Classifications

• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
  • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
  • H01B1/20—Conductive material dispersed in non-conductive organic material
  • H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys

Definitions

• the present invention is for forming an electric circuit, an antenna, etc. on a conductive material precursor for use in the production of various antenna materials such as circuit materials for flexible printed circuit boards and mobile phones, especially on a substrate having a curved shape.
• the present invention relates to a conductive material precursor that is preferably used, and a conductive material manufactured using the same.
• Various methods such as a subtracting method, a printing method, and a photographic method have been proposed as a method for producing a flexible conductive material by forming a pattern made of a metal part on a flexible resin support. ing.
• a metal portion can be formed on the curved surface by attaching the flexible conductive material to the curved surface.
• the softer the conductive material the more unlikely to occur during bonding, which is preferable.
• the higher the rigidity the less likely to cause wrinkles during the production. Accordingly, there is a need for a conductive material precursor that has a high rigidity at the manufacturing stage and that can provide a conductive material with a low rigidity at the time of bonding.
• Patent Document 1 a carrier film is bonded to a rigid metal foil, followed by half-cut processing, and the patterned metal part is peeled off together with the carrier film to form a pattern.
• a portion that cannot be peeled off by a complicated pattern such as a loop antenna is generated.
• the peeling method as shown in FIG. 3 of Patent Document 1 the metal foil may be cut at the time of peeling. To prevent this, it is necessary to increase the thickness of the metal foil. Has the problem of becoming difficult.
• Patent Document 2 and Patent Document 3 Although it is not processing of a curved surface, for example, in Patent Document 2 and Patent Document 3, a metal foil is bonded onto a support, and this metal foil is patterned by etching by a known method, and then transferred to a transfer object. A method to do this has also been proposed. However, in the transfer method, the support and the metal foil are bonded together before patterning. If the strength of the paste at the time of bonding is too strong, when the metal foil is peeled off, a part that cannot be peeled off or the strength is increased. If it is too weak, there arises a problem that the metal foil peels off in the process up to the transfer, and there is a problem that it is difficult to adjust the adhesive strength of the glue. In addition, since the ease of peeling differs depending on the shape and size of the pattern to be peeled off, transfer may not be possible depending on the pattern pattern.
• Patent Document 4 Patent Document 5, and the like, an active energy ray adhesive disappearance type adhesive is used to bond a support and a metal foil together.
• the adhesive strength is easily adjusted by irradiating the active energy rays immediately before the transfer, so that the adhesive strength can be easily adjusted.
• the pressure-sensitive adhesive layer is on the surface when patterning the metal part, the pressure-sensitive adhesive may be destroyed due to the contamination of the process or the transfer body being wound around the roll by the pressure-sensitive adhesive.
• the metal part is transferred to the adherend using an adhesive or the like, but since the cured active energy ray adhesive disappearing adhesive is also bonded together, In some cases, transcription was not possible.
• Patent Document 6 proposes a method in which a metal mesh prepared by using a silver salt photograph transfer method is peeled off by enzyme treatment.
• Patent Document 7 also proposes a method for manufacturing a metal mesh alone. In these methods, since the pattern is peeled off from the substrate, there is no problem until the pattern is created, and a fine pattern can be easily created. However, although it is good that the patterns are connected like a mesh, the array antennas and the like are separated when they are peeled off, and therefore, they are not a solution to the problem of processing the array antennas and the like.
• a method is known in which a transfer film is used in an insert molding method as in Patent Document 8, a hard coat layer is provided on the transfer film, the hard coat layer is photocured after insert molding to form a metal portion, and then peeled off from the transfer film. It has been. However, there have been no proposals so far that the metal part is firmly adhered to the hard coat layer and that the metal part is not peeled off or deformed when peeled from the transfer film.
• an object of the present invention is to provide a high rigidity at the time of manufacture and a low rigidity at the time of completion, without causing troubles in processes such as wrinkling and folding, and at least a metal part from the conductive material precursor.
• Another object of the present invention is to provide a conductive material precursor that can be uniformly and easily peeled off when a conductive material having an easy-adhesion layer is peeled off.
• Another object is to provide a conductive material capable of forming a fine metal portion on a curved surface.
• the present invention has been achieved by the following invention.
• the conductive material precursor according to (1) above which contains a polymer compound and contains 8% by mass or more of an epoxy compound with respect to the total solid content of the resin layer.
• An active energy ray-curable polymer compound having an unsaturated double bond having a mass average molecular weight of 15000 or more of 50 to 90% by mass with respect to the total solid content of the active energy ray adhesion-reducing resin layer described above The conductive material precursor according to any one of the above (1) to (3), comprising: (5) An active energy ray-curable polymer having an unsaturated double bond having a mass average molecular weight of 15000 or more and 60 to 70% by mass with respect to the total solid content of the active energy ray adhesion-reducing resin layer.
• (6) The conductivity according to any one of (2) to (5) above, which contains 10 to 30% by mass of an epoxy compound based on the total solid content of the active energy ray-adhesion-reducing resin layer.
• Material precursor. (7) The conductivity according to any one of (2) to (6) above, which contains 15 to 25% by mass of an epoxy compound based on the total solid content of the active energy ray adhesion lowering resin layer.
• a protective film is bonded to the metal part side of the conductive material precursor and supported.
• a conductive material produced by peeling a material comprising at least an easy-adhesion layer, a metal part, and the protective film from the body.
• the conductive material precursor of the present invention comprises an active energy ray-adhesive resin layer containing an active energy ray-curable polymer compound having an unsaturated double bond having a mass average molecular weight of 15000 or more on a support, It has an adhesive layer and a metal part at least in this order.
• the support used for the conductive material precursor of the present invention is not particularly limited as long as it is a material that transmits active energy rays, but a support having a total light transmittance of 50% or more is particularly preferable. A support having a transmittance of 80% or more is preferred.
• Such a support examples include resin films such as polyester resin typified by polyethylene terephthalate, diacetate resin, triacetate resin, acrylic resin, polycarbonate resin, polyvinyl chloride, polyimide resin, polyvinylidene fluoride, cellophane, and celluloid.
• resin films such as polyester resin typified by polyethylene terephthalate, diacetate resin, triacetate resin, acrylic resin, polycarbonate resin, polyvinyl chloride, polyimide resin, polyvinylidene fluoride, cellophane, and celluloid.
• a polyester resin is preferable because it has rigidity, is easy to handle, and provides good peelability.
• waxes such as paraffin, carnauba, and polyethylene
• resins such as acrylic, melamine, epoxy, aliphatic ester, olefin, silicon resin, and fluororesin are used alone or in combination. It may be used and may contain a surfactant or the like. It is also possible to provide a known functional layer such as an antistatic layer on the opposite surface of the support.
• the active energy ray adhesion-reducing resin layer of the conductive material precursor used in the present invention contains an active energy ray-curable polymer compound having an unsaturated double bond having a mass average molecular weight of 15000 or more.
• an active energy ray-curable polymer compound is (1) a polymer compound having a molecular weight of 15000 or more having active hydrogen such as hydroxyl group, carboxyl group, amino group, mercapto group, amide group, such as polyvinyl alcohol, polyvinyl butyral, polyvinyl formal, etc.
• acrylic polymer such as a homopolymer of these monomers or a copolymer obtained by polymerization of two or more of these monomers is added to an epoxy group-containing polymerizable unsaturated compound such as allyl glycidyl ether.
• Polymer compounds obtained by a method of reacting an isocyanate group-containing polymerizable unsaturated compound for example, a compound having an unsaturated double bond with a group capable of reacting with active hydrogen such as methacryloyloxyethyl isocyanate.
• a polymer obtained by synthesis by a known method such as a method of adding an unsaturated carboxylic acid to an epoxy group-containing acrylic polymer as described in pamphlet of International Publication No. 2005/87831 Compounds.
• active energy ray-curable polymer compounds a polymer compound obtained by addition-reacting an unsaturated compound with an acrylic polymer is preferable in that good peelability can be obtained.
• the active energy ray-curable polymer compound having an unsaturated double bond having a mass average molecular weight of 15000 or more synthesized by these methods may be used alone or in combination.
• the active energy ray-curable polymer compound having an unsaturated double bond having a mass average molecular weight of 15000 or more can be used as the active energy ray-curable polymer compound having an unsaturated double bond having a mass average molecular weight of 15000 or more.
• Hitachi Chemical 7975 average molecular weight 50000 of Hitachi Chemical Co., Ltd. can be used preferably.
• the active energy ray-adhesion-reducing resin layer of the present invention preferably contains a photopolymerization initiator.
• a photopolymerization initiator those generally known can be used. Specifically, benzoin, benzophenone, benzoin ethyl ether, benzoin isopropyl ether, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropane-1- ON, azobisisobutyronitrile, benzoyl peroxide, and the like, but are not limited thereto. These photoinitiators may be used independently and 2 or more types may be used together.
• the photopolymerization initiator is preferably contained in an amount of 0.1 to 20% by mass, more preferably 1 to 10% by mass with respect to the active energy ray-curable polymer compound having an unsaturated double bond having a mass average molecular weight of 15000 or more. % By mass.
• At least one kind of photosensitizer can be added to control the curing time and the cured state.
• the photosensitizer can be selected from amine compounds, phosphorus compounds, nitrile compounds, benzoin compounds, carbonyl compounds, sulfur compounds, naphthalene compounds, condensed aromatic hydrocarbons, metal salts and mixtures thereof.
• amine compounds such as triethylamine, diethylaminoethyl methacrylate, N-methyldiethanolamine, phosphorus compounds such as acylphosphine oxide and tributylphosphine, nitrile compounds such as 5-nitroacenaphthene, 4-dimethylaminoethylbenzoate, 4 -Benzoin compounds such as dimethylaminoisoamylbenzoate, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isobutyl ether, benzoin octyl ether, diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, 4'-isopropyl-2- Hydroxy-2-methylpropiophenone, methylanthraquinone, acetophenone, benzophenone, methyl benzoylformate, benzi Carbonyl compounds such as dimethyl ketal, 1-hydroxycyclohex
• photosensitizers may be used alone or in combination of two or more.
• the content of the photosensitizer is preferably 0.1 to 5% by mass, more preferably 0.5 to the active energy ray-curable polymer compound having an unsaturated double bond having a mass average molecular weight of 15000 or more. To 3% by mass.
• the active energy ray adhesion lowering resin layer of the present invention preferably contains a thermal cationic polymerization initiator.
• Thermal cationic polymerization initiators are compounds that generate cationic species or Lewis acids upon heating, such as benzylsulfonium salts, thiophenium salts, thiolanium salts, benzylammonium, pyridinium salts, hydrazinium salts, carboxylic acid esters, sulfonic acid esters, amine imides, etc. Can be mentioned. Commercially available products of these thermal cationic polymerization initiators can be easily obtained.
• thermal cationic polymerization initiators are preferably used in an amount of 0.5 to 10% by mass, more preferably 1 to 5% by mass, based on the solid content of the crosslinking agent.
• the active energy ray-adhesive resin layer of the present invention is a polymer compound having no unsaturated double bond Can also be used to increase the strength and flexibility at the time of peeling, and to prevent the conductive material from being broken or broken in the peeling process.
• polymer compound having no unsaturated double bond examples include various polyvinyl acetal resins such as polyvinyl alcohol, polyvinyl butyral and polyvinyl formal, acrylic acid esters such as acrylic acid and alkyl acrylate, acrylamide, acrylonitrile, methacrylic acid, Acrylic polymers such as methacrylates such as alkyl methacrylate, homopolymers of monomers such as methacrylamide and methacrylonitrile, or copolymers obtained by polymerization of two or more of these monomers, polystyrene, polychlorinated Vinyl, polyvinylidene chloride, polyvinylidene fluoride, polytetrafluoroethylene, polyethylene oxide, polypropylene oxide, polystyrene sulfonic acid, polyvinyl pyrrolidone, polyurethane, etc.
• polyvinyl acetal resins such as polyvinyl alcohol, polyvinyl butyral and polyvinyl formal
• polyvinyl acetal resin that allows easy adjustment of the adhesion, more preferably a polyvinyl acetal resin having a Tg (glass transition point) of 60 ° C. or higher, more preferably a Tg of 80 to 150 ° C.
• the polymer compound having no unsaturated double bond contained in the resin layer having reduced active energy ray adhesion that the conductive material precursor of the present invention contains is 50% by mass or less based on the total solid content of the resin layer. It is preferable that it is 0.1 to 40% by mass.
• the active energy ray-adhesive resin layer of the conductive material precursor used in the present invention preferably contains a crosslinking agent.
• a polymer compound other than the active energy ray-curable polymer compound having an unsaturated double bond having a mass average molecular weight of 15000 or more is contained, it is preferably crosslinked by a crosslinking agent.
• known crosslinking agents such as aldehyde compounds, epoxy compounds, isocyanate compounds, carbodiimide compounds, aziridine compounds, oxazoline compounds, active halogen compounds, and compounds having at least two vinylsulfonyl groups can be used.
• crosslinking agents are preferably contained in an amount of 0.1% by mass or more based on the total amount of resin components in the active energy ray-adhesion-reducing resin layer.
• a preferable crosslinking agent is an epoxy compound.
• the epoxy compound is a monomer having at least one epoxy group in the molecule, more preferably two or more epoxy groups, and the compound includes both a high molecular compound and a low molecular compound.
• phenyl glycidyl ether ethylene glycol diglycidyl ether, glycerin diglycidyl ether, polyglycerol polydiglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, pentaerythritol polyglycidyl ether, sorbitol polyglycidyl ether, vinylcyclohexene dioxide 1,2,8,9-diepoxy limonene, 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexanecarboxylate, bis (3,4-epoxycyclohexyl) adipate, alkoxysilane compound having an epoxy group
• silane coupling agents having an epoxy group such as ⁇ -glycidoxypropyltrimethoxysilane
• the active energy ray-adhesion-reducing resin layer has an active energy ray curing having an unsaturated double bond having a mass average molecular weight of 5 to 100% by mass of 15000 or more based on the total solid content of the resin layer.
• the epoxy compound is contained in an amount of 8% by mass or more
• the conductive material precursor that has been irradiated with active energy is immediately removed from the conductive material including the easy-adhesion layer and the metal part without peeling off. It is more preferable because the conductive material can be peeled stably and uniformly over a period of time. Moreover, since the process with respect to a curved surface becomes easy, it is more preferable.
• the active energy ray-curable polymer compound having an unsaturated double bond having a mass average molecular weight of 15000 or more is more preferably contained in an amount of 50 to 90% by weight, more preferably 60 to 70% by weight based on the total solid content of the resin layer. % Content is particularly preferable.
• the epoxy compound is more preferably contained in an amount of 10 to 30% by mass, particularly preferably 15 to 25% by mass, based on the total solid content of the resin layer.
• the total solid content of the active energy ray adhesion lowering resin layer of the conductive material precursor used in the present invention is preferably 0.1 g / m 2 or more, more preferably 0.1 to 8 g / m 2 . More preferably, it is 1 to 5 g / m 2 .
• a resin component which an active energy ray adhesive force fall type resin layer contains it is preferable that it is at least 0.2 g / m ⁇ 2 > or more.
• the active energy ray adhesion lowering resin layer of the conductive material precursor used in the present invention contains an antistatic agent, a surfactant, a matting agent, a filler, a lubricant, an ultraviolet absorber, and the like. It can be included.
• the conductive material precursor used in the present invention has an easy-adhesion layer on the active energy ray adhesion-reducing resin layer.
• the preferred form of the easy-adhesion layer varies depending on the method for producing the metal part provided thereon, but when the easy-adhesion layer is provided, it should be applied with an aqueous coating solution so as not to dissolve the active energy ray adhesion-reducing resin layer. Is preferred.
• the most preferable method for providing the metal portion on the easily adhesive layer of the conductive material precursor is a method using a silver salt diffusion transfer method.
• a preferred method for forming an easy-adhesion layer and a metal part used in this method will be described.
• the easy-adhesion layer and the metal part are formed by a method of printing a conductive ink such as silver paste using a screen printing method, a conductive material made of a metal such as copper by electroless plating or the like.
• a method for forming a conductive layer or a method in which a conductive layer is formed on an easily adhesive layer by vapor deposition or sputtering, a resist film is formed thereon, exposure, development, etching, and removal of the resist layer, etc.
• the method can be preferably used.
• the easy adhesion layer preferably contains various polymer latexes.
• various polymer latexes it is preferable to contain an aqueous dispersion of polyester latex, acrylic latex, and urethane latex from the viewpoint of weather resistance, and urethane latex from the viewpoint of adhesion to various materials, particularly non-yellowing urethane polycarbonate latex having high weather resistance.
• These polymer latexes preferably have an average particle size of 0.01 to 0.3 ⁇ m, more preferably 0.02 to 0.1 ⁇ m.
• these polymer latexes can be used by mixing a plurality of types of latex, but polyester latex, acrylic latex and urethane latex are preferably 30% by mass or more of the resin component in the easy-adhesion layer, More preferably, it is 50 mass% or more.
• an easily bonding layer is an easily bonding layer which contains the water-soluble high molecular compound further, and was bridge
• water-soluble polymer compounds include polyacrylic acid, polyacrylamide, polyvinyl alcohol, polyvinyl pyrrolidone, copolymers of maleic anhydride and styrene, and proteins such as gelatin, albumin, casein, polylysine, carrageenan, Mucopolysaccharides such as hyaluronic acid, “chemical reaction of macromolecules” (published by Nobu Okawara, 1972, published by Chemical Dojinsha) Chapter 2.6.4, aminated cellulose, polyethyleneimine, polyallylamine, polydiallylamine, allylamine and diallylamine Examples thereof include a copolymer, a copolymer of diallylamine and maleic anhydride, and a copolymer of diallylamine and sulfur dioxide.
• the water-soluble polymer compound is preferably 60% by mass or less, more preferably 2 to 40% by mass of the resin component in the easy-adhesion layer. Further, the amount of the resin component used for the easy-adhesion layer is preferably 100 mg / m 2 or more because no trouble such as breakage occurs when peeling, and the upper limit is preferably 2500 mg / m 2 . More preferably, it is 200 to 2000 mg / m 2 , and still more preferably 300 to 1000 mg / m 2 .
• crosslinking agent examples include inorganic compounds such as chromium alum, aldehydes such as formaldehyde, glyoxal, malealdehyde, and glutaraldehyde, N-methylol compounds such as urea and ethylene urea, mucochloric acid, 2,3-dihydroxy- Aldehyde equivalents such as 1,4-dioxane, 2,4-dichloro-6-hydroxy-s-triazine salts, compounds having active halogen such as 2,4-dihydroxy-6-chloro-triazine salts, divinyl Sulfone, divinyl ketone, N, N, N-triacryloylhexahydrotriazine, compounds having two or more active three-membered ethyleneimino groups, compounds having two or more epoxy groups in the molecule, such as sorbitol Polyglycidyl ether and polyglycerol polyglycid Ether, Diglycerol poly
• polymer chemical reaction (Nobuyoshi Okawara, 1972, published by Kagaku Dojinsha) -Well-known polymer crosslinking agents, such as a crosslinking agent as described in Chapters 6-7, 5-2, 9-3, etc., can also be contained.
• a water-soluble crosslinking agent having two or more epoxy groups in the molecule or a vinylsulfone crosslinking agent is preferable.
• the vinylsulfone-based crosslinking agent refers to a compound having at least two vinylsulfonyl groups in the molecule, and refers to a compound represented by the following general formula I or general formula II.
• L 1 and L 2 each represent a divalent linking group that may or may not be present. When present, it preferably represents an alkylene group having 1 to 5 carbon atoms, an arylene group, a carbamoyl group, a sulfamoyl group, oxygen, sulfur, an imino group and the like, and these may be combined.
• R 1 represents a hydrogen atom, an optionally substituted alkyl group having 1 to 5 carbon atoms, an optionally substituted aryl group such as benzene, naphthalene, etc. Among them, a hydrogen atom is preferable.
• L is an m-valent group having at least one hydroxyl group, and m is 2 to 4.
• L is a divalent to tetravalent acyclic hydrocarbon group having 1 to 10 carbon atoms, a 5- or 6-membered heterocyclic group containing a nitrogen atom, an oxygen atom and / or a sulfur atom, 5 or Examples thereof include a 6-membered cyclic hydrocarbon group and a cycloalkylene group having 7 to 10 carbon atoms.
• the acyclic hydrocarbon group is preferably an alkylene group having 1 to 8 carbon atoms.
• Each group represented by L may have a substituent, or may be bonded to each other via a hetero atom (for example, a nitrogen atom, an oxygen atom and / or a sulfur atom), a carbonyl group or a carbamide group. Also good. L may be substituted with, for example, one or more alkoxy groups having 1 to 4 carbon atoms such as methoxy group and ethoxy group, halogen atoms such as chlorine atom and bromine atom, acetoxy group and the like.
• a hetero atom for example, a nitrogen atom, an oxygen atom and / or a sulfur atom
• L may be substituted with, for example, one or more alkoxy groups having 1 to 4 carbon atoms such as methoxy group and ethoxy group, halogen atoms such as chlorine atom and bromine atom, acetoxy group and the like.
• the addition amount of the crosslinking agent in the easy-adhesion layer is preferably 1 to 20% by mass, more preferably 3 to 15% by mass with respect to the total resin component amount in the easy-adhesion layer.
• the easy-adhesion layer can contain a matting agent such as silica, a lubricant, a pigment, a dye, a surfactant, an ultraviolet absorber and the like.
• a matting agent such as silica, a lubricant, a pigment, a dye, a surfactant, an ultraviolet absorber and the like.
• the silver salt diffusion transfer method when used as the most preferable method for providing the metal part on the easy adhesion layer of the conductive material precursor, it is preferable to contain physical development nuclei in the easy adhesion layer.
• the physical development nuclei may be uniformly distributed in the easy-adhesion layer by being included in the easy-adhesion layer coating liquid, or the surface thereof may be applied by applying a coating liquid containing physical development nuclei after the easy-adhesion layer is applied. May be distributed.
• the physical development nuclei used in the present invention fine particles (having a particle size of about 1 to several tens of nm) made of heavy metals or sulfides thereof are used.
• examples thereof include metal colloids such as gold and silver, metal sulfides obtained by mixing water-soluble salts such as palladium and zinc and sulfides, and the like.
• the content of physical development nuclei in the easy-adhesion layer is suitably about 0.1 to 10 mg / m 2 in terms of solid content.
• a method for providing a metal part on the easy-adhesion layer of the conductive material precursor a method of printing a conductive ink such as silver nano ink by an inkjet method can also be used.
• the preferred easy adhesion layer in this method is preferably a porous easy adhesion layer comprising fine particles and a resin binder. It is also possible to have an easy-adhesion layer consisting of two layers, a porous easy-adhesion layer comprising fine particles and a resin binder, and a fixing easy-adhesion layer mainly composed of a resin.
• the porous easy-adhesion layer in the present invention is a layer containing fine particles and a resin binder of 80% by mass or less based on the fine particles.
• fine particles used known fine particles can be widely used.
• inorganic fine particles light calcium carbonate, heavy calcium carbonate, kaolin, talc, magnesium carbonate, amorphous synthetic silica, alumina, and alumina hydrate are more preferable.
• Amorphous synthetic silica, alumina, and alumina hydrate are particularly preferred, and alumina hydrate is particularly preferred.
• the average primary particle size of these inorganic fine particles is preferably 50 nm or less, more preferably 3 to 40 nm, and the average secondary particle size of the inorganic fine particles is preferably 500 nm or less, more preferably 20 to 300 nm.
• the alumina ⁇ -alumina, which is a ⁇ -type crystal of aluminum oxide, is preferable, and among them, a ⁇ group crystal is preferable.
• the average primary particle diameter referred to in the present invention is an average particle diameter obtained by observing the diameter of a circle equal to the projected area of each of 100 primary particles existing within a certain area by observation with an electron microscope. It is a thing.
• the average secondary particle diameter can be determined by photography using a transmission electron microscope.
• the number median diameter can be determined using a laser scattering particle size distribution analyzer (for example, LA910, manufactured by Horiba, Ltd.). Can be measured as
• the content of fine particles in the easy-adhesion layer is preferably 0.5 to 20 g / m 2 , more preferably 2 to 15 g / m 2 .
• Examples of the resin binder used together with the fine particles constituting the porous easy-adhesion layer include various modified polyvinyl alcohols such as polyvinyl alcohol, silanol-modified polyvinyl alcohol, and silyl-modified polyvinyl alcohol, oxidized starch, etherified starch, carboxymethylcellulose, and hydroxyethylcellulose.
• modified polyvinyl alcohols such as polyvinyl alcohol, silanol-modified polyvinyl alcohol, and silyl-modified polyvinyl alcohol, oxidized starch, etherified starch, carboxymethylcellulose, and hydroxyethylcellulose.
• Cellulose derivatives such as casein, gelatin, soybean protein and other proteins, styrene-butadiene copolymers, conjugated diene copolymer latexes such as methyl methacrylate-butadiene copolymers, and various types of these polymers
• Functional group-modified polymer latex with functional group-containing monomers such as carboxyl groups
• water-based adhesives such as thermosetting synthetic resin systems such as melamine resin and urea resin, polymethyl methacrylate, poly Urethane resin, unsaturated polyester resin, vinyl chloride - vinyl acetate copolymer, polyvinyl butyral, or the like
• synthetic resin adhesive such as alkyd resins, can be used alone or in combination.
• Particularly preferred resin binders are polyvinyl alcohol and polyvinyl alcohols such as silanol-modified polyvinyl alcohol and silyl-modified polyvinyl alcohol.
• the use of known natural or synthetic resin binders alone or in combination is not particularly limited.
• the content of the resin binder with respect to the fine particles is preferably 80% by mass or less, further preferably 3 to 80% by mass, more preferably 5 to 60% by mass, and particularly preferably 10 to 40% by mass with respect to the fine particles. % Range.
• the coating amount of the resin binder is preferably 100 mg / m 2 or more so as to be easily peeled, more preferably 200 to 2000 mg / m 2 , and still more preferably 500 to 1500 mg / m 2 .
• the porous easy-adhesion layer can use a hardening agent together with the resin binder as necessary.
• the hardener include aldehyde compounds such as formaldehyde and glutaraldehyde, ketone compounds such as diacetyl and chloropentanedione, bis (2-chloroethyl) urea, 2-hydroxy-4,6-dichloro-1 , 3,5-triazine, a compound having a reactive halogen as described in US Pat. No. 3,288,775, a compound having a reactive olefin as described in US Pat. No. 3,635,718, N-methylol compounds as described in US Pat. No.
• 2,732,316 isocyanates as described in US Pat. No. 3,103,437, US Pat. Nos. 3,017,280 and 2,983,611 Aziridine compounds, carbodiimide compounds as described in US Pat. No. 3,100,704, US Pat. No. 3,091,
• Such epoxy compounds No. 37 described such as dioxane derivatives of dihydroxy dioxane, borax, boric acid, there is an inorganic crosslinking agent such as boric acid salts, it can be used in combination thereof one or more.
• Particularly preferred hardeners in the present invention are borax, boric acid, and borates.
• the amount of the hardener used is not particularly limited, but is preferably 50% by mass or less, more preferably 40% by mass or less, and particularly preferably 1 to 30% by mass with respect to the resin binder.
• Resins that can form a film by coating such as various water-soluble polymer compounds, various organic solvent-soluble resins, and various polymer latexes, can be widely used as the resin.
• the easily adhesive layer having a resin as a main component may be formed as a dense film on the porous easily adhesive layer, and the easily adhesive layer having fixing may have innumerable fine holes.
• water-soluble polymer compounds used in the easy-to-fix adhesive layer include water-soluble celluloses such as methylcellulose, ethylcellulose, and propylcellulose; gelatins such as glue, acid-treated gelatin, alkali-treated gelatin, and phthalated gelatin; polyvinyl alcohol, silanol modified Polyvinyl alcohols such as polyvinyl alcohol and diacetone acrylamide modified polyvinyl alcohol, polysaccharides such as carrageenan and gum arabic can be widely used.
• One type of water-soluble polymer compound may be used, or two or more types may be mixed and used.
• the mass average molecular weight of the water-soluble polymer compound is preferably 15000 or more, more preferably 50000 or more. When a water-soluble polymer compound is used, it is preferable that water is contained in the ink or paste containing ultrafine metal particles.
• Polymer latex used for the easy-fixing adhesive layer is acrylic resin, styrene-acrylic resin, vinyl acetate-acrylic resin, vinyl acetate resin, ethylene-vinyl acetate resin, ethylene-vinyl chloride resin, polyolefin resin, chlorinated polyolefin resin, ethylene -Multi-component resins such as vinyl acetate-acrylic, SBR, NBR, MBR, carboxylated SBR, carboxylated NBR, carboxylated MBR, vinylpyridine resin, vinyl chloride resin, vinylidene chloride resin, urethane resin, methacrylic resin, methyl methacrylate resin
• the emulsion can be widely selected from emulsions in which conventionally known resins such as epoxy resins are dispersed.
• organic solvent-soluble resin used for the easy-to-fix adhesive layer resins contained in the emulsion described in paragraph [0050] can be widely used. Moreover, a polyester resin, a polyvinyl acetal resin, a nylon resin, etc. can also be used.
• organic solvent solvents that can dissolve the resin to be used, such as ethanol, ethyl acetate, methyl ethyl ketone, and toluene, can be widely used.
• One type of organic solvent-soluble resin may be used, or two or more types may be mixed and used.
• the mass average molecular weight of the organic solvent-soluble resin is preferably 15000 or more.
• a water-soluble polymer compound or a polymer latex is preferable from the viewpoint of ease of use, and as a water-soluble polymer compound from the viewpoint of adhesion.
• polyvinyl alcohols, gelatins and polysaccharides are used, and polymer latexes are acrylic groups, vinyl groups as monomer units such as acrylic resins, styrene-acrylic resins, vinyl acetate-acrylic resins, and ethylene-vinyl chloride resins. More preferred are resins having a urethane bond and urethane resins having a urethane bond.
• polymer latex To these water-soluble polymer compounds, polymer latex, and organic solvent-soluble resins, water, organic solvents, leveling agents, surfactants, etc., are added as necessary to form a resin-based adhesive layer. It is adjusted as a coating liquid.
• the solid content coating amount of the fixing adhesive layer is preferably 0.01 ⁇ 5g / m 2, more preferably 0.05 ⁇ 1g / m 2. If it is less than 0.01 g / m 2 , the adhesion of the metal part may be insufficient, and if it exceeds 5 g / m 2 , the ink absorbability of the porous easy adhesion layer may be lowered.
• a metal foil such as a copper foil is pasted, a resist film is further formed thereon, exposure, development, etching, resist layer removal
• epoxy adhesives urethane adhesives, ultraviolet curable adhesives, hot melt adhesives such as EVA and acrylic can be used as the easy adhesion layer.
• a method using a silver salt photosensitive material, electroless plating or electrolytic plating is further applied to a silver image obtained using the same method.
• Method of applying Method of printing conductive ink such as silver paste using screen printing method, Method of printing conductive ink such as silver ink by inkjet method, Conductive layer made of metal such as copper by electroless plating
• a known method such as a method of attaching a metal foil such as the above, further forming a resist film thereon, exposing, developing, etching, and removing the resist layer can be used.
• a silver salt diffusion transfer method in which the thickness of the metal part to be manufactured can be reduced and a very fine metal part can be easily formed.
• a method for producing a metal portion using such a silver salt diffusion transfer method for example, a method proposed in Japanese Patent Application Laid-Open No. 2003-77350 can be used.
• the conductive material irradiates the conductive material precursor with active energy rays, crosslinks the active energy ray adhesion lowering resin layer, and the adhesion between the support and the active energy ray lowering resin layer. And the conductive material comprising at least the easy-adhesion layer and the metal part is peeled from the support. Visible light, ultraviolet light (UV) and electron beam (EB) can be used as the active energy ray, but it is preferable to use visible light or ultraviolet light from the viewpoint of safety.
• UV ultraviolet light
• EB electron beam
• examples of the light source include low-pressure mercury lamp, medium-pressure mercury lamp, high-pressure mercury lamp, ultra-high-pressure mercury lamp, xenon mercury lamp, xenon lamp, gallium lamp, metal halide lamp, quartz halogen lamp, tungsten lamp, and ultraviolet light.
• a fluorescent lamp, a carbon arc lamp, an electrodeless microwave ultraviolet lamp, etc. are preferably used.
• the active energy ray is preferably irradiated from the support side of the conductive material precursor so that the metal part does not get in the way.
• the preferable irradiation light amount varies depending on the photopolymerization initiator, the sensitizer and the like, but is 50 to 5000 mJ / cm 2 .
• the surface temperature of the conductive material precursor does not become 100 ° C. or higher, preferably 60 ° C. or higher so that peeling in the peeling step after irradiation with active energy rays becomes easy.
• the irradiation of the active energy ray may be performed before or after the protective film bonding step described later, but is preferably before the protective film bonding step.
• the active energy ray irradiation step in the present invention changes the adhesion when the conductive material including the metal part and the easy-adhesion layer is peeled from the conductive material precursor.
• the adhesion between the support and the conductive material after irradiation with active energy rays by the 180 ° peeling method is preferably 0.5 N / 25 mm or less, more preferably 0.001 to 0.1 N / 25 mm. It is.
• a conductive material comprising an easy adhesion layer and a metal part is peeled from a conductive material precursor irradiated with active energy rays. Accordingly, it is possible to produce a conductive material that is one of the objects of the present invention and has a high rigidity at the time of manufacture and a low rigidity by the amount of the peeled support at the time of completion.
• the conductive material of the present invention is peeled off from the support, and the rigidity is lowered accordingly. For this reason, it may curl at the time of peeling, and it may become difficult to handle.
• a protective film is bonded to the metal part side of the conductive material precursor before peeling, and the conductive material is peeled together with the protective film.
• the protective film a commercially available film in which an ethylene-vinyl acetate copolymer layer or an acrylic pressure-sensitive adhesive layer is provided on a low-rigidity support made of polyethylene, polypropylene, polyvinyl chloride or the like can be used.
• the adhesion force when bonded to the precursor must be stronger than the adhesion force when peeling the conductive material including the metal part and the easy-adhesion layer from the support of the conductive material precursor.
• the adhesive force is too strong, it is difficult to peel the protective film from the conductive material. Accordingly, the preferable adhesive strength of the protective film varies depending on the active energy ray adhesive strength-reducing resin layer, but it is preferable to select a protective film having an adhesive strength of 0.001 to 0.5 N / 25 mm.
• Examples of such commercially available protective films include Pyrene DC042 manufactured by Toyobo, E2035, E203, EC625 manufactured by Sumilon, and 622AX, 622F manufactured by Sekisui Chemical Co., Ltd.
• the thickness of the protective film is preferably 30 to 50 ⁇ m.
• a known laminating method such as room temperature laminating or warming laminating can be used.
• the lamination is performed at 60 ° C. or less, preferably at room temperature so as not to affect the thermal expansion of the resin part such as the metal part and the easy adhesion layer.
• the protective film When the protective film is bonded, the conductive material is peeled off from the support together with the protective film, and then the protective film is peeled off from the conductive material.
• the protective film can be peeled off from the conductive material as a single sheet, or the pro-protective film can be peeled off from the conductive material by a roll-to-roll method. It may be peeled off.
• the protective film is peeled off from the conductive material, for example, the protective film may be peeled off after the conductive material is adhered to the adherend using an adhesive or the like, or the protective film is directly protected from the conductive material. It is also possible to peel the film.
• Example 1 The product name “Tetron HLY” made by Teijin DuPont as a support is 100% thick PET. Total light transmittance is 91%.
• One-side easy-adhesion treatment is a hydrophilic treatment on one side of the support.
• the active energy ray-adhesion-reducing resin layer coating solution 1 having the following formulation was prepared and applied on the untreated surface of the untreated surface) and dried at 70 ° C. for 5 minutes. The thickness of the Tetoron HLY film was measured before and after the formation of the active energy ray adhesion-reducing resin layer, and the thickness of the active energy ray adhesion-reducing resin layer was calculated. The results are shown in Table 1.
• an easy-adhesion layer coating solution 1 was prepared according to the following formulation, applied onto the active energy ray-adhesion-reducing resin layer, and dried at 50 ° C. for 10 minutes. After drying, it was heated at 50 ° C. for 24 hours.
• the thickness of the obtained easy-adhesion layer was measured using a confocal microscope (manufactured by Lasertec Co., Ltd.) having a trade name “Optelix C120”, and was 0.1 ⁇ m.
• an intermediate layer 1, a silver halide emulsion layer 1, and an outermost layer 1 having the following composition were coated on the easy-adhesion layer in this order from the side closer to the support.
• the backing layer 1 was applied to the surface of the support opposite to the active energy ray adhesion-reducing resin layer side.
• the silver halide emulsion was prepared by a general double jet mixing method for photographic silver halide emulsions. This silver halide emulsion was prepared with 95 mol% of silver chloride and 5 mol% of silver bromide, and an average grain size of 0.15 ⁇ m.
• the silver halide emulsion thus obtained was subjected to gold sulfur sensitization using sodium thiosulfate and chloroauric acid according to a conventional method.
• the silver halide emulsion thus obtained contains 0.5 g of gelatin per gram of silver.
• a positive transmission original having a mesh pattern portion having a fine line width of 20 ⁇ m and a lattice interval of 250 ⁇ m and a portion having no pattern is brought into close contact with a contact printer using a mercury lamp as a light source through a resin filter that cuts light of 400 nm or less. It exposed with the exposure amount of / cm ⁇ 2 >.
• the film was immersed in a diffusion transfer developer having the following composition at 15 ° C. for 90 seconds, and then the silver halide emulsion layer 1, intermediate layer 1, outermost layer 1 and backing layer 1 were removed by washing with warm water at 40 ° C. Then, it dried and obtained the electroconductive material precursor 1.
• a metal part having a thin line width of 20 ⁇ m and a lattice spacing of 250 ⁇ m was formed on the easy-adhesion layer. It was 0.1 micrometer when the thickness of the metal part was measured using the confocal microscope (made by Lasertec) of brand name "Optelix C120".
• ⁇ Diffusion transfer developer composition Potassium hydroxide 25g Hydroquinone 18g 1-phenyl-3-pyrazolidone 2g Potassium sulfite 80g N-methylethanolamine 15g Potassium bromide 1.2g The total amount of the above-mentioned diffusion transfer developer composition was added to 1000 mL of water, and the pH adjusted to 12.2 with an 85 mass% phosphoric acid aqueous solution was used.
• the obtained conductive material precursor 1 was subjected to measurement of Clark stiffness and adhesion as a peel test before irradiation with active energy rays.
• Clark stiffness was measured according to JIS-P8143.
• the adhesion force is measured by attaching a Nichiban vehicle masking tape No241 to the non-metal part of the conductive material precursor 1 (corresponding to the part without the pattern of the positive transmission original and without the metal part).
• the adhesive strength was measured by a 180 ° peeling method using a product name “IPT200-5N” manufactured by Imada. Moreover, it was observed visually where peeling occurred. The results are shown in Table 1.
• this protective film is bonded to the non-metal part (corresponding to the part without the pattern of the positive transmission original, where the metal part is not formed) of the active energy ray adhesion-reducing resin layer before irradiation with the active energy ray. Then, it was cut to a width of 25 mm, and the adhesion was measured by 180 ° peeling method using a product name “IPT200-5N” manufactured by Imada, and it was 0.5N.
• Conductive material precursor obtained by bonding a trade name “EC625” (60 ⁇ m thick protective film) manufactured by Sumilon Co., Ltd. to the surface of the metal part opposite to the surface of the support irradiated with the active energy ray and the surface of the easy adhesion layer.
• the conductive material including the metal part, the easy-adhesion layer, and the active energy ray-adhesion-reducing resin layer together with the protective film was peeled from the support of 1 to obtain a conductive material 1.
• the protective film was peeled off from the conductive material 1 and the thickness thereof was measured with a thickness gauge, the thickness of the metal part was 7.2 ⁇ m and the thickness of the non-metal part was 7.1 ⁇ m.
• ⁇ Spherical adhesion test> The conductive material 1 is bonded to an acrylic ball having an outer diameter of 300 mm and 200 mm using a trade name “Loctite U-30FL” (urethane adhesive) manufactured by Henkel Japan Co., Ltd., and 30 minutes have passed after the bonding.
• the protective film with the trade name “EC625” was peeled off. An evaluation was given as ⁇ when the conductive material 1 had a good peeled surface without wrinkles and tears, and when the conductive material 1 was flawed or broken.
• a conductive material precursor 1 heated for 3 days at 50 ° C. before irradiation with active energy rays with a high-pressure mercury lamp is also produced, and the heated conductive material precursor 1 is not heated.
• the conductive material precursor 1 after irradiating the active energy ray, measurement of adhesion force, measurement of Clark stiffness, and evaluation of peeling by 180 ° peeling method were performed. The results are shown in Table 1.
• the conductive material precursor 2 of Example 2 was obtained in the same manner as in Example 1 except that the modified polyvinyl acetal resin solution prepared above was used in place of the hyaloid 7975 (with the same solid coating amount per m 2 ). It produced and evaluated similarly to Example 1. The results are shown in Table 1. Although the peelability slightly decreased because of the high adhesion after irradiation with active energy rays, the same results as in Example 1 were obtained.
• Comparative Example 1 The same as in Example 1 except that the trade name “UA340P” (Shin Nakamura Chemical Urethane acrylate oligomer. Mass average molecular weight 13000) was used in place of Hitaroid 7975 (with the same solid content per 1 m 2 ).
• the conductive material precursor of Comparative Example 1 was prepared and tried to be evaluated. However, after irradiating active energy rays and attaching a protective film, an attempt was made to peel off the conductive material including the metal part, the easy-adhesion layer, and the active energy ray adhesion-reducing resin layer together with the protective film from the support. , Can not be peeled.
• Comparative Example 2 This comparative example shows that a fine metal part cannot be formed on a curved surface with a conductive material having a high Clark stiffness.
• a conductive material precursor of Comparative Example 2 was prepared and evaluated in the same manner as in Example 1 except that the active energy ray adhesion lowering resin layer was not applied.
• the product name “Loctite U-30FL” manufactured by Henkel Japan is applied to acrylic balls with outer diameters of 300 mm and 200 mm without the active energy ray irradiation process, the protective film bonding process, and the protective film peeling process. (Urethane adhesive) was used, and the support surface of the conductive material and the acrylic ball were bonded together. The results are shown in Table 1.
• Comparative Example 3 The conductive material of Comparative Example 3 was prepared in the same manner as in Example 1 except that the physical development nucleus coating liquid having the following formulation was applied on the resin layer having reduced adhesion to active energy rays instead of providing the easy-adhesion layer of Example 1. A precursor was made and tried to be evaluated. However, in the peeling process, the conductive material could not be peeled off successfully, and the conductive material was broken on the way. The results are shown in Table 1 for the items that could be evaluated.
• Example 3 In Example 1, in place of the active energy ray adhesion lowering resin layer coating solution 1, the following active energy ray adhesion lowering resin layer coating solution 2 was prepared and used in the same manner as in Example 1, The conductive material precursor 3 of Example 3 was produced and evaluated in the same manner as in Example 1. The results are shown in Table 1.
• Example 4 In Example 1, in place of the active energy ray adhesion-reducing resin layer coating solution 1, the following active energy ray adhesion-reducing resin layer coating solution 3 was prepared and used in the same manner as in Example 1, The conductive material precursor 4 of Example 4 was produced and evaluated in the same manner as in Example 1. The results are shown in Table 1.
• Example 5 In the same manner as in Example 2, a modified polyvinyl acetal resin solution having a solid content concentration of 10% was obtained.
• a conductive material precursor 5 of Example 5 was produced in the same manner as in Example 4 except that the produced modified polyvinyl acetal resin solution was used in place of Hitaroid 7975 (with the same solid coating amount per 1 m 2 ). Evaluation was performed in the same manner as in Example 1. The results are shown in Table 1. Although the peel strength slightly decreased because of the high adhesion after irradiation with active energy rays, the same results as in Example 4 were obtained.
• Comparative Example 4 Example 4 except that the trade name “UA340P” (Shin Nakamura Chemical Co., Ltd. urethane acrylate oligomer. Mass average molecular weight 13000) was used in place of Hitaroid 7975 (with the same solid content per 1 m 2 ).
• a conductive material precursor of Comparative Example 4 was prepared and evaluated. However, after irradiating active energy rays and pasting the protective film, an attempt was made to peel off the conductive material including the metal part, the easy-adhesion layer, and the active energy ray adhesion-reducing resin layer together with the protective film. There wasn't.
• Comparative Example 5 The product name “A-DPH” (dipentaerythritol hexaacrylate manufactured by Shin-Nakamura Chemical Co., Ltd., mass average molecular weight 578) was used in place of Hitaroid 7975 (the same solid content per 1 m 2 ).
• a conductive material precursor of Comparative Example 5 was prepared and tried to be evaluated. However, it tried to peel off by irradiating active energy rays and pasting the protective film, but it could not be peeled off.
• Example 6 The conductivity of Example 6 was the same as Example 4 except that instead of the active energy ray adhesion reducing resin layer coating solution 3, the following active energy ray adhesion reducing resin layer coating solution 4 was prepared and used. A functional material precursor 6 was prepared and evaluated in the same manner as in Example 1. The results are shown in Table 1.
• Example 7 The conductivity of Example 7 was the same as Example 4 except that the following active energy ray adhesion reducing resin layer coating solution 5 was prepared and used instead of the active energy ray adhesion reducing resin layer coating solution 3.
• the conductive material precursor 7 was prepared and evaluated in the same manner as in Example 1. The results are shown in Table 1.
• Example 8 The conductivity of Example 8 was the same as Example 4 except that instead of the active energy ray adhesion reducing resin layer coating solution 3, the following active energy ray adhesion reducing resin layer coating solution 6 was prepared and used. A functional material precursor 8 was prepared and evaluated in the same manner as in Example 1. The results are shown in Table 1.
• Example 9 The conductivity of Example 9 was the same as Example 4 except that the following active energy ray adhesion reducing resin layer coating solution 7 was prepared and used instead of the active energy ray adhesion reducing resin layer coating solution 3.
• the conductive material precursor 9 was prepared and evaluated in the same manner as in Example 1. The results are shown in Table 1.
• Example 10 The conductivity of Example 10 was the same as Example 4 except that the following active energy ray adhesion reducing resin layer coating solution 8 was prepared and used instead of the active energy ray adhesion reducing resin layer coating solution 3.
• a functional material precursor 10 was prepared and evaluated in the same manner as in Example 1. The results are shown in Table 1.
• Example 11 The conductivity of Example 11 was the same as Example 4 except that instead of the active energy ray adhesion reducing resin layer coating solution 3, the following active energy ray adhesion reducing resin layer coating solution 9 was prepared and used. A functional material precursor 11 was prepared and evaluated in the same manner as in Example 1. The results are shown in Table 1.
• Example 12 The conductivity of Example 12 was the same as Example 4 except that the following active energy ray adhesion reducing resin layer coating solution 10 was prepared and used instead of the active energy ray adhesion reducing resin layer coating solution 3.
• the conductive material precursor 12 was prepared and evaluated in the same manner as in Example 1. The results are shown in Table 1.
• Example 13 The conductivity of Example 13 was the same as Example 4 except that the following active energy ray adhesion reducing resin layer coating solution 11 was prepared and used instead of the active energy ray adhesion reducing resin layer coating solution 3.
• a functional material precursor 13 was prepared and evaluated in the same manner as in Example 1. The results are shown in Table 1.
• Example 14 The conductivity of Example 14 was the same as Example 4 except that instead of the active energy ray adhesion reducing resin layer coating solution 3, the following active energy ray adhesion reducing resin layer coating solution 12 was prepared and used. A functional material precursor 14 was prepared and evaluated in the same manner as in Example 1. The results are shown in Table 1.
• Example 15 The conductivity of Example 15 was the same as Example 4 except that instead of the active energy ray adhesion reducing resin layer coating solution 3, the following active energy ray adhesion reducing resin layer coating solution 13 was prepared and used.
• the material precursor 15 was prepared and evaluated in the same manner as in Example 1. The results are shown in Table 1.
• Example 16 The conductivity of Example 16 was the same as that of Example 4 except that the following active energy ray adhesion reducing resin layer coating solution 14 was prepared and used instead of the active energy ray adhesion reducing resin layer coating solution 3.
• a functional material precursor 16 was prepared and evaluated in the same manner as in Example 1. The results are shown in Table 1.
• Example 17 Nitric acid (2.5 parts) and alumina hydrate (average primary particle size 15 nm) were added to water, and an inorganic fine particle dispersion having a solid content concentration of 30% by mass was obtained using a sawtooth blade type disperser. .
• the average secondary particle diameter of the alumina hydrate dispersed in the inorganic fine particle dispersion was 160 nm.
• a porous easy-adhesion layer coating solution 2 having the following composition was prepared.
• ⁇ Porous easy adhesion layer coating liquid 2 Inorganic fine particle dispersion (as solid content of alumina hydrate) 100g Polyvinyl alcohol 12g (Saponification degree 88%, average polymerization degree 3500, molecular weight about 150,000) Boric acid 0.5g Nonionic surfactant (polyoxyethylene alkyl ether) 0.3g It adjusted with water so that solid content concentration might be 16 mass%.
• Example 2 In the same manner as in Example 1, the same amount of the active energy ray adhesion-reducing resin layer coating solution 1 is applied onto the support as in Example 1, and then the porous easy-adhesion layer coating solution 2 is coated with alumina hydrate. Coating was performed using a slide bead method so that the solid content was 7.5 g / m 2, and dried with a dryer. The thickness of the porous layer formed on the support was about 10 ⁇ m, and the void volume measured using a mercury porosimeter was 5.75 ml / m 2 .
• centrifugation was performed to cleanly separate the silver ultrafine particles and the supernatant, and the supernatant was discarded.
• the remaining ultrafine silver particles were redispersed, repeatedly centrifuged, and the supernatant was discarded.
• pure water was added and redispersed to obtain 110 g of a silver ultrafine particle dispersion 1 having a silver concentration of 47.2% by mass.
• a dry film resist (trade name “SUNFORT series SPG” manufactured by Asahi Kasei Co., Ltd.) having a thickness of 15 ⁇ m is laminated on the support on which the porous easy-adhesion layer is formed as described above, and 400 nm with a contact printer using a mercury lamp as a light source. Without passing through a resin filter that cuts light, a negative transmission original having a mesh pattern with a fine line width of 20 ⁇ m and a lattice interval of 250 ⁇ m was brought into close contact, exposed at an exposure amount of 100 mJ / cm 2 , and 1% by mass at 30 ° C. Development was carried out for 40 seconds while rocking in an aqueous sodium carbonate solution.
• the silver ultrafine particle-containing composition 1 was applied on the patterned dry film resist using a wire bar so that the thickness of silver was 0.2 ⁇ m after drying, and dried at 120 ° C. for 10 minutes. Thereafter, a dry film resist was peeled off and removed by spraying a 3% by mass sodium hydroxide aqueous solution at 40 ° C. by spraying, and the conductive material precursor 17 was produced.
• the obtained conductive material precursor 17 was evaluated in the same manner as in Example 1. The results are shown in Table 1. Further, when the thickness of the conductive material was measured with a thickness gauge in the same manner as in Example 1, it was 17.2 ⁇ m for the metal part and 17.1 ⁇ m for the non-metal part.
• Example 18 As the easy-adhesion layer coating solution formulation of Example 1, a conductive material was obtained in the same manner as in Example 1 except that an easy-adhesion layer coating solution was prepared and applied according to the following easy-adhesion layer coating solution 3 formulation. The same results as in Example 1 were obtained.
• Example 19 To a 10 liter stainless beaker, 272 g of roasted dextrin (trade name “dextrin No. 3” manufactured by Nissho Kagaku Co., Ltd.) having a mass average molecular weight of about 15000 and 4300 g of pure water were added and stirred for dissolution for about 30 minutes. Thereafter, 659 g of silver nitrate was added and dissolved by stirring for about 30 minutes. This solution was cooled to about 5 ° C. in an ice bath, a 10 ° C. solution in which 304.5 g of potassium hydroxide was dissolved in 419.5 g of pure water was added, and the reduction reaction was performed for 1 hour while stirring in the ice bath. Went.
• roasted dextrin trade name “dextrin No. 3” manufactured by Nissho Kagaku Co., Ltd.
• Acetic acid was added to the resulting solution to adjust the pH to 5.6, and 1 g of an enzyme having a trade name “Biozyme F10SD” (manufactured by Amano Enzyme Co., Ltd.) was added and stirred at 45 ° C. for 1 hour.
• an enzyme having a trade name “Biozyme F10SD” manufactured by Amano Enzyme Co., Ltd.
• 800 g of silver ultrafine particle dispersion 2 was obtained by re-dispersing by adding pure water so that the silver concentration was 45% by mass. .
• the silver ultrafine particles contained had an average particle diameter of 20 nm and a yield of 86%.
• the silver ultrafine particle-containing composition 2 was printed in a mesh shape having a line width of 50 ⁇ m and a line interval of 500 microns by flexographic printing. After drying with warm air, it was immersed in a 3N sodium chloride aqueous solution at 80 ° C. for 30 seconds, washed with water and dried to form a silver film on the frame portion. During the printing process, the active energy ray adhesion reducing resin layer was not sticky, and no trouble occurred during printing.
• Example 4 Thereafter, as in Example 4, the high energy mercury lamp was irradiated from the side opposite to the active energy ray adhesion lowering resin layer of the conductive material precursor, and the active energy ray adhesion lowering resin layer of the conductive material precursor was irradiated. It peeled. Even in this peeling process, peeling was possible without any problem.
• the pressure-sensitive adhesive solution obtained above was applied on the same support as used in Example 4, and dried at 70 ° C. for 5 minutes to prepare an ultraviolet-sensitive adhesive film.
• Example 19 In the same manner as in Example 19, an attempt was made to print the silver ultrafine particle-containing composition 2 on a UV adhesive strength disappearing pressure-sensitive adhesive film by flexographic printing in a mesh shape having a line width of 50 ⁇ m and a line interval of 500 ⁇ m. I stuck to the printing board and could not print well.
• the active energy ray-adhesiveness-reducing resin layer containing an active energy ray-curable polymer compound having an unsaturated double bond having a mass average molecular weight of 15000 or more on the support According to the conductive material precursor having at least the adhesive layer and the metal portion in this order, the conductive material can be peeled off without being broken when the conductive material is peeled off from the conductive material precursor. It can be seen that even when the conductive material peeled from the precursor is bonded to the spherical surface, it can be easily bonded without wrinkles.

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• 2011
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