WO2013172229A1 - Motif conducteur, circuit conducteur et procédé permettant de produire un motif conducteur - Google Patents

Motif conducteur, circuit conducteur et procédé permettant de produire un motif conducteur Download PDF

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Publication number
WO2013172229A1
WO2013172229A1 PCT/JP2013/062910 JP2013062910W WO2013172229A1 WO 2013172229 A1 WO2013172229 A1 WO 2013172229A1 JP 2013062910 W JP2013062910 W JP 2013062910W WO 2013172229 A1 WO2013172229 A1 WO 2013172229A1
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WIPO (PCT)
Prior art keywords
mass
primer
coating film
conductive pattern
group
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PCT/JP2013/062910
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English (en)
Japanese (ja)
Inventor
公恵 斉藤
白髪　潤
村川　昭
亘 冨士川
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Dic株式会社
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Application filed by Dic株式会社 filed Critical Dic株式会社
Priority to JP2014514965A priority Critical patent/JPWO2013172229A1/ja
Publication of WO2013172229A1 publication Critical patent/WO2013172229A1/fr

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Classifications

    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
    • H05K3/386—Improvement of the adhesion between the insulating substrate and the metal by the use of an organic polymeric bonding layer, e.g. adhesive
    • H05K3/387—Improvement of the adhesion between the insulating substrate and the metal by the use of an organic polymeric bonding layer, e.g. adhesive for electroless plating

Definitions

  • the present invention relates to a laminate of a conductive pattern or the like that can be used for manufacturing an electromagnetic wave shield, an integrated circuit, an organic transistor, or the like.
  • the conductive pattern that can be used for the electronic circuit is to apply (print) conductive ink containing a conductive material such as silver on the surface of the support by various printing methods, and to heat as necessary. Can be manufactured by.
  • the conductive ink is directly applied to the surface of various supports, the conductive ink is difficult to adhere to the surface of the support, and thus easily peels off, and finally the disconnection of an electronic circuit or the like obtained Etc. may be caused.
  • the support made of polyimide resin or polyethylene terephthalate resin is relatively flexible, it can be used for the production of a foldable flexible device. For this reason, they are easy to peel off when bent, and as a result, there is a case where the finally obtained electronic circuit or the like is disconnected.
  • the conductive pattern obtained by the above method may not be sufficient in terms of the adhesion between the ink receiving layer and the conductive ink
  • the conductive pattern obtained by peeling of the conductive substance contained in the conductive ink may be used. There was a case of causing a decline in sex.
  • the printed matter obtained by printing etc. using a conductive ink in order to contact the conductive substances contained in a conductive ink and to provide electroconductivity. are often heated at a relatively high temperature.
  • the ink receiving layer such as the latex layer described in Document 1
  • the adhesion at the interface between the ink receiving layer and the support is not easily affected.
  • the conductive pattern is lost (such as cracks).
  • the support is deformed due to the influence of the high heat, which may cause an increase in resistance value (decrease in conductivity) of the conductive pattern.
  • the problem to be solved by the present invention is that the conductive material has excellent adhesion so that it does not peel from the primer layer (X) with time, and has low resistance and excellent conductivity. Is to provide a pattern.
  • the present inventors combined a fluid (a) having a specific composition and a specific primer (x) that forms a primer layer (X) capable of receiving the fluid (a). It has been found that the problem can be solved when used.
  • the present invention applies a primer to a part or all of the surface of the support, and then applies the following general formula (I) to a part or all of the surface of the coating film (x) formed using the primer.
  • the support obtained by applying the fluid (a) containing the polyhydric alcohol (a1) containing the diol (a1-1) having the structure represented by (2) and the conductive substance (a2) and then heating.
  • a conductive pattern in which a body, a primer layer (X) formed by heating the coating film (x), and a layer (Y) containing the conductive substance (a2) are laminated
  • the conductive film (x) relates to a conductive pattern characterized in that it absorbs 20% by mass to 500% by mass with respect to the mass of the coated film (x) in an environment of 25 ° C. is there.
  • the conductive pattern of the present invention has excellent adhesion at a level that does not cause peeling of the conductive substance (a2) over time, and has excellent conductivity.
  • formation of an electronic circuit Organic solar cells, electronic book terminals, organic EL, organic transistors, flexible printed circuit boards, non-contact IC cards and other layers constituting RFID, etc., formation of peripheral wiring, plasma display electromagnetic wave shielding wiring, integrated circuits, organic transistors It can be used in new fields such as manufacturing, generally referred to as the printed electronics field.
  • a primer is applied to a part or all of the surface of the support, and then a part or all of the surface of the coating film (x) formed using the primer is represented by the following general formula. Obtained by applying a fluid (a) containing a polyhydric alcohol (a1) containing a diol (a1-1) having the structure represented by (I) and a conductive substance (a2) and then heating.
  • a fluid (a) containing a polyhydric alcohol (a1) containing a diol (a1-1) having the structure represented by (I) and a conductive substance (a2) and then heating.
  • a conductive pattern in which a support, a primer layer (X) formed by heating the coating film (x), and a layer (Y) containing the conductive substance (a2) are laminated.
  • the coating film (x) absorbs 20 mass% to 500 mass% of ethanol in an environment of 25 ° C. with respect to the mass of the coating film (x) before applying the fluid (a). It is characterized by
  • the conductive pattern of the present invention comprises at least a support, a primer layer (X), and a layer (Y) containing a conductive substance (a2).
  • the primer layer (X) is formed by heating a coating film (x) formed using a primer described later.
  • the primer layer (X) adheres the support to the conductive material (a2) such as silver contained in the fluid (a) such as conductive ink.
  • the coating film (x) which is a precursor of the primer layer (X) and is formed using a primer, is in contact with the fluid (a) when the fluid (a) contacts the surface.
  • the conductive material (a2) contained in the fluid (a) is supported on the surface of the coating film (x), whereby the support and the conductive material ( Adhesion with a2) is improved.
  • a conductive pattern including a layer (Y) made of the conductive substance (a2) supported on the surface of the primer layer (X) is formed.
  • the primer layer (X) may be provided on a part or all of the surface of the support, or may be provided on one side or both sides of the support.
  • the conductive pattern has a primer layer (X) on the entire surface of the support, and a layer containing the conductive substance (a2) only in a necessary portion of the primer layer (X) ( Those having Y) can be used.
  • the electroconductive pattern in which the said primer layer (X) was provided only in the part in which the said layer (Y) is provided among the surfaces of a support body may be sufficient.
  • the thickness is preferably approximately 0.01 ⁇ m to 300 ⁇ m, and more preferably 0.05 ⁇ m to 20 ⁇ m.
  • the layer (Y) is a layer composed of the conductive substance (a2) contained in the fluid (a), and has a role as a conductive layer or a plating nucleus layer.
  • the layer (Y) is a conductive ink containing silver as the fluid (a)
  • the layer (Y) is formed on a conductive layer or a plating nucleus layer composed of silver contained in the conductive ink. It corresponds to a printed image or pattern made of silver.
  • the layer (Y) is mainly composed of the conductive substance (a2), but other components contained in the fluid (a), for example, the diol (a1-1) represented by the general formula (I)
  • the polyhydric alcohol (a1) etc. may remain in the layer (Y).
  • the layer (Y) may be a layer provided on the entire surface of the primer layer (X), or may be a layer provided on a part of the surface of the primer layer (X). .
  • the layer (Y) present on a part of the surface of the primer layer (X) refers to a fine line-shaped layer formed on the surface of the primer layer (X).
  • the thin line layer is suitable when the conductive pattern of the present invention is used as an electric circuit or the like.
  • the width (line width) of the thin-line layer (pattern) is about 0.01 ⁇ m to 200 ⁇ m, preferably about 0.01 ⁇ m to 150 ⁇ m, from the viewpoint of increasing the density of the conductive pattern.
  • the layer (Y) preferably has a thickness of 0.01 ⁇ m to 100 ⁇ m in order to form a conductive pattern having low resistance and excellent conductivity.
  • the thickness (height) is preferably in the range of 0.1 ⁇ m to 50 ⁇ m.
  • the support which comprises the electroconductive pattern of this invention is demonstrated.
  • the support used in the present invention include acrylic resins such as polyimide resin, polyamideimide resin, polyamide resin, polyethylene terephthalate, polyethylene naphthalate, polycarbonate, acrylonitrile-butadiene-styrene (ABS), and poly (meth) methyl acrylate.
  • ABS acrylonitrile-butadiene-styrene
  • a synthetic fiber such as polyester fiber, polyamide fiber or aramid fiber; a natural fiber such as cotton or hemp can be used.
  • the fibers may be processed in advance.
  • the support generally used as a support in forming a conductive pattern such as a circuit board, from polyimide resin, polyethylene terephthalate, polyethylene naphthalate, glass, cellulose nanofiber, etc. It is preferable to use a support.
  • the support when used for applications that require flexibility, it is possible to use a material that is relatively flexible and capable of being bent. It is preferable for obtaining a final product. Specifically, it is preferable to use a film or sheet-like support formed by uniaxial stretching or the like.
  • the film or sheet-like support examples include a polyethylene terephthalate film, a polyimide film, and a polyethylene naphthalate film.
  • the support preferably has a thickness of about 1 ⁇ m to 2,000 ⁇ m from the viewpoint of reducing the weight and thickness of the conductive pattern and the final product in which it is used, and about 1 ⁇ m to 200 ⁇ m. More preferably, it is a thickness.
  • the laminate is required to be relatively flexible, it is preferable to use a laminate having a thickness of about 1 ⁇ m to 80 ⁇ m.
  • the conductive pattern of the invention is the thickness of the constituent parts other than the support, specifically, the total of the primer layer (X) and the layer (Y).
  • the thickness is preferably in the range of 0.01 ⁇ m to 300 ⁇ m, more preferably 0.05 ⁇ m to 80 ⁇ m.
  • the fluid (a) used for production of the conductive pattern of the present invention includes a polyhydric alcohol (a1) containing a diol (a1-1) having a structure represented by the following general formula (I), a conductive substance (a2), and a solvent if necessary. It contains an additive.
  • the fluid (a) has a viscosity measured at about 23 ° C. with an E-type viscometer (TVE-22LT, manufactured by Toki Sangyo Co., Ltd.) of 0.1 mPa ⁇ s to 500,000 mPa ⁇ s.
  • the liquid is preferably 0.5 mPa ⁇ s to 10,000 mPa ⁇ s, more preferably a liquid or viscous liquid.
  • the fluid (a) When the fluid (a) is applied (printed) to a desired position by an inkjet printing method, an offset printing method, a gravure printing method, a flexographic printing method, or the like, which will be described later, it is approximately 5 mPa ⁇ s to 1,000 mPa ⁇ It is preferable to use a fluid adjusted to a viscosity in the range of s.
  • the fluid (a) include a conductive ink and a plating nucleating agent that can be used when plating is performed.
  • the diol (a1-1) As the polyhydric alcohol (a1) containing the diol (a1-1) used in the fluid (a), the diol (a1-1) is essential, and other polyhydric alcohols are included as necessary. Can be used.
  • the diol (a1-1) can improve the temporal stability of the fluid (a).
  • the diol (a1-1) improves the adhesion and conductivity of the conductive pattern of the present invention by using in combination with the coating film (x) that can form the primer layer (X). be able to.
  • the diol (a1-1) can also improve the discharge stability of the fluid (a) when the fluid (a) is discharged by an ink jet method.
  • R in the general formula (I) is a hydrogen atom or an alkyl group
  • the alkyl group is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms. And more preferably 1 to 3 alkyl groups.
  • the layer (Y) formed by the conductive material (a2) contained in the fluid (a) is at a level that does not cause peeling from the primer layer (X).
  • R in the general formula (I) is a hydrogen atom in order to obtain a conductive pattern having better adhesion, no cracks in the depicted conductive pattern, and even better conductivity 1,3-butylene glycol or isoprene glycol in which R is an alkyl group is preferably used.
  • the diol (a1-1) is preferably contained in the range of 5% by mass to 60% by mass and more preferably in the range of 15% by mass to 50% by mass with respect to the total amount of the fluid (a). Preferably, it is contained in the range of 20% by mass to 40% by mass in order to improve the discharge stability of the fluid (a) and form a wiring pattern having excellent conductivity.
  • polyhydric alcohols that can be used in combination with the diol (a1-1)
  • conventionally known polyhydric alcohols can be used, such as 2-ethyl-1,3-hexanediol, ethylene glycol, and the like.
  • Diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, 1,2-butanediol, 1,4-butanediol, 2,3-butanediol, glycerin and the like can be used.
  • a transition metal or a compound thereof can be used as the conductive substance (a2).
  • an ionic transition metal for example, it is preferable to use a transition metal such as copper, silver, gold, nickel, palladium, platinum, cobalt, and to use copper, silver, gold, or the like. Further, it is more preferable because a conductive pattern having a low electric resistance and strong against corrosion can be formed, and it is more preferable to use silver.
  • the conductive material (a2) is a metal particle composed of a transition metal as described above, and the surface is formed by an oxide or an organic substance of the transition metal.
  • One or more types of coated ones can be used.
  • the transition metal oxide is usually in an inactive (insulating) state, even if a fluid containing it is simply applied to the surface of the support, it may not exhibit conductivity. Many. Therefore, when the fluid containing the oxide is applied to the surface of the support, the transition metal is exposed and activated by treating the surface with a reducing agent such as dimethylaminoborane. It is possible to form a layer having conductivity.
  • examples of the metal whose surface is coated with the organic substance include those in which a metal is contained in resin particles (organic substance) formed by an emulsion polymerization method or the like. Like the transition metal oxides, these are usually in an inactive (insulating) state. Therefore, even if a fluid containing the same is simply applied to the surface of the support, it exhibits conductivity. Often not. Therefore, when a fluid containing a metal surface-coated with the organic material is applied to the surface of the support, the transition metal is exposed by irradiating the surface with a laser or the like and removing the organic material. Thus, a layer having activity (conductivity) can be formed.
  • a particulate material having an average particle diameter of about 1 nm to 100 nm is preferably used, and a material having an average particle diameter of 1 nm to 50 nm is preferably used.
  • the “average particle size” is a volume average value measured by a dynamic light scattering method after diluting the conductive substance (a2) with a dispersion good solvent. For this measurement, Nanotrac UPA-150 manufactured by Microtrac can be used.
  • the conductive substance (a2) is preferably contained in the range of 5% by mass to 90% by mass with respect to the total amount of the fluid (a) used in the present invention. More preferably, it is contained in the range of 10% by mass to 60% by mass, and particularly preferably in the range of 20% by mass to 40% by mass.
  • the fluid preferably contains a solvent from the viewpoint of improving ease of application and the like.
  • a solvent an organic solvent or an aqueous medium can be used.
  • an aqueous medium such as distilled water, ion-exchanged water, pure water, and ultrapure water
  • organic solvents such as alcohol, ether, ester, and ketone
  • Examples of the alcohol include methanol, ethanol, n-propanol, isopropyl alcohol, n-butanol, isobutyl alcohol, sec-butanol, tert-butanol, heptanol, hexanol, octanol, nonanol, decanol, undecanol, dodecanol, tridecanol, tetradecanol, and tetradecanol.
  • the fluid (a) may be, if necessary, a ketone solvent such as acetone, cyclohexanone, methyl ethyl ketone, ethyl acetate, butyl acetate, 3-methoxybutyl acetate, 3-methoxy-3- Ester solvents such as methyl-butyl acetate, hydrocarbon solvents such as toluene, octane, nonane, decane, dodecane, tridecane, tetradecane, cyclooctane, xylene, mesitylene, ethylbenzene, dodecylbenzene, tetralin, trimethylbenzenecyclohexane, mineral spirit, solvent A solvent such as naphtha can also be used in combination.
  • a ketone solvent such as acetone, cyclohexanone, methyl ethyl ketone, ethyl acetate, buty
  • the fluid (a) of the present invention can be produced, for example, by mixing the polyhydric alcohol (a1), the conductive substance (a2) and, if necessary, the solvent. Among them, by producing a composition containing the conductive substance (a2) and the solvent, and then mixing the composition and the polyhydric alcohol (a1) containing the diol (a1-1) It is more preferable to improve the dispersion stability of the conductive substance and prevent the occurrence of cracks in the layer (Y).
  • composition containing the conductive substance (a2) and the solvent a dispersion in which the conductive substance (a2) is dispersed in a solvent such as the aqueous medium or the organic solvent can be used.
  • the dispersion can be produced by mixing and stirring the conductive substance (a2) and the solvent.
  • SW1000 manufactured by Bando Chemical Co., Ltd.
  • Silk Auto A-1 manufactured by Mitsubishi Materials Corporation
  • MDot-SLP manufactured by Mitsuboshi Belting Co., Ltd.
  • an apparatus such as a mixer, a disper, a bead mill, or an ultrasonic homogenizer can be used.
  • the fluid (a) used in the present invention further improves the dispersion stability of the conductive substance (a2) in the solvent, and also on the surface of the coating film (x) of the fluid (a).
  • a surfactant, an antifoaming agent, a rheology adjusting agent and the like may be contained.
  • the fluid (a) from the viewpoint of removing impurities and the like after being manufactured by the above-described method, a fluid filtered using a micropore filter or the like, or a material processed using a centrifugal separator or the like is used. You can also
  • the primer forms a coating film (x) that can carry the conductive substance (a2) contained in the fluid (a) and can form the conductive pattern layer (Y) of the present invention. is there.
  • any primer can be used as long as it can form a coating film (x) capable of absorbing ethanol in an environment of 25 ° C. by 20 mass% to 500 mass% with respect to the mass of the coating film (x). Things can also be used.
  • the primer capable of forming the coating film (x) those containing various resins and solvents can be used.
  • the resin examples include urethane resin (x1), vinyl resin (x2), urethane-vinyl composite resin (x3), phenol resin, epoxy resin, melamine resin, urea resin, unsaturated polyester resin, alkyd resin, polyimide resin, A fluororesin or the like can be used.
  • the resin examples include a urethane resin having a polycarbonate structure as the urethane resin (x1), a urethane resin having an aliphatic polyester structure, an acrylic resin having a structural unit derived from methyl methacrylate as the vinyl resin (x2), and
  • the use of one or more resins (x-1) selected from the group consisting of urethane-acrylic composite resins as the urethane-vinyl composite resin (x3) results in a coating film (x ) Is preferable, and it is more preferable to use a urethane-acrylic composite resin.
  • the primer it is preferable to use a primer containing 10% by mass to 70% by mass of the resin with respect to the whole primer, in order to maintain ease of application and the like, and it contains 10% by mass to 50% by mass. It is more preferable to use one.
  • solvent that can be used for the primer various organic solvents and aqueous media can be used.
  • organic solvent for example, toluene, ethyl acetate, methyl ethyl ketone and the like can be used.
  • aqueous medium include water, organic solvents miscible with water, and mixtures thereof.
  • organic solvent miscible with water examples include alcohols such as methanol, ethanol, n-propanol, isopropanol, ethyl carbitol, ethyl cellosolve, and butyl cellosolve; ketones such as acetone and methyl ethyl ketone; and polymers such as ethylene glycol, diethylene glycol, and propylene glycol.
  • alcohols such as methanol, ethanol, n-propanol, isopropanol, ethyl carbitol, ethyl cellosolve, and butyl cellosolve
  • ketones such as acetone and methyl ethyl ketone
  • polymers such as ethylene glycol, diethylene glycol, and propylene glycol.
  • alkylene glycols alkyl ethers of polyalkylene glycols
  • lactams such as N-methyl-2-pyrrolidone.
  • only water may be used, or a mixture of water and an organic solvent miscible with water may be used, or only an organic solvent miscible with water may be used.
  • the primer it is preferable to use a primer containing 25% by mass to 90% by mass of the solvent with respect to the whole primer, in order to maintain ease of application, etc., and it contains 50% by mass to 85% by mass. It is more preferable to use one.
  • a resin having a hydrophilic group is used as the resin in order to impart good water dispersibility to the primer and improve its storage stability.
  • hydrophilic group examples include an anionic group, a cationic group, and a nonionic group.
  • anionic group for example, a carboxyl group, a carboxylate group, a sulfonic acid group, a sulfonate group, and the like can be used.
  • a sulfonate group it is preferable to use in order to impart good water dispersibility.
  • Examples of basic compounds that can be used for neutralizing the anionic group include organic amines such as ammonia, triethylamine, pyridine, and morpholine; alkanolamines such as monoethanolamine; metal bases including sodium, potassium, lithium, calcium, and the like Compounds and the like.
  • organic amines such as ammonia, triethylamine, pyridine, and morpholine
  • alkanolamines such as monoethanolamine
  • metal bases including sodium, potassium, lithium, calcium, and the like Compounds and the like.
  • the carboxylate group or sulfonate group When used as the anionic group, they are present in the range of 50 mmol / kg to 2,000 mmol / kg with respect to the whole resin, so that the resin has good water dispersion stability. It is preferable for maintaining the property.
  • a tertiary amino group etc. can be used, for example.
  • the acid that can be used for neutralizing part or all of the tertiary amino group include organic acids such as acetic acid, propionic acid, lactic acid, and maleic acid; organic acids such as sulfonic acid and methanesulfonic acid. Sulfonic acid; inorganic acids such as hydrochloric acid, sulfuric acid, orthophosphoric acid and orthophosphorous acid can be used alone or in combination of two or more.
  • organic acids such as acetic acid, propionic acid, lactic acid, maleic acid, or the like because the chlorine and sulfur may slightly inhibit the conductivity and the like.
  • nonionic group for example, polyoxyalkylene groups such as polyoxyethylene group, poly (oxyethylene-oxypropylene) group, and polyoxyethylene-polyoxypropylene group can be used.
  • polyoxyalkylene groups such as polyoxyethylene group, poly (oxyethylene-oxypropylene) group, and polyoxyethylene-polyoxypropylene group
  • urethane resin (x1) that can be used as the resin contained in the primer, a urethane resin obtained by reacting a polyol, a polyisocyanate, and, if necessary, a chain extender can be used.
  • a urethane resin which has a polycarbonate structure and the urethane resin which has an aliphatic polyester structure from a viewpoint of forming the coating film (x) provided with the absorptivity of the said predetermined
  • the polycarbonate structure and the aliphatic polyester structure are structures derived from a polyol used for producing the urethane resin.
  • the urethane resin having the polycarbonate structure can be produced by using a resin containing a polycarbonate polyol described later as the polyol.
  • the urethane resin which has the said aliphatic polyester structure can be manufactured by using what contains the aliphatic polyester polyol mentioned later as the said polyol.
  • polystyrene resin (x1) As the polyol that can be used for the production of the urethane resin (x1), as described above, polycarbonate polyol, aliphatic polyester polyol, and the like can be used. Moreover, as said polyol, another polyol can be combined and used as needed.
  • polycarbonate polyol for example, those obtained by reacting a carbonate with a polyol, or those obtained by reacting phosgene with bisphenol A or the like can be used.
  • carbonate ester methyl carbonate, dimethyl carbonate, ethyl carbonate, diethyl carbonate, cyclocarbonate, diphenyl carbonate and the like can be used.
  • polyol that can react with the carbonate ester examples 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-
  • aliphatic polyester polyol examples include an aliphatic polyester polyol obtained by esterification reaction of a low molecular weight polyol and a polycarboxylic acid; a ring-opening polymerization reaction of a cyclic ester compound such as ⁇ -caprolactone or ⁇ -butyrolactone. Aliphatic polyesters obtained as above; these copolyesters can be used.
  • Examples of the low molecular weight polyol that can be used in the production of the polyester polyol include ethylene glycol, 1,2-propanediol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, 3- Methyl-1,5-pentanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, glycerin, trimethylolpropane and the like can be used alone or in combination of two or more thereof.
  • Ethylene glycol 1,2-propanediol
  • 1,3-butanediol or 1,4-butanediol in combination with 3-methyl-1,5-pentanediol or neopentyl glycol.
  • polycarboxylic acid examples include succinic acid, adipic acid, sebacic acid, dodecanedicarboxylic acid, azelaic acid and anhydrides or ester-forming derivatives thereof, and aliphatic polycarboxylic acids such as adipic acid can be used. It is preferable to use it.
  • the polycarbonate polyol and aliphatic polyester polyol preferably have a number average molecular weight of 500 to 4,000, more preferably 500 to 2,000.
  • polyol that can be used in the production of the urethane resin (x1)
  • other polyols can be used in combination with the above-described ones as necessary.
  • Examples of the other polyol include ethylene glycol, 1,2-propanediol, 1,3-butanediol, 1,4-butanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, neopentyl glycol, diethylene glycol, dipropylene glycol, glycerin, trimethylolpropane, and the like are acrylic polyols having a hydroxyl group introduced into an acrylic copolymer, and copolymers of butadiene having a hydroxyl group in the molecule.
  • Polybutadiene polyol, hydrogenated polybutadiene polyol, partially saponified product of ethylene-vinyl acetate copolymer, and the like can be used as appropriate.
  • a polyol having a hydrophilic group As the urethane resin (x1), it is preferable to use a polyol having a hydrophilic group as the other polyol.
  • polyol having a hydrophilic group examples include a polyol having a carboxyl group such as 2,2-dimethylolpropionic acid, 2,2′-dimethylolbutanoic acid, 2,2-dimethylolvaleric acid, and the like; 5-sulfoisophthalic acid Polyols having a sulfonic acid group such as sulfoterephthalic acid, 4-sulfophthalic acid, and 5 [4-sulfophenoxy] isophthalic acid can be used.
  • polyol having a hydrophilic group a polyester polyol having a hydrophilic group obtained by reacting the above-described polyol having a low molecular weight hydrophilic group with various polycarboxylic acids such as adipic acid is used. You can also
  • Examples of the polyisocyanate that can react with the polyol to form a urethane resin include 4,4′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate, carbodiimide-modified diphenylmethane diisocyanate, crude diphenylmethane diisocyanate, phenylene diisocyanate, tolylene diisocyanate, and naphthalene.
  • Polyisocyanates having an aromatic structure such as diisocyanate; aliphatic polyisocyanates such as hexamethylene diisocyanate, lysine diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, or aliphatic cyclic structures Po It is possible to use the isocyanate.
  • aliphatic polyisocyanates such as hexamethylene diisocyanate, lysine diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, or aliphatic cyclic structures Po It is possible to use the isocyanate
  • chain extender that can be used when producing the urethane resin
  • polyamine, hydrazine compounds, and other compounds having active hydrogen atoms can be used.
  • polyamine examples include ethylenediamine, 1,2-propanediamine, 1,6-hexamethylenediamine, piperazine, 2,5-dimethylpiperazine, isophoronediamine, 4,4'-dicyclohexylmethanediamine, 3,3'- Diamines such as dimethyl-4,4′-dicyclohexylmethanediamine, 1,4-cyclohexanediamine; N-hydroxymethylaminoethylamine, N-hydroxyethylaminoethylamine, N-hydroxypropylaminopropylamine, N-ethylaminoethylamine, N -Methylaminopropylamine, diethylenetriamine, dipropylenetriamine, triethylenetetramine, etc. can be used, preferably ethylenediamine.
  • hydrazine compound examples include hydrazine, N, N′-dimethylhydrazine, 1,6-hexamethylenebishydrazine, succinic acid dihydrazide, adipic acid dihydrazide, glutaric acid dihydrazide, sebacic acid dihydrazide, isophthalic acid dihydrazide, ⁇ -semicarbazide propion Acid hydrazide, 3-semicarbazide-propyl-carbazate, semicarbazide-3-semicarbazide methyl-3,5,5-trimethylcyclohexane can be used.
  • Examples of the other active hydrogen-containing compounds include ethylene glycol, diethylene recall, triethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, hexamethylene glycol, Glycols such as saccharose, methylene glycol, glycerin, sorbitol; phenols such as bisphenol A, 4,4′-dihydroxydiphenyl, 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxydiphenylsulfone, hydrogenated bisphenol A, hydroquinone, Water or the like can be used.
  • the chain extender is preferably used, for example, in such a range that the equivalent ratio between the amino group of the polyamine and the isocyanate group is 1.9 or less (equivalent ratio), and 0.3 to 1 (equivalent ratio) It is more preferable to use in the range.
  • the urethane resin (x1) is produced, for example, by reacting the polyol, the polyisocyanate, and, if necessary, the chain extender by a conventionally known method in the absence of a solvent or in the presence of an organic solvent. can do.
  • reaction temperature 50 ° C. to 120 ° C., more preferably 80 ° C. to 100 ° C.
  • reaction temperature 50 ° C. to 120 ° C., more preferably 80 ° C. to 100 ° C.
  • reaction temperature 50 ° C. to 120 ° C., more preferably 80 ° C. to 100 ° C.
  • the primer containing the water dispersion of the said urethane resin (x1) manufactures a urethane resin (x1) by making the said polyol, the said polyisocyanate, and a chain extender react as needed by the above-mentioned method. If necessary, after neutralizing a part or all of hydrophilic groups such as anionic groups of the urethane resin (x1), it is mixed with an aqueous medium used as a solvent for the primer. Thus, a primer composed of an aqueous dispersion of urethane resin (x1) in which urethane resin (x1) is dispersed or partially dissolved in an aqueous medium can be obtained.
  • a urethane prepolymer having an isocyanate group at the terminal is produced, and if necessary, the anionic group possessed by the urethane prepolymer.
  • the urethane resin (x1) is mixed with an aqueous medium and, if necessary, chain-extended using the chain extender, whereby the urethane resin (x1) becomes an aqueous medium.
  • a primer composed of an aqueous dispersion of urethane resin (x1) dispersed or dissolved therein can be obtained.
  • the reaction between the polyisocyanate and the polyol is preferably performed, for example, in a range where the equivalent ratio of the isocyanate group of the polyisocyanate and the hydroxyl group of the polyol [isocyanate group / hydroxyl group] is 0.9 to 2.
  • an organic solvent can also be used as a solvent as above-mentioned.
  • the organic solvent include ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran and dioxane; acetic esters such as ethyl acetate and butyl acetate; nitriles such as acetonitrile; amides such as dimethylformamide and N-methylpyrrolidone. Can do.
  • the organic solvent is preferably removed by distillation or the like after the production of the urethane resin (x1). However, when the primer containing the urethane resin (x1) and the organic solvent is used, the organic solvent used when the urethane resin (x1) is produced is used as the primer solvent. May be.
  • the urethane resin (x1) it is preferable to use a resin having a weight average molecular weight of 5,000 to 500,000 in order to form a conductive pattern having excellent adhesion and excellent conductivity. 20,000 to 100,000 are more preferable.
  • urethane resin (x1) those having various functional groups can be used as necessary.
  • the functional group include crosslinkable functional groups such as an alkoxysilyl group, a silanol group, a hydroxyl group, and an amino group.
  • the crosslinkable functional group is suitable for forming a pattern (layer (Y)) having excellent durability by forming a crosslinked structure in the primer layer (X) carrying the fluid (a). is there.
  • the alkoxysilyl group and silanol group can be introduced into the urethane resin by using ⁇ -aminopropyltriethoxysilane or the like when the urethane resin (x1) is produced.
  • the urethane resin (x1) is used in combination with a crosslinking agent (D) described later, one having a functional group capable of reacting with the functional group of the crosslinking agent (D) can be used.
  • a functional group although depending on the selection of the crosslinking agent (D) to be used in combination, for example, when a crosslinking agent such as a blocked isocyanate compound is used, a hydroxyl group or an amino group can be used.
  • the vinyl resin (x2) that can be used for the resin contained in the primer a monomer polymer having a polymerizable unsaturated double bond can be used.
  • a monomer polymer having a polymerizable unsaturated double bond can be used.
  • polyethylene, polypropylene, polybutadiene, ethylene-propylene copolymer, natural rubber, synthetic isopropylene rubber, ethylene-vinyl acetate copolymer, acrylic resin, etc. can be used, and a structure derived from methyl methacrylate. It is preferable to use an acrylic resin having units.
  • acrylic resin a polymer or copolymer obtained by polymerizing a (meth) acrylic monomer can be used.
  • a (meth) acryl monomer points out any one or both of an acrylic monomer and a methacryl monomer.
  • acrylic resin it is preferable to use an acrylic resin having a structural unit derived from methyl (meth) acrylate from the viewpoint of forming the coating film (x) having the predetermined ethanol absorption rate.
  • the acrylic resin can be produced, for example, by polymerizing various (meth) acrylic monomers described later.
  • Examples of the (meth) acrylic monomer include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, and (meth) acrylic acid t.
  • methyl methacrylate is preferably used for forming a coating film (x) having a predetermined ethanol absorption rate, such as heat in a heating step or the like in producing a conductive pattern. Regardless of the influence, it is preferable to use the methyl methacrylate in order to provide excellent adhesion between the primer layer (X) and the support. Also, a fine line having a width of about 0.01 ⁇ m to 200 ⁇ m, preferably about 0.01 ⁇ m to 150 ⁇ m, which is required when forming a conductive pattern such as an electronic circuit, is printed without causing bleeding (thin line). The use of the methyl methacrylate is more preferable in order to enable improvement of the property.
  • the methyl (meth) acrylate is preferably 10% by mass to 70% by mass, more preferably 30% by mass to 65% by mass with respect to the total amount of the (meth) acrylic monomer mixture, and
  • the acrylic acid alkyl ester having an alkyl group having 2 to 12 carbon atoms, preferably the acrylic acid alkyl ester having an alkyl group having 3 to 8 carbon atoms is the total amount of the (meth) acrylic monomer mixture. Is preferably 20% by mass to 80% by mass, and more preferably 35% by mass to 70% by mass.
  • (meth) acrylic monomers that can be used for producing the acrylic resin include, in addition to those described above, acrylic acid, methacrylic acid, ⁇ -carboxyethyl (meth) acrylate, 2- (meth) Carboxyl groups such as acryloylpropionic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, itaconic acid half ester, maleic acid half ester, maleic anhydride, itaconic anhydride, ⁇ - (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.
  • the acrylic resin includes at least one amide group selected from the group consisting of a methylolamide group and an alkoxymethylamide group, an amide group other than the above, a hydroxyl group, a glycidyl group,
  • the body can be used.
  • Examples of the vinyl monomer having one or more amide groups selected from the group consisting of a methylolamide group and an alkoxymethylamide group that can be used for the (meth) acrylic monomer having a crosslinkable functional group include N- Methylol (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-methoxyethoxymethyl (meth) acrylamide, N-ethoxymethyl (meth) acrylamide, N-propoxymethyl (meth) acrylamide, N-isopropoxymethyl (meta ) Acrylamide, Nn-butoxymethyl (meth) acrylamide, N-isobutoxymethyl (meth) acrylamide, N-pentoxymethyl (meth) acrylamide, N-ethoxymethyl-N-methoxymethyl (meth) acrylamide, N, N'-dimethylol (Meth) acrylamide, N-ethoxymethyl-N-propoxymethyl (meth) acrylamide, N, N′
  • Nn-butoxymethyl (meth) acrylamide and N-isobutoxymethyl (meth) acrylamide can provide a level of durability that can prevent peeling of the conductive material (a2) in the plating process. It is preferable when forming the electroconductive pattern provided with.
  • Examples of the (meth) acrylic monomer having a crosslinkable functional group include those other than those described above, for example, a vinyl monomer having an amide group such as (meth) acrylamide, 2-hydroxyethyl (meth) acrylate, (Meth) acrylic acid 2-hydroxypropyl, (meth) acrylic acid 2-hydroxybutyl, (meth) acrylic acid 4-hydroxybutyl, (meth) acrylic acid 6-hydroxyhexyl, (meth) acrylic acid (4-hydroxymethyl) Cyclohexyl) methyl, glycerol (meth) acrylate, polyethylene glycol (meth) acrylate, vinyl monomers having a hydroxyl group such as N-hydroxyethyl (meth) acrylamide: glycidyl (meth) acrylate, allyl (meth) acrylate Polymerizable monomers having a glycidyl group such as glycidyl ether; Polymerizable monomers having an amino group such as aminoethyl
  • the (meth) acrylic monomer having a crosslinkable functional group can be used in the range of 0% by mass to 50% by mass with respect to the total amount of the (meth) acrylic monomer mixture.
  • the (meth) acrylic monomer having the amide group has a (meth) acrylic group for introducing a self-crosslinking reactive methylolamide group. It is preferably used in the range of 0.1% by mass to 50% by mass and more preferably in the range of 1% by mass to 30% by mass with respect to the total amount of the monomer mixture.
  • the (meth) acryl monomer having another amide group and the (meth) acryl monomer having a hydroxyl group used in combination with the self-crosslinking reactive methylolamide group are the (meth) acryl monomer.
  • the total amount is preferably 0.1 to 30% by mass, and more preferably 1 to 20% by mass.
  • the (meth) acrylic monomer having a hydroxyl group and the (meth) acrylic monomer having an acid group are used as a crosslinking agent ( Depending on the type of D), etc., it is preferably used in a range of approximately 0.05% by mass to 50% by mass with respect to the total amount of the (meth) acrylic monomer mixture, preferably 0.05% by mass to 30%. It is preferably used in the range of mass%, more preferably 0.1 mass% to 10 mass%.
  • the acrylic resin when the acrylic resin is produced, together with the (meth) acrylic monomer, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl versatate, methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, amyl Vinyl ether, hexyl vinyl ether, (meth) acrylonitrile, styrene, ⁇ -methylstyrene, vinyl toluene, vinyl anisole, ⁇ -halostyrene, vinyl naphthalene, divinyl styrene, isoprene, chloroprene, butadiene, ethylene, tetrafluoroethylene, vinylidene fluoride, N -Vinylpyrrolidone, polyethylene glycol mono (meth) acrylate, glycerol mono (meth) acrylate, vinyl sulfonic acid, styrene sulfonic acid, Allyl s
  • the acrylic resin can be produced by polymerizing a mixture of various vinyl monomers as described above by a conventionally known method, but produces a conductive pattern having excellent adhesion and excellent conductivity. In addition, it is preferable to apply an emulsion polymerization method.
  • emulsion polymerization method for example, water, a (meth) acrylic monomer mixture, a polymerization initiator, and if necessary, a chain transfer agent, an emulsifier, a dispersion stabilizer, and the like are collectively supplied into a reaction vessel.
  • a pre-emulsion method that drops and polymerizes in a reaction vessel can be applied.
  • the reaction temperature of the emulsion polymerization method varies depending on the type of the (meth) acrylic monomer and the polymerization initiator used, but is about 30 ° C. to 90 ° C., for example, and the reaction time is about 1 hour to 10 hours, for example. preferable.
  • polymerization initiator examples include persulfates such as potassium persulfate, sodium persulfate, and ammonium persulfate, organic peroxides such as benzoyl peroxide, cumene hydroperoxide, and t-butyl hydroperoxide, hydrogen peroxide Radical polymerization using only these peroxides, or aspercolic acid, erythorbic acid, sodium erythorbate, metal salts of formaldehyde sulfoxylate, sodium thiosulfate, sodium bisulfite, Polymerization can also be achieved by a redox polymerization initiator system combined with a reducing agent such as ferric chloride, and 4,4′-azobis (4-cyanovaleric acid), 2,2′-azobis (2-amidinopropane) It is also possible to use an azo initiator such as dihydrochloride, and these compounds can be used alone. Well it may be used in combination of two or more.
  • persulfates such as
  • anionic surfactant examples include sulfates of higher alcohols and salts thereof, alkylbenzene sulfonates, polyoxyethylene alkylphenyl sulfonates, polyoxyethylene alkyl diphenyl ether sulfonates, and polyoxyethylene alkyl ethers.
  • 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.
  • cationic surfactant for example, an alkyl ammonium salt or the like can be used.
  • alkyl (amido) betaine alkyldimethylamine oxide and the like can be used.
  • emulsifier in addition to the above surfactants, fluorine surfactants, silicone surfactants, emulsifiers having a polymerizable unsaturated group generally called “reactive emulsifier” in the molecule, etc. Can also be used.
  • Examples of the reactive emulsifier include “Latemul S-180” (manufactured by Kao Corporation) having a sulfonic acid group and a salt thereof, and “Eleminol JS-2, RS-30” (manufactured by Sanyo Chemical Industries).
  • lauryl mercaptan or the like can be used, and it is 0% by mass to the total amount of the (meth) acrylic monomer mixture. It is preferably used in the range of 1% by mass, and more preferably in the range of 0% by mass to 0.5% by mass.
  • urethane-vinyl composite resin (x3) that can be used as the resin contained in the primer
  • urethane resin (x3-1) and vinyl polymer (x3-2) form composite resin particles in an aqueous medium. Can be dispersed.
  • the composite resin particles include those in which a part or all of the vinyl polymer (x3-2) is contained in the resin particles formed by the urethane resin (x3-1). It is preferable to form core-shell type composite resin particles composed of the vinyl polymer (x3-2) as the core layer and the urethane resin having the hydrophilic group as the shell layer. In particular, when forming a conductive pattern, it is preferable to use the core-shell type composite resin particles that do not require the use of a surfactant or the like that can lower the electrical characteristics. As the composite resin particles, it is preferable that the vinyl polymer (x3-2) is almost completely covered with the urethane resin (x3-1), but this is not essential and the effect of the present invention is impaired. A part of the vinyl polymer (x3-2) may be present on the outermost part of the composite resin particle as long as it does not exist.
  • the vinyl polymer (x3-2) is more hydrophilic than the urethane resin (x3-1)
  • the vinyl polymer (x3- In the resin particles formed in 2) a part or all of the urethane resin (x3-1) may be present to form composite resin particles.
  • the urethane resin (x3-1) and the vinyl polymer (x3-2) may form a covalent bond, but preferably do not form a bond.
  • urethane-vinyl composite resin (x3) it is preferable to use a urethane-acrylic composite resin in which the vinyl polymer (x3-2) is an acrylic resin.
  • the composite resin particles preferably have an average particle diameter in the range of 5 nm to 100 nm from the viewpoint of maintaining good water dispersion stability.
  • the average particle diameter here refers to an average particle diameter on a volume basis measured by a dynamic light scattering method, as will be described later in Examples.
  • the urethane resin (x3-1) constituting the urethane-vinyl composite resin the same resin as the urethane resin (x1) can be used.
  • the urethane resin (x3-1) constituting the urethane-vinyl composite resin includes, for example, a urethane resin having a polyether structure and an aromatic polyester structure other than those exemplified as the urethane resin (x1). Urethane resin can also be used.
  • Examples of the polyol, polyisocyanate, and chain extender that can be used in the production of the urethane resin (x3-1) include those exemplified as those that can be used in the production of the urethane resin (x1). The same agent can be used.
  • the urethane resin which has the said polyether structure can be manufactured by using what contains the polyether polyol mentioned later as the said polyol.
  • the polyether polyol for example, one obtained by addition polymerization of alkylene oxide using one or more compounds having two or more active hydrogen atoms as an initiator can be used.
  • the initiator examples 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.
  • alkylene oxide examples include ethylene oxide, propylene oxide, butylene oxide, styrene oxide, epichlorohydrin, and tetrahydrofuran.
  • an aromatic polyester polyol can also be used as the polyol.
  • aromatic polyester polyol for example, those obtained by an esterification reaction of a low molecular weight polyol and an aromatic polycarboxylic acid can be used.
  • Examples of the low molecular weight polyol that can be used in the production of the aromatic polyester polyol include ethylene glycol, 1,2-propanediol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, 3-Methyl-1,5-pentanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, glycerin, trimethylolpropane, etc. can be used alone or in combination of two or more thereof.
  • Ethylene glycol 1,2-propane It is preferable to use a combination of diol, 1,3-butanediol, 1,4-butanediol, or the like, and 3-methyl-1,5-pentanediol, neopentyl glycol, or the like.
  • aromatic polycarboxylic acid for example, terephthalic acid, isophthalic acid, phthalic acid, naphthalenedicarboxylic acid, and anhydrides or esterified products thereof can be used.
  • polyether polyol and the aromatic polyester polyol those having a number average molecular weight of 500 to 4,000 are preferably used, more preferably 500 to 2,000.
  • the vinyl polymer (x3-2) constituting the urethane-vinyl composite resin it is possible to use a polymer having a glass transition temperature of 10 ° C. to 70 ° C. It is preferable for forming (x) and improving the adhesion with the conductive substance (a2) contained in the fluid (a) and the conductivity of the resulting conductive pattern.
  • the glass transition temperature of the vinyl polymer (x3-2) is a value determined by calculation mainly based on the composition of the vinyl monomer used for the production of the vinyl polymer (x3-2). is there. Specifically, the vinyl polymer (x3-2) having the predetermined glass transition temperature can be obtained by using a combination of the vinyl polymer (x3-2) described later.
  • a coating film (x) having the predetermined ethanol absorption rate is formed, and the conductive polymer (a2) contained in the fluid (a) is formed.
  • the upper limit of the weight average molecular weight of the vinyl polymer (x3-2) is not particularly limited, but is preferably approximately 10 million or less, and preferably 5 million or less.
  • the vinyl polymer (x3-2) may have various functional groups as necessary.
  • the functional group include an amide group, a hydroxyl group, a glycidyl group, an amino group, a silyl group, and aziridinyl.
  • the same polymer as the vinyl polymer (x2) can be used.
  • examples of the (meth) vinyl monomer that can be used for the production of the vinyl polymer (x3-2) include the vinyl monomers exemplified as those that can be used for the production of the vinyl resin (x2).
  • the same as the (meth) acrylic monomer can be used.
  • the vinyl polymer (x3-2) it is preferable to use the same acrylic resin having a structural unit derived from methyl methacrylate exemplified as usable for the vinyl resin (x2).
  • urethane-vinyl composite resin (x3) for example, an aqueous dispersion of the urethane resin (x3-1) is produced by reacting the polyisocyanate, a polyol and, if necessary, a chain extender and dispersing in water. And the step (W) of polymerizing the (meth) acrylic monomer in the aqueous dispersion to produce a vinyl polymer (x3-2).
  • the urethane resin (x3-1) is reacted by reacting the polyisocyanate with a polyol in the absence of a solvent, in an organic solvent, or in the presence of a reactive diluent such as a (meth) acrylic monomer. And then neutralizing part or all of the hydrophilic group of the urethane resin (x3-1) with a basic compound, if necessary, and further reacting with a chain extender as necessary. And dispersing it in an aqueous medium to produce an aqueous dispersion of urethane resin (x3-1).
  • a vinyl monomer such as the (meth) acrylic monomer is supplied into the aqueous dispersion of the urethane resin (x3-1) obtained above, and within the urethane resin (x3-1) particles.
  • the vinyl monomer is radically polymerized to produce a vinyl resin (x3-2).
  • the production of the urethane resin (x3-1) is performed in the presence of a vinyl monomer, the production of the urethane resin (x3-1) is followed by supplying a polymerization initiator and the like.
  • a vinyl resin (x3-2) is produced by radical polymerization of a vinyl monomer such as a (meth) acrylic monomer.
  • the urethane resin (x3-1) has a high viscosity and is not excellent in workability
  • a normal organic material such as methyl ethyl ketone, N-methylpyrrolidone, acetone, dipropylene glycol dimethyl ether or the like is used.
  • Solvents and reactive diluents can be used.
  • a vinyl monomer such as a (meth) acrylic monomer that can be used in the production of the vinyl polymer (x3-2) as the reactive diluent. It is preferable for improving the production efficiency.
  • resins that can be used for the primer for example, phenol resin, epoxy resin, melamine resin, urea resin, unsaturated polyester resin, alkyd resin, polyimide resin, fluorine resin, etc. can be used. it can.
  • the above-mentioned resins may be used in appropriate combination.
  • two or more of the urethane resin (x1), vinyl resin (x2), and urethane-vinyl composite resin (x3) can be used in appropriate combination.
  • the urethane resin (x1) a urethane resin having a polyether structure and a urethane resin having a polycarbonate structure can be used in combination.
  • the primer may be a combination of the urethane resin (x1) and the vinyl resin (x2).
  • those having a crosslinkable functional group can be used as described above.
  • the crosslinkable functional group forms a crosslink structure in the primer layer (X) carrying the fluid (a), thereby causing a pattern (layer (excellent in adhesion and conductivity) without causing bleeding or the like.
  • Y) can be used suitably.
  • the coating film (x) formed using the primer may have a crosslinked structure before the fluid (a) is applied (printed) on a part or all of the surface thereof, It is necessary to adjust the ethanol absorption rate to fall within the range of 20% by mass to 500% by mass.
  • the coating layer (x) does not have a crosslinked structure before the fluid (a) is applied (printed) to the surface thereof, and after the fluid (a) is applied, the primer layer You may form the primer layer which has a crosslinked structure as (X).
  • crosslinkable functional group examples include an alkoxysilyl group and a silanol group, as well as an amino group and a hydroxyl group.
  • the alkoxysilyl group and the silanol group are hydrolyzed and condensed in an aqueous medium that is a solvent for the primer to form a crosslinked structure.
  • the coating film (x) having already formed the crosslinked structure is formed before applying the fluid (a).
  • the crosslinkable functional group is heated to approximately 100 ° C. or higher, preferably 120 ° C. or higher to cause a crosslink reaction between the crosslinkable functional groups or a cross-linking agent (D) described later to form the crosslink structure.
  • a crosslink reaction between the crosslinkable functional groups or a cross-linking agent (D) described later to form the crosslink structure.
  • one or more thermally crosslinkable functional groups selected from the group consisting of a methylolamide group and an alkoxymethylamide group.
  • alkoxymethylamide group examples include an amide group formed by bonding a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, a butoxymethyl group or the like to a nitrogen atom, and among them, a methylolamide group and It is preferable to use one having at least one selected from the group consisting of alkoxymethylamide groups in order to greatly improve the durability of the primer layer (X) and the adhesion to various supports.
  • a primer including a resin having a functional group capable of undergoing a crosslinking reaction by heating to about 100 ° C. or more, preferably about 120 ° C. as described above, when the primer is applied to the support surface and dried.
  • the temperature is preferably less than 100 ° C.
  • the primer layer After applying (printing) the fluid (a) to the coating film not having the crosslinked structure, the primer layer is heated at a temperature of 100 ° C. or higher, or by heating separately from the heating step.
  • a primer layer having a crosslinked structure is formed as (X).
  • the primer layer (X) is exposed to a plating agent made of a strong alkali or strongly acidic substance in the plating process described later. Even in such a case, it is possible to form a conductive pattern having extremely excellent durability without causing peeling of the primer layer (X) from the support.
  • the phrase “substantially has no cross-linked structure” includes an embodiment in which the cross-linked structure is not formed at all, and within about 5% of the number of functional groups capable of forming the cross-linked structure is partially cross-linked. Refers to the structure formed.
  • the crosslinkable functional group is preferably present in a total range of 0.005 equivalent / kg to 1.5 equivalent / kg with respect to the total amount of resin used in the primer.
  • the said primer is a range which does not impair the effect of this invention, A crosslinking agent (D) as needed, A pH adjuster, a film formation adjuvant, a leveling agent, a thickener, a water repellent, a defoaming agent You may use suitably well-known things, such as an agent.
  • crosslinking agent (D) examples include a metal chelate compound, a polyamine compound, an aziridine compound, a metal salt compound, and an isocyanate compound, which can react at a relatively low temperature of about 25 ° C. to less than 100 ° C. to form a crosslinked structure. Reacts at a relatively high temperature of about 100 ° C. or higher, such as one or more selected from the group consisting of a thermal crosslinking agent (d1-1), a melamine compound, an epoxy compound, an oxazoline compound, a carbodiimide compound, and a blocked isocyanate compound.
  • a thermal crosslinking agent (d1-2) capable of forming a crosslinked structure and various photocrosslinking agents can be used.
  • the primer containing the thermal crosslinking agent (d1-1) is, for example, applied to the surface of a support, dried at a relatively low temperature, and then applied (printed) to a temperature of less than 100 ° C.
  • the primer containing the thermal cross-linking agent (d1-2) forms a cross-linked structure by, for example, applying it to the surface of a support and drying at a low temperature of room temperature (25 ° C.) to less than about 100 ° C.
  • the coating film (x) is produced and then the fluid (a) is applied, it is heated at a temperature of, for example, 150 ° C. or higher, preferably 200 ° C. or higher to form a cross-linked structure.
  • a temperature of, for example, 150 ° C. or higher, preferably 200 ° C. or higher it is possible to obtain a conductive pattern having exceptionally excellent durability that does not cause peeling of the conductive material.
  • thermal crosslinking agent (d1-1) instead of the thermal crosslinking agent (d1-2) as the crosslinking agent.
  • Examples of the metal chelate compound that can be used for the thermal crosslinking agent (d1-1) include acetylacetone, which is a polyvalent metal such as aluminum, iron, copper, zinc, tin, titanium, nickel, antimony, magnesium, vanadium, chromium, and zirconium. Coordination compounds, acetoacetate coordination compounds and the like can be used, and it is preferable to use acetylacetone aluminum which is an acetylacetone coordination compound of aluminum.
  • a polyamine compound that can be used for the thermal crosslinking agent (d1-1) for example, a tertiary amine such as triethylamine, triethylenediamine, dimethylethanolamine or the like can be used.
  • Examples of the aziridine compound that can be used in the thermal crosslinking agent (d1-1) include 2,2-bishydroxymethylbutanol-tris [3- (1-aziridinyl) propionate] and 1,6-hexamethylenediethylene urea. Diphenylmethane-bis-4,4′-N, N′-diethyleneurea and the like can be used.
  • Examples of the metal base compound that can be used as the crosslinking agent (d1-1) include aluminum sulfate, aluminum alum, aluminum sulfite, aluminum thiosulfate, polyaluminum chloride, aluminum nitrate nonahydrate, and aluminum chloride hexahydrate. Products, water-soluble metal salts such as titanium tetrachloride, tetraisopropyl titanate, titanium acetylacetonate, and titanium lactate can be used.
  • isocyanate compounds that can be used in the thermal crosslinking agent (d1-1) include tolylene diisocyanate, hydrogenated tolylene diisocyanate, triphenylmethane triisocyanate, methylene bis (4-phenylmethane) triisocyanate, isophorone diisocyanate, hexamethylene.
  • Polyisocyanates such as diisocyanates and xylylene diisocyanates; isocyanurate-type polyisocyanate compounds obtained by using them; adducts composed of these with trimethylolpropane; and the like, the polyisocyanate compound and a polyol such as trimethylolpropane are reacted.
  • Urethanes having a polyisocyanate group obtained in the above manner can be used.
  • hexamethylene diisocyanate nurate, adduct of hexamethylene diisocyanate and trimethylolpropane, adduct of tolylene diisocyanate and trimethylol propane, adduct of xylylene diisocyanate and trimethylol propane, etc. are used. It is preferable.
  • Examples of the melamine compound that can be used in the thermal crosslinking agent (d1-2) include hexamethoxymethyl melamine, hexaethoxymethyl melamine, hexapropoxymethyl melamine, hexabutoxymethyl melamine, hexapentyloxymethyl melamine, and hexahexyloxy. Methylmelamine or a mixed etherified melamine obtained by combining these two types can be used. Of these, trimethoxymethyl melamine and hexamethoxymethyl melamine are preferably used. Examples of commercially available products include Becamine M-3, APM, J-101 (manufactured by DIC Corporation), and the like. The melamine compound can form a crosslinked structure by a self-crosslinking reaction.
  • a catalyst such as an organic amine salt may be used to promote the self-crosslinking reaction.
  • catalyst ACX, 376 etc. can be used.
  • the catalyst is preferably in the range of approximately 0.01% by mass to 10% by mass with respect to the total amount of the melamine compound.
  • Examples of the epoxy compound that can be used for the thermal crosslinking agent (d1-2) include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, hexamethylene glycol diglycidyl ether, cyclohexanediol diglycidyl ether, and glycerin diglycidyl ether.
  • Polyglycidyl ethers of aliphatic polyhydric alcohols such as glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, pentaerythritol tetraglycidyl ether; polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, polytetramethylene glycol diglycidyl ether, etc.
  • polyalkylene glycols 1,3-bis (N, N ′ Polyglycidylamines such as diglycidylaminoethyl) cyclohexane; polyglycidyl esters of polycarboxylic acids [succinic acid, adipic acid, butanetricarboxylic acid, maleic acid, phthalic acid, terephthalic acid, isophthalic acid, benzenetricarboxylic acid, etc.]; bisphenol A Bisphenol A-based epoxy resins such as ethylene oxide adducts of bisphenol A and epichlorohydrin condensates, phenol novolak resins, various vinyl (co) polymers having an epoxy group in the side chain, etc. it can.
  • 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 ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycidoxypropyltriethoxysilane, ⁇ -glycidoxypropylmethyldimethoxysilane, and ⁇ -glycidoxypropyl other than those described above.
  • a silane compound having a glycidyl group such as ⁇ -glycidoxypropyltriisopropenyloxysilane can also be used.
  • Examples of the oxazoline compound that can be used for the thermal crosslinking agent (d1-2) include 2,2′-bis- (2-oxazoline), 2,2′-methylene-bis- (2-oxazoline), 2 , 2'-ethylene-bis- (2-oxazoline), 2,2'-trimethylene-bis- (2-oxazoline), 2,2'-tetramethylene-bis- (2-oxazoline), 2,2'- Hexamethylene-bis- (2-oxazoline), 2,2'-octamethylene-bis- (2-oxazoline), 2,2'-ethylene-bis- (4,4'-dimethyl-2-oxazoline), 2 , 2'-p-phenylene-bis- (2-oxazoline), 2,2'-m-phenylene-bis- (2-oxazoline), 2,2'-m-phenylene-bis- (4,4'- Dimethyl-2-oxa Phosphorus), bis - (2-oxazolinyl sulfony
  • oxazoline compound for example, a polymer having an oxazoline group obtained by polymerizing a combination of the following addition polymerizable oxazoline and other monomers as necessary can be used.
  • Examples of the addition polymerizable oxazoline include 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2-isopropenyl-2-oxazoline. , 2-isopropenyl-4-methyl-2-oxazoline, 2-isopropenyl-5-methyl-2-oxazoline, 2-isopropenyl-5-ethyl-2-oxazoline, etc., alone or in combination Can do. Of these, the use of 2-isopropenyl-2-oxazoline is preferred because it is easily available industrially.
  • carbodiimide compound that can be used for the thermal crosslinking agent (d1-2) examples include poly [phenylenebis (dimethylmethylene) carbodiimide], poly (methyl-1,3-phenylenecarbodiimide), and the like. .
  • Carbodilite V-01, V-02, V-03, V-04, V-05, V-06 manufactured by Nisshinbo Co., Ltd.
  • UCARLINK XL-29SE, XL-29MP Union Carbide Corp.
  • the blocked isocyanate compound that can be used in the thermal crosslinking agent (d1-2) a part or all of the isocyanate groups of the isocyanate compound exemplified as the thermal crosslinking agent (d1-1) are formed by a blocking agent. What was sealed can be used.
  • the blocking agent examples 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, ⁇ -caprolactam, ⁇ -valerolactam, ⁇ -butyrolactam, succinimide, maleic imide, imidazole, 2-methylimidazole, urea, thiourea, Ethyleneurea, formamide oxime, acetaldoxime, acetone oxime, methyl ethyl ketoxime, methyl isobutyl ketoxime, cyclohexa N'okishimu,
  • Elastolon BN-69 (Daiichi Kogyo Seiyaku Co., Ltd.) or the like can be used as a water-dispersed commercial product.
  • the crosslinking agent (D) it is preferable to use a resin having a group capable of reacting with the crosslinking functional group of the crosslinking agent (D) as the resin contained in the primer.
  • a resin having a group capable of reacting with the crosslinking functional group of the crosslinking agent (D) as the resin contained in the primer.
  • the (block) isocyanate compound, the melamine compound, the oxazoline compound, and the carbodiimide compound as a crosslinking agent and a resin having a hydroxyl group or a carboxyl group as the resin.
  • crosslinking agent (D) varies depending on the type and the like, it is usually preferable to use in the range of 0.01% by mass to 60% by mass with respect to 100 parts by mass of the total resin contained in the primer. More preferably, it is used in the range of 1% by mass to 10% by mass, and in the range of 0.1% by mass to 5% by mass is excellent in adhesion and conductivity and excellent in the durability. It is preferable because a conductive pattern can be formed.
  • crosslinking agent (D) is added and used in advance before the primer of the present invention is applied or impregnated on the surface of the support.
  • the additive various fillers such as inorganic particles can be used.
  • the amount of the filler used in the primer of the present invention is preferably as small as possible, and more preferably 5% by mass or less based on the total amount of the primer of the present invention.
  • the amount of the additive used is not particularly limited as long as the effect of the present invention is not impaired, but is preferably in the range of 0.01% by mass to 40% by mass with respect to the total amount of solids in the primer. .
  • a primer is applied to part or all of the surface of the support, and then the fluid is applied to part or all of the surface of the coating film (x) formed using the primer. It can manufacture by heating after apply
  • the coating film (x) forms the primer layer (X) by being heated after the fluid (a) is applied.
  • the said coating film (x) can be formed by the method of apply
  • the primer that can be applied to part or all of the surface of the support to form the coating film (x) can form the primer layer (X) of the conductive pattern of the present invention.
  • Examples of a method for applying the primer to the surface of the support include a gravure method, a coating method, a screen method, a roller method, a rotary method, a spray method, a spin coater method, and an ink jet method.
  • a method for removing the solvent contained in the primer for example, a method of drying using a dryer and volatilizing the solvent is common.
  • the drying temperature may be set to a temperature that can volatilize the solvent and does not adversely affect the support.
  • the coating amount of the primer on the support is preferably in the range where the film thickness of the coating film (x) is 0.01 ⁇ m to 300 ⁇ m from the viewpoint of imparting excellent adhesion and conductivity. A range of 0.05 ⁇ m to 20 ⁇ m is more preferable.
  • the film thickness of the coating film (x) obtained by the above method may be used in a range where the thickness of the primer layer (X) constituting the finally obtained conductive pattern is 0.01 ⁇ m to 300 ⁇ m. Is preferred.
  • the coating film (x) is a coating film capable of absorbing 20% by mass to 500% by mass with respect to the mass of the coating film (x) in an environment of 25 ° C. Indispensable to resolve.
  • the mass ratio of ethanol absorbed by the coating film (x) to the mass of the coating film (x) [absorption rate of ethanol] is a value obtained by measurement by the following method.
  • the primer is applied to the surface of the release paper using an applicator, dried, and then the release paper is removed to form a coating film having a length of 3 cm, a width of 3 cm, and a thickness of 50 ⁇ m.
  • the coating film is immersed in 30 g of ethanol adjusted to 25 ° C. in an environment of 25 ° C.
  • the coating film was taken out from the ethanol, and it was placed on a stack of three becots, on which three becots were stacked, Further, leave it on for 10 seconds with a weight of 500 g.
  • the mass of the coating film is measured, and the mass of ethanol absorbed in the coating film after the immersion is determined.
  • the mass ratio obtained by dividing the mass of ethanol absorbed in the coating film after immersion by the mass of the coating film before immersion and multiplying by 100 was defined as the ethanol absorption rate.
  • the ethanol absorptivity is less than 20% by mass, specifically, when the fluid (a) is applied to a coating film of 10% by mass, the decrease in conductivity and adhesion May cause decreased sex. Specifically, since the solvent contained in the fluid (a) is not easily absorbed by the coating film (x), the adhesion between the coating film (x) and the conductive pattern may be deteriorated.
  • the ethanol absorptivity is preferably in the range of 20% by mass to 300% by mass and more preferably in the range of 20% by mass to 200% by mass from the viewpoint of imparting even better adhesion and conductivity. Is more preferable, and the range of 45% by mass to 190% by mass is more preferable.
  • the coating film (x) having the predetermined absorption rate it is not only necessary to use the coating film (x) having the predetermined absorption rate, but a pattern is formed using the predetermined fluid (a) on the coating film (x).
  • the problem can be solved only by printing.
  • the primer layer (X) constituting the conductive pattern does not necessarily have the predetermined absorption rate. It is essential to solve the above-mentioned problems that the coating film (x) before the heating and before the fluid (a) is applied has the predetermined absorption rate. .
  • the coating film (x) is appropriately dissolved by the solvent contained in the fluid (a) and absorbs the solvent, whereby a conductive substance (a2) such as a metal contained in the fluid (a). Therefore, it is possible to contribute to obtaining a conductive pattern without bleeding. Further, by using the coating film (x), it is possible to form a transparent primer layer as compared with a conventionally known porous type receiving layer.
  • Examples of the method for applying the fluid (a) to part or all of the surface of the coating film (x) include a reverse printing method such as a letterpress reverse printing method, an ink jet printing method, a screen printing method, and an offset printing method.
  • a reverse printing method such as a letterpress reverse printing method, an ink jet printing method, a screen printing method, and an offset printing method.
  • the conductive ink is directly or inverted on the receiving substrate.
  • Examples include a printing method.
  • the fluid (a) is applied (printed) in the form of a thin wire of about 0.01 ⁇ m to 100 ⁇ m, which is required when realizing high density electronic circuits, etc.
  • an ink jet printing method is adopted. It is preferable to do.
  • an ink jet printer As the ink jet printing method, what is generally called an ink jet printer can be used. Specific examples include Konica Minolta EB100, XY100 (manufactured by Konica Minolta IJ Co., Ltd.), Dimatics Material Printer DMP-3000, Dimatics Material Printer DMP-2831 (manufactured by Fuji Film Co., Ltd.), and the like.
  • the conductive material (a2) such as metal contained in the fluid (a) is in close contact and joined. It is preferable to be heated.
  • the heating is preferably performed in the range of approximately 80 ° C. to 300 ° C. for approximately 2 minutes to 200 minutes.
  • the said heating may be performed in air
  • the conductive pattern of the present invention can form a pattern with excellent adhesion and conductivity even when heated at a relatively low temperature of about 80 ° C. to 120 ° C.
  • the heating step can be performed using, for example, an oven, a hot air drying furnace, an infrared drying furnace, laser irradiation, microwaves, or the like.
  • the fluid (a) is applied by using the crosslinking agent (d1-2).
  • the crosslinked structure is formed after coating (printing) by passing through the heating step.
  • the heating temperature varies depending on the type of the crosslinking agent (D) used, the combination of the crosslinkable functional groups, etc., but is generally in the range of 80 ° C. to 300 ° C. It is preferably 100 ° C to 300 ° C, particularly preferably 120 ° C to 300 ° C.
  • the upper limit of the temperature is preferably 150 ° C. or less, more preferably 120 ° C. or less.
  • a conductive pattern is formed by a conductive material such as a metal contained in the fluid (a).
  • a conductive material such as a metal contained in the fluid (a).
  • Such conductive patterns include the formation of electronic circuits using silver ink or the like, organic solar cells, electronic book terminals, organic EL, organic transistors, flexible printed boards, formation of RFID, peripheral wiring formation, plasma display It can be made suitable also in the field of printed electronics such as wiring of an electromagnetic wave shield.
  • the conductive pattern was plated with a metal such as copper in order to form a highly reliable wiring pattern capable of maintaining good conductivity without causing disconnection or the like over a long period of time. Things can be used.
  • a part or all of the surface of the support has a coating film (x) formed using the primer, and the surface of the coating film (x)
  • the plating nucleating agent as the fluid (a) to a part or all of the coating nuclei
  • the plating nuclei are supported on the surface of the coating film (x), and a heating step or the like is performed as necessary.
  • a plating layer (Z) which consists of an electroplating process, an electroless-plating process, or the plating film formed by performing an electroplating process after the said electroless-plating process is mentioned.
  • the electroless plating treatment step is included in the electroless plating solution by bringing the electroless plating solution into contact with the surface of a plating nucleus such as palladium or silver supported on the primer layer (X).
  • a metal such as copper is deposited to form an electroless plating layer (coating) made of a metal coating.
  • a solution containing a conductive substance made of a metal such as copper, nickel, chromium, cobalt, tin, a reducing agent, and a solvent such as an aqueous medium or an organic solvent is used.
  • reducing agent for example, dimethylaminoborane, hypophosphorous acid, sodium hypophosphite, dimethylamine borane, hydrazine, formaldehyde, sodium borohydride, phenol and the like can be used.
  • monocarboxylic acids such as acetic acid and formic acid
  • dicarboxylic acids such as malonic acid, succinic acid, adipic acid, maleic acid, fumaric acid
  • malic acid lactic acid, glycolic acid Hydroxycarboxylic acids such as gluconic acid and citric acid
  • amino acids such as glycine, alanine, arginine, aspartic acid and glutamic acid
  • aminopolycarboxylic acids such as iminodiacetic acid, nitrilotriacetic acid, ethylenediaminediacetic acid, ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid
  • the organic acid may contain a complexing agent such as an organic acid, a soluble salt of these organic acids (sodium salt, potassium salt, ammonium salt, etc.), an amine such as ethylenediamine, diethylenetriamine, and triethylenetetramine.
  • the temperature of the electroless plating solution when the electroless plating solution is brought into contact with the surface of the primer layer (X) carrying the plating nucleus in the plating nucleating agent is generally in the range of 20 ° C to 98 ° C. It is preferable.
  • the electrolytic plating treatment step is performed by bringing an electrolytic plating solution into contact with, for example, the surface of the primer layer (X) carrying the plating nucleus or the surface of the electroless plating layer (coating) formed by the electroless treatment.
  • the surface of the primer layer (X) placed on the negative electrode or the electroless plating layer (coating) formed by the electroless treatment is obtained by energizing the electroplating solution. And forming an electrolytic plating film (metal film).
  • a solution containing a conductive substance made of a metal such as copper, nickel, chromium, cobalt, tin, sulfuric acid, and an aqueous medium can be used.
  • the temperature of the electrolytic plating solution when the electrolytic plating solution is brought into contact with the surface of the primer layer (X) carrying the plating nuclei in the plating nucleating agent is generally in the range of 20 ° C to 98 ° C. Is preferred.
  • the primer layer with respect to the support is formed in the plating step for the primer layer (X) in which the crosslinked structure is formed.
  • (X) does not cause peeling.
  • the primer layer (X) is not peeled off, and therefore can be used very suitably for the production of the conductive pattern.
  • Such conductive patterns include, for example, formation of electronic circuits using silver ink, organic solar cells, electronic book terminals, organic EL, organic transistors, flexible printed circuit boards, layers constituting RFID, etc., peripheral wiring It can be suitably used for forming and forming a conductive pattern, more specifically, a circuit board in manufacturing an electromagnetic wave shield wiring of a plasma display.
  • coating (printing) fluid (a) such as electroconductive ink or a plating nucleating agent among the electroconductive patterns obtained by the said method
  • a crosslinked structure is formed in the said primer layer (X).
  • the conductive pattern subjected to the plating treatment can form a highly reliable wiring pattern capable of maintaining good conductivity without causing disconnection or the like over a long period of time.
  • CCL Copper Clad Laminate
  • FPC flexible printed circuit board
  • TAB automatic tape bonding
  • COF chip-on-film
  • PWB printed wiring board
  • Preparation Example 1 Preparation of Primer 1 In a reaction vessel equipped with a stirrer, reflux condenser, nitrogen inlet tube, thermometer, and dropping funnel, 115 parts by mass of deionized water, Latemul E-118B (manufactured by Kao Corporation: effective (25% by mass of component) 4 parts by mass was added, and the temperature was raised to 75 ° C. while blowing nitrogen.
  • Latemul E-118B manufactured by Kao Corporation: effective (25% by mass of component
  • a vinyl monomer mixture consisting of 60 parts by weight of methyl methacrylate, 3 parts by weight of methacrylic acid and 37 parts by weight of n-butyl acrylate and Aqualon KH-1025 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd .: 25 parts by mass of active ingredient)
  • a part (5 parts by mass) of a monomer pre-emulsion obtained by mixing 4 parts by mass and 15 parts by mass of deionized water was added, followed by 0.1 parts by mass of potassium persulfate. The polymerization was carried out for 60 minutes while maintaining the temperature in the reaction vessel at 75 ° C.
  • the temperature in the reaction vessel was cooled to 40 ° C., and aqueous ammonia (active ingredient 10% by mass) was used so that the pH of the aqueous dispersion in the reaction vessel was 8.5.
  • primer 1 was prepared by using deionized water so that the non-volatile content was 30% by mass and then filtering with a 200 mesh filter cloth.
  • a polyester polyol P (several number) obtained by reacting neopentyl glycol, 1,4-butanediol and adipic acid in a four-necked flask equipped with a thermometer, a stirring device, a reflux condenser, and a dropping device. 1070 parts by mass and 770 parts by mass of ethyl acetate were added, and the temperature was raised to 70 ° C. with stirring. After stirring and mixing them, 281 parts by mass of dicyclohexylmethane diisocyanate and 0.2 parts by mass of stannous octylate were added and reacted at 70 ° C. for 2 hours.
  • Primer 2 having a non-volatile content of 30% by mass was prepared by subjecting this aqueous dispersion to distillation under reduced pressure.
  • aqueous dispersion of urethane resin (L-1) was obtained.
  • the urethane resin (L-1) obtained here had an acid value of 30 and a weight average molecular weight of 53,000.
  • the temperature in the reaction vessel was cooled to 40 ° C., then deionized water was used so that the non-volatile content was 20% by mass, and then filtered with a 200 mesh filter cloth to prepare Primer 3.
  • the temperature in the reaction vessel was cooled to 40 ° C., and then deionized water was used so that the non-volatile content was 20% by mass, followed by filtration with a 200 mesh filter cloth to prepare Primer 4.
  • the temperature in the reaction vessel was cooled to 40 ° C., and then deionized water was used so that the non-volatile content became 20% by mass, followed by filtering with a 200 mesh filter cloth to prepare Primer 5.
  • urethane resin (L-2) was obtained.
  • the urethane resin (L-2) obtained here had an acid value of 30 and a weight average molecular weight of 88,000.
  • An aqueous dispersion of urethane-acrylic composite resin constituted was obtained.
  • the temperature in the reaction vessel was cooled to 40 ° C., and then deionized water was used so that the non-volatile content was 20% by mass, followed by filtration with a 200 mesh filter cloth to prepare primer 6.
  • Preparation Example 7 Preparation of primer 7 for comparative example In a nitrogen-substituted container equipped with a thermometer, a nitrogen gas introduction tube, and a stirrer, ethylene glycol, 1,4-butanediol, isophthalic acid, terephthalic acid Polyester polyol S having an aromatic structure obtained by reacting (hydroxyl equivalent 840 g / equivalent) 64 parts by mass, 1,4-cyclohexanedimethanol 6 parts by mass, 2,2-dimethylolpropionic acid 7 parts by mass, and 47 parts by mass of dicyclohexylmethane diisocyanate was mixed with 80 parts by mass of methyl ethyl ketone, and reacted under conditions of a temperature of 80 ° C. in the reaction vessel to obtain an organic solvent solution of a urethane prepolymer having an isocyanate group at the terminal.
  • aqueous solution of urethane resin (L-3) having a nonvolatile content of 35% by mass and a pH of 8 is obtained by adding 7 parts by mass of a 20% by mass ethylenediamine aqueous solution and subjecting it to chain extension reaction.
  • a comparative primer 7 comprising a liquid was obtained.
  • the weight average molecular weight of the urethane resin (L-3) was 50,000.
  • the primer 7 for comparative example is obtained. Prepared.
  • Preparation Example 8 Preparation of Primer 8 for Comparative Example First, 100 parts by mass of polyethylene glycol having a number average molecular weight of 600 in a nitrogen-substituted container equipped with a thermometer, a nitrogen gas introduction tube, and a stirrer, By reacting 17.6 parts by mass of 2-dimethylolpropionic acid, 21.7 parts by mass of 1,4-cyclohexanedimethanol, and 106.2 parts by mass of dicyclohexylmethane diisocyanate in 178 parts by mass of methyl ethyl ketone, isocyanate is terminated at the end. An organic solvent solution of a urethane prepolymer having a group was obtained.
  • aqueous dispersion of urethane resin (L-4) was obtained.
  • the urethane resin (L-4) obtained here had an acid value of 30 and a weight average molecular weight of 30,000.
  • a monomer mixture containing 100 parts by mass of ethyl acrylate and 20 parts by mass of an aqueous ammonium persulfate solution (non-volatile content 0.5% by mass) were stirred from a separate dropping funnel. While maintaining the temperature in the reaction vessel at 80 ⁇ 2 ° C., polymerization was carried out dropwise over 120 minutes.
  • An aqueous dispersion of urethane-acrylic composite resin constituted was obtained.
  • the temperature in the reaction vessel was cooled to 40 ° C., and then deionized water was used so that the non-volatile content was 20.0% by mass, followed by filtration with a 200 mesh filter cloth. 8 was prepared.
  • the said ethanol absorption rate is a mass ratio of the ethanol which the said coating film absorbs with respect to the mass of the coating film obtained using the said primer.
  • the primer was applied to the surface of the release paper using an applicator, dried, and then the release paper was removed to prepare a coating film having a length of 3 cm, a width of 3 cm, and a thickness of 50 ⁇ m.
  • the coating film was immersed in 30 g of ethanol adjusted to 25 ° C. in an environment of 25 ° C.
  • the coating film was taken out from the ethanol, and it was placed on a stack of three becots, on which three becots were stacked, Furthermore, it was left to stand for 10 seconds with a weight of 500 g placed thereon.
  • the mass of the coating film after the immersion was determined by measuring the mass of the coating film.
  • the mass ratio obtained by dividing the mass of ethanol absorbed in the coating film after immersion by the mass of the coating film before immersion and multiplying by 100 was defined as the ethanol absorption rate.
  • fluid (a-1) By dispersing 30 parts by mass of silver particles having an average particle diameter of 30 nm in a mixed solvent consisting of 30 parts by mass of 1,3-butylene glycol, 37 parts by mass of ion-exchanged water and 3 parts by mass of glycerin, and filtering with a micropore filter, A fluid (a-1) which is a conductive ink was prepared.
  • fluid (a-2) By dispersing 30 parts by mass of silver particles having an average particle diameter of 30 nm in a mixed solvent consisting of 15 parts by mass of 1,3-butylene glycol, 40 parts by mass of ion-exchanged water, and 15 parts by mass of glycerin, and filtering through a micropore filter. Then, a fluid (a-2) which is a conductive ink was prepared.
  • fluid (a′-1) By dispersing 60 parts by mass of silver particles having an average particle diameter of 30 nm in a mixed solvent consisting of 37 parts by mass of ion-exchanged water and 3 parts by mass of glycerin and filtering with a micropore filter, a fluid (a ′ -1) was prepared.
  • Example 1 ⁇ Production of Conductive Pattern>
  • the primer 1 obtained above was placed on the entire surface of one side of a support made of a polyimide film (Kapton 200H manufactured by Toray DuPont Co., Ltd., thickness 50 ⁇ m) so that the thickness of the coating film after drying would be 3 ⁇ m. It was applied using a coater. Subsequently, the receiving base material (1) in which the coating film formed on the surface of the said support body was obtained by drying for 3 minutes at 70 degreeC using a hot air dryer.
  • a polyimide film Kerpton 200H manufactured by Toray DuPont Co., Ltd., thickness 50 ⁇ m
  • the fluid (a-1) and the fluid (a-2) are applied to the surface of the coating film formed using the primer constituting the receiving substrate (1) obtained above, by an inkjet printer (Konica).
  • Konica inkjet printer
  • a rectangular area (area) of 3 cm in length and 1 cm in width was printed with a film thickness of 0.5 ⁇ m, respectively.
  • Two types of conductive patterns were obtained by drying for 30 minutes at 120 ° C.
  • the fluid (a-3) is 3 cm long using a screen plate of a metal mesh 250.
  • a conductive pattern was obtained by printing a rectangular range (area) 1 cm wide and printing at a film thickness of 1 ⁇ m and then drying at 120 ° C. for 30 minutes.
  • Example 2 ⁇ Production of Conductive Pattern> Three types of conductive patterns were obtained in the same manner as in Example 1 except that primer 2 was used instead of primer 1.
  • the primer layer constituting the conductive pattern and the coating film forming the primer layer had a crosslinked structure.
  • Example 3 Provide of Conductive Pattern> Three types of conductive patterns were obtained in the same manner as in Example 1 except that primer 3 was used instead of primer 1.
  • Example 4 ⁇ Production of Conductive Pattern> Three types of conductive patterns were obtained in the same manner as in Example 1 except that primer 4 was used instead of primer 1.
  • the primer layer constituting the conductive pattern had a crosslinked structure formed after application of the fluid.
  • Example 5 Provide of Conductive Pattern> Three types of conductive patterns were obtained in the same manner as in Example 1 except that primer 5 was used instead of primer 1.
  • the primer layer constituting the conductive pattern had a crosslinked structure formed after application of the fluid.
  • Example 6 Provide of Conductive Pattern> Three types of conductive patterns were obtained in the same manner as in Example 1 except that primer 6 was used instead of primer 1.
  • the primer layer constituting the conductive pattern and the coating film forming the primer layer had a crosslinked structure.
  • Comparative Example 1 ⁇ Production of Conductive Pattern> Three types of conductive patterns were obtained in the same manner as in Example 1 except that the primer 7 for comparative example was used instead of the primer 1.
  • Comparative Example 2 ⁇ Production of Conductive Pattern (2 ')> Three types of conductive patterns were obtained in the same manner as in Example 1 except that the primer 8 for comparative example was used instead of the primer 1.
  • Comparative Example 3 ⁇ Production of Conductive Pattern> One type of conductivity is obtained in the same manner as in Example 3 except that the fluid (a′-1) is used instead of the fluid (a-1) to the fluid (a-3). Got a pattern.
  • a cellophane adhesive tape (manufactured by Nichiban Co., Ltd., CT405AP-24, 24 mm) was pressure-bonded to the surface of the conductive layer constituting the conductive pattern obtained by the above method, and then the cellophane adhesive tape was peeled off. The adhesive surface of the peeled cellophane adhesive tape was visually observed, and the adhesiveness was evaluated based on the presence or absence of the adhering matter.
  • A indicates that the conductive layer constituting the conductive pattern was not attached at all, and a small portion of the conductive layer was observed.
  • B indicates that no disconnection occurs in the wire portion), and
  • C indicates that the conductive layer in the range of about 30% to 50% of the entire conductive layer adheres to the adhesive surface and the disconnection occurs.
  • What volume resistivity is less than 5 ⁇ 10 -6 ⁇ ⁇ cm "A”, 5 ⁇ 10 -6 or 9 ⁇ 10 -6 ⁇ ⁇ less than cm "B what is sufficient available levels “C”, a level that is 9 ⁇ 10 ⁇ 6 or more and less than 5 ⁇ 10 ⁇ 5 ⁇ ⁇ cm and that can be used, and “C” that is 5 ⁇ 10 ⁇ 5 or more and less than 9 ⁇ 10 ⁇ 5 ⁇ ⁇ cm Was evaluated as “E” when it was “D”, 9 ⁇ 10 ⁇ 5 or more and difficult to use practically.
  • Example 1 [Method for evaluating adhesion after electroless plating]
  • the conductive patterns obtained in Example 1 and Comparative Examples 1 to 3 were immersed in a catalyst bath (OPC-SALM / OPC-80 manufactured by Okuno Pharmaceutical Co., Ltd.) for 5 minutes and then washed with water.
  • a catalyst bath OPC-SALM / OPC-80 manufactured by Okuno Pharmaceutical Co., Ltd.
  • a plating layer having a thickness of 8 ⁇ m was formed by immersing in a company-made ATS ad-copper and washing with water.
  • the cellophane adhesive tape manufactured by Nichiban Co., Ltd., CT405AP-24, 24 mm
  • the cellophane adhesive tape is applied to the surface of the plating structure. And peeled in the direction of 90 degrees. The adhesive surface of the peeled cellophane adhesive tape was visually observed, and the adhesiveness was evaluated based on the presence or absence of the adhering matter.
  • the adhesive surface of the peeled cellophane pressure-sensitive adhesive tape is “A” where no deposits are seen, and is supported by either the plating layer or the conductive layer in a range of less than about 5% of the adhesive tape application area.
  • “B” peels off the body and adheres to the adhesive tape, and either the plating layer or the conductive layer peels off from the support within a range of about 5% to less than 50% of the adhesive tape application area.
  • “C” indicates that the material adheres to the tape
  • “D” indicates that either the plating layer or the conductive layer peels off from the support within a range of about 50% or more of the adhesive tape application area, and adheres to the adhesive tape. It was evaluated.
  • Example 1 The surface (conductive layer) of the conductive pattern obtained in Example 1 and Comparative Examples 1 to 3 is set as a cathode, phosphorous copper is set as an anode, and current density is 2 A using an electroplating solution containing copper sulfate. By performing electroplating at / dm 2 for 15 minutes, a copper plating layer having a thickness of 8 ⁇ m was laminated on the surface of the conductive layer.
  • the cellophane adhesive tape manufactured by Nichiban Co., Ltd., CT405AP-24, 24 mm
  • the cellophane adhesive tape is applied to the surface of the plating structure. Peeled in the direction of 90 degrees. The adhesive surface of the peeled cellophane adhesive tape was visually observed, and the adhesiveness was evaluated based on the presence or absence of the adhering matter.
  • the adhesive surface of the peeled cellophane pressure-sensitive adhesive tape is “A” where no deposits are seen, and is supported by either the plating layer or the conductive layer in a range of less than about 5% of the adhesive tape application area. Either the plating layer or the conductive layer is peeled off from the support within the range of about 5% or more and less than 50% of the adhesive area of the “B” pressure-sensitive adhesive tape. “C” is attached to the adhesive, and “D” is attached to the adhesive tape when either the plating layer or the conductive layer is peeled off from the support in a range of about 50% or more of the adhesive tape sticking area. evaluated.
  • the conductive pattern described in Example 1 produced by printing on a receiving substrate provided with a primer layer having an ethanol absorption rate of 26% by mass using a fluid containing 1,3-butylene glycol is the primer layer Have good adhesion to the conductive layer and excellent conductivity.
  • the conductive pattern described in Example 2 produced by printing using a fluid containing 1,3-butylene glycol on a receiving substrate provided with a primer layer having an ethanol absorption rate of 28% by mass is the primer layer It was excellent in adhesion between the conductive layer and the conductive layer, and also excellent in conductivity.
  • the conductive patterns described in Examples 3 and 4 produced by printing using a fluid containing 1,3-butylene glycol on a receiving substrate having an ethanol absorption rate of 180% by mass and 174% by mass are primers It was particularly excellent in terms of adhesion between the layer and the conductive layer and conductivity.
  • the conductive patterns described in Examples 5 and 6 produced by printing using a fluid containing 1,3-butylene glycol on a receiving substrate having an ethanol absorption rate of 50% by mass and 21% by mass are the primers It was particularly excellent in terms of adhesion between the layer and the conductive layer, and the conductivity was also excellent.
  • the conductive pattern described in Comparative Example 1 produced by printing using a fluid containing 1,3-butylene glycol on a receiving substrate provided with a primer layer having an ethanol absorption rate of 1% by mass, In terms of adhesion between the primer layer and the conductive layer, it was not practically sufficient, and was insufficient in terms of conductivity.
  • the conductive pattern described in Comparative Example 2 produced by printing using a fluid containing 1,3-butylene glycol on a receiving substrate provided with a primer layer having an ethanol absorption rate of 550% by mass is the primer layer In terms of adhesion and conductivity between the conductive layer and the conductive layer, it was not practically sufficient.
  • the conductive material according to Comparative Example 3 produced by printing using a fluid (a′-1) containing no 1,3-butylene glycol on a receiving substrate provided with a primer layer having an ethanol absorption rate of 180% by mass.
  • the nature pattern was not practically sufficient in terms of adhesion between the primer layer and the conductive layer and conductivity.

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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Manufacturing Of Printed Wiring (AREA)
  • Parts Printed On Printed Circuit Boards (AREA)
  • Shielding Devices Or Components To Electric Or Magnetic Fields (AREA)

Abstract

La présente invention a pour objectif de fournir un motif conducteur qui présente une faible résistance et une excellente conductivité tout en présentant une excellente adhésion qui est suffisante pour empêcher la séparation d'une substance conductrice du motif conducteur. La présente invention se rapporte à un motif conducteur qui est obtenu par application d'un primaire sur un corps de support et ensuite par application d'un fluide (a) contenant un alcool polyhydrique (a1) qui contient un diol prédéterminé (a1-1), et d'une substance conductrice (a2) sur la surface du film de revêtement (x) qui est formé à l'aide du primaire et par chauffage du fluide appliqué, le corps de support, la couche de primaire (x) qui est formée par chauffage du film de revêtement (x) et une couche (Y) qui contient la substance conductrice (a2), étant stratifiés. Le film de revêtement (x) absorbe une quantité d'éthanol comprise entre 20 et 500 % en masse par rapport à la masse du film de revêtement (x).
PCT/JP2013/062910 2012-05-14 2013-05-08 Motif conducteur, circuit conducteur et procédé permettant de produire un motif conducteur WO2013172229A1 (fr)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015143021A (ja) * 2013-12-27 2015-08-06 トッパン・フォームズ株式会社 積層体及び電子機器
JP2016120604A (ja) * 2014-12-24 2016-07-07 Dic株式会社 積層体、導電性パターン及び電子回路
JP6053246B1 (ja) * 2015-07-30 2016-12-27 バンドー化学株式会社 電極の製造方法
WO2017017911A1 (fr) * 2015-07-30 2017-02-02 バンドー化学株式会社 Procédé de fabrication d'électrode

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010024526A (ja) * 2008-07-23 2010-02-04 Tosoh Corp 銅微粒子分散体及びその製造方法
JP2010225659A (ja) * 2009-03-19 2010-10-07 Fujifilm Corp 電子回路基板製造方法

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Publication number Priority date Publication date Assignee Title
JP2010010548A (ja) * 2008-06-30 2010-01-14 Konica Minolta Holdings Inc インク受容基材及びそれを用いた導電性パターンの作製方法

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010024526A (ja) * 2008-07-23 2010-02-04 Tosoh Corp 銅微粒子分散体及びその製造方法
JP2010225659A (ja) * 2009-03-19 2010-10-07 Fujifilm Corp 電子回路基板製造方法

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015143021A (ja) * 2013-12-27 2015-08-06 トッパン・フォームズ株式会社 積層体及び電子機器
JP2016120604A (ja) * 2014-12-24 2016-07-07 Dic株式会社 積層体、導電性パターン及び電子回路
JP6053246B1 (ja) * 2015-07-30 2016-12-27 バンドー化学株式会社 電極の製造方法
WO2017017911A1 (fr) * 2015-07-30 2017-02-02 バンドー化学株式会社 Procédé de fabrication d'électrode

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TW201406710A (zh) 2014-02-16

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