplating process)
In Example 55, instead of using the conductive material obtained in Example 1, electroplating was performed in the same manner as in Example 55 using the test pieces shown in Table 14. The copper layer formed on the resin layer has an average film thickness of 15 to 16 μm, and a conductive material having a conductive layer of about 16 μm thickness on a 38 μm-thick polyimide film can be produced via the resin layer. did it. The peel strength of copper formed on the polyimide film via the resin layer was about 8 to 9 N / cm, indicating good adhesion strength.

Comparative Example 7
In Example 1, except that the silver concentration was changed from 5% to 30%, a K-control was used in the same manner as in Example 1, except that the dispersion of silver particles was No. 0 K101 bar (wet film thickness 6 μm). Coating (bar coating) was performed on a polyimide film (Kapton EN150-C, 38 μm thickness, manufactured by Toray DuPont) on which a resin layer was formed under the condition of a speed scale 4 of a coater (K101, manufactured by RK Print Court Instruments). . The film was dried at room temperature and then baked at 100 ° C. for 30 minutes. When the surface of this film was observed with a scanning electron microscope, the coverage of the polyimide surface with silver particles was 100%, and the average number of nanosilver layers on the polyimide surface converted from the film thickness was 15. When the resistance of the silver coating film surface was measured, a conductive film having a surface resistivity of about 0.4Ω / □ was formed.

(Electroless copper plating process)
When the above-mentioned polyimide film with conductive silver particle film was used as a test piece for plating and electroless plating was performed in the same manner as in Example 1, the surface resistance value of the copper film formed by electroless plating was 0. A conductive material having a copper conductive layer on a 38 μm-thick polyimide film as an insulating substrate could be obtained, but when the tape peeling test was performed, the silver particle layer was destroyed. As a result, about 30 to 50% of the film surface peeled off. When the peeled surface was observed, it was found that copper was not sufficiently precipitated in the voids formed by fusion between the silver particles.

Example 90
In Example 1 and Example 3, except that the insulating base material was changed from Kapton EN150-C to the polyimide film shown in the table below, on the film on which the resin layer was formed in the same manner as in Example 1 and Example 3. After silver particles were applied to the film and a nonconductive layer made of silver particles was formed, electroless plating was performed in the same manner as in Examples 1 and 3. In each case, the surface resistivity was 0.04. A copper conductive layer of ˜0.05Ω / □ could be formed on the film. As a result of performing a tape peeling test using a cellophane tape (manufactured by Nichiban), it was confirmed that the copper layer did not peel and a film having sufficient adhesion was formed.

  Using these conductive materials, electro (copper sulfate) plating was performed in the same manner as in Example 55. The average film thickness of the copper layer formed on the polyimide film after electroplating was 16 μm. The peel strength of copper formed on the polyimide film was about 6 to 7 N / cm, and sufficient peel strength was obtained.

Example 91
In Examples 1 and 3, epoxy glass lamination was performed in the same manner as in Examples 1 and 3, except that the insulating base material was changed from Kapton EN150-C to an epoxy glass laminate (thickness 3 mm) manufactured by Nikko Kasei Co., Ltd. After forming a resin resin layer on the plate, applying a dispersion of silver particles to form a non-conductive layer containing silver particles, electroless plating was performed in the same manner as in Examples 1 and 3. In any case, a copper conductive layer having a surface resistivity of 0.04 to 0.05Ω / □ could be formed on the epoxy glass laminate. As a result of performing a tape peeling test using a cellophane tape (manufactured by Nichiban), it was confirmed that the copper layer did not peel and a copper film having sufficient adhesion was formed. When this electroconductive material was used for electroplating (copper sulfate) in the same manner as in Example 55, the average film thickness of the copper layer formed on the epoxy glass laminate after electroplating was 16 μm.

Example 92
In Examples 1 and 3, the insulating base material was dispersed on the film on which the resin layer was formed in the same manner as in Examples 1 and 3 except that Kapton EN150-C was changed to Kuraray Bexter CT-Z. After applying the liquid and forming a nonconductive layer containing silver particles, electroless plating was performed in the same manner as in Examples 1 and 3. In each case, the surface resistivity was 0.04 to A 0.05 Ω / □ copper conductive layer could be formed on the Bexter CT-Z film.

Example 93
Except that a through hole of 150 μmφ was formed on a polyimide film (Kapton EN150-C, 38 μm thick, manufactured by Toray DuPont) using a film puncher F602 manufactured by Yamaha Finetech, the same as in Examples 1 and 3, A resin layer is formed on both surfaces and the inner wall of the through hole, and a silver non-conductive layer is coated on the polyimide film (both the surface on which the resin layer is formed and the inner wall of the through hole) by applying a silver particle dispersion. After forming, electroless copper plating treatment was performed.
As a result of the tape peeling test using the cellophane tape (manufactured by Nichiban), the copper conductive layer formed in this manner was not peeled off and had good adhesion. When the electric tester probe was brought into contact with both the front and back surfaces, energization could be confirmed, and it was confirmed that both the front and back surfaces were connected through the through hole.

1 Insulating substrate (A)
2 Resin layer (B)
3 Non-conductive layer (D)
3 'Non-conductive layer (D) (The void portion of the non-conductive layer (D) is filled with electroless copper plating to form a conductive layer as a whole, but the portion that was originally a non-conductive layer therein .)
4 Conductive layer by electroless plating (E)
5 Conductive layer by electrolytic plating (F)

Claims (25)

(1) A step of applying a resin layer forming composition (b) on the insulating substrate (A) to form a resin layer (B),
(2) A group consisting of gold, silver, copper and platinum whose surface is protected with a compound (c1) having a nitrogen atom, sulfur atom, phosphorus atom or oxygen atom on the resin layer (B) obtained in (1) A step of applying a dispersion (C) containing 0.5% by mass or more of one or more metal fine particles (c2) selected from the above, and forming a nonconductive layer (D) having a resistance value of 10 ⁷ Ω or more ,
(3) performing electroless plating on the substrate having the nonconductive layer (D) obtained in (2) to form a conductive layer (E);
A method for producing a conductive material comprising:
The resin layer forming composition (b)
A method for producing a conductive material, which is a resin layer forming composition containing a urethane resin (b1), a vinyl polymer (b2), and an aqueous medium (b3). The urethane resin (b1) has an aliphatic cyclic structure of 2,000 mmol / kg to 5,500 mmol / kg with respect to the total amount of the urethane resin (b1) and a hydrophilic group. The manufacturing method of the electroconductive material as described in any one of. And (4) a step of electroplating the base material having the conductive layer (E) obtained in (3) to form a metal conductive layer (F) on the conductive layer (E),
The manufacturing method of the electroconductive material of Claim 1 or 2 which has these. A resin layer (B) is formed by applying the resin layer forming composition (b) on the insulating substrate (A) and drying the resin layer forming composition (b) under a condition that does not cause a crosslinking reaction. Then, after the dispersion (C) is applied to the surface of the resin layer (B), the resin layer (B), which is the base layer of the non-conductive layer (D), is crosslinked by heating. The method for producing a conductive material according to claim 1, which forms a structure. After applying the resin layer forming composition (b) on the insulating substrate (A) and heating to form a crosslinked structure in the resin layer (B), the dispersion (C) is applied. The method for producing a conductive material according to any one of claims 1 to 3, wherein the nonconductive layer (D) is formed. The method for producing a conductive material according to any one of claims 1 to 5, wherein the insulating substrate (A) is a substrate formed by molding a polyimide resin, a liquid crystal polymer, or a glass epoxy resin. The method for producing a conductive material according to claim 6, wherein the insulating substrate (A) is a film, sheet, or plate-like substrate. The method for producing a conductive material according to claim 7, wherein the film, sheet, or plate-like insulating base material (A) has through-holes connecting the front and back surfaces thereof. The urethane resin (b1) and the vinyl polymer (b2) form composite resin particles composed of a shell layer that is the urethane resin (b1) and a core layer that is the vinyl polymer (b2). The method for producing a conductive material according to claim 1, wherein the conductive material is produced. The mass ratio [(b1) / (b2)] of the urethane resin (b1) and the vinyl polymer (b2) constituting the composite resin particle is in a range of 70/30 to 10/90. The manufacturing method of the electroconductive material as described in any one of. The vinyl polymer (b2) is 10% by mass to 70% by mass of methyl methacrylate and 10% by mass to 50% by mass of (meth) acrylic acid alkyl ester having an alkyl group having 2 to 12 carbon atoms. The method for producing a conductive material according to any one of claims 1 to 10, which is obtained by polymerizing a vinyl monomer mixture contained therein. The method for producing a conductive material according to claim 1, wherein the vinyl resin (b2) has a crosslinkable functional group. The method for producing a conductive material according to claim 12, wherein the crosslinkable functional group is one or more thermally crosslinkable functional groups selected from the group consisting of a methylolamide group and an alkoxymethylamide group. The resin-forming composition (b) further contains a crosslinking agent (b4), and the crosslinking agent (b4) can undergo a crosslinking reaction by heating to 100 ° C. or higher. Item 12. The method for producing a conductive material according to any one of Items 1 to 11. The method for producing a conductive material according to claim 1, wherein the compound (c1) has a number average molecular weight in the range of 3,000 to 50,000. The method for producing a conductive material according to any one of claims 1 to 15, wherein the compound (c1) contains two or more of a nitrogen atom, a sulfur atom, a phosphorus atom, or an oxygen atom in one molecule. . The compound (c1) is a compound having an amino group, carboxy group, hydroxy group, thiol group, phosphate group, quaternary ammonium group, quaternary phosphonium group, cyano group, ether group, thioether group or disulfide group. Item 16. A method for producing a conductive material according to any one of Items 1 to 15. The compound (c1) is a compound (P1) having a polyethyleneimine block and a polyethylene glycol block,
A (meth) acrylate macromonomer having a polyethylene glycol chain and a (meth) acrylate monomer having a phosphate ester residue represented by -OP (O) (OH) ₂ are represented by -SR (R is carbon An alkyl group having 1 to 18 carbon atoms, a phenyl group optionally having a substituent on the benzene ring, or a hydroxy group, an alkoxy group having 1 to 18 carbon atoms, an aralkyloxy group having 1 to 18 carbon atoms, and a benzene ring A phenyloxy group, a carboxy group, a carboxy group salt, a monovalent or polyvalent alkylcarbonyloxy group having 1 to 18 carbon atoms, and a monovalent or polyvalent group having 1 to 18 carbon atoms, which may have a substituent. A chain transfer agent having a functional group represented by a C1-C8 alkyl group having one or more functional groups selected from the group consisting of valent alkoxycarbonyl groups. (Meth) acrylic polymer (P2) obtained by polymerization in the presence of
_{^{X- (OCH 2 CHR 1) n}} -O-CH 2 -CH (OH) -CH 2 -S-Z (1)
Wherein (1), X is an alkyl group of _C ¹ _{~C 8,} ^R 1 is a hydrogen atom or a methyl radical, n is an integer indicating the number of repetitions of 2 to 100, ^{R 1} is repeated independently for each unit may be different even in the same, Z is an alkyl group of _C 2 _{-C 12,} an allyl group, an aryl group, an arylalkyl ^{group, -R 2 -OH, -R 2 -NHR} 3 , or ^-R 2 -COR ⁴ (where, ^{R 2} is an alkylene chain of _C 2 _{~C 4,} ^{R 3} is a hydrogen _atom, an acyl group of C 2 -C _4, alkoxycarbonyl group C 2 -C _4, Or a C ₁ -C ₄ alkyl group or a C ₁ -C ₈ alkoxy group which may have a substituent on the aromatic ring, and R ⁴ is a hydroxy group, C ₁ -C ₄ It is alkyl or alkoxy group _C 1 -C ₈ ) Is a group represented by. ]
A thioether-containing organic compound (P3)
The method for producing a conductive material according to any one of claims 1 to 15. The method for producing a conductive material according to claim 1, wherein an average particle diameter of the metal fine particles is in a range of 1 to 200 nm. The method for producing a conductive material according to any one of claims 1 to 19, wherein the content of the metal fine particles (c2) in the dispersion (C) is in the range of 0.5 to 20 wt%. The non-conductive layer (D) is formed so that the coverage of the metal fine particles (c2) on the resin layer (B) formed on the surface of the insulating base (A) is in the range of 20 to 90 area%. It is a layer, The manufacturing method of the electroconductive material in any one of Claims 1-20. A metal particle layer in which the nonconductive layer (D) is formed by laminating metal fine particles (c1) with a number of layers of 5 or less on the resin layer (B) formed on the surface of the insulating substrate (A). The method for producing a conductive material according to any one of claims 1 to 20. The said nonelectroconductive layer (D) is formed on the resin layer (B) formed in both surfaces of the film, sheet | seat, or plate-shaped insulating base material (A), The Claims 1-22 characterized by the above-mentioned. The manufacturing method of the electroconductive material any one of these. The non-conductive layer (D) is formed on a resin layer (B) formed on both surfaces of the film, sheet or plate-like insulating base material (A) and on the inner wall of the through hole connecting the front and back. The method for producing a conductive material according to any one of claims 8 to 22, wherein: The electroconductive which has the insulating base material (A) obtained by the manufacturing method of any one of Claims 1-24, a resin layer (B), a nonelectroconductive layer (D), and a conductive layer (E). The manufacturing method of the laminated base material for printed wiring boards characterized by manufacturing using a material.