JP2017117001A - Method for manufacturing laminate with conductive pattern - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for manufacturing a laminate with a conductive pattern capable of forming a conductive pattern by insulating a conductive resin layer by irradiating the conductive resin layer with a laser without damaging the electrode formed on a substrate.SOLUTION: A method for manufacturing a laminate 20 with a conductive pattern comprises a laminating step and a conductive pattern forming step. The laminating step laminates a conductive resin layer 2 including a conductive fiber 21 and a resin 22 on at least an electrode 4 of a substrate 5 including the electrode 4. The conductive pattern forming step forms a conductive pattern by insulating the conductive resin layer 2 by irradiating the conductive resin layer 2 with a laser light L via a plastic film 6.SELECTED DRAWING: Figure 2

Description

  The present invention relates to a method for producing a laminate with a conductive pattern.

  Liquid crystal display elements, touch panel sensors, and the like are used in large electronic devices such as personal computers and televisions, small electronic devices such as car navigation, mobile phones, and electronic dictionaries, and display devices such as OA devices and FA devices. Various types of touch panels have already been put into practical use, but in recent years, the use of capacitive touch panels has progressed. In a capacitive touch panel, when a fingertip (conductor) contacts the touch input surface, the fingertip and the conductive film are capacitively coupled to form a capacitor. The capacitive touch panel detects the coordinates by capturing the change in charge at the contact position of the fingertip.

  In particular, a projected capacitive touch panel has a good operability such that a complex instruction can be performed because multiple fingertip detection is possible. Due to its good operability, a projected capacitive touch panel is increasingly used as an input device on a display surface in a device having a small display device such as a mobile phone or a portable music player. In general, in a projected capacitive touch panel, a plurality of X electrodes and a plurality of Y electrodes perpendicular to the X electrodes form a two-layer structure in order to express two-dimensional coordinates based on the X and Y axes. doing. A transparent electrode material is used for these electrodes.

  Conventionally, ITO (Indium-Tin-Oxide), indium oxide, tin oxide, and the like have been used for transparent electrode materials because they exhibit high light transmittance. However, recently, attempts have been made to form a transparent electrode (transparent conductive pattern) using a material instead of these. For example, Patent Documents 1 and 2 propose a method for forming a conductive pattern using a photosensitive conductive film having a photosensitive layer containing conductive fibers. If this technique is used, a conductive pattern can be easily formed directly on various substrates by a photolithography process.

  In Patent Documents 3 and 4, a method of forming a conductive pattern by irradiating a transparent conductive film obtained by dispersing and curing metal nanowires in a binder resin with a laser beam and using the laser beam irradiated portion as an insulating portion. Is disclosed.

International Publication No. 2010/021224 International Publication No. 2012/051516 JP 2010-140859 A JP 2010-044968 A

  In the photosensitive conductive films described in Patent Documents 1 and 2 above, it is possible to easily form a conductive pattern on various substrates, but the conductive pattern is formed by removing conductive fibers by development. Therefore, there is a problem that a step is formed between the conductive portion and the insulating portion, and the pattern is easily visible.

  On the other hand, in the pattern formation method by laser beam irradiation described in Patent Documents 3 and 4, since there is no step between the conductive portion and the insulating portion, a pattern that is difficult to visually recognize can be formed. However, when a conductive resin layer having conductive fibers is formed on a substrate having electrodes, and the conductive resin layer is patterned by laser light irradiation, the energy of the laser light is strong. There is a problem of being damaged by the laser.

  An object of the present invention is to provide a method for manufacturing a laminate with a conductive pattern, in which a conductive resin layer is insulated and a conductive pattern is formed by irradiating the conductive resin layer with a laser without damaging an electrode formed on the substrate. It is to provide.

  As a result of studying to solve the above problems, the present inventors have found that a conductive pattern can be formed without damaging the electrodes of the substrate by performing laser irradiation on the conductive resin layer through a plastic film, The present invention has been completed.

  The present invention provides a laminating step of laminating a conductive resin layer containing conductive fibers and a resin on at least an electrode of a substrate having electrodes, and insulating the conductive fibers by irradiating the conductive resin layer with a laser. By this, the manufacturing method of the laminated body with a conductive pattern which comprises a conductive pattern formation process which forms a conductive pattern, and irradiates a laser to a conductive resin layer via a plastic film in a conductive pattern formation process is provided.

  In the lamination step, a transfer type conductive film including a conductive resin layer and a plastic film may be laminated on at least the electrode of the substrate. Thereby, since it becomes possible to perform simultaneously formation of the conductive resin layer on the board | substrate which has an electrode, and arrangement | positioning of a plastic film, a conductive pattern can be formed more simply.

  It is preferable to dispose a plastic film so as to contact at least part of the conductive resin layer laminated on at least the electrode of the substrate. Thereby, the kind of plastic can be selected arbitrarily and processing likelihood, such as the irradiation amount at the time of laser irradiation, can be widened.

  The conductive fiber may be a metal fiber. When the conductive fiber is a metal fiber, processing by laser irradiation becomes easy.

  The conductive fiber may be a silver nanowire. When the conductive fiber is a silver nanowire, the conductive fiber can be easily produced, and processing of the conductive resin layer containing the conductive fiber by laser irradiation becomes easy.

  The conductive resin layer laminated in the laminating step may further contain a compound having a thermally polymerizable group or a compound having a photopolymerizable group. Thereby, the conductive resin layer can be easily formed on the substrate.

  The conductive resin layer laminated in the lamination step may further contain a compound having a photopolymerizable group and a photopolymerization initiator. Thereby, a conductive resin layer can be easily formed on the substrate by light irradiation.

  The electrode may contain metal fibers. Thereby, the board | substrate which has an electrode can be produced simply.

  According to the present invention, there is provided a method for manufacturing a laminate with a conductive pattern that forms a conductive pattern by insulating a conductive fiber by irradiating a conductive resin layer with a laser without damaging an electrode formed on the substrate. can do.

It is a schematic cross section of a transfer type conductive film. It is a schematic cross section for demonstrating a conductive pattern formation process. It is a schematic cross section for demonstrating damage of the electrode on the board | substrate by the laser irradiation in the conventional method. It is an electron micrograph of the insulation part of the conductive resin layer formed by laser irradiation by the conventional method.

  Hereinafter, embodiments of the present invention will be described in detail. In the present specification, “(meth) acrylate” means “acrylate” and “methacrylate”. Similarly, “(meth) acrylic acid” means “acrylic acid” and “methacrylic acid”, and “(meth) acryloyl group” means “acryloyl group” and “methacryloyl group”. Moreover, the numerical value range shown using "to" shows the range which includes the numerical value described before and behind "to" as a minimum value and a maximum value, respectively.

[Method for producing laminate with conductive pattern]
The manufacturing method of the laminated body with a conductive pattern of this embodiment includes a laminating step of laminating a conductive resin layer containing conductive fibers and a resin on at least an electrode of a substrate having electrodes, and a laser on the conductive resin layer. A conductive pattern forming step of forming a conductive pattern by irradiating and insulating the conductive resin layer.

(Lamination process)
In the laminating step, the method for laminating the conductive resin layer on at least the electrode of the substrate having electrodes is not particularly limited, and may be a known method (for example, a method exemplified in Patent Documents 1 and 2). In the lamination step, for example, the conductive resin layer may be laminated using a transfer type conductive film described later.

<Substrate with electrode>
The board | substrate which has an electrode in this embodiment can be selected without a restriction | limiting in particular. Conductors used as electrode materials include metals such as gold, silver, copper, and aluminum, metal oxides such as ITO, indium oxide, and tin oxide, metal fibers such as silver nanowires and copper nanowires, and conductivity such as carbon nanotubes. Organic conductors such as fibers, polymers of thiophene derivatives and aniline derivatives, specifically, polyethylenedioxythiophene, polyhexylthiophene, polyaniline, polyvinylpyrrolidone, and the like can be used. A substrate having electrodes is prepared by, for example, preparing a substrate on which the above-described conductor layer is formed, forming a resist by a known technique, removing the conductor by etching, and then removing the resist. Can do. The substrate can be selected without particular limitation, and may be a glass substrate or a polymer film. Examples of the polymer film include a polyethylene terephthalate film, a polyethylene film, a polypropylene film, and a polycarbonate film. Among these polymer films, a polyethylene terephthalate film is preferable from the viewpoint of transparency and heat resistance.

  Also, methods for producing a substrate having electrodes include known methods such as the methods exemplified in Patent Documents 1 and 2, and methods for producing a substrate having electrodes by laser irradiation as exemplified in Patent Documents 3 and 4. It may be the method of.

<Conductive resin layer>
The conductive resin layer according to the present embodiment contains conductive fibers and a resin. The conductive resin layer may be provided by, for example, disposing a conductive fiber on a substrate using a conductive fiber dispersion containing conductive fibers, and forming a resin layer on the conductive fiber. May be provided by arranging conductive fibers on the substrate, and may be provided by applying and drying a resin solution containing the conductive fibers on the substrate.

  For example, the conductive fiber may be dried after the conductive fiber described above is applied on a substrate or a resin layer with a conductive dispersion added with water or an organic solvent and a dispersion stabilizer such as a surfactant. Can be arranged. The conductive fibers arranged in this way may be laminated as necessary.

  The coating can be performed by a known method such as a roll coating method, a comma coating method, a gravure coating method, an air knife coating method, a die coating method, a bar coating method, or a spray coating method. The drying can be performed at 30 to 150 ° C. for about 1 to 30 minutes using a hot air convection dryer or the like. In the conductive resin layer, the conductive fiber may coexist with a surfactant, a dispersion stabilizer and the like.

  A conductive resin layer may be laminated | stacked by bonding together the laminated body film provided with a support film and a conductive resin layer so that a conductive resin layer may contact | connect on a board | substrate. In this case, since the laminate film is used for transferring the conductive resin layer onto the substrate, it can also be said to be a transfer type conductive film.

  FIG. 1 is a schematic cross-sectional view of a transfer type conductive film. As shown in FIG. 1A, the transfer conductive film 10 includes a support film 1 and a conductive resin layer 2. The conductive resin layer 2 contains conductive fibers 21 and a resin 22. There is no particular limitation on the region where the conductive fibers 21 exist, and it is sufficient that conductivity is obtained over the entire principal surface direction of the conductive resin layer 2, and the conductive fibers 21 are dispersed substantially uniformly in the resin 22. Alternatively, the conductive fibers 21 may be unevenly distributed on the support film 1 side or the opposite side in the thickness direction of the conductive resin layer 2.

  Examples of the support film 1 include a polymer film having heat resistance and solvent resistance. Examples of such a polymer film include a polyethylene terephthalate film, a polyethylene film, a polypropylene film, and a polycarbonate film. Among these polymer films, a polyethylene terephthalate film is preferable from the viewpoint of transparency and heat resistance. These polymer films may be subjected to a surface treatment so as to be easily peeled off from the conductive resin layer 2, and are materials that can be easily peeled off from the conductive resin layer 2. It is preferable that a polymer film is formed.

  The thickness of the support film 1 is preferably 5 to 300 μm, more preferably 10 to 200 μm, and still more preferably 15 to 100 μm. In the step of applying a conductive fiber dispersion, a resin solution, or a resin solution containing conductive fibers to form the conductive resin layer 2, or the step of peeling the support film 1 from the conductive resin layer 2, From the viewpoint of preventing the mechanical strength from being lowered and the support film 1 from being damaged, it is preferably 5 μm or more, more preferably 10 μm or more, and further preferably 15 μm or more. In addition, when the conductive resin layer 2 is insulated by laser irradiation through the support film 1 (details will be described later), it is preferably 15 μm or more, and preferably 30 μm or more, from the point that it hardly damages the electrodes of the substrate. More preferably, it is more preferably 50 μm or more, and particularly preferably 100 μm or more.

  Examples of the conductive fiber 21 include metal fibers such as gold, silver, copper, and platinum, or carbon fibers such as carbon nanotubes. From the point that the method for preparing the conductive fiber is simple, the shape of the conductive fiber is easy to control, the high visible light transmittance in the wavelength range of 400 to 700 nm, and the high conductivity. The conductive fibers are preferably silver fibers, and more preferably silver nanowires. Here, the nanowire has a small difference in size between two dimensions (X, Y) (specifically, the size in the Y direction is not more than 5 times the size in the X direction, where X ≦ Y), and X In addition, it means a substance having a size in the Y direction of 300 nm or less and a remaining dimension (Z) of 10 or more times the size in the X and Y directions. The conductive fiber 21 may be used alone or in combination of two or more.

The conductive fibers including silver fibers or silver nanowires can be prepared by, for example, a method of reducing silver ions with a reducing agent such as NaBH ₄ or a polyol method.

  The fiber diameter of the conductive fiber 21 is preferably 1 nm to 100 nm, more preferably 2 nm to 50 nm, and still more preferably 3 nm to 30 nm. The fiber length of the conductive fiber is preferably 1 μm to 100 μm, more preferably 2 μm to 50 μm, and further preferably 3 μm to 10 μm. The fiber diameter and fiber length can be measured with a scanning electron microscope.

  The surface resistivity of the conductive resin layer 2 and the transfer type conductive film 10 including the conductive resin layer 2 can be adjusted by the amount of the conductive fibers 21. As the amount of the conductive fiber 21 increases, the surface resistivity decreases and the conductivity can be increased. On the other hand, as the amount of the conductive fibers 21 increases, the transmittance of the conductive resin layer 2 and the transfer type conductive film 10 decreases.

  Examples of the resin 22 include (A) a binder polymer, (B) a photopolymerizable compound, and (C) a photopolymerization initiator (hereinafter referred to as “component (A)”, “component (B)”, and What is formed from the photosensitive resin composition containing "(C) component") is mentioned.

  (A) As a binder polymer, for example, obtained by reaction of acrylic resin, styrene resin, epoxy resin, amide resin, amide epoxy resin, alkyd resin, phenol resin, ester resin, urethane resin, epoxy resin and (meth) acrylic acid Examples thereof include epoxy acrylate resins, acid-modified epoxy acrylate resins obtained by reaction of epoxy acrylate resins and acid anhydrides, and the like. These resins can be used alone or in combination of two or more.

  Among these, from the viewpoint of excellent film formability, it is preferable to use an acrylic resin, and the acrylic resin has a monomer unit derived from (meth) acrylic acid and (meth) acrylic acid alkyl ester as a constituent unit. preferable. Here, the “acrylic resin” refers to a polymer mainly having monomer units derived from a polymerizable monomer having a (meth) acryloyl group (for example, having 50 mol% or more based on the total amount of monomer units). means.

  As the acrylic resin, one produced by radical polymerization of a polymerizable monomer having a (meth) acryloyl group can be used.

  Examples of the polymerizable monomer having a (meth) acryloyl group include acrylamide such as diacetone acrylamide; (meth) acrylic acid alkyl ester, 2-hydroxyalkyl (meth) acrylate, (meth) acrylic acid tetrahydrofurfuryl ester, ( (Meth) acrylic acid dimethylaminoethyl ester, (meth) acrylic acid diethylaminoethyl ester, (meth) acrylic acid glycidyl ester, (meth) acrylic acid benzyl ester, 2,2,2-trifluoroethyl (meth) acrylate, 2, (Meth) acrylic acid esters such as 2,3,3-tetrafluoropropyl (meth) acrylate; (meth) acrylic acid, α-bromo (meth) acrylic acid, α-chloro (meth) acrylic acid, β-furyl ( (Meth) acrylic acid, β-styryl (meth) (Meth) acrylic acid such as acrylic acid. These can be used alone or in combination of two or more.

  In addition to the polymerizable monomer having the (meth) acryloyl group as described above, the acrylic resin includes styrene derivatives; acrylonitrile; esters of vinyl alcohol such as vinyl-n-butyl ether; maleic acid; maleic anhydride; Maleic acid monoesters such as monomethyl maleate, monoethyl maleate, monoisopropyl maleate; fumaric acid; cinnamic acid; α-cyanocinnamic acid; itaconic acid; one or more polymerizable monomers such as crotonic acid It may be produced by copolymerizing the body.

  As the (meth) acrylic acid alkyl ester, (meth) acrylic acid methyl ester, (meth) acrylic acid ethyl ester, (meth) acrylic acid propyl ester, (meth) acrylic acid butyl ester, (meth) acrylic acid hexyl ester, Examples include (meth) acrylic acid heptyl ester, (meth) acrylic acid octyl ester, (meth) acrylic acid 2-ethylhexyl ester, (meth) acrylic acid nonyl ester, and the like. These can be used alone or in combination of two or more.

  (A) The weight average molecular weight of the binder polymer is preferably 5,000 to 300,000, more preferably 20,000 to 150,000, and further preferably 30,000 to 100,000, from the viewpoint of balancing mechanical strength and film properties. preferable. In terms of excellent developer resistance, the weight average molecular weight is preferably 5000 or more. From the viewpoint of development time, the weight average molecular weight is preferably 300000 or less. In this specification, the weight average molecular weight is a value measured by a gel permeation chromatography method (GPC) and converted by a calibration curve created using standard polystyrene.

  (B) The photopolymerizable compound is a compound having a photopolymerizable group, and preferably has an ethylenically unsaturated bond.

  Examples of the photopolymerizable compound having an ethylenically unsaturated bond include 2,2-bis (4-((meth) acryloxypolyethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxypoly). Bisphenol A di (meth) acrylate compounds such as propoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxypolyethoxypolypropoxy) phenyl) propane; polyethylene glycol di (meth) acrylate, polypropylene glycol di Polyalkylene glycol di (meth) acrylates such as (meth) acrylate and polyethylene polypropylene glycol di (meth) acrylate; trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane ethoxy Trimethylolpropane (meth) acrylates such as li (meth) acrylate and trimethylolpropane triethoxytri (meth) acrylate; tetramethylolmethane such as tetramethylolmethane tri (meth) acrylate and tetramethylolmethanetetra (meth) acrylate (meta ) Acrylates; dipentaerythritol (meth) acrylates such as dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate, urethane monomers, and the like.

  (B) A photopolymerizable compound may be used individually by 1 type, and may be used in combination of 2 or more type.

  (B) It is preferable that the content rate of a photopolymerizable compound is 30-80 mass parts with respect to a total of 100 mass parts of a binder polymer and a photopolymerizable compound, and it is more preferable that it is 40-70 mass parts. . (B) The content of the photopolymerizable compound is preferably 30 parts by mass or more in terms of excellent photocurability and coating properties of the resin solution, and is excellent in storage stability when wound as a film. Then, it is preferable that it is 80 mass parts or less.

  (C) If a photoinitiator selects what matches the light wavelength of the exposure machine to be used, and a wavelength required for function expression, there will be no restriction | limiting in particular. Examples of the photopolymerization initiator include benzophenone, N, N, N ′, N′-tetramethyl-4,4′-diaminobenzophenone (Michler ketone), N, N, N ′, N′-tetraethyl-4,4. '-Diaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2-methyl-1- [4- (methylthio) Aromatic ketones such as phenyl] -2-morpholino-propanone-1; benzoin ether compounds such as benzoin methyl ether, benzoin ethyl ether and benzoin phenyl ether; benzoin compounds such as benzoin, methyl benzoin and ethyl benzoin; 1,2-octane Dione-1- [4- (phenylthio) phenyl]- Oxime ester compounds such as-(O-benzoyloxime), ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime); Benzyl derivatives such as benzyldimethyl ketal; 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (O-chlorophenyl) -4,5-di (methoxyphenyl) imidazole dimer, 2- (O-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (O-methoxyphenyl) -4,5-diphenylimidazole dimer, 2- (p-methoxyphenyl) -4,5-diphenyl 2,4,5-triarylimidazole dimer such as imidazole dimer; 9-phenylacridine, 1,7-bis (9,9′- Kurijiniru) acridine derivatives such as hexane and heptane; N- phenylglycine, N- phenylglycine derivatives, phosphine oxide compounds, and oxazole compounds.

  Among these, as a photopolymerization initiator, an oxime ester compound or a phosphine oxide compound is preferable from the viewpoint of transparency and excellent pattern forming ability when the conductive resin layer 2 is a thin film (for example, 10 μm or less).

  Examples of the oxime ester compound include a compound represented by the following general formula (C-1) and a compound represented by the general formula (C-2). As an oxime ester compound, the compound represented by general formula (C-1) is preferable from a viewpoint of quick curability and transparency.

In General Formula (C-1), R ¹ represents an alkyl group having 1 to 12 carbon atoms or a cycloalkyl group having 3 to 20 carbon atoms. Among these, R ¹ is preferably an alkyl group having 3 to 9 carbon atoms. Unless the effect of this invention is inhibited, the aromatic ring in general formula (C-1) may have a substituent. Examples of the substituent include an alkyl group having 1 to 12 carbon atoms.

In general formula (C-2), R ² represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, R ³ represents an alkyl group having 1 to 12 carbon atoms or a cycloalkyl group having 3 to 20 carbon atoms, R ⁴ represents an alkyl group having 1 to 12 carbon atoms, and R ⁵ represents an alkyl group or aryl group having 1 to 20 carbon atoms. p1 represents an integer of 0 to 3. When p1 is 2 or more, the plurality of R ⁴ may be the same or different. The carbazole ring may have a substituent as long as the effects of the present invention are not impaired. Examples of the substituent include an alkyl group having 1 to 12 carbon atoms.

In general formula (C-2), R ² and R ⁴ are each preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms, and 1 to 1 carbon atoms. More preferably, it is an alkyl group of 4.

In general formula (C-2), R ³ is preferably an alkyl group having 1 to 8 carbon atoms or a cycloalkyl group having 4 to 15 carbon atoms, and an alkyl group having 1 to 4 carbon atoms or 4 to 4 carbon atoms. It is more preferably 10 cycloalkyl groups, and further preferably a methyl group or an ethyl group.

In general formula (C-2), R ⁵ is preferably an alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 16 carbon atoms, and an alkyl group having 1 to 8 carbon atoms or 6 to 14 carbon atoms. Is more preferably an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 12 carbon atoms.

  Examples of the compound represented by the general formula (C-1) include 1,2-octanedione-1- [4- (phenylthio) phenyl] -2- (O-benzoyloxime), and IRGACURE OXE 01 It is commercially available as (trade name) manufactured by BASF Corporation. Examples of the compound represented by the general formula (C-2) include etanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime). ) And the like, and is commercially available as IRGACURE OXE 02 (trade name, manufactured by BASF Corporation).

As a phosphine oxide compound, the compound represented by the following general formula (C-3) and the compound represented by general formula (C-4) are mentioned. As a phosphine oxide compound, the compound represented by general formula (C-3) is preferable from a viewpoint of quick curability and transparency.

In general formula (C-3), R < ⁶ >, R < ⁷ > and R < ⁸ > show a C1-C20 alkyl group or aryl group each independently. In general formula (C-4), R <^9> , R < ¹⁰ > and R < ¹¹ > show a C1-C20 alkyl group or an aryl group each independently.

When R ⁶ , R ⁷ or R ⁸ in General Formula (C-3) is an alkyl group having 1 to 20 carbon atoms, and R ⁹ , R ¹⁰ or R ¹¹ in General Formula (C-4) is the number of carbon atoms In the case of an alkyl group having 1 to 20, the alkyl group may be linear, branched or cyclic, and more preferably the alkyl group has 5 to 10 carbon atoms.

When R ⁶ , R ⁷ or R ⁸ in the general formula (C-3) is an aryl group, and when R ⁹ , R ¹⁰ or R ¹¹ in the general formula (C-4) is an aryl group, the aryl group May have a substituent. Examples of the substituent include an alkyl group having 1 to 6 carbon atoms and an alkoxy group having 1 to 4 carbon atoms.

Among these, it is preferable that R < ⁶ >, R < ⁷ > and R < ⁸ > in general formula (C-3) are an aryl group. Moreover, it is preferable that R <^9> , R < ¹⁰ > and R < ¹¹ > in general formula (C-4) are an aryl group.

  As the compound represented by the general formula (C-3), from the transparency of the formed conductive pattern and the pattern forming ability when the film thickness of the conductive resin layer 2 is reduced (for example, 10 μm or less), 2, 4 , 6-Trimethylbenzoyl-diphenyl-phosphine oxide is preferred. 2,4,6-Trimethylbenzoyl-diphenyl-phosphine oxide is commercially available, for example, as LUCIRIN TPO (trade name, manufactured by BASF Corporation).

  As the compound represented by the general formula (C-4), the transparency of the conductive pattern to be formed and the ability to form a pattern when the thickness of the conductive resin layer 2 is reduced (for example, 10 μm or less), bis (2 , 4,6-Trimethylbenzoyl) -phenyl-phosphine oxide is preferred. Bis (2,4,6-trimethylbenzoyl) -phenyl-phosphine oxide is commercially available, for example, as Irgacure 819 (trade name, manufactured by BASF Corporation).

  Other than the oxime ester compound and the phosphine oxide compound, as a compound having good transparency and pattern forming ability when the conductive resin layer 2 is thinned, 2,2-dimethoxy-1,2-diphenylethane- 1-one is mentioned. 2,2-dimethoxy-1,2-diphenylethane-1-one is commercially available, for example, as Irgacure 651 (trade name, manufactured by BASF Corporation).

  (C) A photoinitiator may be used individually by 1 type and may be used in combination of 2 or more type.

  (C) It is preferable that the content rate of a photoinitiator is 0.1-20 mass parts with respect to a total of 100 mass parts of a binder polymer and a photopolymerizable compound, and it is 1-10 mass parts. More preferred is 1 to 5 parts by mass. (C) The content of the photopolymerization initiator is preferably 0.1 parts by mass or more from the viewpoint of excellent photosensitivity, and preferably 20 parts by mass or less from the viewpoint of excellent photocurability.

  In the conductive resin layer 2 of the present embodiment, an adhesiveness imparting agent such as a silane coupling agent, a leveling agent, a plasticizer, a filler, an antifoaming agent, a flame retardant, a stabilizer, and an antioxidant, as necessary. , Fragrance, thermal crosslinking agent, polymerization inhibitor and the like can be contained in an amount of about 0.01 to 20 parts by mass with respect to 100 parts by mass of the total amount of component (A) and component (B). These can be used alone or in combination of two or more.

  The conductive resin layer 2 may contain a compound having a thermally polymerizable group in addition to the component (B) or instead of the component (B). Examples of the thermally polymerizable group include an epoxy group, a glycidyl group, an isocyanate group, an acetylene group, a maleimide group, and an oxetanyl group. Specific examples of the compound having a thermally polymerizable group include dipentaerythritol hexaglycidyl ether, pentaerythritol tetraglycidyl ether, pentaerythritol triglycidyl ether, trimethylolethane triglycidyl ether, trimethylolpropane triglycidyl ether, glycerol poly Examples thereof include glycidyl ether and glycerin triglycidyl ether.

  The conductive resin layer 2 is made of, for example, a resin 22 dissolved in a solvent such as methanol, ethanol, acetone, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, toluene, N, N-dimethylformamide, propylene glycol monomethyl ether, or a mixed solvent thereof. The solution can be formed by coating and drying on the support film 1 on which the conductive fibers 21 are arranged. However, in this case, the amount of the remaining organic solvent in the resin 22 after drying is preferably 2% by mass or less in order to prevent the organic solvent from diffusing in the subsequent step.

  The application of the resin 22 solution can be performed by a known method such as a roll coating method, a comma coating method, a gravure coating method, an air knife coating method, a die coating method, a bar coating method, or a spray coating method. After coating, drying for removing the organic solvent and the like can be performed at 70 to 150 ° C. for about 5 to 30 minutes with a hot air convection dryer or the like.

  The thickness of the conductive resin layer 2 varies depending on the application, but is preferably 1 to 50 μm, more preferably 1 to 15 μm, and even more preferably 1 to 10 μm after drying. If the thickness is less than 1 μm, coating tends to be difficult, and if it exceeds 50 μm, the sensitivity due to the decrease in light transmission is insufficient, and the photocurability of the conductive resin layer 2 to be transferred tends to decrease. The thickness of the layer (cured film) after curing the conductive resin layer 2 is also preferably within these ranges.

  In the transfer type conductive film 10 used in the present embodiment, the conductive resin layer 2 has a minimum visible light transmittance of 85% or more in a wavelength region of 400 nm to 700 nm when the film thickness is 1 to 10 μm. It is preferable that it is 90% or more. When the conductive resin layer 2 satisfies such a condition, it is easy to increase the brightness in a display panel or the like.

  About the transfer type conductive film 10 used by this embodiment, it is preferable that the surface resistivity when it is set as a electrically conductive film or a conductive pattern is 1000 ohms / square or less from a viewpoint of utilizing effectively as a transparent electrode, 500 ohms / square. More preferably, it is more preferably 300Ω / □ or less. The surface resistivity can be adjusted by, for example, the concentration of the conductive fiber dispersion or the coating amount.

  As shown in FIG. 1B, the transfer type conductive film used in this embodiment is a transfer type further provided with a protective film 3 so as to contact the surface of the conductive resin layer 2 opposite to the support film 1. The conductive film 11 may be used.

  As the protective film 3, a polymer film having heat resistance and solvent resistance such as a polyethylene terephthalate film, a polypropylene film, and a polyethylene film can be used. Moreover, you may use the polymer film similar to the above-mentioned support film 1 as the protective film 3. FIG.

  The adhesive force between the protective film 3 and the conductive resin layer 2 is greater than the adhesive force between the conductive resin layer 2 and the support film 1 so that the protective film 3 can be easily peeled off from the conductive resin layer 2. Is preferably small.

The number of fish eyes having a diameter of 80 μm or more contained in the protective film 3 is preferably 5 / m ² or less. “Fisheye” means that materials are melted, kneaded, extruded, biaxially stretched, casting materials, etc., and foreign materials, undissolved materials, oxidized degradation products, etc. are taken into the film. It is a thing.

  The thickness of the protective film 3 is preferably 1 to 100 μm, more preferably 5 to 50 μm, still more preferably 5 to 30 μm, and particularly preferably 15 to 30 μm. When the thickness of the protective film 3 is less than 1 μm, the protective film 3 tends to be damaged during lamination, and when it exceeds 100 μm, the price tends to increase.

(Conductive pattern formation process)
FIG. 2 is a schematic cross-sectional view for explaining the conductive pattern forming step. As shown in FIG. 2, in the conductive pattern forming step, the conductive resin layer 2 is insulated by irradiating laser light L. In this step, a laser irradiation apparatus is used. The laser irradiation apparatus includes a laser light generation unit that generates laser light L, a condensing lens such as a convex lens that is a condensing unit that condenses the laser light L, and a sample (a substrate having an electrode 4) that is processed by laser light irradiation. 5 and a stage on which a laminate 20) including a conductive resin layer 2 laminated on at least the electrode 4 of the substrate 5 and a plastic film 6 arranged on the conductive resin layer 2 is disposed. Yes. In this laser beam irradiation apparatus, a laser beam L is irradiated from a laser beam generator to a sample via a condenser lens. As this laser beam irradiation apparatus, a commercially available apparatus can be used without particular limitation.

Examples of the laser light L generated from the laser light generating means include pulsed laser light such as YAG and YVO ₄ and continuous wave laser light such as a carbon dioxide gas laser. Among these, a pulsed laser beam of 532 nm using a wavelength of 1064 nm such as YAG or YVO ₄ or a secondary higher wavelength thereof is preferable because it is simple. In the pulsed laser beam, the pulse width is preferably 300 nsec or less, and more preferably 70 nsec or less.

  The focal point F of the condensing lens is usually set for each surface of the conductive resin layer 2, but when the conductive resin layer 2 has irregularities or the like, or when the laser light L is irradiated over a wide area. Is preferably set at a position away from the conductive resin layer 2. Specifically, the condenser lens is disposed so that the focal point F of the laser light L is located between the conductive resin layer 2 and the condenser lens. That is, the focal point F of the condenser lens (laser light L) is formed between the conductive resin layer 2 and the condenser lens. As a result, the spot diameter of the laser light L that strikes the substrate 5 having the electrodes 4 is larger than the spot diameter of the laser light L irradiated onto the conductive resin layer 2. As a result, the energy density of the laser beam L is ensured in the conductive resin layer 2 and the insulation of the conductive resin layer 2 is reliably achieved, while the laser beam L is generated in the substrate 5 having the base electrode 4. It is possible to reduce the energy density of the electrode 4 and prevent the electrode 4 from being damaged. In the present embodiment, the conductive resin layer 2 is irradiated with the laser light L through the plastic film 6. At that time, the focal point F of the laser beam L may be in the plastic film 6 or between the condenser lens and the plastic film 6. The focal point F is preferably in the plastic film 6 from the viewpoint that the spot diameter of the laser light L in the conductive resin layer 2 can be reduced and fine processing can be performed with a laser.

  A condenser lens having a low numerical aperture (NA <0.1) is preferable. That is, by setting the numerical aperture of the condensing lens to NA <0.1, it becomes easy to set the irradiation condition of the laser light L. In particular, the focal point F of the laser light L is between the conductive resin layer 2 and the condensing lens. It is possible to prevent energy loss and diffusion of the laser light L due to the plasma of air at the focal point F due to being positioned in between.

  The stage can be moved two-dimensionally in the horizontal direction. The stage is preferably composed of a member having at least an upper surface side that is transparent or a member having light absorption. When the output of the laser beam L exceeds 1 W, the stage is preferably made of a nylon-based or fluorine-based resin material or a silicone rubber-based polymer material.

  Next, the laser light L is emitted from the laser light generating means, and the laser light L is condensed by the condenser lens. The condensed laser light L is applied to the conductive resin layer 2 through the plastic film 6. At that time, the stage is moved so that the irradiation of the laser beam L has a predetermined pattern. Here, the predetermined pattern is a pattern for forming a conductive pattern.

  As described above, by irradiating the conductive resin layer 2 with the laser beam L in a predetermined pattern, the conductive fiber 21 in the irradiated portion of the laser beam L is removed, the irradiated portion of the laser beam L is insulated, and the conductive portion An insulating part is formed in the conductive resin layer 2 so that a conductive pattern having a thickness of 1 is obtained.

The energy density of the laser light L applied to the conductive resin layer 2 is 1 × 10 ^{16 to} 7 × 10 ¹⁷ W / m ² , and the irradiation energy per unit area is 1 × 10 ⁵ to 1 × 10 ⁶ J / m ^2. preferable. That is, when the energy density / irradiation energy is set to a value smaller than the above numerical range, the conductive resin layer 2 may be insufficiently insulated. Further, when the value is set to a value larger than the above numerical range, the processing trace becomes conspicuous and the damage to the substrate on which the base electrode is formed tends to increase.

These values are defined by dividing the output value of the laser beam in the processing area by the condensing spot area of the processing area. For convenience, the output is converted to the output value from the laser oscillator by the optical system. It is obtained by multiplying by the loss factor. The spot diameter area S is defined by the following formula.
S = S ₀ × D / FL
S ₀ : Beam area of laser focused by lens FL: Focal length of lens D: Distance between surface (upper surface) of conductive resin layer 2 and focal point

  In addition, although the focus F mentioned above demonstrated the case where aberration was sufficiently small by the condensing means, such as a lens, for example, there exist elements which increase aberrations, such as a spherical lens with a short focal distance, and protective glass. In this case, the focal point F is defined as the position where the energy density at the focal point is the highest.

  Here, the distance D is set within a range of 0.2 to 3% of the focal length FL in a normal laser beam machine. Preferably, the distance D is set within a range of 0.5 to 2% of the focal length FL. More preferably, the distance D is set within a range of 0.7 to 1.5% of the focal length FL. By setting the distance D in the above numerical range, it is possible to reliably remove the conductive fibers 21 (form voids) and form an electrically reliable insulating pattern, and to form the conductive resin layer 2. It is possible to reliably prevent machining traces resulting from damage to the surface.

  In the conductive pattern forming step, laser irradiation to the conductive resin layer 2 is performed through the plastic film 6. For example, the plastic film 6 is disposed so as to contact at least a part of the conductive resin layer 2 laminated on at least the electrode 4 of the substrate 5. The plastic film 6 can be used without any particular limitation, and examples thereof include a polymer film having heat resistance and solvent resistance. Examples of such a polymer film include a polyethylene terephthalate film, a polyethylene film, a polypropylene film, and a polycarbonate film. Among these polymer films, a polyethylene terephthalate film is preferable from the viewpoint of transparency and heat resistance.

  The thickness of the plastic film 6 is preferably 5 to 300 μm, more preferably 10 to 200 μm, and still more preferably 15 to 100 μm. From the viewpoint of reducing damage to the underlying electrode 4 when the laser beam L is irradiated, the thickness is preferably 5 μm or more, more preferably 10 μm or more, and further preferably 15 μm or more. The thickness of the plastic film 6 is preferably 300 μm or less, more preferably 200 μm or less, further preferably 100 μm or less, and more preferably 50 μm or less from the viewpoint that the conductive resin layer 2 can be finely processed. Is particularly preferred.

  In the lamination process, when the conductive resin layer 2 is laminated on the substrate 5 having the electrodes 4 using the transfer type conductive films 10 and 11, the transfer type conductive film is used as the plastic film 6 in the conductive pattern formation process. The conductive resin layer 2 can be irradiated with the laser light L through the support film 1 using the support films 1 and 11. Thereby, since it is not necessary to arrange a plastic film anew on the conductive resin layer 2, a conductive pattern can be easily formed.

  The manufacturing method of the laminated body with a conductive pattern in the case of using the transfer type conductive film 11 in a lamination process is summarized below. First, the protective film 3 is peeled from the transfer type conductive film 11 and laminated so that the conductive resin layer 2 is in close contact with at least the electrode 4 of the substrate 5 having the electrode 4. Thereby, the laminated body 20 which the board | substrate 5 which has the electrode 4, the conductive resin layer 2, and the support film 1 laminated | stacked in this order is producible. Thereafter, the conductive resin layer 2 is irradiated with the laser beam L through the support film 1 in accordance with a desired conductive pattern to insulate the conductive resin layer 2. Then, by peeling off the support film 1, the conductive resin layer 2 can be insulated and a conductive pattern can be formed without damaging the underlying electrode 4. In addition, before irradiating the laser beam L, before irradiating the laser beam L and peeling the support film 1, and after peeling the support film 1, the conductive resin layer 2 is irradiated with the laser beam L. Alternatively, the conductive resin layer 2 may be photocured by light irradiation. That is, the conductive resin layer 2 in the conductive pattern forming step includes both modes of the conductive resin layer before being cured and the conductive resin layer after being cured.

  On the other hand, as shown in FIG. 3, in the conventional method, since the conductive resin layer 2 is irradiated with the laser light L without using a plastic film, the energy of the laser light L irradiated to the electrode 4 on the substrate 5 is used. The density increases and damage d occurs in the electrode 4. In this case, the insulating part of the conductive resin layer 2 is formed as shown in the electron micrograph shown in FIG.

  The manufacturing method of the laminated body with a conductive pattern of this embodiment may be further equipped with the reirradiation process after the conductive pattern formation process. In the re-irradiation step, the insulating portion formed in the conductive pattern formation step is further irradiated with pulsed laser light once or more. In the re-irradiation step, since the conductive resin layer 2 is colored or removed, the insulating portion can be easily visualized.

  The irradiation method and irradiation conditions of the pulsed laser light in the re-irradiation step are the same as the irradiation method and irradiation conditions in the conductive pattern forming step. However, it is not necessary to be the same as the conductive pattern forming step.

<Touch panel sensor>
The manufacturing method of the laminated body with a conductive pattern of this embodiment is preferably applicable to formation of the transparent electrode of an electrostatic capacitance type touch panel, manufacture of an electrostatic capacitance type touch panel sensor, etc.

  EXAMPLES Hereinafter, although this invention is demonstrated further more concretely based on an Example, this invention is not limited to an Example.

The components used in Examples and Comparative Examples are as follows.
(B) component, trimethylolpropane triacrylate (manufactured by Nippon Kayaku Co., Ltd., trade name "TMPTA")
Component (C) 1,2-octanedione, 1- [4- (phenylthio) phenyl-, 2- (O-benzoyloxime)] (trade name “OXE-01” manufactured by BASF Corporation)
2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (BASF Corporation, trade name “LUCIRIN TPO”)
2,2-dimethoxy-1,2-diphenylethane-1-one (manufactured by BASF Corporation, trade name “Irgacure 651”)
(Other ingredients)
Octamethylcyclotetrasiloxane (trade name “SH-30” manufactured by Toray Dow Corning Co., Ltd.) (leveling agent)
・ Methyl ethyl ketone (manufactured by Tonen Chemical Co., Ltd.) (solvent)

Production Example 1
<Preparation of silver fiber dispersion (conductive fiber dispersion (coating liquid for forming conductive film))>
[Preparation of silver fiber by polyol method]
In a 2000 mL three-necked flask, 500 mL of ethylene glycol was added and heated to 160 ° C. using an oil bath while stirring with a magnetic stirrer under a nitrogen atmosphere. A separately prepared solution 1 (a solution in which 2 mg of PtCl ₂ was dissolved in 50 mL of ethylene glycol) was added dropwise thereto. After 4 to 5 minutes, 5 g of solution 2 (a solution in which 5 g of AgNO ₃ was dissolved in 300 mL of ethylene glycol) and 5 g of solution 3 (polyvinylpyrrolidone (manufactured by Wako Pure Chemical Industries, Ltd., weight average molecular weight: 58000)) were added to 150 mL of ethylene glycol. The dissolved solution was dropped from each dropping funnel over 1 minute, and the reaction solution was stirred at 160 ° C. for 60 minutes.

  The reaction solution was allowed to stand at 30 ° C. or lower and then diluted 10 times with acetone. The diluted solution of the reaction solution was centrifuged at 2000 rpm for 20 minutes using a centrifuge, and the supernatant was decanted. Acetone was added to the precipitate, and after stirring, the mixture was centrifuged under the same conditions as described above, and acetone was decanted. Then, it centrifuged twice similarly using distilled water, and obtained the silver fiber. When the obtained silver fiber was observed with an optical microscope, the fiber diameter (diameter) was 30 nm, and the fiber length was 3 μm.

[Preparation of silver fiber dispersion]
Disperse silver fiber in pure water so that the silver fiber obtained above has a concentration of 0.2% by mass and dodecyl-pentaethylene glycol has a concentration of 0.1% by mass. A liquid was obtained.

Production Example 2
<Preparation of binder polymer (A1) solution>
A flask equipped with a stirrer, reflux condenser, inert gas inlet and thermometer was charged with (1) shown in Table 1 and heated to 80 ° C. in a nitrogen gas atmosphere. While maintaining the reaction temperature at 80 ° C. ± 2 ° C., (2) shown in Table 1 was uniformly added dropwise over 4 hours. After dropping (2), stirring was continued at 80 ° C. ± 2 ° C. for 6 hours to obtain a binder polymer (A1) solution (solid content 50% by mass) having a weight average molecular weight of 45,000. The acid value of the binder polymer (A1) was 78 mgKOH / g. Moreover, the glass transition temperature (Tg) of the binder polymer (A1) was 60 ° C.

  The characteristics of the prepared polymer solution were measured by the following method.

(1) Weight average molecular weight The weight average molecular weight (Mw) was measured by gel permeation chromatography (GPC), and was derived by conversion using a standard polystyrene calibration curve. The GPC conditions are shown below.
Pump: Hitachi L-6000 type (manufactured by Hitachi, Ltd., trade name)
Column: Gelpack GL-R420, Gelpack GL-R430, Gelpack GL-R440 (above, manufactured by Hitachi Chemical Co., Ltd., trade name)
Eluent: Tetrahydrofuran Measurement temperature: 40 ° C
Flow rate: 2.05 mL / min Detector: Hitachi L-3300 type RI (trade name, manufactured by Hitachi, Ltd.)

(2) Acid value The acid value was measured as follows. First, the binder polymer solution was heated at 130 ° C. for 1 hour to remove volatile components, thereby obtaining a solid polymer. Then, after precisely weighing 1 g of the solid polymer, the precisely weighed polymer was put into an Erlenmeyer flask, and 30 g of acetone was added and dissolved uniformly. Next, an appropriate amount of an indicator, phenolphthalein, was added to the solution, and titration was performed using a 0.1N aqueous KOH solution. And the acid value was computed by following Formula.
Acid value = 0.1 × Vf × 56.1 / (Wp × I / 100)
In the formula, Vf represents the titration amount (mL) of the KOH aqueous solution, Wp represents the mass (g) of the measured resin solution, and I represents the proportion (mass%) of the non-volatile content in the measured resin solution.

(3) Glass transition temperature (Tg)
The prepared binder polymer solution was uniformly applied onto a polyethylene terephthalate film (trade name “Purex A53” manufactured by Teijin DuPont Films Ltd.), and dried for 10 minutes with a hot air convection dryer at 90 ° C. A film made of a binder polymer having a thickness of 40 μm after drying was formed. Next, using an exposure machine having a high pressure mercury lamp (trade name “EXM-1201” manufactured by Oak Manufacturing Co., Ltd.), the amount of irradiation energy is 400 mJ / cm ² (measured value at i-line (wavelength 365 nm)). The film was exposed. The exposed film was heated on a hot plate at 65 ° C. for 2 minutes, then at 95 ° C. for 8 minutes, heated at 180 ° C. for 60 minutes in a hot air convection dryer, and then peeled off from the polyethylene terephthalate film, Using TMA / SS6000 (manufactured by Seiko Instruments Inc.), the coefficient of thermal expansion of the cured film is measured when the temperature is increased at a temperature rising rate of 5 ° C./min, and the inflection point obtained from the curve is the glass transition. It calculated | required as temperature Tg.

<Preparation of transfer type conductive film V1>
[Preparation of conductive fiber layer]
The silver fiber dispersion obtained in Production Example 1 above is uniformly 25 g / m ² on a 50 μm thick polyethylene terephthalate film (PET film, manufactured by Teijin Ltd., trade name “G2-50”) (support film). And dried for 3 minutes with a hot air convection dryer at 100 ° C. to form a conductive fiber layer.

[Preparation of resin solution X1]
The materials shown in Table 2 were mixed at the blending amounts (parts by mass) shown in Table 2 for 15 minutes using a stirrer to prepare a resin solution X1. (A) The compounding quantity of a component is the mass of solid content.

[Preparation of transfer-type conductive film V1]
The resin solution X1 was uniformly applied on the conductive fiber layer, and dried for 10 minutes with a hot air convection dryer at 100 ° C. to form a conductive resin layer. Thereafter, the conductive resin layer was covered with a polyethylene film (trade name “NF-13” manufactured by Tamapoly Co., Ltd.) to obtain a transfer type conductive film V1. The thickness of the conductive resin layer after drying was 5 μm.

<Evaluation of conductive resin layer>
[Measurement of light transmittance of conductive resin layer]
Laminator (manufactured by Hitachi Chemical Co., Ltd., trade name “HLM-3000 type”) so that the conductive resin layer is in contact with the glass substrate having a thickness of 1 mm while peeling off the polyethylene film of the obtained transfer type conductive film V1. Was used, a roll temperature of 110 ° C., a substrate feed rate of 1 m / min, and a pressure bonding pressure (cylinder pressure) of 4 × 105 Pa (thickness of 1 mm, length of 10 cm × width of 10 cm, a linear pressure at this time was 9. 8 × 10 ³ N / m) was laminated to prepare a substrate in which a transfer type conductive film V1 including a support film was laminated on a glass substrate.

Next, using a parallel light exposure machine (EXM1201 manufactured by Oak Manufacturing Co., Ltd.) on the transfer type conductive film on the glass substrate, an exposure amount of 5 × 10 ² J / m ² (i-line ( The measurement value at a wavelength of 365 nm) was irradiated with ultraviolet rays. Thereafter, the support film is removed, and further irradiated with ultraviolet rays at an exposure dose of 1 × 10 ⁴ J / m ² (measured value at i-line (wavelength 365 nm)) from the conductive resin layer side with a parallel light exposure machine. A sample for measuring transmittance of a resin layer (film thickness: 5.0 μm) was obtained.

  Next, using the ultraviolet-visible spectrophotometer (trade name “U-3310”, manufactured by Hitachi Instrument Service Co., Ltd.), the obtained sample was measured for the ultraviolet light transmittance in the measurement wavelength range of 300 to 380 nm, and the measurement wavelength. Visible light transmittance was measured in the region of 400-700 nm. Note that the transmittance of the conductive resin layer alone was measured using the glass substrate as a background.

[Measurement of surface resistivity of conductive resin layer]
In the same manner as the method for measuring the light transmittance of the conductive resin layer, a sample for measuring the surface resistivity in which the conductive resin layer was laminated on the glass substrate was produced. The surface resistivity of the sample was measured by a non-contact resistance measuring instrument (trade name “EC-80P” manufactured by Napson Co., Ltd.) and found to be 100 ± 5Ω / □.

<Preparation of substrate with electrodes>
A laminator (Hitachi Chemical Co., Ltd.) is made so that the conductive resin layer is in contact with the easy-adhesion surface of a PET film substrate (thickness 50 μm, manufactured by Toyobo, trade name “A4100”) while peeling the polyethylene film of the transfer type conductive film V1. Using a product made by the company, trade name “HLM-3000 type”), laminating on a PET film substrate with a roll temperature of 110 ° C., a substrate feed rate of 1 m / min, and a pressure (cylinder pressure) of 4 × 10 ⁵ Pa. A film substrate was prepared in which a transfer type conductive film including a support film was laminated.

Next, a photo film made of PET having a wiring pattern (number of lines: 10) having a line width / space width of 1 mm / 1 mm and a length of 100 mm on the support film of the transfer type conductive film on the film substrate. The mask was brought into close contact, and exposed using a parallel light exposure machine (trade name “EXM1201” manufactured by Oak Seisakusho Co., Ltd.) from the support film side through a photomask (first stage exposure). The exposure dose was 2 × 10 ² J / m ² (measured value at i-line (wavelength 365 nm)), and ultraviolet rays were irradiated. Next, the photomask and the support film were removed, and the entire surface of the film was exposed from above the conductive resin layer in an atmospheric environment (in the presence of oxygen) (second stage exposure). The exposure amount was set to be three times that of the first-stage exposure described above.

After exposure, the film was allowed to stand at room temperature (23 ° C. to 25 ° C.) for 15 minutes, and then developed by spraying a 1% by mass aqueous sodium carbonate solution at 30 ° C. for 30 seconds. Thereafter, ultraviolet rays were irradiated from above the conductive resin layer at 1 × 10 ⁴ J / m ² (measured value at i-line (wavelength 365 nm)). As a result, an electrode made of conductive fiber having a 1 mm line pattern was formed on the PET film, and a substrate S1 with an electrode was produced.

Example 1
A laminator (manufactured by Hitachi Chemical Co., Ltd., trade name: HLM-3000) so that the conductive resin layer is in contact with the electrode-forming surface of the substrate with electrode S1 produced above while peeling the polyethylene film of the transfer type conductive film V1. Is laminated under the conditions of a roll temperature of 110 ° C., a substrate feed rate of 1 m / min, and a pressure bonding pressure (cylinder pressure) of 4 × 10 ⁵ Pa, and a conductive resin layer is supported on the electrode-equipped substrate S1. A laminate in which films (plastic films) were laminated was produced.

Next, laser processing was performed using a YVO ₄ fundamental wave laser processing machine (MD-V9920, manufactured by Keyence Corporation) equipped with a galvano mirror as a laser light irradiation device. Laser irradiation was applied to the conductive resin layer through the support film. The processing pattern of the laser irradiation was performed by irradiating the laser in the direction perpendicular to the line pattern of the underlying substrate with 1 mm line pattern electrode. Irradiation conditions were as follows.
Distance from focus to conductive resin layer: 0mm
Output: 30%
Movement speed: 600 mm / sec Oscillation frequency: 100 kHz

  Next, after peeling off the support film, a tester was applied to both ends of the underlying 1 mm line pattern electrode to confirm whether the 1 mm line pattern electrode was conductive without damage. As a result, it was confirmed that the line pattern was conducted without any problem, and the conductive resin layer was laser processed without damaging the underlying electrode.

Example 2
In the same manner as in Example 1, a laminator (manufactured by Hitachi Chemical Co., Ltd., trade name “Product Name”) is formed so that the conductive resin layer is in contact with the electrode forming surface of the electrode-attached substrate S1 while peeling the polyethylene film of the transfer conductive film V1. HLM-3000 type "), and laminates under the conditions of a roll temperature of 110 ° C., a substrate feed rate of 1 m / min, and a pressure bonding pressure (cylinder pressure) of 4 × 10 ⁵ Pa, and a conductive resin on the substrate with electrode S1. A laminate in which a layer and a support film (plastic film) were laminated thereon was produced.

Then, it exposed from the support film side using the parallel light exposure machine (Oak Manufacturing Co., Ltd. product, EXM1201). The exposure amount was 5 × 10 ² J / m ² (measured value at i-line (wavelength 365 nm)), and ultraviolet rays were irradiated. Then, after peeling off the support film, a polyethylene film (manufactured by Tamapoly Co., Ltd., trade name “NF-13”) was bonded so as to adhere to the exposed conductive resin layer.

  Thereafter, in the same manner as in Example 1, laser irradiation was performed through a polyethylene film (plastic film). Further, when the conduction of the line pattern electrode was confirmed in the same manner as in Example 1, it was confirmed that the line pattern was conducted without any problem and the conductive resin layer could be laser processed without damaging the electrode.

Comparative Example 1
Laser irradiation of the conductive resin layer was performed in the same manner as in Example 2 except that the polyethylene film was not bonded to the conductive resin layer. That is, processing was performed by irradiating the conductive resin layer with laser without using a plastic film. When the 1 mm line pattern electrode of the base material with an electrode was examined, it was confirmed that the line pattern was not conductive and the electrode was damaged.

  DESCRIPTION OF SYMBOLS 1 ... Support film, 2 ... Conductive resin layer, 3 ... Protective film, 4 ... Electrode, 5 ... Board | substrate, 6 ... Plastic film, 21 ... Conductive fiber, 22 ... Resin, L ... Laser beam.

Claims (8)

A laminating step of laminating a conductive resin layer containing conductive fibers and a resin on at least the electrode of the substrate having an electrode;
A conductive pattern forming step of forming a conductive pattern by irradiating the conductive resin layer with a laser to insulate the conductive resin layer; and
The manufacturing method of the laminated body with a conductive pattern which irradiates the said laser to the said conductive resin layer through a plastic film in the said conductive pattern formation process.   The manufacturing method of the laminated body with a conductive pattern of Claim 1 which laminate | stacks the transcription | transfer type conductive film provided with the said conductive resin layer and the said plastic film on the said electrode of the said board | substrate at least in the said lamination process.   The manufacturing method of the laminated body with a conductive pattern of Claim 1 which arrange | positions the said plastic film so that at least one part of the said conductive resin layer laminated | stacked on the said electrode of the said board | substrate may be contacted.   The manufacturing method of the laminated body with a conductive pattern as described in any one of Claims 1-3 whose said conductive fiber is a metal fiber.   The manufacturing method of the laminated body with a conductive pattern as described in any one of Claims 1-4 whose said conductive fiber is silver nanowire.   With the conductive pattern as described in any one of Claims 1-5 in which the said conductive resin layer laminated | stacked in the said lamination process further contains the compound which has a compound which has a thermopolymerizable group, or a photopolymerizable group. A manufacturing method of a layered product.   The laminate with a conductive pattern according to any one of claims 1 to 6, wherein the conductive resin layer laminated in the lamination step further contains a compound having a photopolymerizable group and a photopolymerization initiator. Production method.   The manufacturing method of the laminated body with a conductive pattern as described in any one of Claims 1-7 in which the said electrode contains a metal fiber.