JP2016120604A - Laminate, conductive pattern and electronic circuit - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminate having a primer layer, a conductive layer and a metal plating layer sequentially formed on a support, where the occurrence of electrochemical migration is prevented, and provide a conductive pattern and an electronic circuit prepared with the laminate.SOLUTION: A laminate has a primer layer (B), a conductive layer (C) and a metal plating layer (D) sequentially formed on a support (A), with the primer layer (B) having the surface free energy of 20-45 mJ/m.SELECTED DRAWING: None

Description

  The present invention relates to a laminate that can be used as a conductive pattern provided in a wired electronic circuit such as a printed circuit board, an electromagnetic wave shield, an integrated circuit, and an organic transistor, and a method for manufacturing the same.

  2. Description of the Related Art In recent years, with higher performance, smaller size and thinner electronic devices, there is a strong demand for higher density, smaller size and thinner electronic circuits and integrated circuits used therein.

  As a conductive pattern that can be used in the above electronic circuit, etc., for example, a conductive material layer is formed on the support surface by applying a coating material containing a conductive material to the support surface and baking it. Then, a conductive pattern in which a plating layer is provided on the surface of the conductive material layer by plating the surface of the conductive material layer is known (see, for example, Patent Documents 1 and 2). ). However, in order to increase the density of the conductive pattern, when the interval between adjacent wirings (between wirings) is narrowed, when a voltage is applied under high temperature and high humidity, the conductive component of the wiring is ionized, Ionic components migrate between the wirings to form dendritic crystals. Due to this dendritic crystal, there is a problem that a short circuit occurs between adjacent wirings. This phenomenon is generally called electrochemical migration.

  Therefore, there is a need for a conductive pattern that is a highly reliable wiring circuit that does not cause a short circuit or the like in any environment. As a laminate that can be used as the conductive pattern, a high temperature, high There has been a demand for a material that is less likely to cause electrochemical migration under humidity. However, in a laminate in which a primer layer, a conductive layer, and a metal plating layer are sequentially formed on a support, a laminate that hardly causes electrochemical migration has not yet been found.

JP-A-60-246695 JP 2005-286158 A

  The problem to be solved by the present invention is to provide a laminate in which a primer layer, a conductive layer and a metal plating layer are sequentially formed on a support so that electrochemical migration is unlikely to occur. Moreover, the conductive pattern and electronic circuit using this laminated body are provided.

  As a result of diligent research to solve the above problems, the present inventors have found that the surface free energy of the primer layer is in a certain range in a laminate in which a primer layer, a conductive layer and a metal plating layer are formed on a support. If it is within the range, it was found that electrochemical migration hardly occurs, and the present invention was completed.

That is, the present invention is a laminate in which a primer layer (B), a conductive layer (C) and a metal plating layer (D) are sequentially formed on a support (A), and the surface of the primer layer (B) The present invention relates to a laminate having a free energy of 20 to 45 mJ / m ² and a manufacturing method thereof. The present invention also relates to a conductive pattern and an electronic circuit using this laminate.

  The laminate of the present invention is less likely to cause electrochemical migration between conductive pattern lines in a state where voltage is applied under high temperature and high humidity. For example, the conductive pattern, electronic circuit, flexible printed circuit board, electromagnetic wave shield, etc. Members having wiring circuits such as: organic solar cells, electronic terminals, organic EL devices, organic transistors, peripheral wiring members such as RFID (for example, non-contact IC cards), etc. Can be used.

It is a schematic diagram of the produced wiring. It is an enlarged photograph between the wirings after the evaluation test of the electrochemical migration of the laminated body of Example 1. It is an enlarged photograph between the wirings after the evaluation test of the electrochemical migration of the laminated body of the comparative example 1.

The laminate of the present invention has a structure in which a primer layer (B), a conductive layer (C), and a metal plating layer (D) are sequentially formed on a support (A), and the surface of the primer layer (B) The free energy is 20 to 45 mJ / m ² .

  The said support body (A) becomes a base material of the laminated body of this invention. Examples of the material of the support (A) include polyimide resin, polyamideimide resin, polyamide resin, polyethylene terephthalate resin, polybutylene terephthalate resin, polyethylene naphthalate resin, polycarbonate resin, acrylonitrile-butadiene-styrene (ABS) resin, Graft copolymerization of liquid crystal polymer, polyether ether ketone, polyphenylene sulfide resin, acrylic resin such as poly (meth) acrylate, polyvinylidene fluoride resin, polytetrafluoroethylene, polyvinyl chloride resin, polyvinylidene chloride resin, acrylic resin Vinyl chloride resin, polyvinyl alcohol resin, polyethylene resin, polypropylene resin, urethane resin, silicon, silicon carbide, gallium nitride, sapphire, Mix, glass, glass epoxy resin, glass polyimide, paper phenol, diamond like carbon, alumina, polyester fiber, polyamide fiber, polyaramid fiber and other synthetic fibers, carbon fiber and other inorganic fibers, cellulose nanofiber and other natural fibers It is done. These supports are preferably insulating, and porous ones can be used.

  As said support body (A), when the laminated body of this invention is used for the use calculated | required the softness | flexibility which can be bend | folded, it is preferable to use a flexible and flexible support body. Specifically, it is preferable to use a film or sheet-like support.

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

  When the shape of the support (A) is a film or sheet, the thickness of the film or sheet is preferably 1 to 5,000 μm, and preferably 1 to 300 μm. More preferably. Moreover, when using the laminated body of this invention for the thing as which flexibility is requested | required, such as a flexible printed circuit board, it is preferable to use a film-like thing about 1-200 micrometers thick as a support body.

  Moreover, when providing the primer layer mentioned later on the said support body (A), since the adhesiveness of the said support body (A) and the said primer layer can be improved, on the surface of the said support body (A), Surface treatment for forming fine irregularities, cleaning dirt adhering to the surface of the support (A), introducing a functional group such as a hydroxyl group, a carbonyl group, or a carboxyl group may be performed. Specifically, a plasma discharge treatment such as a corona discharge treatment, a dry treatment such as an ultraviolet treatment, a wet treatment using an aqueous solution such as water, an acid / alkali, or an organic solvent may be applied.

The primer layer (B) has a surface free energy of 20 to 45 mJ / m ^{2 on} the surface of the coating film. When the surface free energy is lower than 20 mJ / m ² , the adhesion between the support (A) and the primer layer (B) is lowered, and the wiring is peeled off and cannot be used as an electronic circuit. On the other hand, when the surface free energy exceeds 45 mJ / m ² , the hydrophilicity of the surface of the primer layer becomes strong, and water and water vapor are adsorbed on the surface of the primer layer (B) at high temperature and high humidity. Cause.

The surface free energy of the primer layer (B) is the contact angle when droplets of ion-exchanged water, ethylene glycol and diiodomethane are dropped on the surface of the primer layer (B) as a solvent having a known surface free energy. For example, measurement is performed using a contact angle meter (“Drop Master 700” manufactured by Kyowa Interface Science Co., Ltd.). The value shown in Table 1 is used for the surface free energy of each solvent. The contact angle in each solvent is measured, and the surface free energy γ ^LW , γ ⁺ , γ ⁻ of the base material is calculated by solving the simultaneous equations by substituting into the following formula (1), and further, the following formula (2 The surface free energy γ ^tot can be calculated by substituting the calculated γ ^LW , γ ⁺ , γ ⁻ for).

The resin used for the primer layer (B) can be used without particular limitation as long as the surface free energy of the primer layer (B) is in the range of ²⁰ to 45 mJ / m ^2. Specifically, The following are mentioned.

  Examples of the resin used for the primer layer (B) include urethane resins, acrylic resins, urethane-acrylic composite resins, epoxy resins, imide resins, amide resins, melamine resins, phenol resins, urea formaldehyde resins, and phenol blocking agents. And polyisocyanate, polyvinyl alcohol, polyvinyl pyrrolidone, and a resin having a fluorine atom. These resins can be used alone or in combination of two or more. Among these resins, since the electrochemical migration can be further suppressed, a resin having a structure represented by the following general formula (I) is preferable, and a urethane resin (b1) having the above structure is more preferable.

(In general formula (I), R ¹ and R ² each independently represent an alkyl group, and m and n each independently represent an integer of 1 to 20)

R ¹ and R ² in the general formula (I) are each independently an alkyl group, but an alkyl group having 1 to 20 carbon atoms is preferable because the raw material is easily available. 5-10 alkyl groups are more preferred. The alkyl group may be linear or branched.

  Moreover, although m and n in the said general formula (I) are respectively independently the integers of 1-20, the integer of 5-10 is preferable.

  As the urethane resin (b1) having a structure represented by the general formula (I), the surface of the primer layer (B) can be sufficiently hydrophobized, and electrochemical migration can be suppressed. What has 5-50 mass% of structures represented by the said general formula (I) is preferable, and what has 10-40 mass% is more preferable. The mass ratio of the structure represented by the general formula (I) is a raw material that contributes to the introduction of the structure represented by the general formula (I) among the raw materials used when the urethane resin is produced, that is, It is a value obtained by dividing the total mass of the raw materials having the structure represented by the general formula (I) by the total mass of the urethane resin (b1).

  When the urethane resin (b1) is applied to the support (A), it is preferably diluted or dispersed in a solvent. When an aqueous medium is used as the solvent, it is preferable to introduce a hydrophilic group into the urethane resin (b1). Examples of the hydrophilic group include an anionic group such as a carboxylate group and a sulfonate group partially or wholly neutralized with a basic compound, a cationic group, and a nonionic group, and an anionic group is preferable. .

  Examples of the basic compound include ammonia; amine compounds such as triethylamine and ethanolamine; and metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide.

  Moreover, the said urethane resin (b1) may have functional groups, such as a carboxyl group and a hydroxyl group, at the terminal. A functional group such as a carboxyl group or a hydroxyl group can be utilized as a functional group to undergo a crosslinking reaction when a crosslinking agent is used.

  The urethane resin (b1) used by being dissolved or dispersed in an aqueous medium is, for example, a polyol (b1-1) having a structure represented by the general formula (I), a compound having a hydrophilic group and an active hydrogen atom It can be produced by reacting (b1-2) with polyisocyanate (b1-3). In addition, when using the said urethane resin (b1) melt | dissolving in an organic solvent, the hydrophilic group of the said compound (b1-2) is not essential.

  Examples of the polyol (b1-1) include a hydrogenated dimer diol (b1-1-1), a polyester polyol (b1) obtained by reacting a hydrogenated dimer diol (b1-1-1) with a polycarboxylic acid. -1-2) and polyester polyol (b1-1-3) obtained by reacting a hydrogenated dimer acid with a polyol. These can be used alone or in combination of two or more.

  The hydrogenated dimer diol (b1-1-1) is a compound having a hydroxyl group obtained mainly by high-pressure catalytic hydrogen reduction of dimer acid, which is a dimer of unsaturated fatty acid. Examples of the unsaturated fatty acid include oleic acid, linoleic acid, linolenic acid, and the like.

  Moreover, the said hydrogenated dimer diol (b1-1-1) can be manufactured from natural vegetable oil fatty acid, Usually, in addition to the said hydrogenated dimer diol (b1-1-1), the commercial item is. Generally, by-products such as a trimer of the unsaturated fatty acid and a compound having a hydroxyl group obtained by reducing it are mixed.

  The polyester polyol (b1-1-2) is an esterified product obtained by reacting the hydrogenated dimer diol (b1-1-1) with a polycarboxylic acid by a known method.

  Examples of the polycarboxylic acid used for producing the polyester polyol (b1-1-2) include succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, maleic acid, fumaric acid, 1, 3 -Cyclopentanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, 1,4-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, naphthalic acid, biphenyldicarboxylic acid, 1,2- Polycarboxylic acids such as bis (phenoxy) ethane-p, p′-dicarboxylic acid, trimellitic acid, pyromellitic acid; acid anhydrides or esterified products thereof. These can be used alone or in combination of two or more.

  The polyester polyol (b1-1-3) is an esterified product obtained by reacting a hydrogenated dimer acid with a polyol by a known method. The hydrogenated dimer acid is a compound in which a hydrogen atom is added to an unsaturated double bond of a dimer acid that is a dimer of the unsaturated fatty acid. Hydrogenated dimer acid can be produced from natural vegetable oil fatty acids. In general, commercially available products thereof can be obtained by trimming unsaturated fatty acids in addition to the hydrogenated dimer acids or by reducing them. In general, by-products such as a hydroxyl group-containing compound are mixed.

  Examples of the polyol used in producing the polyester polyol (b1-1-3) include ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, and 1,4-butanediol. 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, 1, 4-cyclohexanediol, 1,4-cyclohexanedimethanol, trimethylolpropane, trimethylolethane, pentaerythritol, sorbitol, bisphenol A, hydrogenated bisphenol A, bisphenol A or hydrogenated Alkylene oxide adducts of bisphenol A and the like. These can be used alone or in combination of two or more. Among these, those having a number average molecular weight in the range of 60 to 200 such as ethylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, 1,4-cyclohexanedimethanol and the like are preferable.

  Furthermore, as a polyol used when manufacturing the said polyester polyol (b1-1-3), in addition to the above, for example, polyethylene glycol having a number average molecular weight in the range of 300 to 6,000, number average molecular weight of 300 to 6 Polypropylene glycol in the range of 1,000, ethylene oxide-propylene oxide copolymer having a number average molecular weight in the range of 300 to 6,000, and the like.

  Examples of the compound (b1-2) include 2-hydroxyethanesulfonic acid, phenolsulfonic acid, sulfobenzoic acid, sulfosuccinic acid, 5-sulfoisophthalic acid, sulfanilic acid, 1,3-phenylenediamine-4, Compounds having a sulfonic acid group such as 6-disulfonic acid and 2,4-diaminotoluene-5-sulfonic acid; 2,2-dimethylolpropionic acid, 2,2-dimethylolbutyric acid, 2,2-dimethylolvaleric acid, di Compounds having a carboxyl group such as oxymaleic acid, 2,6-dioxybenzoic acid, 3,4-diaminobenzoic acid; derivatives thereof and the like. These can be used alone or in combination of two or more.

  Examples of the polyisocyanate (b1-3) include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 2 , 4'-diphenylmethane diisocyanate, 2,2'-diphenylmethane diisocyanate, 3,3'-dimethyl-4,4'-biphenylene diisocyanate, 3,3'-dimethoxy-4,4'-biphenylene diisocyanate, 3,3'- Dichloro-4,4′-biphenylene diisocyanate, 1,5-naphthalene diisocyanate, 1,5-tetrahydronaphthalene diisocyanate, tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, dodeca Tylene diisocyanate, trimethylhexamethylene diisocyanate, 1,3-cyclohexylene diisocyanate, 1,4-cyclohexylene diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, hydrogenated xylylene diisocyanate, lysine diisocyanate, isophorone diisocyanate, 4,4 ' -Polyisocyanates such as dicyclohexylmethane diisocyanate and 3,3'-dimethyl-4,4'-dicyclohexylmethane diisocyanate; and trimers thereof. These can be used alone or in combination of two or more.

  Among the polyisocyanates (b1-3), 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 2 are relatively inexpensive and easy to obtain raw materials. , 4'-diphenylmethane diisocyanate, 2,2'-diphenylmethane diisocyanate, 1,6-hexamethylene diisocyanate, 1,3-cyclohexylene diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 3,3'-dimethyl- 4,4′-dicyclohexylmethane diisocyanate is preferred.

  Moreover, when manufacturing the said urethane resin (b1), the polyol (b1-1) which has a structure represented by the said general formula (I), the said hydrophilic group, and the compound (b1-2) which has an active hydrogen atom ) And the polyisocyanate (b1-3), other raw materials can be used in combination as required.

  Examples of the other raw material include other polyols other than the polyol (b1-1) having the structural unit represented by the general formula (I), for example, the polyester polyol (b1-1-2). And polyester polyols other than the polyester polyol (b1-1-3), polyether polyols, polycarbonate polyols, polyester amide polyols, polyacetal polyols, polythioether polyols, and polybutadiene glycols.

  As said polyester polyol, what is obtained by esterifying a polyol and polycarboxylic acid is mentioned, for example. As said polyol, the thing similar to the polyol illustrated as what is used when manufacturing the said polyester polyol (b1-1-3) is mentioned.

  Examples of the polyester polyol include those obtained by ring-opening polymerization of a cyclic ester compound such as ε-caprolactone.

  In addition, as the polyether polyol, for example, one or more compounds such as ethylene oxide, propylene oxide, butylene oxide, styrene oxide, epichlorohydrin, tetrahydrofuran, cyclohexylene, etc., using a compound having at least two active hydrogen atoms as an initiator Can be obtained by addition polymerization.

  Examples of the compound having at least two active hydrogen atoms include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, hexamethylene. Glycol, saccharose, methylene glycol, glycerin, sorbitol; actinic acid, trimellitic acid, hemimellitic acid, phosphoric acid, ethylenediamine, propylenediamine, diethylenetriamine, triisopropanolamine, pyrogallol, dihydrobenzoic acid, hydroxyphthalic acid, 1,2,3 -Propane trithiol etc. are mentioned.

  The polycarbonate polyol is obtained by esterifying carbonic acid and an aliphatic polyol or a polyol having an alicyclic structure. Examples of the polycarbonate polyol include 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, diethylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, 1 A reaction product of a diol such as 1,4-cyclohexanedimethanol and a dialkyl carbonate such as dimethyl carbonate or a cyclic carbonate such as ethylene carbonate.

  As said other polyol, what has the range of number average molecular weight 200-10,000 is preferable, and the thing of the range of number average molecular weight 300-5,000 is more preferable.

  Examples of the method for producing the urethane resin (b1) dissolved or dispersed in an aqueous medium include the following methods 1 to 5.

[Method 1]
The polyol containing the polyol (b1-1), the compound (b1-2), and the polyisocyanate (b1-3) are charged all at once or divided, and they are reacted in a solvent or under no solvent. A method of producing a urethane resin, neutralizing part or all of the hydrophilic group of the urethane resin with a neutralizing agent, and then adding or dispersing or dissolving the aqueous medium.

[Method 2]
The polyol containing the polyol (b1-1), the compound (b1-2), and the polyisocyanate (b1-3) are charged all at once or divided, and they are reacted in a solvent or under no solvent. After producing a urethane prepolymer having an isocyanate group at the terminal, a urethane resin is produced by chain extension using a compound having an active hydrogen atom such as polyamine, and then one of the hydrophilic groups possessed by the urethane resin. A method in which an aqueous medium is added and dispersed or dissolved after neutralizing part or all with a neutralizing agent.

[Method 3]
The polyol containing the polyol (b1-1), the compound (b1-2), and the polyisocyanate (b1-3) are charged all at once or divided, and they are reacted in a solvent or under no solvent. The urethane prepolymer having an isocyanate group at the terminal is produced by neutralizing a part or all of the hydrophilic group of the obtained urethane prepolymer with a neutralizing agent, and then introducing the aqueous medium into the urethane prepolymer. A method in which a polymer is dispersed in water or dissolved in water and then chain-extended using a compound having an active hydrogen atom.

[Method 4]
The polyol containing the polyol (b1-1), the compound (b1-2), and the polyisocyanate (b1-3) are charged all at once or divided, and they are reacted in a solvent or under no solvent. After producing a urethane prepolymer having an isocyanate group at the terminal by neutralizing part or all of the hydrophilic groups of the obtained urethane prepolymer with a neutralizing agent, the urethane prepolymer is used with a machine such as a homogenizer. A method in which a polymer is forcibly emulsified and dispersed in an aqueous medium, followed by chain elongation using a compound having an active hydrogen atom.

[Method 5]
A polyol containing the polyol (b1-1), the compound (b1-2), the polyisocyanate (b1-3), and a compound having an active hydrogen atom are charged all at once, and they are added in a solvent or A urethane resin is produced by reacting in the absence of a solvent, and after neutralizing part or all of the hydrophilic groups of the urethane resin with a neutralizing agent, the urethane resin is dispersed in water or water by adding an aqueous medium. To dissolve in.

  As a compound which has an active hydrogen atom which can be used when manufacturing the said urethane resin (b1), a polyamine etc. are mentioned, for example.

  Examples of the polyamine include ethylenediamine, 1,2-propanediamine, 1,6-hexamethylenediamine, piperazine, 2,5-dimethylpiperazine, isophoronediamine, 4,4′-dicyclohexylmethanediamine, and 3,3′-. Diamine compounds such as dimethyl-4,4′-dicyclohexylmethanediamine and 1,4-cyclohexanediamine; N-hydroxymethylaminoethylamine, N-hydroxyethylaminoethylamine, N-hydroxypropylaminopropylamine, N-ethylaminoethylamine, Diamine compounds having one primary amine and one secondary amine such as N-methylaminopropylamine; polyamine compounds such as diethylenetriamine, dipropylenetriamine and triethylenetetramine; Hydrazine compounds such as N, N′-dimethylhydrazine and 1,6-hexamethylenebishydrazine; dihydrazide compounds such as succinic acid dihydrazide, adipic acid dihydrazide, glutaric acid dihydrazide, sebacic acid dihydrazide, and isophthalic acid dihydrazide; β-semicarbazide propion And semicarbazide compounds such as acid hydrazide, 3-semicarbazide-propyl-carbazate, semicarbazide-3-semicarbazidemethyl-3,5,5-trimethylcyclohexane, and the like.

  In addition to the polyamine, other active hydrogen atom-containing compounds include, for example, ethylene glycol, diethylene recall, triethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4 -Low molecular weight polyols such as butanediol, hexamethylene glycol, saccharose, methylene glycol, glycerin and sorbitol; bisphenol A, 4,4'-dihydroxydiphenyl, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenylsulfone , Hydrogenated bisphenol A, phenol compounds such as hydroquinone; water and the like.

  In the methods 1 to 5 for producing the urethane resin (b1), a urethanization catalyst may be used as necessary. Examples of the catalyst include stannous compounds such as stannous octylate, dibutyltin dilaurate, dibutyltin dimaleate, dibutyltin diphthalate, dibutyltin dimethoxide, dibutyltin diacetyl acetate, and dibutyltin diversate, tetrabutyl titanate, and tetraisopropyl titanate. And titanate compounds such as triethanolamine titanate, tertiary amines, and quaternary ammonium salts can be used.

  Moreover, as resin used for the said primer layer, the acrylic resin (b2) which has a fluorine atom is mentioned, for example.

  The acrylic resin (b2) having a fluorine atom is obtained by polymerizing an acrylic monomer having a fluorine atom.

  Examples of the acrylic monomer having a fluorine atom include 2,2,2-trifluoroethyl acrylate, 2,2,3,3-tetrafluoropropyl acrylate, 1H, 1H, 5H-octapentylfluoroacrylate, and 1H. , 1H, 2H, 2H-tridecafluorooctyl acrylate and the like. Among these, 1H, 1H, 5H-octapentylfluoroacrylate is preferable because it can easily adjust the surface free energy when used as a primer layer.

  The acrylic resin (b2) having a fluorine atom may be copolymerized with another monomer other than the acrylic monomer having a fluorine atom in order to adjust the surface free energy of the coating film.

  Examples of the other monomers include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, isobutyl (meth) acrylate, ethyl vinyl ether, isoprene, and chloroprene. , Butadiene, vinyl acetate, vinyl propionate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, glycerol mono (meth) acrylate, glycidyl (meth) acrylate, Allyl glycidyl ether, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, γ- (meth) acryloxypropyl Trimethoxysilane, γ- (meth) acryloxypropyltriethoxysilane, γ- (meth) acryloxypropylmethyldimethoxysilane, γ- (meth) acryloxypropylmethyldiethoxysilane, γ- (meth) acryloxypropyltri Examples include isopropoxysilane, N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane, and its hydrochloride.

  Moreover, when coating the said acrylic resin (b2) to the said support body (A), it is preferable to use it diluting or disperse | distributing to a solvent. When an aqueous medium is used as the solvent, it is preferable to introduce a hydrophilic group into the acrylic resin (b2). Examples of the hydrophilic group include an anionic group such as a carboxylate group and a sulfonate group partially or wholly neutralized with a basic compound, a cationic group, and a nonionic group, and an anionic group is preferable. .

  For example, when a carboxylate group is introduced as a hydrophilic group into the acrylic resin (b2), a single group having an unsaturated double bond such as (meth) acrylic acid, maleic acid, itaconic acid, fumaric acid, and a carboxyl group. Using the monomer as a raw material, the acrylic resin (b2) is produced, and then a part or all of the carboxyl groups are neutralized with a basic compound to form carboxylate groups.

  The acrylic resin (b2) having a fluorine atom can be produced by a known method, for example, a solution polymerization method in which polymerization is performed in an organic solvent, an emulsion polymerization method in which polymerization is performed in an aqueous medium, or the like. Is mentioned.

  Examples of the polymerization initiator used in the production of the acrylic resin having a fluorine atom (b2) include azo initiators such as azonitrile, azoester, azoamide, azoamidine, azoimidazoline; peroxyketal, hydroperoxide Organic peroxides such as dialkyl peroxide, diacyl peroxide, peroxydicarbonate and peroxyester; inorganic peroxides such as ammonium persulfate, potassium persulfate and hydrogen peroxide.

  Since the resin solution or resin dispersion used for forming the primer layer (B) has good coatability, the resin content in the liquid is preferably in the range of 1 to 50% by mass. Since the layer (B) can be coated with a thin film and the adhesion between the support (A) and the conductive layer (C) can be improved, the range of 1 to 5% by mass is more preferable.

  Examples of the solvent used for the resin solution or resin dispersion used to form the primer layer (B) include various organic solvents and aqueous media. Examples of the organic solvent include toluene, ethyl acetate, methyl ethyl ketone, and the like, and examples of the aqueous medium include water, an organic solvent miscible with water, and a mixture thereof.

  Examples of the organic solvent miscible with water include alcohol solvents such as methanol, ethanol, n-propanol, isopropanol, ethyl carbitol, ethyl cellosolve, butyl cellosolve; ketone solvents such as acetone and methyl ethyl ketone; ethylene glycol, diethylene glycol, propylene Examples include alkylene glycol solvents such as glycol; polyalkylene glycol solvents such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol; and lactam solvents such as N-methyl-2-pyrrolidone.

  Examples of a method for removing the solvent contained in the coating layer after coating the primer on the surface of the support (A) include a method of drying using a dryer and volatilizing the solvent. . The drying temperature is preferably set to a temperature in which the solvent can be volatilized and does not adversely affect the support (A).

  Although the thickness of the primer layer (B) varies depending on the use of the laminate of the present invention, it can further improve the adhesion between the support (A) and the conductive layer (C) described later, and is 10 nm to 30 μm. The range of 10 nm to 1 μm is more preferable, and the range of 10 nm to 500 nm is more preferable.

In order to improve the adhesion of the primer layer (B) to the conductive layer (C), for example, a plasma discharge treatment method such as a corona discharge treatment method, a dry treatment method such as an ultraviolet treatment method, water, The surface treatment may be performed by a wet treatment method using an acidic or alkaline chemical solution, an organic solvent, or the like. However, when the surface treatment is performed, the surface of the primer layer is oxidized and becomes hydrophilic, so that the surface free energy is increased, so that electrochemical migration is likely to occur. Therefore, the surface treatment of the primer layer (B) is preferably performed so that the surface free energy is in the range of ²⁰ to 45 mJ / m ² .

  As a method for adjusting the surface free energy of the primer layer (B), a monomolecular film (Self-Assembled Monolayer; hereinafter abbreviated as “SAM”) is formed on the surface of the primer layer (B) by chemical adsorption of an organic compound. May be formed. The SAM is a monomolecular film formed by self-assembly or self-assembly, and is a modification method in which one molecule of an organic compound is chemically adsorbed on the surface of the primer layer (B).

  Examples of organic compounds used in the SAM include organic sulfur compounds such as alkyl thiols, alkyl disulfides, and alkyl thioisocyanides; organic selenium compounds such as alkyl selenolates and dialkyl diselenides; organic tellurium compounds such as alkyl tellurates; alkyl isocyanides and the like Nitrile compounds; carboxylic acids such as fatty acids; organophosphorus compounds such as alkylphosphonic acids and alkylphosphate esters; organosilane compounds such as alkylsilanes, fluorinated alkylsilanes, phenylsilanes, and aminosilanes; unsaturated hydrocarbons such as alkynes and alkenes Organic halogen compounds such as alkyl bromide and alkyl iodide; diazo compounds; alcohols; aldehydes; Among these, it is preferable to use an organosilane compound because the surface free energy can be easily adjusted.

  Examples of the method for forming the SAM include a gas phase process. In the gas phase process, a vacuum apparatus having an exhaust pump and a decompression chamber is usually used. When using an organic silane compound, as a simpler method, an electric furnace in which the support (A) and the organic silane compound are sealed in a polytetrafluoroethylene sealed container at atmospheric pressure, and the sealed container is heated. Install in. Next, the vaporized organosilane compound reacts with the functional group on the surface of the primer layer (B), and the surface treatment is completed.

The surface treatment with the SAM is preferably performed so that the surface free energy is in the range of ²⁰ to 45 mJ / m ² in order to suppress electrochemical migration.

In addition, when a fluid containing nano-sized metal powder and a dispersant used to form a conductive layer (C) described later is applied by a printing method described later, the fluid is applied to the non-image area (between wirings). When the dispersant or solvent contained in is transferred, the primer layer (B) in the non-image area (between wirings) can be surface-treated. After printing, the surface free energy on the surface of the primer layer (B) in the non-image area (between wirings) is preferably in the range of ²⁰ to 45 mJ / m ² in order to suppress electrochemical migration.

  Examples of the metal constituting the conductive layer (C) include a transition metal or a compound thereof, and among them, an ionic transition metal is preferable. Examples of the ionic transition metal include copper, silver, gold, nickel, palladium, platinum, and cobalt. Among these ionic transition metals, copper, silver, and gold are preferable because they have a low electrical resistance and provide a conductive pattern that is resistant to corrosion.

  Moreover, copper, nickel, chromium, cobalt, tin etc. are mentioned as a metal which comprises the said metal plating layer (D). Among these, copper is preferable because a conductive pattern having low electric resistance and strong against corrosion can be obtained.

  As a method for producing the laminate of the present invention, for example, a primer layer (B) is applied and dried on a support (A), and then a fluid containing nano-sized metal powder and a dispersant is applied. And baking to form a conductive layer (C ′), and then removing the organic compound containing the dispersant present in the conductive layer (C ′) to form voids to form a porous conductive layer (C). Then, a method of forming the metal plating layer (D) by electrolysis or electroless plating is mentioned.

  The shape of the nano-sized metal powder used for forming the conductive layer (C) is not particularly limited as long as the conductive layer becomes porous, but is preferably in the form of particles or fibers. In addition, the size of the metal powder is nano-sized. Specifically, when the shape of the metal powder is particulate, a fine conductive pattern can be formed, and the resistance value after firing is further reduced. Therefore, the average particle diameter is preferably in the range of 1 to 100 nm, and more preferably in the range of 1 to 50 nm. The “average particle size” is a volume average value measured by a dynamic light scattering method after diluting the conductive substance with a good dispersion solvent. For this measurement, “Nanotrack UPA-150” manufactured by Microtrack Co. can be used.

  On the other hand, when the shape of the metal powder is fibrous, a fine conductive pattern can be formed, and the resistance value after firing can be further reduced. Therefore, the fiber diameter is preferably in the range of 5 to 100 nm, and in the range of 5 to 50 nm. Is more preferable. The length of the fiber is preferably in the range of 0.1 to 100 μm, and more preferably in the range of 0.1 to 30 μm.

  The content ratio of the nano-sized metal powder in the fluid is preferably in the range of 5 to 90% by mass, and more preferably in the range of 10 to 60% by mass.

  The components blended in the fluid include a dispersant and a solvent for dispersing the nano-sized metal powder in a solvent, and, if necessary, a surfactant, a leveling agent, a viscosity modifier, and a film forming aid. Organic compounds such as antifoaming agents and preservatives are included.

  In order to disperse the nano-sized metal powder in a solvent, a low molecular weight or high molecular weight dispersant is used. Examples of the dispersant include dodecanethiol, 1-octanethiol, triphenylphosphine, dodecylamine, polyethylene glycol, polyvinylpyrrolidone, polyethyleneimine, polyvinylpyrrolidone; fatty acids such as myristic acid, octanoic acid, stearic acid; cholic acid, Examples thereof include polycyclic hydrocarbon compounds having a carboxyl group such as glycyrrhizic acid and avintinic acid. In order to suppress electrochemical migration, a polymer dispersant is preferable, and examples of the polymer dispersant include polyalkyleneimines such as polyethyleneimine and polypropyleneimine, and compounds obtained by adding polyoxyalkylene to the polyalkyleneimine. .

  The amount of the dispersant used for dispersing the nano-sized metal powder is preferably 0.01 to 50 parts by mass, and 0.01 to 10 parts by mass with respect to 100 parts by mass of the nano-sized metal powder. Is more preferable.

  As the solvent used for the fluid, an aqueous medium or an organic solvent can be used. Examples of the aqueous medium include distilled water, ion exchange water, pure water, and ultrapure water. Examples of the organic solvent include alcohol compounds, ether compounds, ester compounds, and ketone compounds.

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

  In addition to the above metal powder and solvent, ethylene glycol, diethylene glycol, 1,3-butanediol, isoprene glycol, and the like can be used for the fluid as necessary.

  As the surfactant, a general surfactant can be used. For example, di-2-ethylhexylsulfosuccinate, dodecylbenzenesulfonate, alkyldiphenyletherdisulfonate, alkylnaphthalenesulfonate, hexametaphosphate Examples include salts.

  As the leveling agent, a general leveling agent can be used, and examples thereof include silicone compounds, acetylenic diol compounds, and fluorine compounds.

  The viscosity of the fluid (value measured using a B-type viscometer at 25 ° C.) is preferably in the range of 0.1 to 500,000 mPa · s, more preferably in the range of 0.5 to 10,000 mPa · s. . Moreover, when the fluid is coated (printed) by a method such as an ink jet printing method or letterpress reverse printing described later, the viscosity is preferably in the range of 5 to 20 mPa · s.

  Examples of the method for coating the fluid on the support (A) include an inkjet printing method, a reverse printing method, a screen printing method, an offset printing method, a spin coating method, a spray coating method, a bar coating method, Examples thereof include a die coating method, a slit coating method, a roll coating method, and a dip coating method.

  Among these coating methods, in the case of forming the conductive layer (C) patterned in a thin line shape of about 0.01 to 100 μm, which is required when realizing a high density of an electronic circuit or the like, an inkjet is used. It is preferable to use a printing method or a reverse printing method.

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

  Further, as the reversal printing method, a letterpress reversal printing method and an intaglio reversal printing method are known, for example, the fluid is applied to the surface of various blankets and brought into contact with the plate from which the non-image portion protrudes, By selectively transferring a fluid corresponding to the non-image area to the surface of the plate, the pattern is formed on the surface of the blanket or the like, and then the pattern is formed on the support layer (A). The method of transferring to the top (surface) is mentioned.

  In order to form the conductive layer (C), the firing step performed after coating the fluid containing metal powder has conductivity by closely contacting and joining the metal powders contained in the fluid. This is performed to form the conductive layer (C). The firing is preferably performed at a temperature range of 80 to 300 ° C. for about 2 to 200 minutes. The firing may be performed in the air, but a part or all of the firing step may be performed in a reducing atmosphere in order to prevent all of the metal powder from being oxidized. By passing through this firing step, the particulate or fibrous metal powders used for forming the conductive layer (C) are brought into close contact with each other, and the conductive layer (C) becomes porous.

  Moreover, the said baking process can be performed using oven, a hot-air drying furnace, an infrared drying furnace, laser irradiation, a microwave, light irradiation (flash irradiation apparatus) etc., for example.

  The thickness of the conductive layer (C ′) obtained by the firing step is preferably in the range of 10 nm to 10 μm, more preferably in the range of 10 nm to 3 μm, considering the adhesion with the metal plating layer (D) described later. preferable.

  After the baking step, the porous conductive layer (C) can be obtained by removing the organic compound containing the dispersant present in the conductive layer (C ′) to form voids. As a method for removing the organic compound, the conductive layer (C ′) is redispersed with a plasma discharge treatment method, an electromagnetic wave irradiation treatment method, a laser irradiation treatment method, an organic compound containing a dispersant with water or an organic solvent. There is a method of performing a treatment such as a dissolution treatment method. These treatment methods are preferable because they can be used alone or in combination of two or more, and the organic compound can be removed more efficiently by combining two or more. The organic compound referred to here is a component blended in the fluid and includes a dispersant, a solvent, a surfactant, a leveling agent, a viscosity modifier, a film forming aid, an antifoaming agent, a preservative, and the like. An organic compound.

  Next, as described above, the primer layer (B) is applied onto the support (A), and the organic compound in the conductive layer (C ′) is removed to remove the organic compound. After forming a quality conductive layer (C), the laminated body of this invention can be obtained by forming a metal plating layer (D) on the said conductive layer (C).

  The metal plating layer (D) also has a role of suppressing the electrochemical migration of the conductive layer (C). For example, when the conductive layer (C) is a conductive layer made of silver nanoparticles and the metal plating layer (D) is a copper plating layer, silver is more likely to cause electrochemical migration than copper, but the silver nanoparticles are copper plated. Therefore, electrochemical migration can be suppressed.

  The metal plating layer (D) constituting the laminate of the present invention has a reliability capable of maintaining good electrical conductivity without disconnection or the like over a long period of time, for example, when the laminate is used for a conductive pattern or the like. This layer is provided for the purpose of forming a highly reliable wiring pattern.

  Although the said metal plating layer (D) is a layer formed on the said conductive layer (C), the method of forming by a plating process is preferable as the formation method. Examples of the plating treatment include wet plating methods such as electrolytic plating methods and electroless plating methods, and dry plating methods such as sputtering methods and vacuum deposition methods. Further, the metal plating layer (D) may be formed by combining two or more of these plating methods.

  Among the above plating processes, the metal constituting the metal plating layer (D) is easily filled in the voids of the porous conductive layer (C), and the conductive layer (C) and the metal plating layer (D) Therefore, wet plating methods such as an electrolytic plating method and an electroless plating method are preferred, and an electrolytic plating method is more preferred.

  In the electroless plating method, for example, the metal constituting the conductive layer (C) is brought into contact with an electroless plating solution, so that a metal such as copper contained in the electroless plating solution is deposited and the metal film is formed. This is a method of forming an electroless plating layer (film).

  As said electroless-plating liquid, what contains metals, such as copper, nickel, chromium, cobalt, tin, a reducing agent, and solvents, such as an aqueous medium and an organic solvent, is mentioned, for example.

  Examples of the reducing agent include dimethylaminoborane, hypophosphorous acid, sodium hypophosphite, dimethylamine borane, hydrazine, formaldehyde, sodium borohydride, phenol and the like.

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

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

  In the electrolytic plating method, for example, electricity is supplied in a state where an electrolytic plating solution is in contact with the surface of the metal constituting the conductive layer (C) or the electroless plating layer (coating) formed by the electroless treatment. Thus, a metal such as copper contained in the electrolytic plating solution is made of a conductive substance constituting the conductive layer (C) installed on the cathode or an electroless plating layer (coating) formed by the electroless treatment. This is a method of depositing on the surface and forming an electrolytic plating layer (metal coating).

  Examples of the electrolytic plating solution include those containing metal sulfides such as copper, nickel, chromium, cobalt, and tin, sulfuric acid, and an aqueous medium. Specifically, what contains copper sulfate, sulfuric acid, and an aqueous medium is mentioned.

  The electrolytic plating solution is preferably used in the range of 20 to 98 ° C.

  In the electrolytic plating treatment method, workability is good without using a highly toxic substance. Therefore, it is preferable to form a metal plating layer (D) made of copper using the electrolytic plating method.

  Moreover, as the dry plating process, a sputtering method, a vacuum deposition method, or the like can be used. In the sputtering method, an inert gas (mainly argon) is introduced in a vacuum, negative ions are applied to the forming material of the metal plating layer (D) to generate glow discharge, and then the inert gas Atoms are ionized, gas ions are struck violently at the surface of the metal plating layer (D) forming material at high speed, and atoms and molecules constituting the metal plating layer (D) forming material are ejected vigorously. ) To form the metal plating layer (D).

  Examples of the material for forming the metal plating layer (D) by sputtering include chrome, copper, titanium, silver, platinum, gold, nickel-chromium alloy, stainless steel, copper-zinc alloy, indium tin oxide (ITO), and dioxide. Examples include silicon, titanium dioxide, niobium oxide, and zinc oxide.

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

  The thickness of the metal plating layer (D) is preferably in the range of 1 to 50 μm. The thickness of the metal plating layer (D) is adjusted by controlling the processing time, the current density, the usage amount of the plating additive, etc. in the plating process when forming the metal plating layer (D). Can do.

  The laminate of the present invention obtained by the above method can be used as a conductive pattern. When the laminate of the present invention is used for a conductive pattern, in order to form the conductive layer (C) at a position corresponding to a desired pattern shape to be formed, a fluid containing the metal powder is applied, Or the electroconductive pattern which has a desired pattern can be manufactured by printing and baking.

  The conductive pattern may be, for example, a photolithographic etching method such as a subtractive method or a semi-additive method in which a conductive layer (C) or a metal plating layer (D) is etched from a solid metal film to produce a conductive pattern, Or it can manufacture by the method of plating on the printing pattern of a conductive layer (C).

  In the subtractive method, an etching resist layer having a shape corresponding to a desired pattern shape is formed on the metal plating layer (D) constituting the laminate of the present invention that has been manufactured in advance, and by subsequent development processing, In this method, a desired pattern is formed by dissolving and removing the metal plating layer (D) and the conductive layer (C) in the removed portion of the resist with a chemical solution. As the chemical solution, a chemical solution containing copper chloride, iron chloride or the like can be used.

  In the semi-additive method, after the primer layer (B) is formed on the support (A), the conductive layer (C ′) is formed, and if necessary, the conductive layer (C ') After removing the organic compound containing the dispersant present therein, a plating resist layer having a shape corresponding to a desired pattern is formed on the surface of the obtained conductive layer (C), and then electroplating method A method of forming a desired pattern by forming a metal plating layer (D) by an electroless plating method and then dissolving and removing the plating resist layer and the conductive layer (C) in contact therewith in a chemical solution or the like It is.

  In addition, the method of plating on the printed pattern of the conductive layer (C) is to form the primer layer (B) on the support (A), and then the conductive layer (C ′) by an inkjet method, a reverse printing method or the like. After removing the organic compound containing the dispersant present in the conductive layer (C ′) by plasma discharge treatment or the like as necessary, on the surface of the obtained conductive layer (C), In this method, a desired pattern is formed by forming the metal plating layer (D) by electrolytic plating or electroless plating.

  The conductive pattern obtained by the above method is less likely to cause electrochemical migration between wirings of the conductive pattern in a state where voltage is applied under high temperature and high humidity. It can be used for formation of circuit forming substrates used for circuits, etc., organic solar cells, electronic terminals, organic EL devices, organic transistors, flexible printed boards, formation of peripheral wiring constituting RFID, etc., and electromagnetic shielding materials. In particular, it can be suitably used for applications requiring high durability, such as flexible printed circuit board (FPC), tape automatic bonding (TAB), chip-on-film (COF), printed wiring board (PWB), etc. It can be used for an application called a copper clad laminate (CCL: Copper Clad Laminate).

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

[Synthesis Example 1: Production of primer layer resin (1)]
In a four-necked flask equipped with a thermometer, a stirrer, a reflux condenser, and a dropping device, 59.4 parts by mass of hydrogenated dimer diol (“Prepol 2033” manufactured by Croda Japan Co., Ltd., hydroxyl equivalent 271 g / equivalent), 2 , 2-dimethylolpropionic acid 36.7 parts by mass and methyl ethyl ketone (hereinafter abbreviated as “MEK”) 128.9 parts by mass were added and mixed thoroughly. Next, 97.2 parts by mass of isophorone diisocyanate and 0.1 part by mass of stannous octylate were added and reacted at 75 ° C. for 15 hours to obtain a MEK solution of a urethane prepolymer having an isocyanate group at the terminal. Subsequently, 29.5 parts by mass of a 10% by mass MEK solution of diethylenetriamine was added and reacted at 40 ° C. for 1 hour. After cooling, MEK was added so that the nonvolatile content was 2% by mass, and the mixture was filtered through a 200 mesh wire net to obtain a 2% by mass MEK solution of the primer layer resin (1).

[Synthesis Example 2: Production of resin (2) for primer layer]
To a reaction vessel equipped with a stirrer, reflux condenser, nitrogen inlet tube, thermometer, and dropping funnel, 180 parts by mass of ethyl acetate was added, and the temperature was raised to 80 ° C. while blowing nitrogen. Next, while stirring
A monomer mixture of 80 parts by weight of methyl methacrylate, 10 parts by weight of n-butyl methacrylate and 10 parts by weight of 1H, 1H, 5H-octapentylfluoroacrylate, and 1 part by weight of azoisobutyronitrile in 20 parts by weight of ethyl acetate The polymerization initiator solution dissolved in was dripped and polymerized from a separate dropping funnel over 240 minutes while maintaining the temperature in the reaction vessel at 80 ± 1 ° C. After completion of dropping, the mixture was stirred at the same temperature for 120 minutes, and then the temperature in the reaction vessel was cooled to 30 ° C. Next, ethyl acetate was added so that the nonvolatile content was 2% by mass, and the mixture was filtered through a 200 mesh wire net to obtain a 2% by mass ethyl acetate solution of the primer layer resin (2).

[Preparation Example 1: Preparation of fluid (1)]
By dispersing silver particles having an average particle size of 30 nm in a mixed solvent of 45 parts by mass of ethylene glycol and 55 parts by mass of ion-exchanged water using a compound in which polyoxyethylene is added to polyethyleneimine as a dispersant, a nano-sized metal A fluid containing powder and dispersant was prepared. Subsequently, the fluid (1) which is a conductive ink for inkjet printing was prepared by adding ion-exchange water and surfactant to the obtained fluid, and adjusting a viscosity to 10 mPa * s.

<Measurement method of surface free energy of primer layer>
The surface free energy of the primer layer was determined by measurement and calculation by the following method. The contact angle when droplets of ion-exchanged water, ethylene glycol and diiodomethane were dropped on the surface of the primer layer was measured using a contact angle meter (“Drop Master 700” manufactured by Kyowa Interface Science Co., Ltd.). In addition, the value shown in said Table 1 was used for the surface free energy of ion-exchange water, ethylene glycol, and diiodomethane. The surface free energies γ ^LW , γ ⁺ , and γ ⁻ of the substrate are calculated by substituting the contact angles of the respective solvents into the above equation (1) and solving the simultaneous equations, and further, the above equation (2 The surface free energy γ ^tot was calculated by substituting the calculated γ ^LW , γ ⁺ , and γ ⁻ for).

[Example 1: Production of laminate (1)]
Spin the 2% by mass MEK solution of the primer layer resin (1) obtained in Synthesis Example 1 on the surface of a support made of a polyimide film (“Kapton150EN-C” manufactured by Toray DuPont Co., Ltd., thickness 50 μm). Using a coater, coating was performed so that the thickness after drying was 0.1 μm. Next, a primer layer was formed on the surface of the polyimide film by drying at 120 ° C. for 5 minutes using a hot air dryer. The surface free energy of this primer layer was 28 mJ / m ² .

  Next, the fluid (1) obtained in Preparation Example 1 was used on the surface of the primer layer using an inkjet printer (“Inkjet Testing Machine EB100” manufactured by Konica Minolta, Inc., evaluation printer head KM512L, discharge amount 42 pL). As shown in FIG. 1, a comb electrode was produced. The line width was 90 μm and the line width was 110 μm, and 10 wires on one side and 20 wires in total on both sides were alternately arranged. The overlap margin was 10 mm, and the distance (d) from the tip of the comb wiring to the other comb was 5 mm. Next, by baking at 250 ° C. for 30 minutes, a silver layer (thickness: about 0.2 μm) corresponding to the conductive layer (C) was formed.

Next, electroplating is performed for 15 minutes at a current density of 2 A / dm ² using an electroplating solution containing copper sulfate using the conductive layer (C) obtained above as a cathode, phosphorous copper as an anode, and copper sulfate. A copper plating layer having a thickness of 10 μm was laminated on the surface of the silver layer. In order to grow isotropically in the thickness direction and the lateral direction, it was confirmed that the line width of the comb electrode after plating was 100 μm and the width between lines was 100 μm, and a laminate (1) was obtained. As the electrolytic plating solution, 70 g / L of copper sulfate, 200 g / L of sulfuric acid, 50 mg / L of chloride ions, and 5 ml / L of additives (“Top Lucina SF-M” manufactured by Okuno Pharmaceutical Co., Ltd.) were used.

[Example 2: Production of laminate (2)]
Example 1 except that a 2% by mass ethyl acetate solution of the primer layer resin (2) obtained in Synthesis Example 2 was used instead of the 2% by mass MEK solution of the primer layer resin (1) used in Example 1. In the same manner as above, a laminate (2) was obtained. The surface free energy of this primer layer was 20 mJ / m ² .

[Example 3]
A 2% by mass MEK solution of the primer layer resin (1) obtained in Synthesis Example 1 is applied to the surface of a support made of a polyimide film (“Kapton 150EN-C” manufactured by Toray DuPont Co., Ltd., thickness 38 μm). Was applied so that the thickness after drying was 0.1 μm. Next, a primer layer was formed on the surface of the polyimide film by drying at 120 ° C. for 5 minutes using a hot air dryer. Further, the surface of the primer layer was subjected to corona treatment with a corona surface modification evaluation apparatus (“TEC-4AX” manufactured by Kasuga Denki Co., Ltd.). The primer layer after the corona treatment was hydrophilized, and its surface free energy was 45 mJ / m ² .

  Next, the fluid (1) obtained in Preparation Example 1 was used on the surface of the primer layer using an inkjet printer (“Inkjet Testing Machine EB100” manufactured by Konica Minolta, Inc., evaluation printer head KM512L, discharge amount 42 pL). As shown in FIG. 1, a comb electrode was produced. The line width was 90 μm and the line width was 110 μm, and 10 wires on one side and 20 wires in total on both sides were alternately arranged. The overlap margin was 10 mm, and the distance (d) from the tip of the comb wiring to the other comb was 5 mm. Next, by baking at 250 ° C. for 30 minutes, a silver layer (thickness: about 0.2 μm) corresponding to the conductive layer (C) was formed.

Next, electroplating is performed for 15 minutes at a current density of 2 A / dm ² using an electroplating solution containing copper sulfate using the conductive layer (C) obtained above as a cathode, phosphorous copper as an anode, and copper sulfate. A copper plating layer having a thickness of 10 μm was laminated on the surface of the silver layer. In order to grow isotropically in the thickness direction and the lateral direction, it was confirmed that the comb electrode had a line width of 100 μm and a line-to-line width of 100 μm after plating, and a laminate 3 was obtained. As the electrolytic plating solution, 70 g / L of copper sulfate, 200 g / L of sulfuric acid, 50 mg / L of chloride ions, and 5 ml / L of additives (“Top Lucina SF-M” manufactured by Okuno Pharmaceutical Co., Ltd.) were used.

[Comparative Example 1]
A laminate (R1) was obtained in the same manner as in Example 1 except that the conductive layer (C) was directly provided on the polyimide film without using the primer layer resin (1) used in Example 1. The surface free energy of the polyimide film was 48 mJ / m ² .
[Comparative Example 2]
In place of the primer layer resin (1) used in Example 1, a primer layer is formed using a polytetrafluoroethylene resin solution ("AF2400S" manufactured by Mitsui DuPont Fluorochemical Co., Ltd.) adjusted to 2% by mass of non-volatility. Except having done, it carried out similarly to Example 1 and obtained the laminated body (R2). The surface free energy of the polytetrafluoroethylene primer layer was 10 mJ / m ² .

<Electrochemical migration evaluation method>
As a test apparatus, temperature and humidity were adjusted with “SH-641” manufactured by Espec Co., Ltd., and a resistance value was measured with “AMI” manufactured by Espec Co., Ltd. After raising the temperature from room temperature to 85 ° C., the humidity was adjusted to 85%. The voltage was applied at a DC voltage of 50 V, and the test was performed up to 1000 hours. In addition, it determined with having short-circuited when the resistance value became 1 × 10 ⁶ Ω or less.

  It was confirmed that the laminates (1) to (3) obtained in Examples 1 to 3 which are the laminates of the present invention have reliability that does not short-circuit for a long time even in an environment of high temperature and high humidity.

On the other hand, the laminate (R1) of Comparative Example 1 is an example in which the primer layer was not provided, but a short circuit occurred in a short time of 1 hour, and it was confirmed that the reliability was poor. Further, the laminate (R2) of Comparative Example 2 is a primer layer of tetrafluoroethylene of 10 mJ / m ² which is less than 20 mJ / m ² which is the lower limit of the surface free energy of the primer layer (B) defined in the present invention. In this example, it was confirmed that there was a problem that the wiring easily peeled off in a very short time under a high temperature and high humidity environment.

Claims (7)

A laminate in which a primer layer (B), a conductive layer (C) and a metal plating layer (D) are sequentially formed on a support (A), and the surface free energy of the primer layer (B) is 20 to A laminate having a range of 45 mJ / m ² . The laminate according to claim 1, wherein the primer layer (B) contains a resin having a structure represented by the following general formula (I).
(In general formula (I), R ¹ and R ² each independently represent an alkyl group, and m and n each independently represent an integer of 1 to 20)   The laminate according to claim 2, wherein the primer layer (B) contains a urethane resin having a structure represented by the general formula (I).   The laminate according to claim 1, wherein the primer layer (B) contains an acrylic resin having a fluorine atom.   The laminate according to claim 1, wherein the metal constituting the conductive layer (C) is silver and the metal constituting the metal plating layer (D) is copper.   It consists of a laminated body of any one of Claims 1-5, The electroconductive pattern characterized by the above-mentioned.   An electronic circuit comprising the conductive pattern according to claim 6.