JP2018116841A - Conductive layer with base material, method for producing the same, and sensor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a base material with a conductive layer having excellent elasticity and a method of producing the same.SOLUTION: A conductive layer with a base material 10 has a base material 1 with an elongation at break of 200% or more, and a conductive layer 2 provided on the base material 1. The conductive layer 2 has a conductive fiber. A method for producing a conductive layer with a base material 10 has the step of disposing a conductive film, which has a support film, a conductive layer provided on the support film, and a resin layer provided on the conductive layer, so that the resin layer turns to the base material side, on the base material; and the peeling step of peeling the support film, where the conductive layer has a conductive fiber.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a substrate with a conductive layer, a method for producing the same, and a sensor.

  Liquid crystal display elements and touch screens are used in large electronic devices such as personal computers and televisions, small electronic devices such as car navigation systems, mobile phones, and electronic dictionaries, and display devices such as OA devices and FA devices. These liquid crystal display elements and touch screens require a substrate with a conductive layer. As a method for obtaining a substrate with a conductive layer, for example, a method using a photosensitive conductive film having a photosensitive layer containing conductive fibers has been proposed (for example, see Patent Document 1 below). If this technique is used, a transparent conductive pattern can be formed on various substrates by a photolithography process.

International Publication No. 2010/021224

  By the way, the electronic device which provided the elasticity was proposed against the background of the spread of consumers' preference now, and the elasticity is calculated | required also by the base material with a conductive layer mounted in these. However, in base materials with conductive layers mounted on existing electronic devices, polyethylene terephthalate (PET), polycarbonate (PC), etc. are used as base materials, and these base materials have low elongation at break and are elastic. There is a problem with low nature. Moreover, as a transparent conductive material which comprises a base material with a conductive layer, ITO (indium oxide), a tin oxide, etc. may be used, but these also have the subject that a fracture elongation is low and a stretching property is low. The base material with a conductive layer using a base material having a low elongation at break has a problem that it breaks when stretched (particularly when stretched) and loses conductivity.

  This invention is made | formed in view of the said situation, and aims at providing the base material with the conductive layer which has the outstanding elasticity, and its manufacturing method. Moreover, an object of this invention is to provide a sensor provided with the said base material with a conductive layer.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have used a base material having a breaking elongation of 200% or more as the base material of the base material with a conductive layer. It has been found that a substrate with a layer can be formed.

  That is, a first aspect of the present invention includes a base material having a breaking elongation of 200% or more and a conductive layer provided on the base material, wherein the conductive layer includes conductive fibers. The present invention relates to a substrate with an adhesive.

  The substrate preferably contains polyurethane or silicone rubber. In this case, even if the base material with a conductive layer is stretched to 200% or more, the conductivity can be easily ensured without breaking.

  It is preferable that the base material with a conductive layer according to the first aspect further includes a resin layer provided between the base material and the conductive layer. In this case, the conductive fibers necessary for obtaining the same electric resistance value can be reduced, and the light transmittance of the substrate with the conductive layer can be improved. The resin layer may contain a photosensitive resin composition or a cured product thereof.

  The conductive fiber preferably contains silver fiber. In this case, the conductive fibers necessary for obtaining the same electric resistance value can be reduced, and the light transmittance of the substrate with the conductive layer can be improved.

  The conductive layer may be a conductive pattern.

  The second aspect of the present invention is a method for producing the above-mentioned substrate with a conductive layer, comprising a support film, a conductive layer provided on the support film, and a resin layer provided on the conductive layer. A step of disposing the conductive film on the substrate in a direction in which the resin layer is positioned on the substrate side, and a peeling step of peeling the support film, wherein the conductive layer includes conductive fibers. The present invention relates to a method for producing a substrate with a conductive layer.

  The manufacturing method of the base material with a conductive layer which concerns on a 2nd aspect may further be equipped with the exposure process which irradiates an active ray to the said resin layer, and the aspect in which the said resin layer contains the photosensitive resin composition may be sufficient. When the resin layer contains the photosensitive resin composition, pattern forming ability can be easily imparted to the resin layer, and formation of a conductive pattern (wiring) on the substrate is facilitated.

  The manufacturing method of the base material with a conductive layer which concerns on a 2nd aspect is further equipped with the process of forming a conductive pattern by removing the unexposed part of the said resin layer after the said peeling process and the said exposure process, The said exposure In the step, the resin layer may be irradiated with an actinic ray in a pattern.

  A 3rd aspect of this invention is related with a sensor provided with the above-mentioned base material with a conductive layer.

  ADVANTAGE OF THE INVENTION According to this invention, the base material with the conductive layer which has the outstanding stretching property, and its manufacturing method can be provided. Moreover, according to this invention, a sensor provided with the said base material with a conductive layer can be provided.

It is a schematic cross section which shows one Embodiment of a base material with a conductive layer. It is a schematic cross section which shows other one Embodiment of the base material with a conductive layer. It is a figure which shows one Embodiment of a conductive film. It is a schematic cross section for explaining one embodiment of a manufacturing method of a substrate with a conductive layer. It is a schematic cross section for demonstrating other one Embodiment of the manufacturing method of the base material with a conductive layer.

  Hereinafter, embodiments of the present invention will be described in detail. In the present specification, “(meth) acrylate” means “acrylate” or “methacrylate” corresponding thereto. Similarly, “(meth) acrylic” means “acrylic” or “methacrylic” corresponding thereto, and “(meth) acrylic acid” means “acrylic acid” or “methacrylic acid” corresponding thereto. “(Meth) acryloyl” means “acryloyl” or “methacryloyl” corresponding thereto. Further, “(meth) acrylic acid alkyl ester” means “acrylic acid alkyl ester” or “methacrylic acid alkyl ester” corresponding thereto.

  “EO” represents ethylene oxide, and “EO-modified” means a compound having an ethylene oxide group. Similarly, “PO” represents propylene oxide, and “PO-modified” means a compound having a propylene oxide group.

  The base material with a conductive layer according to the present embodiment includes a base material having a breaking elongation of 200% or more and a conductive layer provided on the base material, and the conductive layer includes conductive fibers. The sensor according to the present embodiment includes the base material with a conductive layer according to the present embodiment. According to the base material with a conductive layer according to this embodiment, a sensor having good stretchability can be formed. Examples of the substrate with a conductive layer include a substrate with a conductive layer (conductive substrate). The base material with a conductive layer is, for example, a transparent conductive substrate in which a constituent member such as a base material is transparent. The conductive layer may be a conductive pattern (wiring).

  From the viewpoint of further improving the stretchability of the substrate with a conductive layer, the breaking elongation of the substrate is preferably 300% or more, more preferably 400% or more, still more preferably 500% or more, and particularly preferably 700% or more. The upper limit of the breaking elongation of the substrate is, for example, 900%.

  The breaking elongation of the substrate can be measured, for example, by the following method. Specifically, it can be measured in a tensile mode such as a precision universal testing machine under conditions such as a width of 15 mm for each film, a gap between chucks of 40 mm, and a tensile speed of 200 mm / min.

  The base material with a conductive layer according to the present embodiment may further include a resin layer provided between the base material and the conductive layer. The resin layer may contain a photosensitive resin composition or a cured product thereof.

  FIG. 1 is a schematic cross-sectional view showing an embodiment of a substrate with a conductive layer. The base material 10 with a conductive layer shown in FIG. 1 includes a base material 1 having a breaking elongation of 200% or more and a conductive layer 2 provided on the base material 1. The conductive layer 2 may be a layer containing conductive fibers and made of conductive fibers.

  FIG. 2 is a schematic cross-sectional view showing another embodiment of the substrate with a conductive layer. The base material 20 with a conductive layer shown in FIG. 2 includes a base material 1 having a breaking elongation of 200% or more, a resin layer 3 provided on the base material 1, and a conductive layer 4 provided on the resin layer 3. . The conductive layer 4 may be a layer containing conductive fibers and made of conductive fibers. The resin layer 3 is a layer that does not contain conductive fibers, for example.

  As the base material 1, any base material having a breaking elongation of 200% or more can be used without particular limitation. By selecting such a substrate, stretchability can be imparted to the substrate with a conductive layer. The base material 1 is transparent, for example.

  Examples of the substrate 1 include a substrate containing polyurethane or silicone rubber, and specific examples include a polyurethane film and a silicone rubber sheet. The polyurethane film preferably does not contain an aromatic ring in the molecular structure. By not containing an aromatic ring, the stretchability of the base material is further improved, and a suitable base material with a conductive layer can be obtained.

  The thickness of the substrate 1 is preferably 20 to 200 μm, more preferably 30 to 150 μm, and still more preferably 50 to 100 μm. When the thickness of the substrate 1 is 20 μm or more, handling becomes easy, and it becomes easy to suppress tearing of the substrate. When the thickness of the substrate 1 is 200 μm or less, it is easy to suppress a decrease in the flexibility of the substrate due to an increase in rigidity.

  Examples of the conductive fibers contained in the conductive layers 2 and 4 include metal fibers such as gold, silver, copper, and platinum; carbon fibers such as carbon nanotubes, and the like, and conductive fibers including silver fibers (silver nanowires). Is preferably used.

Conductive fibers containing silver fibers (silver nanowires and the like) can be produced 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 is preferably 1 to 50 nm, more preferably 2 to 20 nm, and still more preferably 3 to 10 nm. The fiber length of the conductive fiber is preferably 1 to 100 μm, more preferably 2 to 50 μm, and still more preferably 3 to 10 μm. The fiber diameter and fiber length can be measured with a scanning electron microscope.

  The conductive layers 2 and 4 can contain an organic conductor together with conductive fibers. The organic conductor can be used without any particular limitation, but a conductive polymer such as a thiophene derivative or an aniline derivative is preferably used. Specifically, polyethylenedioxythiophene, polyhexylthiophene, polyaniline, or the like can be used. By using an organic conductor, the rate of change in resistance value before and after expansion and contraction can be reduced.

  The thickness of the conductive layers 2 and 4 varies depending on the use of the substrate with the conductive layer to be formed and the required conductivity, but is preferably 1 μm or less, more preferably 1 nm to 0.5 μm. More preferably, it is 5 nm-0.1 micrometer. When the thickness of the conductive layers 2 and 4 is 1 μm or less, the light transmittance in the wavelength region of 450 to 650 nm is high, the pattern forming property is excellent, and particularly suitable for the production of a substrate with a conductive layer. In addition, the thickness of the conductive layers 2 and 4 points out the value measured by a scanning electron micrograph.

  The resin layer 3 can be comprised with arbitrary resin compositions or its hardened | cured material. Specific examples of the resin composition include a thermosetting resin composition and a photosensitive resin composition. Among these, the photosensitive resin composition is preferable from the viewpoint of excellent productivity of the substrate with a conductive layer. When the resin layer 3 contains a photosensitive resin composition, the resin layer 3 is a photosensitive resin layer.

  The photosensitive resin composition can contain (a) a binder polymer, (b) a polymerizable compound having an ethylenically unsaturated bond, and (c) a photopolymerization initiator. When the photosensitive resin composition contains these components, a pattern can be formed by exposure / development photolithography.

  (A) As a binder polymer, for example, 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 obtained and acid-modified epoxy acrylate resins obtained by reaction of epoxy acrylate resins and acid anhydrides. A binder polymer can be used individually by 1 type or in combination of 2 or more types.

  Among these, it is preferable to use an acrylic resin from the viewpoint of excellent alkali developability and film formability. The “acrylic resin” means a polymer mainly having a structural unit derived from a polymerizable monomer having a (meth) acryloyl group. The acrylic resin can be produced, for example, by radical polymerization of a polymerizable monomer having a (meth) acryloyl group. An acrylic resin can be used individually by 1 type or in combination of 2 or more types.

  Examples of the polymerizable monomer having a (meth) acryloyl group include acrylamide (such as diacetone acrylamide), (meth) acrylic acid alkyl ester, (meth) acrylic acid tetrahydrofurfuryl ester, and (meth) acrylic acid dimethylamino. Ethyl ester, (meth) acrylic acid diethylaminoethyl ester, (meth) acrylic acid glycidyl ester, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, (Meth) acrylic acid, α-bromo (meth) acrylic acid, α-chloro (meth) acrylic acid, β-furyl (meth) acrylic acid, and β-styryl (meth) acrylic acid.

  Examples of (meth) acrylic acid alkyl esters include (meth) acrylic acid methyl ester, (meth) acrylic acid ethyl ester, (meth) acrylic acid propyl ester, (meth) acrylic acid butyl ester, (meth) acrylic acid pentyl ester. Ester, (meth) acrylic acid hexyl ester, (meth) acrylic acid heptyl ester, (meth) acrylic acid octyl ester, (meth) acrylic acid 2-ethylhexyl ester, (meth) acrylic acid nonyl ester, (meth) acrylic acid decyl ester Examples include esters, (meth) acrylic acid undecyl esters, and (meth) acrylic acid dodecyl esters. The (meth) acrylic acid alkyl ester can be used alone or in combination of two or more.

  The acrylic resin preferably has a structural unit derived from (meth) acrylic acid and a structural unit derived from (meth) acrylic acid alkyl ester. The acrylic resin may be a copolymer of a polymerizable monomer having a (meth) acryloyl group and another polymerizable monomer. Examples of the other polymerizable monomer include styrene, Polymerizable styrene derivatives substituted in the α-position or aromatic ring, such as vinyltoluene, α-methylstyrene; acrylonitrile; esters of vinyl alcohol such as vinyl-n-butyl ether; maleic acid; maleic anhydride Maleic acid monoesters such as monomethyl maleate, monoethyl maleate and monoisopropyl maleate; fumaric acid; cinnamic acid; α-cyanocinnamic acid; itaconic acid; crotonic acid and the like. Other polymerizable monomers can be used singly or in combination of two or more.

  (A) The binder polymer preferably has a carboxyl group from the viewpoint of further improving alkali developability. Examples of the polymerizable monomer having a carboxyl group for obtaining such a binder polymer include (meth) acrylic acid as described above.

  (A) The ratio of the carboxyl group which a binder polymer has is 10-50 mass% as a ratio of the polymerizable monomer which has a carboxyl group with respect to the whole quantity of the polymerizable monomer used in order to obtain a binder polymer. It is preferably 12 to 40% by mass, more preferably 15 to 30% by mass, and particularly preferably 15 to 25% by mass. The ratio is preferably 10% by mass or more from the viewpoint of excellent alkali developability, and is preferably 50% by mass or less from the viewpoint of excellent alkali resistance of the non-developed portion.

  (A) It is preferable that the acid value of a binder polymer is 50-150 mgKOH / g from a viewpoint of improving the developability with respect to various well-known developing solutions in a image development process.

(A) The acid value of the binder polymer can be measured as follows. First, 1 g of binder polymer whose acid value is to be measured is precisely weighed. Subsequently, 30 g of acetone is added to the binder polymer, and this is uniformly dissolved to obtain a resin solution. Next, an acid value can be measured by adding an appropriate amount of an indicator, phenolphthalein, to the above solution and titrating a 0.1N KOH aqueous solution. The acid value can be calculated by the following formula.
Acid value = 10 × Vf × 56.1 / (Wp × I)
[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 ratio (mass%) of the non-volatile content in the measured resin solution. Indicates. ]

  When the binder polymer contains a synthetic solvent or a diluting solvent, the volatile matter may be removed in advance by heating at a temperature about 10 ° C. higher than the boiling point of the solvent for 1 to 4 hours before precise weighing. it can. At this time, volatile components such as a low molecular weight polymerizable compound may be removed.

  (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 more preferably 30,000 to 100,000 from the viewpoint of balancing the mechanical strength and alkali developability. Further preferred. The weight average molecular weight is preferably 5000 or more from the viewpoint of excellent developer resistance of the non-developed portion. The weight average molecular weight is preferably 300000 or less from the viewpoint of shortening the development time. In addition, the measurement conditions same as the conditions as described in an Example can be used for the measurement conditions of a weight average molecular weight.

  (A) A binder polymer can use the resin mentioned above individually by 1 type or in combination of 2 or more types. When two or more kinds of resins are used in combination, for example, a binder polymer made of a mixture containing two or more kinds of resins composed of different copolymerization components, or a mixture containing two or more kinds of resins having different weight average molecular weights. Examples thereof include a binder polymer and a binder polymer composed of a mixture containing two or more kinds of resins having different degrees of dispersion.

  (B) A known compound can be used as the polymerizable compound having an ethylenically unsaturated bond. For example, a compound obtained by reacting a polyhydric alcohol with an α, β-unsaturated carboxylic acid; a compound obtained by reacting a glycidyl group-containing compound with an α, β-unsaturated carboxylic acid; having a urethane bond (meth) Urethane monomers such as acrylate compounds; γ-chloro-β-hydroxypropyl-β ′-(meth) acryloyloxyethyl-o-phthalate, β-hydroxyethyl-β ′-(meth) acryloyloxyethyl-o-phthalate, β -Phthalic acid compounds such as hydroxypropyl-β '-(meth) acryloyloxyethyl-o-phthalate; (meth) acrylic acid alkyl esters. (B) The polymeric compound which has an ethylenically unsaturated bond can be used individually by 1 type or in combination of 2 or more types.

  As the compound obtained by reacting the polyhydric alcohol with an α, β-unsaturated carboxylic acid, a known compound can be used, and a bisphenol A-based (meth) acrylate compound (2,2-bis (4 -((Meth) acryloxypolyethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxypolypropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxypoly) Ethoxypolypropoxy) phenyl) propane), polyethylene glycol di (meth) acrylate having 2 to 14 ethylene groups, polypropylene glycol di (meth) acrylate having 2 to 14 propylene groups, number of ethylene groups Is 2 to 14 and the number of propylene groups is 2 to 14 in polyethylene polypropylene glycol di (medium T) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, trimethylolpropane ethoxytri (meth) acrylate, trimethylolpropane diethoxytri (meth) Acrylate, trimethylolpropane triethoxytri (meth) acrylate, trimethylolpropanetetraethoxytri (meth) acrylate, trimethylolpropane pentaethoxytri (meth) acrylate, tetramethylolmethanetri (meth) acrylate, tetramethylolmethanetetra (meth) ) Acrylate, polypropylene glycol di (meth) acrylate having 2 to 14 propylene groups, dipentaerythritol pen (Meth) acrylate, dipentaerythritol hexa (meth) acrylate.

  Examples of the urethane monomer include a (meth) acrylic monomer having a hydroxyl group at the β-position and a diisocyanate compound such as isophorone diisocyanate, 2,6-toluene diisocyanate, 2,4-toluene diisocyanate, and 1,6-hexamethylene diisocyanate. Addition reaction product; tris [(meth) acryloxytetraethylene glycol isocyanate] hexamethylene isocyanurate; EO-modified urethane di (meth) acrylate; EO / PO-modified urethane di (meth) acrylate.

  Examples of the EO-modified urethane di (meth) acrylate include “UA-11” (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name). Examples of the EO / PO-modified urethane di (meth) acrylate include “UA-13” (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd.).

  (B) The content ratio of the polymerizable compound having an ethylenically unsaturated bond is 30 to 80 masses per 100 parts by mass of the total amount of the polymerizable compound having (a) the binder polymer and (b) ethylenically unsaturated bonds. Part, preferably 35 to 70 parts by mass. The content ratio is preferably 30 parts by mass or more from the viewpoint of excellent photocurability and coatability on the formed conductive layer, and is excellent in storage stability when wound as a film. Therefore, the amount is preferably 80 parts by mass or less.

  (C) As a photoinitiator, if a photosensitive resin composition can be hardened by irradiation of actinic light, it will not restrict | limit in particular. (C) As the photopolymerization initiator, a radical polymerization initiator is preferably used from the viewpoint of excellent photocurability. (C) As a photopolymerization initiator, benzophenone, N, N, N ′, N′-tetramethyl-4,4′-diaminobenzophenone (also known as Michler ketone), N, N, N ′, N′-tetraethyl- 4,4′-diaminobenzophenone, 4-methoxy-4′-dimethylaminobenzophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone, 2-methyl-1- [4- Aromatic ketones such as (methylthio) phenyl] -2-morpholino-1-propanone; 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; 2-Octanedione-1- [4- (phenylthio) phenyl Oxime ester compounds such as 2- (O-benzoyloxime), 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone 1- (O-acetyloxime); 2 Phosphine compounds such as 1,4,6-trimethylbenzoyl-diphenyl-phosphine oxide; 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 2,4 such as 2-mer, 2- (p-methoxyphenyl) -4,5-diphenylimidazole dimer 5-triarylimidazole dimers; acridine derivatives such as 9-phenylacridine, 1,7-bis (9,9′-acridinyl) heptane; N-phenylglycine, N-phenylglycine derivatives, coumarin compounds, oxazole compounds Compound etc. are mentioned. (C) A photoinitiator can be used individually by 1 type or in combination of 2 or more types. Further, the substituents of the aryl groups of two 2,4,5-triarylimidazoles may give the same target compound or differently give asymmetric compounds. Moreover, you may combine a thioxanthone type compound and a tertiary amine compound like the combination of diethyl thioxanthone and dimethylaminobenzoic acid.

  Among these, at least one selected from the group consisting of an aromatic ketone, an oxime ester compound and a phosphine compound is preferable from the viewpoint of transparency and excellent pattern forming ability when the thickness of the photosensitive resin layer is 10 μm or less. -Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone, 1,2-octanedione-1- [4- (phenylthio) phenyl] -2- (O-benzoyloxime), and At least one selected from the group consisting of 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide is preferable. These can be used individually by 1 type or in combination of 2 or more types.

  (C) The content rate of a photoinitiator is 0.1-20 mass parts with respect to 100 mass parts of total amounts of the polymerizable compound which has (a) binder polymer and (b) ethylenically unsaturated bond. Is more preferable, 1 to 15 parts by mass is more preferable, and 1 to 10 parts by mass is particularly preferable. The content is preferably 0.1 parts by mass or more from the viewpoint of excellent photosensitivity, and is preferably 20 parts by mass or less from the viewpoint of excellent photocurability inside the photosensitive resin layer.

  The photosensitive resin composition can contain various additives as needed. Additives include plasticizers such as p-toluenesulfonamide, fillers, antifoaming agents, flame retardants, stabilizers, adhesion promoters, leveling agents, peeling accelerators, antioxidants, fragrances, imaging agents, heat A crosslinking agent, an antirust agent, etc. can be used individually by 1 type or in combination of 2 or more types. The content of these additives is preferably 0.01 to 20 parts by mass with respect to 100 parts by mass of the total amount of (a) the binder polymer and (b) the polymerizable compound having an ethylenically unsaturated bond.

  The photosensitive resin layer can be formed, for example, by applying a solution of the photosensitive resin composition on a conductive layer formed on a support film and then drying. The solution of the photosensitive resin composition may be added to 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 as necessary. It can be obtained by dissolving the photosensitive resin composition. The solid content of the solution of the photosensitive resin composition is, for example, about 10 to 60% by mass. The amount of the remaining organic solvent in the photosensitive resin layer after drying is preferably 2% by mass or less in order to prevent diffusion of the organic solvent in the subsequent step.

  The coating for obtaining the photosensitive resin layer can be performed by a known method. Examples of the coating method include 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, and 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.

  Although the thickness (thickness after drying) of the resin layer 3a (photosensitive resin layer or the like) varies depending on the application, it is preferably 1 to 200 μm, more preferably 1 to 50 μm, and more preferably 1 to 30 μm. More preferably, it is 1 to 10 μm. If this thickness is 1 μm or more, layer formation by coating tends to be easy, and if it is 200 μm or less, light transmittance is good and sufficient sensitivity can be obtained. Excellent curability. The thickness of the resin layer can be measured with a scanning electron microscope.

  The base material with a conductive layer according to this embodiment can be obtained using a conductive film. FIG. 3 is a diagram illustrating an embodiment of a conductive film. Fig.3 (a) is a schematic cross section which shows one Embodiment of a conductive film, FIG.3 (b) is a partially notched perspective view which shows one Embodiment of a conductive film. A conductive film 30 shown in FIG. 3 includes a support film 5, a conductive layer 4 provided on the support film 5, and a resin layer 3 a provided on the conductive layer 4. The resin layer 3 in FIG. 2 can be obtained by curing the resin layer 3a.

  As the support film 5, a polymer film having heat resistance and solvent resistance can be used. Examples of the support film 5 include a polyethylene terephthalate film, a polypropylene film, and a polyethylene film.

  From the viewpoint of excellent mechanical strength, the thickness of the support film 5 is preferably 5 μm or more, more preferably 10 μm or more, and further preferably 15 μm or more. By setting the thickness of the support film 5 to the above numerical value or more, for example, a step of applying a conductor dispersion liquid or a conductor solution to form the conductive layer 4 or a resin composition to form a resin layer It is possible to prevent the support film 5 from being broken in the process of coating. The same effect can be expected in the step of peeling the support film 5.

  As shown in FIG. 3B, the conductive layer 4 preferably has a network structure in which conductive fibers are in contact with each other. The conductive layer 4 having such a network structure may be formed on the surface of the resin layer 3a on the support film 5 side, but in the surface direction of the surface of the resin layer 3a exposed when the support film 5 is peeled off. If the conductivity is obtained, the conductive layer 4 may be formed so that part of the resin layer 3a enters, and the conductive layer 4 is included in the surface layer of the resin layer 3a on the support film 5 side. It may be formed.

  For example, the conductive layer 4 is made of a conductive dispersion liquid containing the above-described conductive fibers or organic conductors, water or an organic solvent, a surfactant or a dispersion stabilizer (such as dodecyl-pentaethylene glycol), and the support film 5. It can form by drying after coating on top. After drying, the conductive layer 4 formed on the support film 5 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. Moreover, drying (drying etc. for removing an organic solvent etc.) can be performed with a hot air convection dryer etc. for 30 minutes at 30-150 degreeC, and it is 5-30 at 70-150 degreeC. It can also be performed with a hot air convection dryer for about minutes. In the conductive layer 4, the conductive fiber and the organic conductor may coexist with the surfactant and the dispersion stabilizer.

  In the photosensitive layer of the conductive film 30 (laminated body of the conductive layer 4 and the resin layer 3a), the minimum light transmittance in the wavelength region of 450 to 650 nm is preferably 80% or more, and 85% or more. Is more preferable. When the photosensitive layer satisfies such a condition, it is easy to increase the brightness in a display panel or the like. Further, when the thickness of the photosensitive layer is 1 to 10 μm, the minimum light transmittance in the wavelength region of 450 to 650 nm is preferably 80% or more, and more preferably 85% or more. When the photosensitive layer satisfies such a condition, it is easy to increase the brightness in a display panel or the like.

  The conductive film 30 may further include a protective film so as to be in contact with the surface of the resin layer 3a opposite to the support film 5 side.

  As the protective film, a polymer film having heat resistance and solvent resistance can be used. Examples of the protective film include a polyethylene terephthalate film, a polypropylene film, and a polyethylene film. As the protective film, a polymer film similar to the above support film may be used.

  The thickness of the protective film is preferably 1 to 100 μm, more preferably 5 to 50 μm, still more preferably 5 to 40 μm, and particularly preferably 15 to 30 μm. The thickness of the protective film is preferably 1 μm or more from the viewpoint of excellent mechanical strength, and preferably 100 μm or less from the viewpoint of being relatively inexpensive.

  The adhesive force between the protective film and the resin layer 3a is such that the protective film is easily peeled from the resin layer 3a, and the adhesive force between the support film 5 and the conductive layer 4 and the support film 5 and the resin layer. It is preferable that it is smaller than the adhesive force between 3a.

The number of fish eyes having a diameter of 80 μm or more contained in the protective film is preferably 5 / m ² or less. "Fish eye" means that when a material is melted by heat, kneaded, extruded, biaxially stretched, casting method, etc., foreign materials, undissolved materials, oxidized degradation products, etc. It is taken in.

  The conductive film 30 may further have layers such as an adhesive layer and a gas barrier layer on the protective film.

  The conductive film 30 can be stored, for example, in the form of a flat plate as it is or in the form of a roll wound around a cylindrical core. At this time, it is preferable that the support film 5 is wound up so as to be the outermost side.

  The material of the core is not particularly limited as long as it is conventionally used. For example, polyethylene resin, polypropylene resin, polystyrene resin, polyvinyl chloride resin, ABS resin (acrylonitrile-butadiene-styrene copolymer), etc. Of plastic. Moreover, it is preferable to install an end surface separator on the end surface of the conductive film wound up in a roll shape from the viewpoint of protecting the end surface, and it is preferable to install a moisture-proof end surface separator from the viewpoint of edge fusion resistance. Moreover, when packing an electroconductive film, it is preferable to wrap and package in a black sheet with small moisture permeability.

  When the conductive film 30 does not have a protective film, the conductive film 30 can be stored as it is in the form of a flat plate.

  The manufacturing method of a base material with a conductive layer according to the present embodiment (a method for forming a base material with a conductive layer) includes an arrangement step of arranging a resin layer on the base material and a curing step of curing the resin layer. When the resin layer contains a photosensitive resin composition, in the curing step (exposure step), the resin layer can be cured by irradiating the resin layer with actinic rays. When a film member (such as a support film for a conductive film) is disposed on the resin layer, a peeling step for peeling the film member from the resin layer can be performed either before or after the curing step. The peeling process is performed after the arranging process.

  FIG. 4 is a schematic cross-sectional view for explaining the method for manufacturing the base material with a conductive layer according to the first embodiment. As shown in FIG. 4, the manufacturing method of the base material with a conductive layer according to the first embodiment is a laminating step in which the conductive film 30 is arranged on the base material 1 in such a direction that the resin layer 3a is positioned on the base material 1 side ( 4 (a) and 4 (b)), a peeling step (FIG. 4 (c)) for peeling the support film 5, and a curing step for curing the resin layer 3a.

  FIG. 5 is a schematic cross-sectional view for explaining a method for producing a substrate with a conductive layer according to the second embodiment. When the resin layer 3a contains the photosensitive resin composition, the manufacturing method of the base material with a conductive layer according to the second embodiment is a laminating step in which the conductive film 30 is disposed on the base material 1 as shown in FIG. 5 (a)), a curing step (exposure step, FIG. 5 (b)) for curing the resin layer 3a by irradiating the resin layer 3a with an actinic ray L in a pattern, and peeling for peeling the support film 5 And a developing step (FIG. 5C) for developing the resin layer 3a and removing the unexposed portions of the resin layer 3a to form a conductive pattern. The development process is performed after the peeling process and the curing process (exposure process).

In the laminating step, for example, the resin layer 3a can be disposed so as to contact the substrate 1. In the laminating step, for example, if there is a protective film, the conductive film 30 can be laminated by removing the protective film and then pressing the resin layer 3a side of the conductive film 30 to the substrate 1 while heating. In addition, it is preferable that a lamination process is performed under reduced pressure from a viewpoint which is excellent in adhesiveness and followable | trackability. The conductive film 30 is preferably laminated while heating the substrate 1 and / or the resin layer 3a to 40 to 60 ° C., and the pressure bonding pressure is about 0.1 to 1.0 MPa (about 1 to 10 kgf / cm ² ). However, these conditions are not particularly limited. In addition, if the resin layer 3a is heated to 40 to 60 ° C. as described above, it is not necessary to pre-heat the base material 1 in advance, but the base material 1 is pre-heated in order to further improve the lamination property. You can also.

  The curing process may be an exposure process for curing the photosensitive resin layer by exposure, or may be a heating process for curing the thermosetting resin layer by heating. As an exposure method in the exposure process, there is a method (mask exposure method) in which an actinic ray L is irradiated in an image form through a negative or positive mask pattern 6 called an artwork as shown in FIG. Can be mentioned.

  As a light source of actinic rays in the exposure step, a known light source can be mentioned. For example, a carbon arc lamp, a mercury vapor arc lamp, an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a xenon lamp, or the like that can effectively radiate ultraviolet rays, visible light, or the like can be used. An Ar ion laser, a semiconductor laser, or the like can also be used. Furthermore, a light source that effectively emits visible light, such as a photographic flood bulb or a solar lamp, can also be used. Further, a method of irradiating actinic rays in an image form by a direct drawing method using a laser exposure method or the like may be used.

Exposure dose in the exposure step may vary depending on the composition of the device or a photosensitive resin composition to be used is preferably from 5~1000mJ / cm ^2, more preferably 10~200mJ / cm ^2. The exposure amount is preferably 10 mJ / cm ² or more from the viewpoint of excellent photocurability, and is preferably 200 mJ / cm ² or less from the viewpoint of excellent resolution.

  The exposure process can be performed in air, vacuum, or the like, and the exposure atmosphere is not particularly limited.

  In the development process, the unexposed areas in the exposure process of the photosensitive layer are removed. Specifically, the uncured portion (unexposed portion) in the resin layer 3 is removed together with the conductive layer 4 by wet development. Thereby, the base material with a conductive layer (transparent conductive substrate) which has the conductive pattern which consists of the photosensitive layer (resin layer 3 and conductive layer 4) hardened | cured by the exposure process is obtained (FIG.5 (c)).

  The wet development can be performed by a known method such as spraying, rocking immersion, brushing, scraping, etc., using, for example, an alkaline aqueous solution, an aqueous developer, an organic solvent developer, or the like.

  The developer is preferably an alkaline aqueous solution from the viewpoint of safety and stability and good operability. As alkaline aqueous solution, 0.1-5 mass% sodium carbonate aqueous solution, 0.1-5 mass% potassium carbonate aqueous solution, 0.1-5 mass% sodium hydroxide aqueous solution, 0.1-5 mass% sodium tetraborate An aqueous solution or the like is preferable. Moreover, it is preferable that pH of the alkaline aqueous solution used for image development is 9-11, and the temperature can be adjusted according to the developability of the photosensitive resin layer. The alkaline aqueous solution may contain a surfactant, an antifoaming agent, a small amount of an organic solvent for promoting development, and the like.

  Further, an aqueous developer composed of water or an aqueous alkali solution and one or more organic solvents can be used. Here, as the base contained in the alkaline aqueous solution, in addition to the above-mentioned bases, for example, borax, sodium metasilicate, tetramethylammonium hydroxide, ethanolamine, ethylenediamine, diethylenetriamine, 2-amino-2-hydroxymethyl-1 , 3-propanediol, 1,3-diamino-2-propanol, and morpholine.

  Examples of the organic solvent include methyl ethyl ketone, acetone, ethyl acetate, alkoxyethanol having an alkoxy group having 1 to 4 carbon atoms, ethyl alcohol, isopropyl alcohol, butyl alcohol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and diethylene glycol monobutyl ether. Is mentioned. An organic solvent can be used individually by 1 type or in combination of 2 or more types.

  The content ratio of the organic solvent in the aqueous developer is preferably 2 to 90% by mass, and the temperature can be adjusted according to the developability. Furthermore, the pH of the aqueous developer is preferably as low as possible within a range where the resist can be sufficiently developed, more preferably pH 8 to 12, and still more preferably pH 9 to 10. The aqueous developer can also contain a small amount of a surfactant, an antifoaming agent and the like.

  Examples of constituents of the organic solvent developer include 1,1,1-trichloroethane, N-methylpyrrolidone, N, N-dimethylformamide, cyclohexanone, methyl isobutyl ketone, and γ-butyrolactone. The organic solvent-based developer preferably contains water in the range of 1 to 20% by mass from the viewpoint of preventing ignition.

  Two or more of the above-described developing solutions may be used in combination as necessary.

  Examples of the development method include a dip method, a paddle method, a spray method, brushing, and scraping. Among these, from the viewpoint of improving the resolution, the spray method is preferable, and the high-pressure spray method is more preferable.

In the method for producing a substrate with a conductive layer (a method for producing a conductive pattern) according to this embodiment, after development, heating at about 60 to 250 ° C. or exposure at about 0.2 to 10 J / cm ^{2 as} necessary. The conductive pattern may be further cured by performing.

  As a form other than the above embodiment, the conductive film may be an aspect including a support film and a conductive layer including conductive fibers without including a resin layer including no conductive fibers. The base material with a conductive layer includes a base material, a conductive layer (a layer including conductive fibers) provided on the base material, a resin layer (a layer not including conductive fibers) provided on the conductive layer, It may be a mode provided with. A base material with a conductive layer can also be obtained by applying and drying a liquid containing a constituent material of a conductive layer on a base material without using a conductive film.

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

<Preparation of conductor dispersion>
(Silver fiber dispersion)
[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. with an oil bath while stirring with a magnetic stirrer under a nitrogen atmosphere. A solution prepared by dissolving ₂ mg of PtCl ₂ separately prepared in 50 mL of ethylene glycol was added dropwise thereto. After 4 to 5 minutes, a solution prepared by dissolving 5 g of AgNO _{3 in} 300 mL of ethylene glycol and a solution prepared by dissolving 5 g of polyvinylpyrrolidone (manufactured by Wako Pure Chemical Industries, Ltd.) having a weight average molecular weight of 40,000 in 150 mL of ethylene glycol were used. The reaction solution was prepared by dropping from the dropping funnel over 1 minute. Thereafter, the reaction solution was stirred at 160 ° C. for 60 minutes.

  The reaction solution was allowed to stand at 30 ° C. or lower, diluted 10-fold with acetone, centrifuged at 2000 rpm for 20 minutes with a centrifuge, and the supernatant was decanted. Acetone was added to the precipitate and stirred, followed by centrifugation 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 a scanning electron micrograph, the fiber diameter (diameter) was about 5 nm, and the fiber length was about 5 μm.

[Preparation of silver fiber dispersion]
The silver fiber obtained above was dispersed in pure water at a content of 0.2% by mass and dodecyl-pentaethylene glycol at a content of 0.1% by mass to obtain a silver fiber dispersion.

<Synthesis of binder polymer (Polymer A)>
In a flask equipped with a stirrer, a reflux condenser, a thermometer, a dropping funnel and a nitrogen gas introduction tube, a mixed solution of 1-methoxy-2-propanol and toluene (1-methoxy-2-propanol / toluene = 3/2). 90% (mass ratio), hereinafter referred to as “solution s”. Next, the mixture was stirred while blowing nitrogen gas and heated to 70 ° C. Next, a solution (hereinafter referred to as “solution a”) prepared by mixing 12 g of methacrylic acid, 58 g of methyl methacrylate and 30 g of ethyl acrylate and 0.8 g of azobisisobutyronitrile was prepared as a monomer. Solution a was added dropwise to solution s heated to 70 ° C. over 4 hours. The solution after dropping was kept warm at 70 ° C. for 2 hours. Further, a solution prepared by dissolving 0.1 g of azobisisobutyronitrile in 8 g of solution s was dropped into the flask over 5 minutes. Then, the solution after dropping was kept at 70 ° C. for 2 hours with stirring, and then heated to 90 ° C. over 30 minutes to produce polymer A by polymerization of the monomer. Then, after heat-retaining at 90 degreeC for 1 hour, it cooled and obtained the binder polymer solution. By adding acetone to the binder polymer solution so that the non-volatile component (solid content) was adjusted to 50% by mass, a binder polymer solution containing the polymer A was obtained. The weight average molecular weight (Mw) of the obtained polymer A was 80000, and the acid value was 78 mgKOH / g.

  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.

[GPC conditions]
Pump: Hitachi L-6000 type (manufactured by Hitachi, Ltd., trade name)
Column: Gelpack GL-R420, Gelpack GL-R430, Gelpack GL-R440 (above, Hitachi Chemical Co., Ltd., trade name)
Eluent: Tetrahydrofuran Measurement temperature: 40 ° C
Flow rate: 2.05 mL / min Detector: Hitachi L-3300 type RI (manufactured by Hitachi, Ltd., trade name)

<Measurement of elongation at break of substrate>
The elongation at break of the base material used for the production of the conductive substrate was measured. Specifically, it can be measured in the tensile mode of a precision universal testing machine under the conditions of a width of 15 mm for each film, a gap between chucks of 40 mm, and a tensile speed of 200 mm / min. The measurement results are shown in Table 1.

<Example 1>
(Preparation of photosensitive resin layer solution)
63 parts by mass of polymer A as a binder polymer in terms of solid content, 37 parts by mass of “KAYARAD T-1420 (T)” manufactured by Nippon Kayaku Co., Ltd. as an acrylic monomer, and BASF Japan Ltd. as a photopolymerization initiator 10 parts by mass of “Lucirin TPO” (Lucirin is a registered trademark), 0.07 parts by mass of the product name “DOW CORNING 8032 ADDITIVE” manufactured by Toray Dow Corning Co., Ltd. as a leveling agent, and 30% by mass of the solid content of the solution % And mixed with methyl ethyl ketone to obtain a photosensitive resin layer solution.

(Preparation of conductive film)
The silver fiber dispersion obtained above was uniformly applied in an amount of 25 g / m ² on a 50 μm-thick polyethylene terephthalate film (PET film, support film, manufactured by Teijin Ltd., trade name “G2-50”). Then, it dried for 3 minutes with a 100 degreeC hot-air convection dryer, and obtained the electrically conductive layer containing silver fiber. The thickness of the conductive layer after drying was about 0.1 μm.

  Next, after apply | coating the solution for photosensitive resin layers obtained above uniformly on a conductive layer, it dried for 10 minutes with a 100 degreeC hot-air convection dryer, and formed the photosensitive resin layer. The photosensitive resin layer was covered with a polyethylene film (trade name “NF-13” manufactured by Tamapoly Co., Ltd.) to obtain a conductive film (photosensitive conductive film). The thickness of the photosensitive resin layer after drying was about 5 μm.

(Extraction / contraction test of conductive substrate)
Laminator (manufactured by Hitachi Chemical Co., Ltd.) so that the photosensitive resin layer is in contact with the polyurethane film (manufactured by Takeda Sangyo Co., Ltd., trade name “Tough Grace”, thickness: 100 μm) while peeling off the polyethylene film of the obtained conductive film. , Product name “HLM-3000 type”), a conductive film is laminated under the conditions of a roll temperature of 60 ° C., a substrate feed rate of 0.6 m / min, and a pressure of pressure (cylinder pressure) of 0.4 MPa. A substrate in which a laminate of layer / conductive layer / support film (PET film) was laminated on a polyurethane film was produced.

Next, using a parallel light exposure machine (EXM1201 manufactured by Oak Seisakusho Co., Ltd.), ultraviolet rays are irradiated on the substrate with an exposure amount of 5 × 10 ² J / m ² (measured value in i-line) from above the support film side. The laminate was irradiated. Then, after removing a support body film, the ultraviolet-ray was irradiated with the exposure amount 1 * 10 < ⁴ > J / m < ² > (measured value in i line | wire) from the upper direction of a conductive layer. After the ultraviolet irradiation, development was performed using a 1% by mass aqueous sodium carbonate solution at 30 ° C. for 40 seconds to obtain a conductive substrate.

  Next, the obtained conductive substrate was cut out into 20 mm × 50 mm, and the sheet resistance value (R0) of the cut out conductive substrate was measured.

  The cut conductive substrate (polyurethane film / photosensitive resin layer / conductive layer laminate) is fixed to a chuck having a chuck distance of 40 mm, stretched to an elongation of 200% under the condition of a pulling speed of 200 mm / min, and then a compression speed of 200 mm. Compressed to 0% elongation under the conditions of / min.

The sheet resistance value (R1) of the conductive substrate after expansion and contraction was measured. Based on the sheet resistance values R0 and R1 before and after the test, the stretchability of the conductive substrate was evaluated according to the following ratings. Here, the ratio of R1 to R0 (R1 / R0) was Rr. As described below, the evaluation result when the resistance increase rate was 20% or less “(R1−R0) /R0≦0.2, that is, Rr ≦ 1.2” was evaluated as “◯”. The evaluation result of the stretchability of Example 1 was “◯”.
○: Rr ≦ 1.2
Δ: 1.2 <Rr ≦ 1.5
X: 1.5 <Rr
XX: Base material breaks

<Example 2>
A conductive substrate was produced in the same manner as in Example 1 except that a silicone rubber sheet (manufactured by Shin-Etsu Polymer Co., Ltd., trade name “silicone rubber sheet BA grade”, thickness: 300 μm) was used as the substrate. When the stretchability was evaluated in the same manner as in Example 1, the evaluation result was “◯”.

<Comparative Example 1>
A conductive substrate was produced in the same manner as in Example 1 except that a PET film (trade name “A4300”, manufactured by Toyobo Co., Ltd., thickness: 125 μm) was used as the substrate. Then, when the stretchability was evaluated in the same manner as in Example 1, the evaluation result was “XX” because the base material broke during elongation.

  Good stretchability was obtained by using a base material having a breaking elongation of 200% or more (Examples 1 and 2). On the other hand, when a base material with low elasticity was used, the base material was broken at the time of extension, and a conductive substrate with elasticity could not be obtained (Comparative Example 1).

  DESCRIPTION OF SYMBOLS 1 ... Base material, 2, 4 ... Conductive layer, 3, 3a ... Resin layer, 5 ... Support film, 6 ... Mask pattern, 10, 20 ... Base material with a conductive layer, 30 ... Conductive film, L ... Actinic ray.

Claims (10)

A base material having a breaking elongation of 200% or more, and a conductive layer provided on the base material,
The base material with a conductive layer in which the said conductive layer contains a conductive fiber.   The base material with a conductive layer according to claim 1, wherein the base material includes polyurethane or silicone rubber.   The base material with a conductive layer according to claim 1, further comprising a resin layer provided between the base material and the conductive layer.   The base material with a conductive layer according to claim 3, wherein the resin layer contains a photosensitive resin composition or a cured product thereof.   The base material with a conductive layer according to any one of claims 1 to 4, wherein the conductive fibers include silver fibers.   The base material with a conductive layer according to any one of claims 1 to 5, wherein the conductive layer is a conductive pattern. It is a manufacturing method of the base material with a conductive layer as described in any one of Claims 1-6,
A support film, a conductive layer provided on the support film, and a conductive film having a resin layer provided on the conductive layer are placed on the base material in a direction in which the resin layer is positioned on the base material side. Arranging, and
A peeling step of peeling the support film,
The manufacturing method of the base material with a conductive layer in which the said conductive layer contains a conductive fiber. Further comprising an exposure step of irradiating the resin layer with actinic rays,
The manufacturing method of the base material with a conductive layer of Claim 7 in which the said resin layer contains the photosensitive resin composition. A step of forming a conductive pattern by removing an unexposed portion of the resin layer after the peeling step and the exposing step;
The manufacturing method of the base material with a conductive layer of Claim 8 which irradiates actinic light to the said resin layer in the pattern form in the said exposure process.   A sensor provided with the base material with a conductive layer as described in any one of Claims 1-6.

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