JP2013031928A - Release film and method of manufacturing conducting material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a conducting material in which the rigidity is high when manufacturing and the rigidity becomes low when completing, a release film that is suitable for the production of an extremely thin conducting material and that can stably release a metal pattern formed on a thin release layer, and to provide a method of manufacturing a conducting material using the same.SOLUTION: The release film at least includes a release layer that includes an active energy ray curability polymer compound having at least 15,000 of a weight average molecular weight and having an unsaturated double bond, and an epoxy compound, on a base material, wherein the release layer includes 40 mass% of the active energy ray curability polymer compound based on the total solid content of the release layer and 8 mass% of the epoxy compound based on the total solid content of the release layer.

Description

  The present invention is a release film used for various optical films such as decorative films and hard coat films, in particular, circuit materials for flexible printed circuit boards, various antenna materials such as mobile phones and in-vehicle antennas, current collectors, electromagnetic wave shielding materials, etc. The present invention relates to a release film used for a conductive material. Moreover, it uses for the manufacturing method of the electroconductive material using this peeling film.

  In recent years, it has been required to form a metal pattern such as an antenna on a molded product having a curved surface, such as an antenna for a car or an antenna for a mobile phone. However, it is very difficult to form a fine metal pattern on the curved surface.

  As a method for producing a flexible conductive material by forming a metal pattern on a flexible resin substrate, various methods such as a subtracting method, a printing method, and a photographic method have been proposed. A metal pattern can be formed on the curved surface by bonding the flexible conductive material to the curved surface. In the case where a conductive material is bonded to a curved surface, the softer the conductive material, the more unlikely to occur during bonding, which is preferable. On the other hand, at the stage of producing a conductive material, the higher the rigidity, the less likely to cause wrinkles during the production. Accordingly, there is a demand for obtaining a conductive material having high rigidity at the stage of manufacturing the conductive material and having low rigidity at the time of bonding.

  For example, in Japanese Patent Application Laid-Open No. 2003-78324 (Patent Document 1), a carrier film is bonded to a rigid metal foil, followed by half-cut processing, and a pattern is formed by peeling the patterned metal pattern for each carrier film. ing. However, in this method, for example, a portion that cannot be peeled off by a complicated pattern such as a loop antenna occurs. Further, when the peeling method as shown in FIG. 3 of Patent Document 1 is used, 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.

  Although it is not processing of a curved surface, a metal foil is bonded on a base material in Japanese Patent Application Laid-Open No. 2006-15662 (Patent Document 2), Japanese Translation of PCT International Publication No. 2009-520251 (Patent Document 3), and the like. There has also been proposed a method of patterning by etching by a known method and then transferring to a transfer target. However, in the transfer method, the substrate and the metal foil are bonded together before patterning, and if the strength of the glue at the time of bonding is too strong, a portion that cannot be peeled off when the metal foil is peeled off, or If the strength is too weak, there arises a problem that the metal foil is peeled 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. Further, since the ease of peeling differs depending on the shape and size of the pattern to be peeled off, transfer may not be successful depending on the pattern pattern.

  In JP-A-2004-82711 (Patent Document 4), JP-A-2008-260227 (Patent Document 5) and the like, an active energy ray adhesive disappearance type adhesive is used to bond a substrate and a metal foil. . In the case of using the active energy ray adhesive strength disappearing type adhesive, 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. However, since the pressure-sensitive adhesive layer comes to the surface when patterning the metal pattern, the pressure-sensitive adhesive may be damaged by fouling the process or the transfer body may be wound around the roll by the pressure-sensitive adhesive. It was. Furthermore, when transferring, the metal pattern is peeled off from the adherend using an adhesive or the like, but the cured active energy ray adhesive disappearing adhesive at this time is also bonded together. In some cases, peeling was not possible.

  Japanese Patent Application Laid-Open No. 2006-1111889 (Patent Document 6) proposes a method in which a metal mesh produced using a silver salt photographic transfer method is peeled off by enzyme treatment. Alternatively, Japanese Patent Laying-Open No. 2002-275661 (Patent Document 7) also proposes a method of manufacturing a single metal mesh. In these methods, since the pattern is peeled from the substrate, there is no problem until the pattern is produced, and a fine pattern can be easily produced. However, a pattern having a connected pattern such as a mesh may be used, but it will be separated when the array antenna or the like is peeled off, so that it is not a solution to the problem of processing the array antenna or the like.

  In recent years, antenna materials and electromagnetic shielding materials are strongly required to be lightweight and thin depending on the application. For example, in the case of mobile phones, the degree of integration of parts has already reached the limit, and further slimming and weight reduction are required. Avoid increasing the weight and thickness of base materials that do not contribute to the conductive function as much as possible. Must be done. Even in an electromagnetic wave shield for automobile electrical components, a thinner conductive material is preferable for reducing the weight of the automobile.

  There are known hard coat transfer sheets in which a protective layer and an adhesive layer are provided on a substrate, such as JP 2010-126633 A (Patent Document 8) and Japanese Patent No. 2779590 (Patent Document 9). It is also known that these transfer sheets are provided with a decorative layer made of a metal thin film between a protective layer and an adhesive layer. Since this transfer sheet has a base material in the production stage, it has high rigidity and is easy to handle, but after peeling, only an extremely thin layer is used. However, since the metal thin film used for this decoration layer is buried between the protective layer and the adhesive layer, it is difficult to use the metal thin film as a conductive material with wiring taken from the outside. Furthermore, since the protective layer has a hard coat function for preventing scratches, the adherend may be cracked at the time of peeling or further torn during the subsequent secondary processing unless the adherend is rigid.

JP 2003-78324 A JP 2006-15662 A Special table 2009-520251 gazette JP 2004-82711 A JP 2008-260227 A JP 2006-1111889 A JP 2002-275661 A JP 2010-126633 A Japanese Patent No. 2779590

  Therefore, the object of the present invention is suitable for the production of a conductive material having a high rigidity at the time of manufacture and a low rigidity at the time of completion, and an extremely thin conductive material, and a metal pattern formed on a thin release layer. It is providing the peeling film which can peel stably, and the manufacturing method of an electroconductive film using the same.

The present invention has been achieved by the following invention.
(1) On a base material, it has at least a release layer containing an active energy ray-curable polymer compound having an unsaturated double bond having a mass average molecular weight of 15000 or more and an epoxy compound, and the release layer has the activity described above. A release film comprising an energy ray-curable polymer compound in an amount of 40% by mass or more based on the total solid content of the release layer, and an epoxy compound in an amount of 8% by mass or more based on the total solid content of the release layer. .
(2) The release film according to (1), wherein the release layer further contains a thermal cationic polymerization initiator.
(3) The step of forming a conductive layer on the side away from the substrate of the release layer of the release film described in (1), the active energy ray irradiation step, the protective film on the side having the conductive layer on the release layer side The manufacturing method of the electroconductive material which comprises at least the process of bonding, and the process of peeling at least a peeling layer and an electroconductive layer with a protective film.

  According to the present invention, the metal pattern formed on the thin release layer is stably peeled off, which is suitable for the production of a conductive material having high rigidity at the time of manufacture and low rigidity at the time of completion, and an extremely thin conductive material. It becomes possible to provide a release film that can be formed. Further, it is possible to provide a method for manufacturing a conductive material that has high rigidity at the time of manufacture and low rigidity at the time of completion.

  The release film of the present invention has at least a release layer containing an active energy ray-curable polymer compound having an unsaturated double bond having a mass average molecular weight of 15000 or more and an epoxy resin on a substrate. The base material used for the release film of the present invention is not particularly limited as long as it is a material that transmits active energy rays, but a resin base material having a total light transmittance of 50% or more is particularly preferable, and a total light transmittance is further preferable. Is preferably a resin base material having 80% or more. Examples of the base material include resin base materials such as polyester resin represented by polyethylene terephthalate, diacetate resin, triacetate resin, acrylic resin, polycarbonate resin, polyvinyl chloride, polyimide resin, polyvinylidene fluoride, cellophane, and celluloid. . Among these base materials, a polyester resin that has rigidity, is easy to handle, and provides good peelability is preferable. Moreover, it is also possible to provide a release layer between a base material and a peeling layer so that a peeling layer can be peeled easily. As the release layer in the present invention, waxes such as paraffin, carnauba, and polyethylene, resins such as acrylic, melamine, epoxy, aliphatic ester, olefin, silicone resin, and fluororesin are used alone or in combination. And a release layer that has been incorporated, and may also 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 substrate.

  The release layer of the release film of 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. Such an active energy ray-curable polymer compound is (1) a polymer compound having an active hydrogen-containing group such as a hydroxyl group, a carboxyl group, an amino group, a mercapto group, and an amide group and having a molecular weight of 15000 or more, such as polyvinyl alcohol and polyvinyl butyral. Various polyvinyl acetal resins such as polyvinylformal, polyallylamine, acrylic esters such as acrylic acid and alkyl acrylate, methacrylic esters such as acrylamide, acrylonitrile, methacrylic acid and alkyl methacrylate, methacrylamide and methacrylonitrile An epoxy group-containing polymerizable unsaturated compound such as allyl glycol is added to an acrylic polymer such as a homopolymer of any of the above monomers or a copolymer obtained by polymerization of two or more of these monomers. Highly obtained by a method of reacting a compound having an unsaturated double bond with a group capable of reacting with an active hydrogen such as an isocyanate group-containing polymerizable unsaturated compound such as methacryloyloxyethyl isocyanate. It was obtained by synthesizing by a known method such as a molecular compound or (2) an addition reaction of unsaturated carboxylic acid to an epoxy group-containing acrylic polymer as described in WO 2005/87831. A high molecular compound is mentioned. Among these active energy ray-curable polymer compounds, a polymer obtained by addition-reacting an unsaturated compound with an acrylic polymer is preferable in that good peelability can be obtained. These active energy ray-curable polymer compounds having an unsaturated double bond having a mass average molecular weight of 15000 or more may be used alone or in combination.

  Commercially available products may 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. As a commercial item, Hitachi Chemical 7975 (average molecular weight 50000) of Hitachi Chemical Co., Ltd. can be used preferably.

  In the release layer of the release film of the present invention, the active energy ray-curable polymer compound having an unsaturated double bond having a molecular weight of 15000 or more is contained in an amount of 40% by mass or more based on the total solid content of the release layer. Furthermore, it is preferable to contain 50-90 mass%, More preferably, it is 60-70 mass%.

  The release layer of the release film of the present invention contains 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. For example, 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-diepoxylimonene, 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexanecarboxylate, bis (3,4-epoxycyclohexyl) adipate, alkoxysilane compound having an epoxy group And silane coupling agents having an epoxy group such as γ-glycidoxypropyltrimethoxysilane, Can be used bisphenol A type epoxy resin, bisphenol F type epoxy resins, tetra-hydroxyphenyl methane type epoxy resin, novolak type epoxy resins, the known epoxy compounds such as resorcin type epoxy resins.

  In the release layer of the release film of the present invention, the epoxy compound is preferably used in an amount of 8% by mass or more, preferably 10 to 30% by mass, more preferably 15 to 25% by mass with respect to the total solid content of the release layer.

  The release layer of the release film of the present invention preferably contains a thermal cationic polymerization initiator. Thermal cationic polymerizers 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. These initiators can be easily obtained as commercial products. For example, both of them are trade names such as Adeka Opton CP77 and Adeka Opton CP66 (manufactured by ADEKA Co., Ltd.), CI-2623 and CI-2624 ( As mentioned above, Nippon Soda Co., Ltd.), Sun-Aid SI-60L, Sun-Aid SI-80L, and Sun-Aid SI-100L (above, Sanshin Chemical Industry Co., Ltd.) are included. These compounds may use only 1 type and may use 2 or more types together. These 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 epoxy compound.

  The release layer of the release film of the present invention preferably contains a photopolymerization initiator. As the 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, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 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 the solid content of the active energy ray-curable polymer compound having an unsaturated double bond having a mass average molecular weight of 15000 or more. 1 to 10% by mass.

  In addition to the photopolymerization initiator, at least one kind of photosensitizer can be added as necessary 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. Specific examples include amine compounds such as triethylamine, diethylaminoethyl methacrylate and N-methyldiethanolamine, phosphorus compounds such as acylphosphine oxide and tributylphosphine, nitrile compounds such as 5-nitroacenaphthene, and 4-dimethylaminoethylbenzoate. Benzoin compounds such as 4-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, Carbonyl compounds such as dimethyl dimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- (4- (methylthio) phenyl) -2-morpholino-propene-1, 2,2-dimethoxy-2-phenylacetophenone, diphenyl Examples thereof include sulfur compounds such as disulfide and dithiocarbamate, naphthalene compounds such as α-chloromethylnaphthalene, condensed aromatic hydrocarbons such as anthracene, and metal salts such as iron chloride. These may be used alone or in combination of two or more. The content is preferably 0.1 to 10% by mass, more preferably 0.5 to 10% by mass with respect to the solid content of the active energy ray-curable polymer compound having an unsaturated double bond having a mass average molecular weight of 15000 or more. 5% by mass.

  The release layer of the release film of the present invention uses a polymer compound having no unsaturated double bond in addition to the active energy ray-curable polymer compound having an unsaturated double bond having a molecular weight of 15000 or more. It is also possible to increase the strength and flexibility of the layer so that the conductive material is not broken or broken in the peeling process. Examples of the polymer compound having no unsaturated double bond 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. And the like. It is also possible to use a plurality of these polymer compounds having no unsaturated double bond. In the present invention, it is preferable to use a polyvinyl acetal resin that allows easy adjustment of adhesion, and more preferably a polyvinyl acetal resin having a Tg of 60 ° C. or higher, more preferably a Tg of 80 to 150 ° C. It is preferable that the high molecular compound which does not have the unsaturated double bond which the peeling layer of the peeling film of this invention contains is 50 mass% or less with respect to the total solid content of a peeling layer, More preferably, it is 0.1-0.1%. 40% by mass.

  The release layer of the release film of the present invention can also contain a known crosslinking agent. Examples of the crosslinking agent include aldehyde compounds, isocyanate compounds, carbodiimide compounds, aziridine compounds, oxazoline compounds, active halogen compounds, and compounds having at least two vinylsulfonyl groups. 0.1-5 mass% is preferable with respect to the total resin component amount of a peeling layer, and, as for the addition amount of a crosslinking agent, More preferably, it is 0.5-3 mass%. A compound having an unsaturated double bond having a molecular weight of 15000 or less, such as an acrylic monomer or an acrylic oligomer, can also be contained, but if the amount is 5% by mass or less of the total resin component amount, blocking or the like occurs. This is preferable.

  In addition to the components described above, the release layer of the release film used in the present invention can contain an antistatic agent, a surfactant, a matting agent, a filler, a lubricant, an ultraviolet absorber, and the like.

Preferably the total solids content of the release layer is 0.1 g / ^{m 2} or more, more preferably 0.5 to 8 g / ^{m 2,} more preferably from 1 to 5 g / ^{m 2.}

  In the present invention, on the release layer, various known functional layers such as an antireflection layer, a hard coat layer, a printing layer, an antiglare layer, an adhesive layer, an ink jet receiving layer, a conductive layer and an easy adhesion layer are provided. Is possible. In particular, the release film of the present invention can be suitably used for the production of extremely thin conductive materials such as various antenna materials, current collectors, and electromagnetic shielding materials. A conductive layer can be preferably provided. In addition, various functional layers described above may be further provided on the conductive layer.

  The conductive layer can be provided directly on the release layer, but when the conductive layer is a fine conductive pattern (for example, a fine pattern with a fine line width of less than 50 μm) or when it contains an isolated pattern, It is preferable to provide an easy-adhesion layer between the release layer and the conductive layer. By providing the easy-adhesion layer, it is particularly easy to maintain a fine conductive pattern or isolated pattern and handle a conductive material.

  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 easy-adhesion layer preferably contains various polymer latexes. Among these, it is preferable to contain an aqueous dispersion of polyester latex, acrylic latex, and urethane latex from the viewpoint of weather resistance. Further, urethane latex from the viewpoint of adhesion to various materials, particularly non-yellowing urethane polycarbonate latex having high weather resistance. Is preferred. These polymer latexes preferably have an average particle size of 0.01 to 0.3 μm, more preferably 0.02 to 0.1 μm. In addition, these polymer latexes can be used by mixing a plurality of types of latex, but polyester latex, acrylic latex and urethane latex are preferably contained in an amount of 30% by mass or more of the resin component in the easy adhesion layer, More preferably, it is 50 mass% or more.

The easy-adhesion layer preferably further contains a water-soluble polymer compound, and more preferably contains a crosslinking agent. Examples of such 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 polymers” (Nobu Okawara, 1972, Chemical Dojinsha), chapter 2.6.4, aminated cellulose, polyethyleneimine, polyallylamine, polydiallylamine, allylamine and diallylamine Examples thereof include a polymer, a copolymer of diallylamine and maleic anhydride, and a copolymer of diallylamine and sulfur dioxide. Among these water-soluble polymer compounds, it is preferable to use a protein. 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 failure occurs when peeling, and the upper limit is preferably 2500 mg / m ² . More preferably 200 to 2000 / ^{m 2,} more preferably from 300~1000mg / ^{m 2.}

  Examples of the crosslinking agent 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 equivalent such as 1,4-dioxane, 2,4-dichloro-6-hydroxy-s-triazine salt, compound having active halogen such as 2,4-dihydroxy-6-chloro-triazine salt, 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 polyglycidyl Of ether, diglycerol polyglycidyl ether, glycerol polyglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, etc., or in addition to these, “Polymer chemical reaction” (Nobu Okawara 1972, Kagaku Dojinsha) Known polymer cross-linking agents such as the cross-linking agents described in Chapters 6 and 7, Chapters 5 and 2, and 9 and 3 can also be included. Among these, a water-soluble crosslinking agent having two or more epoxy groups in the molecule is preferable. 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 amount of resin components in the easy adhesion layer.

  Furthermore, the easily adhesive layer can contain a matting agent such as silica, a lubricant, a pigment, a dye, a surfactant, an ultraviolet absorber and the like. Moreover, it is preferable that the thickness of an easily bonding layer is 0.05-0.5 micrometer.

  As will be described later, the most preferable method for providing the metal portion of the conductive material precursor in the present invention is a method using a silver salt diffusion transfer method. In this case, it is preferable to include physical development nuclei in the easy-adhesion layer. The physical development nuclei may be uniformly distributed during easy adhesion by being included in the easy-adhesion layer coating solution, or may be distributed on the surface by re-application after the easy-adhesion layer is applied.

As 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 fluids 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.

  The conductive layer provided on the release layer is preferably a metal pattern, particularly preferably a pattern made of gold, silver, copper, nickel, and aluminum. As a method of forming these conductive layers, a method using a silver salt photosensitive material, a method of applying electroless plating or electrolytic plating to a silver image further obtained using the method, a silver paste using a screen printing method, etc. Method of printing conductive ink, method of printing conductive ink such as silver ink by inkjet method, method of forming conductive layer made of metal such as copper by electroless plating, etc., or conductive by vapor deposition or sputtering A layer is formed, a resist film is formed thereon, exposure, development, etching, a method obtained by removing the resist layer, a metal foil such as a copper foil is pasted, a resist film is further formed thereon, exposure, Known methods such as development, etching, and a method obtained by removing the resist layer can be used. Among them, it is preferable to use a silver salt diffusion transfer method that can reduce the thickness of the metal pattern to be manufactured and can easily form an extremely fine metal pattern.

<Active energy ray irradiation process>
In this invention, a peeling film irradiates an active energy ray, bridge | crosslinks a peeling layer, reduces the adhesive force of a base material and a peeling layer, and peels a peeling layer from a base material. 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. When visible light or ultraviolet light is used, 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 system, an ultraviolet lamp, etc. are preferably used. The active energy ray is preferably irradiated from the substrate side of the release film so that the layer provided on the release layer does not get in the way. Although the preferable irradiation light quantity changes with photoinitiators, a sensitizer, etc., it is preferable that it is 50-5000 mJ / cm < ² >. In addition, the surface temperature should be 100 ° C. or lower so that peeling in the peeling process after active energy ray irradiation is easy, and when a functional layer is provided on the peeling layer, the functional layer is not thermally damaged. Irradiation is preferably performed under the following conditions, preferably 60 ° C. or lower. Furthermore, the active energy ray may be irradiated before or after the protective film bonding step described later, but is preferably before the protective film bonding step.

  As described above, the adhesive force when the release layer is peeled is changed by the active energy ray irradiation step in the present invention. In the present invention, the adhesion 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. Moreover, it is preferable that adhesive force exceeds 0.5 N / 25mm before active energy ray irradiation, More preferably, it is 1 N / 25mm or more.

<Peeling process>
In the present invention, the release layer (or together with the functional layer on the release layer) is released from the release film irradiated with active energy rays. Since the release layer (and the release layer and the functional layer thereon) has low rigidity after peeling, the release layer may be curled or may be difficult to handle. In order to prevent this, it is also a preferable aspect that the protective film is bonded to the release layer side (the side having the functional layer including the conductive layer) of the release film and the release layer is peeled off together with the protect film before the release. . As 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-stiffness substrate made of polyethylene, polypropylene, polyvinyl chloride, or the like can be used. The adhesion of the release film must be stronger than the adhesion between the release layer of the release film and the substrate of the release film. Note that rigidity of the protective film is preferably used as the ^{5 cm} 3/100 or less. On the other hand, if the adhesion with the protect film is too strong, it is difficult to peel the protect film from the release layer in a later step. Therefore, although the preferable adhesive force of the protective film varies depending on the release layer, it is preferable to select a protective film having an adhesive force of 0.001 to 0.5 N / 25 mm. Examples of such commercially available protective films include PYLEN DC042 manufactured by Toyobo Co., Ltd., E2035, E203, and EC625 manufactured by Sumilon Co., Ltd., 622AX and 622F manufactured by Sekisui Chemical Co., Ltd., and the like. The thickness of the protective film is preferably 30 to 100 μm. In order to bond the protective film to the release layer, a known laminating method such as room temperature laminating or warming laminating can be used.

  When the protective film is bonded to the release film and the release layer (and the release layer and the functional layer above it) is peeled off from the base material together with the protective film, the release layer (and the release layer and the functional layer above it) is once again peeled off. It may be necessary to peel from the protective film. In this case, for example, the release layer is bonded to the adherend using an adhesive or the like, and then the release layer (and the release layer and the functional layer thereon) is peeled from the protective film. It is preferable to do so because tearing of the release layer does not occur.

  Examples of the present invention are shown below. In the description, percentages are based on mass unless otherwise specified.

Example 1
"Production of release film 1 and conductive material 1"
A release layer coating solution 1 having the following formulation was prepared on the untreated surface of Teijin DuPont Film Co., Ltd. single-sided easy-adhesion treated Tetron HLY (thickness 100 μm PET, total light transmittance 91%), and the solid content was 4 g / m. ² and dried at 70 ° C. for 5 minutes. The thicknesses of the Tetron HLY film after applying the release layer and the Tetron HLY film before application were measured, and the thickness of the release layer was calculated. The results are shown in Table 1.

<Peeling layer coating solution 1>
Hitaroid 7975 (Acrylic acrylate resin solution manufactured by Hitachi Chemical Co., Ltd .. Average molecular weight 50000. As solid content) 100 parts Irgacure 819 (photopolymerization initiator manufactured by Ciba Geigy Co., Ltd.) 3.74 parts Eslek KS1 (Sekisui Chemical Co., Ltd.) ) Polyvinyl acetal average molecular weight 27000. Tg = 107 ° C.) 14.9 parts Denacol EX512 (epoxy compound manufactured by Nagase ChemteX Corporation) 29.9 parts Sun-Aid SI-60L (manufactured by Sanshin Chemical Industry Co., Ltd.) Polymerization initiator) 1.04 parts

  Subsequently, a palladium sulfide sol solution was prepared as follows.

<Preparation of palladium sulfide sol>
Liquid A Palladium chloride 5g
Hydrochloric acid 40mL
Distilled water 1000mL
B liquid sodium sulfide 8.6g
Distilled water 1000mL
Liquid A and liquid B were mixed with stirring, and 30 minutes later, the solution was passed through a column filled with an ion exchange resin to obtain palladium sulfide sol.

  Then, according to the following prescription, the easily bonding layer coating liquid 1 was produced, it apply | coated on the peeling layer of the peeling film 1, and it was made to dry at 50 degreeC for 10 minutes. After drying, it was heated at 50 ° C. for 24 hours.

<Easily adhesive layer coating solution 1 formulation / m ² >
Hydran WLS210 (DIC Corporation non-yellowing urethane polycarbonate. Average particle size 0.05 μm, solid content) 300 mg
Gelatin 50mg
Nonion OT221 (Non Oil Surfactant manufactured by NOF Corporation) 1mg
EX313 (Epoxy curing agent manufactured by Nagase ChemteX Corporation) 9mg
HIMICRON L271 (Chukyo Yushi Co., Ltd. Lubricant) 4mg
The palladium sulfide sol (as palladium sulfide) 0.4mg

  It was 0.1 micrometer when the thickness of the obtained easily bonding layer was measured using the optical C120 confocal microscope (made by Lasertec Co., Ltd.).

  Subsequently, 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 substrate. Also, the backing layer 1 was applied to the opposite surface of the substrate. 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 μm. 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.

<Intermediate layer 1 composition / 1 m ² >
Gelatin 0.5g
Surfactant (S-1) 5mg

<Silver halide emulsion layer 1 composition / m ² >
Gelatin 0.5g
Silver halide emulsion 3.0g Silver equivalent 1-Phenyl-5-mercaptotetrazole 3mg
Surfactant (S-1) 20mg

<Outermost layer 1 composition / per 1 m ² >
1g of gelatin
Amorphous silica matting agent (average particle size 3.5μm) 10mg
Surfactant S-1 10mg

<Backing layer 1 composition / per 1 m ² >
2g of gelatin
Amorphous silica matting agent (average particle size 5μm) 20mg
Dye 1 200mg
Surfactant (S-1) 400mg

Subsequently, it has a mesh pattern portion (metal pattern) having a fine line width of 20 μm and a lattice interval of 250 μm and a portion without a pattern (non-image portion) through a resin filter that cuts light of 400 nm or less with a contact printer using a mercury lamp as a light source. A positive transmission original was brought into close contact and exposed at an exposure amount of ² mJ / cm ² .

  Then, after immersing in a diffusion transfer developer having the following composition at 15 ° C. for 90 seconds, the silver halide emulsion layer 1, the intermediate layer 1, the outermost layer 1 and the backing layer were subsequently washed away with warm water at 40 ° C. Dried. As a result, a metal pattern having a fine line width of 20 μm and a lattice spacing of 250 μm and a non-image portion were formed on the easy-adhesion layer (formation of a conductive layer), and a release film 1 was obtained.

<Diffusion transfer developer composition>
Potassium hydroxide 25g
Hydroquinone 18g
1-phenyl-3-pyrazolidone 2g
Potassium sulfite 80g
N-methylethanolamine 15g
Potassium bromide 1.2g
Total volume with water 1000mL
The pH was adjusted to 12.2 with an 85 mass% phosphoric acid aqueous solution.

  About the obtained peeling film 1, the measurement of Clark stiffness and the measurement of adhesive force were implemented as a peeling test before active energy ray irradiation. Clark stiffness was measured according to JIS-P8143. Measurement of the adhesion force is carried out by sticking a vehicle masking tape No241 manufactured by Nichiban Co., Ltd. to the non-image part obtained as described above, cutting it to a width of 25 mm, and using an Imada IPT200-5N to adhere with a 180 ° peeling method. The force was measured. Further, it was confirmed whether the metal pattern or the release layer was peeled off. The results are shown in Table 1. In Table 1, when there was no peeling on the metal pattern or the release layer, “◯” was given, and when the metal pattern or the release layer was peeled, “X” was given.

Next, active energy rays with an irradiation amount of 200 mJ / cm ² were irradiated from the opposite side (base material side) of the release film with a high pressure mercury lamp 80 W / cm (2 lamps). Subsequently, an EC625 protect film (thickness: 60 μm) manufactured by Sumilon Co., Ltd. was bonded to the release layer surface side. In addition, when this protective film was bonded to the non-image part of the peeling layer before active energy ray irradiation, it was cut to a width of 25 mm, and the adhesion strength was measured by 180 ° peeling method using Imada IPT200-5N. 5N.

  About the peeling film 1 after active energy ray irradiation, the adhesive force was measured as follows. The results are shown in Table 1.

  The masking tape No241 for vehicles manufactured by Nichiban Co., Ltd. was bonded to the non-image part of the release film 1, and then cut to a width of 25 mm, and the adhesion was measured by 180 ° peeling method using Imada IPT200-5N. Moreover, when peeling from the peeling layer at the time of peeling, it was set as (circle) and what peeled in the other place was set as x.

  Irradiating the aforementioned active energy rays, the metal pattern and the easy adhesion layer together with the protection film from the release film 1 in which the EC625 protection film manufactured by Sumilon Co., Ltd. was bonded to the surface of the metal pattern opposite to the base material and the surface of the easy adhesion layer The conductive material including the release layer was peeled off to obtain a conductive material 1.

  The Clark stiffness of the conductive material 1 obtained as described above was measured according to JIS-P8143. Moreover, the spherical adhesion test by the following method was implemented. The results are shown in Table 1.

<Spherical adhesion test>
The conductive material 1 was bonded to an acrylic ball having an outer diameter of 300 mm and an outer diameter of 200 mm using a Henkel Japan Co., Ltd. Loctite U-30FL (urethane adhesive) adhesive. It peeled. A metal pattern having a good surface on the surface of the acrylic sphere without any wrinkles or tears was evaluated as ◯, and those with wrinkles or tears were evaluated as ×.

  Also, a release film heated at 50 ° C. for 3 days before irradiation with active energy rays with a high-pressure mercury lamp was prepared, and this was evaluated in the same manner as the release film not heated. The results are shown in Table 1.

(Example 2)
"Production of release film 2 and conductive material 2"
15 g of ESREC KS10 (polyvinyl acetal resin manufactured by Sekisui Chemical Co., Ltd., mass average molecular weight 17000, containing 25 mol% of hydroxyl group) was dissolved in 85 g of dioxolane / methyl ethyl ketone 1: 1 solvent, and Karenz AOI (Showa Denko) was stirred at 40 ° C. 10 g of 2-acryloyloxyethylisocyanate) was added dropwise and stirred at 40 ° C. for 1 hour. Ethyl cellosolve was added to the obtained resin solution to obtain a modified polyvinyl acetal resin solution having a solid content of 10%.

A release film 2 was prepared 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 content per 1 m ² ). Subsequently, a conductive material 2 was produced in the same manner as in Example 1 except that the release film 2 was used, and evaluated in the same manner as in 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)
“Preparation of Comparative Release Film 1 and Comparative Conductive Material 1”
Compared with Example 1 except that UA340P (Shin Nakamura Chemical Co., Ltd. urethane acrylate oligomer. Mass average molecular weight 13000) is used instead of Hitaloid 7975 (with the same solid content per 1 m ² ). The conductive material 1 was produced and tried to be evaluated. However, after irradiating active energy rays and bonding the protective film, an attempt was made to peel off the conductive material including the metal pattern, the easy-adhesion layer, and the peeling layer together with the protective film.

(Comparative Example 2)
“Comparison Conductive Material 2, Production of Comparative Conductive Material 2”
Example 1 except that A-DPH (dipentaerythritol hexaacrylate manufactured by Shin-Nakamura Chemical Co., Ltd., mass average molecular weight 578) is used in place of the hitaloid 7975 (with the same coating solid content per 1 m ² ). Similarly, the comparative conductive material 2 was produced 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 3)
"Production of release film 3 and conductive material 3"
A release film 3 was prepared in the same manner as in Example 1 except that the following release layer coating solution 3 was prepared and the coating solid content was 4 g / m ² . Subsequently, a conductive material 3 was produced in the same manner as in Example 1 except that the release film 3 was used, and evaluated in the same manner as in Example 1. The results are shown in Table 1.

<Peeling layer coating solution 3>
Hitaroid 7975 (Acrylic acrylate resin solution manufactured by Hitachi Chemical Co., Ltd .. Average molecular weight 50000. As solid content) 100 parts Irgacure 819 (photopolymerization initiator manufactured by Ciba Geigy Co., Ltd.) 3.74 parts Eslek KS1 (Sekisui Chemical Co., Ltd.) ) Polyvinyl acetal (average molecular weight 27000, Tg = 107 ° C.) 32.5 parts Denacol EX512 (epoxy compound manufactured by Nagase ChemteX Corporation) 11.9 parts Sun-Aid SI-60L (manufactured by Sanshin Chemical Industry Co., Ltd.) 0 .41 parts

Example 4
“Production of release film 4 and conductive material 4”
A release film 4 was prepared in the same manner as in Example 1 except that the following release layer coating solution 4 was prepared and the coating solid content was 4 g / m ² . Subsequently, a conductive material 4 was produced in the same manner as in Example 1 except that the release film 4 was used, and evaluated in the same manner as in Example 1. The results are shown in Table 1.

<Peeling layer coating solution 4>
Hitaroid 7975 (Acrylic acrylate resin solution manufactured by Hitachi Chemical Co., Ltd .. Average molecular weight 50000. As solid content) 100 parts Irgacure 819 (photopolymerization initiator manufactured by Ciba Geigy Co., Ltd.) 3.74 parts Eslek KS1 (Sekisui Chemical Co., Ltd.) ) Polyvinyl acetal, average molecular weight 27000, Tg = 107 ° C.) 29.9 parts Denacol EX512 (epoxy compound manufactured by Nagase ChemteX Corporation) 14.9 parts Sun-Aid SI-60L (manufactured by Sanshin Chemical Industry Co., Ltd.) 0 .52 parts

(Example 5)
"Production of release film 5 and conductive material 5"
A release film 5 was prepared in the same manner as in Example 1 except that the following release layer coating solution 5 was prepared and the coating solid content was 4 g / m ² . Subsequently, a conductive material 5 was produced in the same manner as in Example 1 except that the release film 5 was used, and evaluated in the same manner as in Example 1. The results are shown in Table 1.

<Peeling layer coating solution 5>
Hitaroid 7975 (Acrylic acrylate resin solution manufactured by Hitachi Chemical Co., Ltd .. Average molecular weight 50000. As solid content) 100 parts Irgacure 819 (photopolymerization initiator manufactured by Ciba Geigy Co., Ltd.) 3.74 parts Eslek KS1 (Sekisui Chemical Co., Ltd.) ) Polyvinyl acetal average molecular weight 27000. Tg = 107 ° C.) 22.47 parts Denacol EX512 (epoxy compound manufactured by Nagase ChemteX Corporation) 22.4 parts Sun-Aid SI-60L (manufactured by Sanshin Chemical Industry Co., Ltd.) 0 .78 parts

(Example 6)
"Production of release film 6 and conductive material 6"
A release film 6 was prepared in the same manner as in Example 1 except that the following release layer coating solution 6 was prepared and the coating solid content was 4 g / m ² . Subsequently, a conductive material 6 was produced in the same manner as in Example 1 except that the release film 6 was used, and evaluated in the same manner as in Example 1. The results are shown in Table 1.

<Peeling layer coating liquid 6>
Hitaroid 7975 (Acrylic acrylate resin solution manufactured by Hitachi Chemical Co., Ltd .. Average molecular weight 50000. As solid content) 100 parts Irgacure 819 (photopolymerization initiator manufactured by Ciba Geigy Co., Ltd.) 3.74 parts Eslek KS1 (Sekisui Chemical Co., Ltd.) ) Polyvinyl acetal average molecular weight 27000. Tg = 107 ° C.) 7.49 parts Denacol EX512 (epoxy compound manufactured by Nagase ChemteX Corporation) 37.4 parts Sun-Aid SI-60L (manufactured by Sanshin Chemical Industry Co., Ltd.) 1 .31 parts

(Example 7)
"Preparation of release film 7 and conductive material 7"
A release film 7 was prepared in the same manner as in Example 1 except that the following release layer coating solution 7 was prepared and the coating solid content was 4 g / m ² . Subsequently, a conductive material 7 was produced in the same manner as in Example 1 except that the release film 7 was used, and evaluated in the same manner as in Example 1. The results are shown in Table 1.

<Release layer coating solution 7>
Hitaroid 7975 (Acrylic acrylate resin solution manufactured by Hitachi Chemical Co., Ltd., average molecular weight 50000, as solid content) 100 parts Irgacure 819 (photopolymerization initiator manufactured by Ciba Geigy Co., Ltd.) 3.84 parts S-LEC KS1 (Sekisui Chemical Co., Ltd.) ) Polyvinyl acetal (average molecular weight 27000, Tg = 107 ° C.) 2.3 parts Denacol EX512 (epoxy compound manufactured by Nagase ChemteX Corporation) 46.1 parts Sun-Aid SI-60L (manufactured by Sanshin Chemical Industry Co., Ltd.) 1 .61 parts

(Comparative Example 3)
“Production of comparative release film 3 and comparative conductive material 3”
The following comparative release layer coating solution 3 was prepared, and a comparative release film 3 was prepared in the same manner as in Example 1 except that the coating solid content was 4 g / m ² . Subsequently, a comparative conductive material 3 was produced in the same manner as in Example 1 except that the comparative release film 3 was used, and evaluated in the same manner as in Example 1. The results are shown in Table 1. The release film heated at 50 ° C. for 3 days was irradiated with active energy rays, and after the protective film was bonded, the conductive material including the metal pattern, the easy-adhesion layer and the release layer was peeled off together with the protect film. , Could not be peeled. Moreover, although Nichiban Co., Ltd. vehicle masking tape No241 was bonded to and peeled from the conductive material precursor after irradiation with the active energy ray, the conductive material containing the metal pattern could not be peeled from the substrate.

<Comparative release layer coating solution 3>
Hitaroid 7975 (Acrylic acrylate resin solution manufactured by Hitachi Chemical Co., Ltd .. Average molecular weight 50000. As solid content) 100 parts Irgacure 819 (photopolymerization initiator manufactured by Ciba Geigy Co., Ltd.) 3.74 parts Eslek KS1 (Sekisui Chemical Co., Ltd.) ) Polyvinyl acetal (average molecular weight 27000, Tg = 107 ° C.) 35.5 parts Denacol EX512 (epoxy compound manufactured by Nagase ChemteX Corporation) 9.36 parts Sun-Aid SI-60L (manufactured by Sanshin Chemical Industry Co., Ltd.) 0 .32 parts

(Comparative Example 4)
“Preparation of Comparative Release Film 4 and Comparative Conductive Material 4”
The following comparative release layer coating solution 4 was prepared, and a comparative release film 4 was prepared in the same manner as in Example 1 except that the coating solid content was 9.1 g / m ² . Subsequently, a comparative conductive material 4 was produced in the same manner as in Example 1 except that the comparative release film 4 was used, and evaluated in the same manner as in Example 1. The results are shown in Table 1. The release film heated at 50 ° C. for 3 days was irradiated with active energy rays, and after the protective film was bonded, the conductive material including the metal pattern, the easy-adhesion layer and the release layer was peeled off together with the protect film. , Could not be peeled. Moreover, although Nichiban Co., Ltd. vehicle masking tape No241 was bonded to and peeled from the conductive material precursor after irradiation with the active energy ray, the conductive material containing the metal pattern could not be peeled from the substrate.

<Comparative release layer coating solution 4>
Hitaroid 7975 (Acrylic acrylate resin solution manufactured by Hitachi Chemical Co., Ltd., average molecular weight 50000, as solid content) 100 parts Irgacure 819 (photopolymerization initiator manufactured by Ciba Geigy Co., Ltd.) 3.67 parts Eslek KS1 (Sekisui Chemical Co., Ltd.) ) Polyvinyl acetal, average molecular weight 27000. Tg = 107 ° C.) 10.1 parts Denacol EX512 (epoxy compound manufactured by Nagase ChemteX Corporation) 1.26 parts

(Example 8)
"Production of release film 8 and conductive material 8"
A release film 8 was prepared in the same manner as in Example 1 except that the following release layer coating solution 8 was prepared and the coating solid content was 4 g / m ² . Subsequently, a conductive material 8 was produced in the same manner as in Example 1 except that the release film 8 was used, and evaluated in the same manner as in Example 1. The results are shown in Table 1.

<Peeling layer coating liquid 8>
Hitaroid 7975 (Acrylic acrylate resin solution manufactured by Hitachi Chemical Co., Ltd .. Average molecular weight 50000. As solid content) 100 parts Irgacure 819 (photopolymerization initiator manufactured by Ciba-Geigy Co., Ltd.) 4.16 parts Eslek KS1 (Sekisui Chemical Co., Ltd.) ) Polyvinyl acetal (average molecular weight 27000, Tg = 107 ° C.) 27.9 parts Denacol EX512 (epoxy compound manufactured by Nagase ChemteX Corporation) 33.3 parts Sun-Aid SI-60L (manufactured by Sanshin Chemical Industry Co., Ltd.) 1 .16 parts

Example 9
"Production of release film 9 and conductive material 9"
A release film 9 was prepared in the same manner as in Example 1 except that the following release layer coating solution 9 was prepared and the coating solid content was 4 g / m ² . Subsequently, a conductive material 9 was produced in the same manner as in Example 1 except that the release film 9 was used, and evaluated in the same manner as in Example 1. The results are shown in Table 1.

<Peeling layer coating solution 9>
Hitaroid 7975 (Acrylic acrylate resin solution manufactured by Hitachi Chemical Co., Ltd .. Average molecular weight 50000. As solid content) 100 parts Irgacure 819 (photopolymerization initiator manufactured by Ciba-Geigy Co., Ltd.) 5 parts ESREC KS1 (manufactured by Sekisui Chemical Co., Ltd.) Polyvinyl acetal Average molecular weight 27000. Tg = 107 ° C.) 53.5 parts Denacol EX512 (epoxy compound manufactured by Nagase ChemteX Corporation) 40 parts Sun-Aid SI-60L (manufactured by Sanshin Chemical Industry Co., Ltd.) 1.4 parts

(Example 10)
"Production of release film 10 and conductive material 10"
A release film 10 was prepared in the same manner as in Example 1 except that the following release layer coating solution 10 was prepared and the coating solid content was 4 g / m ² . Subsequently, a conductive material 10 was produced in the same manner as in Example 1 except that the release film 10 was used, and evaluated in the same manner as in Example 1. The results are shown in Table 1.

<Peeling layer coating solution 10>
Hitaroid 7975 (Acrylic acrylate resin solution manufactured by Hitachi Chemical Co., Ltd .. Average molecular weight 50000. As solid content) 100 parts Irgacure 819 (photopolymerization initiator manufactured by Ciba-Geigy Co., Ltd.) 6.25 parts Eslek KS1 (Sekisui Chemical Co., Ltd.) ) Polyvinyl acetal, average molecular weight 27000, Tg = 107 ° C.) 91.8 parts Denacol EX512 (epoxy compound manufactured by Nagase ChemteX Corporation) 50 parts Sun-Aid SI-60L (manufactured by Sanshin Chemical Industry Co., Ltd.) 1.75 Part

(Comparative Example 5)
“Preparation of Comparative Release Film 5 and Comparative Conductive Material 5”
The following comparative release layer coating solution 5 was prepared, and a comparative release film 5 was prepared in the same manner as in Example 1 except that the coating solid content was 4.5 g / m ² . Subsequently, a comparative conductive material 5 was produced in the same manner as in Example 1 except that the comparative release film 5 was used, and evaluated in the same manner as in Example 1. The results are shown in Table 1. The release film heated at 50 ° C. for 3 days was irradiated with active energy rays, and after the protective film was bonded, the conductive material including the metal pattern, the easy-adhesion layer and the release layer was peeled off together with the protect film. , Could not be peeled. Moreover, although Nichiban Co., Ltd. vehicle masking tape No241 was bonded to and peeled from the conductive material precursor after irradiation with the active energy ray, the conductive material containing the metal pattern could not be peeled from the substrate.

<Comparative release layer coating solution 5>
Hitaroid 7975 (Acrylic acrylate resin solution manufactured by Hitachi Chemical Co., Ltd .. Average molecular weight 50000. As solid content) 100 parts Irgacure 819 (photopolymerization initiator manufactured by Ciba Geigy Co., Ltd.) 6.36 parts Eslek KS1 (Sekisui Chemical Co., Ltd.) ) Polyvinyl acetal average molecular weight 27000. Tg = 107 ° C.) 127.3 parts Denacol EX512 (epoxy compound manufactured by Nagase ChemteX Corporation) 50.9 parts Sun-Aid SI-60L (manufactured by Sanshin Chemical Industry Co., Ltd.) 1 .78 parts

(Example 11)
"Production of release film 11 and conductive material 11"
A release film 11 was prepared in the same manner as in Example 1 except that the following release layer coating solution 11 was prepared and the coating solid content was 4 g / m ² . Subsequently, a conductive material 11 was produced in the same manner as in Example 1 except that the release film 11 was used, and evaluated in the same manner as in Example 1. The results are shown in Table 1. The surface of the release film after the release layer was applied and dried was slightly tacky.

<Peeling layer coating solution 11>
Hitaroid 7975 (Acrylic acrylate resin solution manufactured by Hitachi Chemical Co., Ltd .. Average molecular weight 50000. As solid content) 100 parts Irgacure 819 (photopolymerization initiator manufactured by Ciba Geigy Co., Ltd.) 3.74 parts Eslek KS1 (Sekisui Chemical Co., Ltd.) ) Polyvinyl acetal (average molecular weight 27000, Tg = 107 ° C.) 14.9 parts Denacol EX512 (epoxy compound manufactured by Nagase ChemteX Corporation) 29.9 parts

  From Table 1, the effectiveness of the present invention is well understood.

(Example 12)
<Preparation of silver ultrafine particle dispersion 1>
To a 10 L stainless beaker, 272 g of roasted dextrin (manufactured by Nissho Kagaku Co., Ltd., dextrin No. 3) 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. Acetic acid was added to the resulting solution to adjust to pH = 5.6, 1 g of Biozyme F10SD (manufactured by Amano Enzyme) was added, and the mixture was stirred at 45 ° C. for 1 hour. Next, after the obtained ultrafine silver particle dispersion was purified by a centrifugal separation method, pure water was added and redispersed so that the silver concentration was 45% by mass, and 800 g of ultrafine silver particle dispersion 1 was obtained. The silver ultrafine particles contained had an average particle diameter of 20 nm and a yield of 86%.

<Preparation of silver ultrafine particle-containing composition 1>
200 g of the silver ultrafine particle dispersion 1 was taken, and 27 g of U-coat UWS-145 (polyurethane latex, average particle size 0.02 μm, solid content 35% by mass) manufactured by Sanyo Chemical Industries, Ltd. was added as a polymer latex to the surface activity. An agent, pure water, and ethylene glycol were added to obtain a silver ultrafine particle-containing composition 1 having a silver concentration of 30% by mass, a surface tension of 30 mN / m, and a viscosity of 9 mPa · s.

  On the release layer of the release film 1 produced in Example 1, the silver ultrafine particle-containing composition 1 was printed in a mesh shape having a line width of 50 μm and a line interval of 500 μm by flexographic printing, and dried with warm air. The film was immersed in a 3N sodium chloride aqueous solution at 30 ° C. for 30 seconds, washed with water and dried to form a silver film on the frame portion. During this printing process, the release layer was not sticky, so no trouble occurred during printing. Then, the high pressure mercury lamp was irradiated from the opposite side to the peeling layer of the peeling film similarly to Example 1, and the peeling layer of the peeling film was peeled off. Even in this peeling process, peeling was possible without any problem.

(Comparative Example 7)
90 parts by mass of butyl acrylate, 10 parts by mass of acrylic acid and 0.2 parts by mass of azobisisobutyronitrile are dissolved in 300 parts by mass of ethyl acetate and heated to 80 ° C. in a nitrogen gas atmosphere to carry out copolymerization. An acrylic polymer solution having acid groups was synthesized. Next, 5 parts by mass of glycidyl methacrylate is added to the obtained acrylic polymer solution having a carboxylic acid group, and the mixture is heated to 40 ° C. to react the carboxylic acid group in the acrylic polymer with the glycidyl group of glycidyl methacrylate. An acrylic polymer solution having an acid group and a methacryl group was obtained. Next, 2.5 parts by mass of tolylene diisocyanate and 4- (2-hydroxyethoxy) phenyl (2-hydroxy-2-propyl) ketone 0.5 were added to the acrylic polymer solution having a carboxylic acid group and a methacrylic group. Mass parts were added to prepare an adhesive solution.

  The pressure-sensitive adhesive solution obtained above was applied onto the same substrate as used in Example 1, and dried at 70 ° C. for 5 minutes to produce an ultraviolet-ray adhesive-power-resistant pressure-sensitive adhesive film.

  In the same manner as in Example 12, an attempt was made to print the silver ultrafine particle-containing composition 1 in a mesh shape having a line width of 50 μm and a line interval of 500 μm by flexographic printing, but the adhesive layer adhered to the flexographic printing plate and printed well. There wasn't. From this, it was found that the effect of the release film of the present invention having a release layer having no adhesive force was well understood.

Claims (3)

  The substrate has at least a release layer containing an active energy ray-curable polymer compound having an unsaturated double bond with a weight average molecular weight of 15000 or more and an epoxy compound, and the release layer is active energy ray-cured as described above. A release film comprising 40% by mass or more of the conductive polymer compound based on the total solid content of the release layer and 8% by mass or more of the epoxy compound based on the total solid content of the release layer.   The release film according to claim 1, wherein the release layer further contains a thermal cationic polymerization initiator.   A process of forming a conductive layer on the side away from the substrate of the release layer of the release film according to claim 1, an active energy ray irradiation process, and a protective film bonded to the side having the conductive layer on the release layer side And a method for producing a conductive material comprising at least a peeling layer and a conductive layer with the protective film.