WO2020137144A1 - Matériau de transfert photosensible, stratifié, panneau tactile, procédé de production de substrat à motifs, procédé de production de carte de circuit imprimé et procédé de production de panneau tactile - Google Patents

Matériau de transfert photosensible, stratifié, panneau tactile, procédé de production de substrat à motifs, procédé de production de carte de circuit imprimé et procédé de production de panneau tactile Download PDF

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Publication number
WO2020137144A1
WO2020137144A1 PCT/JP2019/042577 JP2019042577W WO2020137144A1 WO 2020137144 A1 WO2020137144 A1 WO 2020137144A1 JP 2019042577 W JP2019042577 W JP 2019042577W WO 2020137144 A1 WO2020137144 A1 WO 2020137144A1
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resin layer
group
thermosetting resin
layer
compound
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PCT/JP2019/042577
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English (en)
Japanese (ja)
Inventor
児玉　邦彦
山田　悟
知樹 松田
正弥 鈴木
豊岡　健太郎
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富士フイルム株式会社
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Priority to CN201980083606.7A priority Critical patent/CN113196891A/zh
Priority to JP2020562868A priority patent/JPWO2020137144A1/ja
Publication of WO2020137144A1 publication Critical patent/WO2020137144A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/11—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having cover layers or intermediate layers, e.g. subbing layers
    • G—PHYSICS
    • G06—COMPUTING; CALCULATING OR COUNTING
    • G06F—ELECTRIC DIGITAL DATA PROCESSING
    • G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
    • G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
    • G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
    • G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
    • G—PHYSICS
    • G06—COMPUTING; CALCULATING OR COUNTING
    • G06F—ELECTRIC DIGITAL DATA PROCESSING
    • G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
    • G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
    • G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
    • G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
    • G06F3/044—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means by capacitive means
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/09—Use of materials for the conductive, e.g. metallic pattern
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern

Definitions

  • the present disclosure relates to a photosensitive transfer material, a laminate, a touch panel, a patterned substrate manufacturing method, a circuit board manufacturing method, and a touch panel manufacturing method.
  • a device capable of inputting information corresponding to an instruction image by touching the instruction image displayed in the image display area of a liquid crystal device with a finger or a touch pen has been widely used.
  • a conductive film made of a material such as ITO (Indium Tin Oxide) is usually used.
  • various techniques using a conductive film containing conductive fibers such as silver fibers have been studied as a conductive film replacing the ITO film.
  • a photosensitive film including a support film, a conductive layer provided on the support film and containing conductive fibers, and a photosensitive resin layer provided on the conductive layer are provided.
  • Conductive conductive films are disclosed.
  • a conductive layer containing a conductive fiber tends to have low adhesiveness to a substrate (for example, a copper substrate). Therefore, a photosensitive transfer material having a conductive layer containing conductive fibers has a problem that it is difficult to bond it to a substrate.
  • a photosensitive transfer material having a conductive layer containing conductive fibers has a problem that it is difficult to bond it to a substrate.
  • the problem of adhesion to the substrate can be solved by having a configuration in which the photosensitive resin layer is provided on the conductive layer.
  • a second photosensitive resin layer is provided on the surface opposite to the surface of the conductive layer containing the conductive fibers on the side of the photosensitive resin layer.
  • the problem of adhesion to the substrate can be solved by providing the first substrate, the first photosensitive resin layer or the first photosensitive resin layer or the first photosensitive resin layer formed on the surface of the conductive layer containing the conductive fiber is formed in the formation of the conductive pattern after bonding.
  • Means for solving the above problems include the following aspects. ⁇ 1> A temporary support, A photosensitive resin layer, A layer containing silver nanowires, A thermosetting resin layer, A photosensitive transfer material having in this order. ⁇ 2> The photosensitive transfer material according to ⁇ 1>, wherein the thermosetting resin layer contains a blocked isocyanate compound. ⁇ 3> The photosensitive transfer material according to ⁇ 2>, wherein the blocked isocyanate compound has at least one of a hydroxyl group and an acid group. ⁇ 4> The photosensitive transfer material according to ⁇ 2> or ⁇ 3>, wherein the thermosetting resin layer further contains a compound having at least one of a hydroxyl group and an acid group.
  • thermosetting resin layer has a thickness of 1 nm to 300 nm.
  • contact resistance of the thermosetting resin layer is 200 ⁇ or less.
  • the layer containing the thermosetting resin is a layer formed by curing the thermosetting resin layer that is the transfer layer, and the layer containing the silver nanowires is the transfer layer ⁇ 7 The laminated body as described in >.
  • thermosetting resin is a crosslinked resin having a urethane bond.
  • a photosensitive transfer material capable of forming a conductive pattern that is difficult to peel from a substrate. Further, according to another embodiment of the present invention, there are provided a laminate, a touch panel, a patterned substrate manufacturing method, a circuit board manufacturing method, and a touch panel manufacturing method using the above-mentioned photosensitive transfer material.
  • the numerical range indicated by using “to” means a range including the numerical values before and after “to” as the minimum value and the maximum value, respectively.
  • the upper limit value or the lower limit value described in a certain numerical range may be replaced with the upper limit value or the lower limit value of another stepwise described numerical range.
  • the upper limit value or the lower limit value described in a certain numerical range may be replaced with the values shown in the examples.
  • a combination of two or more preferable aspects is a more preferable aspect.
  • an “alkyl group” includes not only an alkyl group having no substituent (so-called unsubstituted alkyl group) but also an alkyl group having a substituent (so-called substituted alkyl group).
  • the chemical structural formula may be described as a simplified structural formula in which a hydrogen atom is omitted.
  • (meth)acrylic acid is a term used in a concept including both acrylic acid and methacrylic acid
  • (meth)acrylate is used in a concept including both acrylate and methacrylate.
  • the term "(meth)acryloyl” is used in a concept that includes both acryloyl and methacryloyl
  • (meth)acryloxy” is a word that is used in a concept that includes both acryloxy and methacryloxy. is there.
  • the amount of each component in the composition is the total amount of the plurality of substances present in the composition, unless there is a plurality of substances corresponding to each component in the composition, unless otherwise specified.
  • process is included in this term as long as the intended purpose of the process is achieved, not only when it is an independent process but also when it cannot be clearly distinguished from other processes.
  • the molecular weight in the case where there is a molecular weight distribution represents the weight average molecular weight (Mw; hereinafter the same) unless otherwise specified.
  • the ratio of the structural unit in the resin represents a molar ratio unless otherwise specified.
  • “transparent” means that the total light transmittance at a wavelength of 380 nm to 780 nm is 85% or more (preferably 90% or more, more preferably 95% or more).
  • the total light transmittance is measured at a temperature of 23° C. using a spectrophotometer [for example, a spectrophotometer “U-3310 (trade name)” manufactured by Hitachi, Ltd.].
  • “refractive index” refers to a refractive index at a wavelength of 550 nm, unless otherwise specified. Further, the “refractive index” in the present disclosure means a value measured by an ellipsometry method with visible light having a wavelength of 550 nm at a temperature of 23° C., unless otherwise specified.
  • constituent elements indicated by the same reference numeral in each drawing mean the same constituent elements.
  • the photosensitive transfer material of the present disclosure includes a temporary support, a photosensitive resin layer, a layer containing silver nanowires (hereinafter, also referred to as “silver nanowire layer”), and a thermosetting resin layer. Have in order.
  • the photosensitive transfer material of the present disclosure having the above-described configuration can form a conductive pattern that is difficult to peel from the substrate.
  • the photosensitive transfer material of the present disclosure can form a circuit board having excellent durability, in which the sheet resistance value does not easily increase even when exposed to a humid heat environment.
  • FIG. 1 is a schematic cross-sectional view showing an example of the layer structure of the photosensitive transfer material of the present disclosure.
  • the photosensitive transfer material 100 shown in FIG. 1 has a temporary support 10, a photosensitive resin layer 20, a silver nanowire layer 30, and a thermosetting resin layer 40A in this order. It should be noted that the scale of each element shown in the drawings of the present disclosure is not necessarily accurate. Hereinafter, each component of the photosensitive transfer material of the present disclosure will be described.
  • the photosensitive transfer material of the present disclosure has a temporary support.
  • the temporary support is a support that supports at least the photosensitive resin layer, the silver nanowire layer, and the thermosetting resin layer, and that is removable from the adherend.
  • the temporary support preferably has optical transparency from the viewpoint that pattern exposure can be performed via the temporary support.
  • “having optical transparency” means that the transmittance of the dominant wavelength of light used for pattern exposure is 50% or more.
  • the transmittance of the dominant wavelength of light used for pattern exposure is preferably 60% or more, and more preferably 70% or more, from the viewpoint of improving the exposure sensitivity.
  • Examples of the method of measuring the transmittance include a method of using a spectrophotometer [eg, MCPD-6800 manufactured by Otsuka Electronics Co., Ltd.].
  • the temporary support examples include a glass substrate, a resin film, paper and the like.
  • the temporary support is preferably a resin film from the viewpoint of strength and flexibility.
  • the resin film examples include polyethylene terephthalate film, cycloolefin polymer film, cellulose triacetate film, polystyrene film and polycarbonate film. Among these, the polyethylene terephthalate film is preferable as the temporary support from the viewpoint of optical characteristics.
  • the thickness of the temporary support is not particularly limited and can be appropriately selected depending on the material.
  • the thickness of the temporary support is preferably 5 ⁇ m to 200 ⁇ m, and more preferably 10 ⁇ m to 150 ⁇ m, from the viewpoint of easy handling, versatility and the like.
  • the photosensitive transfer material of the present disclosure has a photosensitive resin layer.
  • the photosensitive resin layer is classified into a negative type in which a portion irradiated with an actinic ray remains as an image and a positive type in which a portion not irradiated with an actinic ray remains as an image, depending on the difference in the photosensitive system.
  • the photosensitive resin layer in the photosensitive transfer material of the present disclosure may be a positive type photosensitive resin layer or a negative type photosensitive resin layer.
  • the positive type photosensitive resin layer is not particularly limited, and a known positive type photosensitive resin layer can be applied. From the viewpoint of sensitivity, resolution, and removability, the positive photosensitive resin layer may include a polymer containing a structural unit having an acid group protected by an acid-decomposable group, and a photoacid generator. preferable.
  • the positive type photosensitive resin layer is described in paragraphs [0033] to [0130] of International Publication No. 2018/179640. These descriptions are incorporated herein by reference.
  • the positive photosensitive resin layer is a polymer containing a structural unit having an acid group protected by an acid-decomposable group (hereinafter, also referred to as “structural unit A”) (hereinafter, also referred to as “polymer A”). ) Is preferably included.
  • the acid group protected by the acid-decomposable group in the polymer A becomes an acid group by the action of a catalytic amount of acid generated by exposure (that is, deprotection reaction).
  • the acid group generated by the deprotection reaction enables the positive photosensitive resin layer to be dissolved in the developing solution.
  • the polymer A is preferably an addition polymerization type polymer, and more preferably a polymer containing a structural unit derived from (meth)acrylic acid or its ester.
  • the acid group in the structural unit A is not particularly limited, and a known acid group can be applied.
  • the acid group in the structural unit A is preferably a carboxy group or a phenolic hydroxyl group.
  • the acid-decomposable group in the structural unit A is not particularly limited, and a known acid-decomposable group can be applied.
  • the acid-decomposable group in the structural unit A include a group that is relatively easily decomposed by an acid (for example, an acetal-type functional group such as a 1-alkoxyalkyl group, a tetrahydropyranyl group, and a tetrahydrofuranyl group), and an acid-releasable group.
  • an acid-releasable group for example, an acetal-type functional group such as a 1-alkoxyalkyl group, a tetrahydropyranyl group, and a tetrahydrofuranyl group
  • groups that are difficult to decompose for example, tertiary alkyl groups such as tert-butyl group.
  • the acid-decomposable group in the structural unit A is preferably a group having a structure that protects the acid group in the form of acetal. Further, the acid-decomposable group is preferably an acid-decomposable group having a molecular weight of 300 or less from the viewpoint of suppressing variation in the line width of the conductive wiring when applied to the formation of a conductive pattern.
  • the structural unit A is a structural unit represented by the following formula A1, a structural unit represented by the following formula A2, and a following formula A3 from the viewpoint of suppressing the deformation of the pattern shape, solubility in a developing solution, and transferability. It is preferably at least one type of structural unit selected from the group consisting of structural units represented, more preferably a structural unit represented by the following formula A3, and a structure represented by the following formula A3-3. More preferably, it is a unit.
  • the structural unit represented by the following formula A1 and the structural unit represented by the following formula A2 are structural units having a phenolic hydroxyl group protected by an acid-decomposable group.
  • the structural unit represented by the following formula A3 is a structural unit having a carboxy group protected by an acid-decomposable group.
  • R 11 and R 12 each independently represent a hydrogen atom, an alkyl group, or an aryl group, at least one of R 11 and R 12 is an alkyl group or an aryl group, and R 13 is an alkyl group.
  • R 11 or R 12 and R 13 may be linked to each other to form a cyclic ether
  • R 14 represents a hydrogen atom or a methyl group
  • X 1 represents a single bond or a divalent group.
  • R 15 represents a substituent
  • n represents an integer of 0 to 4.
  • R 21 and R 22 each independently represent a hydrogen atom, an alkyl group, or an aryl group, at least one of R 21 and R 22 is an alkyl group or an aryl group, and R 23 is an alkyl group.
  • R 21 or R 22 and R 23 may be linked to each other to form a cyclic ether
  • R 24 is independently a hydroxy group, a halogen atom, an alkyl group, an alkoxy group, It represents an alkenyl group, an aryl group, an aralkyl group, an alkoxycarbonyl group, a hydroxyalkyl group, an arylcarbonyl group, an aryloxycarbonyl group, or a cycloalkyl group
  • m represents an integer of 0 to 3.
  • R 31 and R 32 each independently represent a hydrogen atom, an alkyl group, or an aryl group, at least one of R 31 and R 32 is an alkyl group or an aryl group, and R 33 is an alkyl group.
  • R 31 or R 32 and R 33 may combine to form a cyclic ether
  • R 34 represents a hydrogen atom or a methyl group
  • X 0 represents a single bond or a divalent group.
  • Y represents a sulfur atom or an oxygen atom.
  • R 31 or R 32 when R 31 or R 32 is an alkyl group, the alkyl group is preferably an alkyl group having 1 to 10 carbon atoms.
  • the aryl group is preferably a phenyl group.
  • R 31 and R 32 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and at least one of R 31 and R 32 is preferably an alkyl group having 1 to 4 carbon atoms.
  • R 33 is preferably an alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group having 1 to 6 carbon atoms.
  • the alkyl group and aryl group for R 31 to R 33 may have a substituent.
  • R 31 or R 32 and R 33 are preferably linked to each other to form a cyclic ether.
  • the number of ring members in the cyclic ether is not particularly limited, but is preferably 5 or 6, and more preferably 5.
  • X 0 is preferably a single bond or an arylene group, and more preferably a single bond.
  • the arylene group may have a substituent.
  • Y is preferably an oxygen atom from the viewpoint of exposure sensitivity.
  • R 34 represents a hydrogen atom or a methyl group, and is preferably a hydrogen atom from the viewpoint that the glass transition temperature (Tg) of the polymer A can be further lowered. More specifically, the content of the structural unit in which R 34 in Formula A3 is a hydrogen atom is preferably 20 mol% or more based on all the structural units represented by Formula A3 contained in the polymer A. .. The content (unit: mol%) of the structural unit represented by Formula A3 in which R 34 in Formula A3 is a hydrogen atom is determined by 13 C-nuclear magnetic resonance spectrum (NMR) measurement in a conventional manner. It can be confirmed by the intensity ratio of the peak intensity calculated by.
  • NMR 13 C-nuclear magnetic resonance spectrum
  • constitutional unit represented by the formula A3 is more preferable from the viewpoint of further increasing the sensitivity during pattern formation.
  • R 34 represents a hydrogen atom or a methyl group
  • R 35 to R 41 each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
  • R 34 is preferably a hydrogen atom.
  • R 35 to R 41 are preferably hydrogen atoms.
  • R 34 in the following structural units represents a hydrogen atom or a methyl group.
  • the polymer A may include only one type of structural unit A or may include two or more types.
  • the content of the structural unit A in the polymer A is preferably 15 mol% or more, and is 15 mol% to 90 mol% with respect to all the structural units of the polymer A. More preferably, it is more preferably 20 mol% to 70 mol %.
  • the content of the structural unit A in the polymer A can be confirmed by the intensity ratio of the peak intensities calculated by the usual method from 13 C-NMR measurement.
  • the polymer A preferably contains a structural unit having an acid group (hereinafter, also referred to as “structural unit B”).
  • structural unit B a structural unit having an acid group
  • the acid group in the structural unit B means a proton dissociative group having a pKa of 12 or less.
  • the pKa of the acid group is preferably 10 or less, more preferably 6 or less.
  • the pKa of the acid group is preferably ⁇ 5 or more.
  • Examples of the acid group in the structural unit B include a carboxy group, a sulfonamide group, a phosphonic acid group, a sulfonic acid group, a phenolic hydroxyl group, and a sulfonylimide group.
  • the acid group in the structural unit B is preferably a carboxy group or a phenolic hydroxyl group.
  • the introduction of the structural unit having an acid group into the polymer A can be carried out by copolymerizing a monomer having an acid group.
  • the constituent unit B is more preferably a constituent unit in which a constituent unit derived from a styrene compound or a constituent unit derived from a vinyl compound is substituted with an acid group, or a constituent unit derived from (meth)acrylic acid.
  • the structural unit B is preferably at least one structural unit selected from the group consisting of a structural unit having a carboxy group and a structural unit having a phenolic hydroxyl group, from the viewpoint of better sensitivity in pattern formation. ..
  • the structural unit B may contain only one kind or two or more kinds.
  • the content of the structural unit B in the polymer A is 0.1 mol% to 20 mol% with respect to all the structural units of the polymer A from the viewpoint of pattern formability.
  • the amount is preferably 0.5 mol% to 15 mol%, more preferably 1 mol% to 10 mol%.
  • the content of the structural unit B in the polymer A can be confirmed by the intensity ratio of the peak intensities calculated by a conventional method from 13 C-NMR measurement.
  • the polymer A contains a structural unit other than the structural unit A and the structural unit B described above (hereinafter, also referred to as “structural unit C”) as long as the effects of the photosensitive transfer material of the present disclosure are not impaired. Good.
  • the monomer forming the structural unit C is not particularly limited.
  • a styrene compound (meth)acrylic acid alkyl ester, (meth)acrylic acid cyclic alkyl ester, (meth)acrylic acid aryl ester, unsaturated dicarboxylic acid diester, bicyclo unsaturated compound, maleimide
  • examples thereof include compounds, unsaturated aromatic compounds, conjugated diene compounds, unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, unsaturated dicarboxylic acid anhydrides, compounds having an aliphatic cyclic skeleton, and other unsaturated compounds.
  • structural unit C specifically, styrene, tert-butoxystyrene, methylstyrene, ⁇ -methylstyrene, acetoxystyrene, methoxystyrene, ethoxystyrene, chlorostyrene, methyl vinylbenzoate, ethyl vinylbenzoate, (meta ) Methyl acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, (meth ) Structural units formed by polymerizing benzyl acrylate, isobornyl (meth)acrylate, acrylonitrile, ethylene glycol monoacetoacetate mono(meth)acrylate and the like. Further, examples of the structural unit C include the compounds described in paragraphs [0021] to [00
  • the structural unit C is at least one selected from the group consisting of a structural unit having an aromatic ring and a structural unit having an aliphatic cyclic skeleton, from the viewpoint of improving the electrical characteristics of the resulting photosensitive transfer material. It is preferably a structural unit.
  • Examples of the monomer forming at least one structural unit selected from the group consisting of a structural unit having an aromatic ring and a structural unit having an aliphatic cyclic skeleton include styrene, tert-butoxystyrene, methylstyrene, ⁇ -methyl.
  • cyclohexyl (meth)acrylate is preferable as the monomer forming at least one structural unit selected from the group consisting of a structural unit having an aromatic ring and a structural unit having an aliphatic cyclic skeleton.
  • the monomer forming the structural unit C is preferably a (meth)acrylic acid alkyl ester, and more preferably a (meth)acrylic acid alkyl ester having an alkyl group having 4 to 12 carbon atoms.
  • the alkyl (meth)acrylate include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, and (meth)acrylic acid. 2-ethylhexyl and the like can be mentioned.
  • the structural unit C may include only one type or may include two or more types.
  • the content of the structural unit C in the polymer A is preferably 70 mol% or less, and preferably 60 mol% or less, based on all the structural units of the polymer A. More preferably, it is even more preferably 50 mol% or less.
  • the lower limit of the content of the structural unit C in the polymer A may be 0 mol%, but it is preferably 1 mol% or more, and more preferably 5 mol% or more, based on all the structural units of the polymer A.
  • the weight average molecular weight of the polymer A is preferably 60,000 or less.
  • the weight average molecular weight of the polymer A is 60,000 or less, the melt viscosity of the photosensitive resin layer is suppressed to be low, and at the time of bonding with the substrate, bonding at low temperature (for example, 130° C. or less) is realized. be able to.
  • the weight average molecular weight of the polymer A is more preferably 2,000 to 60,000, further preferably 3,000 to 50,000.
  • the weight average molecular weight of the polymer A is a polystyrene equivalent weight average molecular weight measured by the following method.
  • the weight average molecular weight can be measured by GPC (gel permeation chromatography).
  • GPC gel permeation chromatography
  • Various commercially available devices can be used as the measuring device, and the contents of the device and the measuring technique are known to those skilled in the art.
  • HLC registered trademark
  • GPC gel permeation chromatography
  • TSKgel registered trademark
  • Super HZM-M 4.6 mm ID ⁇ 15 cm, Tosoh Corporation
  • the calibration curve is “standard sample TSK standard, polystyrene” manufactured by Tosoh Corporation: “F-40”, “F-20”, “F-4”, “F-1”, “A-5000”, “A-5000”, It is possible to use those manufactured from 7 samples of "A-2500” and "A-1000".
  • the positive photosensitive resin layer contains the polymer A
  • it may contain only one kind of the polymer A or may contain two or more kinds of the polymer A.
  • the content of the polymer A in the positive-type photosensitive resin layer is such that the positive-type photosensitive resin layer exhibits good adhesion to the substrate.
  • the amount is preferably 50% by mass to 99.9% by mass, more preferably 70% by mass to 99% by mass, and further preferably 80% by mass to 98% by mass with respect to the total mass of the conductive resin layer. More preferable.
  • the method for producing the polymer A (so-called synthesis method) is not particularly limited, and a known method can be applied.
  • a polymerizable monomer for forming the structural unit A, a polymerizable monomer for forming the structural unit B, and a polymerizable monomer for forming the structural unit C are A method of polymerizing using a polymerization initiator in a solvent can be mentioned.
  • the positive photosensitive resin layer preferably contains a photo-acid generator.
  • the photo-acid generator is a compound capable of generating an acid when irradiated with radiation such as ultraviolet rays, far ultraviolet rays, X-rays and charged particle beams.
  • the photoacid generator is preferably a compound which reacts with an actinic ray having a wavelength of 300 nm or more, preferably 300 nm to 450 nm to generate an acid.
  • a photo-acid generator which is not directly sensitive to an actinic ray having a wavelength of 300 nm or more when used in combination with a sensitizer, it is a compound which is sensitive to an actinic ray having a wavelength of 300 nm or more and generates an acid. It can be preferably used in combination.
  • the photoacid generator is preferably a photoacid generator that generates an acid with a pKa of 4 or less, more preferably a photoacid generator that generates an acid with a pKa of 3 or less, and a light that generates an acid with a pKa of 2 or less. Acid generators are more preferred.
  • the lower limit of pKa is not particularly limited, but is preferably -10.0 or more, for example.
  • the photoacid generator examples include an ionic photoacid generator and a nonionic photoacid generator. From the viewpoint of sensitivity and resolution, the photoacid generator preferably contains at least one compound selected from the group consisting of an onium salt compound described later and an oxime sulfonate compound described later, and contains an oxime sulfonate compound. More preferable.
  • the ionic photoacid generator examples include onium salt compounds and quaternary ammonium salt compounds.
  • onium salt compounds include diaryl iodonium salt compounds and triaryl sulfonium salt compounds.
  • the ionic photoacid generator is preferably an onium salt compound, and more preferably at least one selected from the group consisting of a triarylsulfonium salt compound and a diaryliodonium salt compound.
  • the ionic photoacid generators described in paragraphs [0114] to [0133] of JP-A-2014-85643 can also be preferably used.
  • nonionic photoacid generator examples include trichloromethyl-s-triazine compounds, diazomethane compounds, imide sulfonate compounds, oxime sulfonate compounds and the like.
  • the nonionic photoacid generator is preferably an oxime sulfonate compound from the viewpoint of sensitivity, resolution, and adhesiveness.
  • Specific examples of the trichloromethyl-s-triazine compound and the diazomethane compound include the compounds described in paragraphs [0083] to [0088] of JP 2011-221494A.
  • oxime sulfonate compound a compound having an oxime sulfonate structure represented by the following formula (B1) is preferable.
  • R 21 represents an alkyl group or an aryl group
  • * represents a bonding site with another atom or another group.
  • any group may be substituted, and the alkyl group represented by R 21 may be linear and have a branched structure. And may have a ring structure.
  • the permissible substituents are described below.
  • the alkyl group represented by R 21 is preferably a linear or branched alkyl group having 1 to 10 carbon atoms.
  • the alkyl group represented by R 21 may be substituted with an aryl group having 6 to 11 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a cycloalkyl group, or a halogen atom.
  • the aryl group represented by R 21 is preferably an aryl group having 6 to 18 carbon atoms, and more preferably a phenyl group or a naphthyl group.
  • the aryl group represented by R 21 may be substituted with one or more groups selected from the group consisting of an alkyl group having 1 to 4 carbon atoms, an alkoxy group, and a halogen atom.
  • the positive photosensitive resin layer contains a photo-acid generator, it may contain only one photo-acid generator or two or more photo-acid generators.
  • the content of the photoacid generator in the positive photosensitive resin layer is the total mass of the positive photosensitive resin layer from the viewpoint of sensitivity and resolution. On the other hand, it is preferably 0.1% by mass to 10% by mass, and more preferably 0.5% by mass to 5% by mass.
  • the positive photosensitive resin layer may contain a surfactant.
  • the uniformity of the film thickness can be improved.
  • surfactant examples include anionic surfactants, cationic surfactants, nonionic (so-called nonionic) surfactants and amphoteric surfactants.
  • anionic surfactants examples include anionic surfactants, cationic surfactants, nonionic (so-called nonionic) surfactants and amphoteric surfactants.
  • nonionic surfactants examples include anionic surfactants, cationic surfactants, nonionic (so-called nonionic) surfactants and amphoteric surfactants.
  • the surfactant is described in paragraph [0017] of Japanese Patent No. 4502784 and paragraphs [0060] to [0071] of Japanese Patent Laid-Open No. 2009-237362. These descriptions are incorporated herein by reference.
  • the surfactant is preferably a nonionic surfactant.
  • nonionic surfactants include polyoxyethylene higher alkyl ether compounds, polyoxyethylene higher alkyl phenyl ether compounds, higher fatty acid diester compounds of polyoxyethylene glycol, silicone surfactants, and fluorine surfactants. .. Among these, fluorine-based surfactants are preferable as the nonionic surfactant.
  • a commercially available product can be used as the nonionic surfactant.
  • nonionic surfactants include KP [manufactured by Shin-Etsu Chemical Co., Ltd.], Polyflow [manufactured by Kyoeisha Chemical Co., Ltd.], F-Top (manufactured by JEMCO), Megafac (registered trademark) [Product Examples: Megafac F551A, manufactured by DIC Co., Ltd., Florard [manufactured by Sumitomo 3M Co., Ltd.], Asahi Guard (registered trademark) [manufactured by AGC Co., Ltd.], Surflon (registered trademark) [manufactured by AGC Seichemical Co., Ltd.] ], PolyFox (manufactured by OMNOVA), Surfynol [manufactured by Nisshin Chemical Industry Co., Ltd.], DOWSIL (registered trademark) [Product Example: SH 8400, manufactured
  • the positive photosensitive resin layer may contain only one kind or two or more kinds of surfactants.
  • the content of the surfactant in the positive-type photosensitive resin layer is the total mass of the positive-type photosensitive resin layer from the viewpoint of film thickness uniformity. On the other hand, it is preferably 0.05% by mass to 10% by mass, and more preferably 0.05% by mass to 5% by mass.
  • the positive photosensitive resin layer may contain a corrosion inhibitor.
  • the positive photosensitive resin layer contains a corrosion inhibitor, the silver nanowires are prevented from being corroded, so that durability can be improved.
  • the corrosion inhibitor is not particularly limited, and a known corrosion inhibitor can be applied.
  • the corrosion inhibitor include compounds containing at least one of nitrogen atom and sulfur atom.
  • the corrosion inhibitor is preferably a heterocyclic aromatic compound containing at least one of a nitrogen atom and a sulfur atom, a compound having a triazole structure, a compound having a benzimidazole structure, and a thiadiazole structure. More preferably, it is at least one compound selected from the group consisting of compounds having
  • the corrosion inhibitor examples include benzimidazole, 1,2,4-triazole, benzotriazole, tolyltriazole, butylbenzyltriazole, alkyldithiothiadiazole, alkylthiol, 2-aminopyrimidine, 5,6-dimethylbenzimidazole, 2-Amino-5-mercapto-1,3,4-thiadiazole, 2,5-dimercapto-1,3,4-thiadiazole, 2-mercaptopyrimidine, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 2-mercapto Examples thereof include benzimidazole. Among these, at least one selected from the group consisting of benzimidazole and 1,2,4-triazole is preferable as the corrosion inhibitor.
  • the positive photosensitive resin layer contains a corrosion inhibitor, it may contain only one kind of corrosion inhibitor or may contain two or more kinds thereof.
  • the content of the corrosion inhibitor in the positive photosensitive resin layer is 0.001% by mass based on the total mass of the positive photosensitive resin layer. It is preferably from 5 to 5 mass %, more preferably from 0.005 to 3 mass %.
  • the positive photosensitive resin layer may contain a component other than the above components (hereinafter, also referred to as “other component”).
  • Other components are not particularly limited and can be appropriately selected depending on the purpose and the like. Examples of other components include an ultraviolet absorber, a development accelerator, a colorant and the like.
  • the negative photosensitive resin layer is not particularly limited, and a known negative photosensitive resin layer can be applied.
  • the negative photosensitive resin layer preferably contains a polymerizable compound, a polymerization initiator, and a binder polymer from the viewpoint of pattern formability.
  • the negative photosensitive resin layer preferably contains a polymerizable compound.
  • the polymerizable compound include polymerizable compounds such as radically polymerizable compounds and cationically polymerizable compounds.
  • the polymerizable compound is preferably a photopolymerizable compound, and more preferably an ethylenically unsaturated compound.
  • An ethylenically unsaturated compound is a compound that has one or more ethylenically unsaturated groups.
  • a (meth)acryloyl group is preferable.
  • As the ethylenically unsaturated compound a (meth)acrylate compound is preferable.
  • the ethylenically unsaturated compound preferably contains a bifunctional or higher functional ethylenically unsaturated compound.
  • bifunctional or higher functional ethylenically unsaturated compound means a compound having two or more ethylenically unsaturated groups in one molecule.
  • bifunctional ethylenically unsaturated compound examples include tricyclodecane dimethanol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, and 1,6-hexanediol di(meth)acrylate.
  • bifunctional ethylenically unsaturated compounds examples include tricyclodecane dimethanol diacrylate [trade name: NK ester A-DCP, Shin Nakamura Chemical Co., Ltd.], tricyclodecane dimethanol dimethacrylate.
  • Examples of the trifunctional or higher functional ethylenically unsaturated compound include dipentaerythritol (tri/tetra/penta/hexa)(meth)acrylate, pentaerythritol (tri/tetra)(meth)acrylate, trimethylolpropane tri(meth)acrylate, Examples thereof include ditrimethylolpropane tetra(meth)acrylate, isocyanuric acid (meth)acrylate, and a (meth)acrylate compound having a glycerin tri(meth)acrylate skeleton.
  • (tri/tetra/penta/hexa)(meth)acrylate is a concept including tri(meth)acrylate, tetra(meth)acrylate, penta(meth)acrylate, and hexa(meth)acrylate. ..
  • (tri/tetra)(meth)acrylate” is a concept including tri(meth)acrylate and tetra(meth)acrylate.
  • the ethylenically unsaturated compound preferably contains an ethylenically unsaturated compound having an acid group.
  • the acid group include a phosphoric acid group, a sulfonic acid group, a carboxy group and the like. Among these, a carboxy group is preferable as the acid group.
  • Examples of the ethylenically unsaturated compound having an acid group include a 3- to 4-functional ethylenically unsaturated compound having an acid group and a 5- to 6-functional ethylenically unsaturated compound having an acid group.
  • the ethylenically unsaturated compound having an acid group is preferably at least one selected from the group consisting of a bifunctional or higher functional ethylenically unsaturated compound having a carboxy group and a carboxylic acid anhydride thereof.
  • Examples of preferable commercial products of a bifunctional or higher-functional ethylenically unsaturated compound having a carboxy group include Aronix (registered trademark) TO-2349 (manufactured by Toagosei Co., Ltd.) and Aronix (registered trademark) M-520 (Toagosei) Co., Ltd.], Aronix (registered trademark) M-510 (manufactured by Toagosei Co., Ltd.) and the like.
  • the negative photosensitive resin layer contains a polymerizable compound
  • it may contain only one kind of the polymerizable compound or may contain two or more kinds thereof.
  • the content of the polymerizable compound in the negative photosensitive resin layer from the viewpoint of photosensitivity, to the total mass of the negative photosensitive resin layer. 1% by mass to 70% by mass, more preferably 10% by mass to 70% by mass, further preferably 20% by mass to 60% by mass, and 20% by mass to 50% by mass. It is particularly preferable that
  • the negative photosensitive resin layer preferably contains a polymerization initiator.
  • a polymerization initiator When the negative photosensitive resin layer contains a polymerization initiator, pattern formability can be improved.
  • the polymerization initiator include a photopolymerization initiator and a thermal polymerization initiator. Among these, the photopolymerization initiator is preferable as the polymerization initiator.
  • the photopolymerization initiator examples include a photopolymerization initiator having an oxime ester structure (hereinafter, also referred to as “oxime-based photopolymerization initiator”) and a photopolymerization initiator having an ⁇ -aminoalkylphenone structure (hereinafter, “ ⁇ - Aminoalkylphenone-based photopolymerization initiator”), a photopolymerization initiator having an ⁇ -hydroxyalkylphenone structure (hereinafter also referred to as " ⁇ -hydroxyalkylphenone-based polymerization initiator”), an acylphosphine oxide structure.
  • oxime-based photopolymerization initiator also referred to as “oxime-based photopolymerization initiator”
  • ⁇ - Aminoalkylphenone-based photopolymerization initiator a photopolymerization initiator having an ⁇ -aminoalkylphenone structure
  • N-phenylglycine-based photopolymerization initiator having N
  • N-phenylglycine-based photopolymerization initiator having an N-phenylglycine structure
  • the photopolymerization initiator is selected from the group consisting of oxime photopolymerization initiators, ⁇ -aminoalkylphenone photopolymerization initiators, ⁇ -hydroxyalkylphenone photopolymerization initiators, and N-phenylglycine photopolymerization initiators. It is preferable to contain at least one kind, and to contain at least one kind selected from the group consisting of an oxime photopolymerization initiator, an ⁇ -aminoalkylphenone photopolymerization initiator, and an N-phenylglycine photopolymerization initiator. More preferable.
  • the photopolymerization initiator is described, for example, in paragraphs [0031] to [0042] of JP2011-95716A and paragraphs [0064] to [0081] of JP2015-014783A. These descriptions are incorporated herein by reference.
  • photopolymerization initiators include 1-[4-(phenylthio)phenyl]-1,2-octanedione-2-(O-benzoyloxime) [trade name: IRGACURE (registered trademark) OXE-01, BASF Co., Ltd.], 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone-1-(O-acetyloxime) [Product name: IRGACURE (registered trademark) OXE-02] BASF Corporation], 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone [trade name: IRGACURE (registered trademark) 379EG, manufactured by BASF], 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one [trade name: IRGACURE (registered trademark) 907, manufactured by BASF
  • the negative photosensitive resin layer contains a polymerization initiator
  • it may contain only one type of polymerization initiator or two or more types.
  • the content of the polymerization initiator in the negative photosensitive resin layer is 0.1% by mass based on the total mass of the negative photosensitive resin layer. It is preferably at least the above, more preferably at least 0.2% by mass, further preferably at least 0.3% by mass.
  • the content of the polymerization initiator in the negative photosensitive resin layer is preferably 10% by mass or less, and more preferably 5% by mass or less, based on the total mass of the negative photosensitive resin layer. More preferable.
  • the negative photosensitive resin layer preferably contains a binder polymer.
  • the binder polymer is preferably an alkali-soluble resin from the viewpoint of developability.
  • the alkali-soluble resin is preferably a resin having an acid value of 40 mgKOH/g or more, and is a (meth)acrylic resin having a carboxyl group and having an acid value of 40 mgKOH/g (hereinafter, also referred to as “polymer B”). Is more preferable.
  • polymer B also referred to as “polymer B”. Is more preferable.
  • alkali-soluble refers to being soluble in a 1 mol/L sodium hydroxide solution at 25° C. Further, “soluble” means that 0.1 g or more is dissolved in 100 mL of solvent.
  • the acid value is a value measured according to the method described in JIS K0070:1992.
  • the total content of the structural units derived from (meth)acrylic acid and the structural units derived from (meth)acrylic acid ester in polymer B is 30 mol% or more based on all the structural units of polymer B. Is preferable, and 50 mol% or more is more preferable.
  • the polymer B contains a structural unit having a carboxy group.
  • the constitutional unit having a carboxy group contained in the polymer B may be only one type, or may be two or more types.
  • the content ratio of the structural unit having a carboxy group in the polymer B is preferably 5 mol% to 50 mol% with respect to all the structural units of the (meth)acrylic resin having a carboxy group, It is more preferably from 5 mol% to 40 mol%, further preferably from 10 mol% to 40 mol%, particularly preferably from 10 mol% to 30 mol%.
  • the binder polymer (particularly the polymer B) preferably contains a structural unit having an aromatic ring from the viewpoint of moisture permeability and strength after curing.
  • the monomer that forms the structural unit having an aromatic ring include styrene, tert-butoxystyrene, methylstyrene, styrene compounds such as ⁇ -methylstyrene, and benzyl (meth)acrylate.
  • styrene compounds are preferable as the monomer forming the structural unit having an aromatic ring.
  • the binder polymer (particularly, the (meth)acrylic resin having a carboxy group) preferably contains a structural unit having an ethylenically unsaturated group from the viewpoint of strength after curing, and has an ethylenically unsaturated group in the side chain. It is more preferable to include a structural unit.
  • the “side chain” means an atomic group branched from the main chain
  • the “main chain” means the relatively longest binding chain in the molecules of the polymer compound constituting the resin. means.
  • a (meth)acryl group is preferable, and a (meth)acryloxy group is more preferable.
  • the acid value of the binder polymer is preferably 40 mgKOH/g or more, more preferably 40 mgKOH/g to 200 mgKOH/g, even more preferably 60 mgKOH/g to 150 mgKOH/g, and 60 mgKOH/g to 130 mgKOH. /G is particularly preferable.
  • the weight average molecular weight of the binder polymer is not particularly limited, but it is preferably more than 3,000, more preferably more than 3,000 and 60,000 or less, and 5,000 or more and 50,000 or less. Is more preferable.
  • the weight average molecular weight of the binder polymer is a polystyrene equivalent weight average molecular weight measured by the method described above (that is, GPC).
  • the negative photosensitive resin layer contains a binder polymer
  • it may contain only one kind of binder polymer or two kinds or more.
  • the content of the binder polymer in the negative photosensitive resin layer is 10% by mass to 90% by mass with respect to the total mass of the negative photosensitive resin layer. Is preferable, 20% by mass to 80% by mass is more preferable, and 30% by mass to 70% by mass is further preferable.
  • the negative photosensitive resin layer may contain a sensitizer.
  • the sensitizer has actions such as further improving the sensitivity of the photopolymerization initiator to actinic rays and suppressing polymerization inhibition of the polymerizable compound by oxygen.
  • sensitizer examples include triethanolamine, p-dimethylaminobenzoic acid ethyl ester, p-formyldimethylaniline, p-methylthiodimethylaniline, N-phenylglycine, tributyltin acetate and trithiane.
  • the negative photosensitive resin layer contains a sensitizer, it may contain only one kind of sensitizer or two or more kinds.
  • the content of the sensitizer in the negative photosensitive resin layer is 0.01% by mass to 10% by mass based on the total mass of the photosensitive resin layer. %, more preferably 0.03% by mass to 5% by mass, and further preferably 0.05% by mass to 3% by mass.
  • the negative photosensitive resin layer may contain a corrosion inhibitor.
  • the silver nanowires are prevented from being corroded, so that the durability can be improved.
  • the corrosion inhibitor has the same meaning as the corrosion inhibitor described in “Positive Photosensitive Resin Layer”, and the preferred examples are also the same, so the description thereof is omitted here.
  • the negative photosensitive resin layer contains a corrosion inhibitor, it may contain only one kind or two or more kinds of corrosion inhibitors.
  • the content of the corrosion inhibitor in the negative photosensitive resin layer is 0.001% by mass based on the total mass of the negative photosensitive resin layer. It is preferably from 5 to 5 mass %, more preferably from 0.005 to 3 mass %.
  • the negative photosensitive resin layer may contain a surfactant.
  • the uniformity of the film thickness can be improved.
  • the surfactant has the same meaning as the surfactant described in “Positive-type photosensitive resin layer”, and the preferred examples are also the same, and therefore the description thereof is omitted here.
  • the negative photosensitive resin layer contains a surfactant, it may contain only one kind or two or more kinds of surfactants.
  • the content of the surfactant in the negative photosensitive resin layer is the total mass of the negative photosensitive resin layer from the viewpoint of film thickness uniformity. On the other hand, it is preferably 0.05% by mass to 10% by mass, and more preferably 0.05% by mass to 5% by mass.
  • the negative photosensitive resin layer may contain components other than the above components (hereinafter, also referred to as “other components”).
  • Other components are not particularly limited and can be appropriately selected depending on the purpose and the like. Examples of other components include a heat-crosslinkable compound, a polymerization inhibitor, an ultraviolet absorber, a development accelerator, and a colorant.
  • the thickness of the photosensitive resin layer is not particularly limited and is, for example, preferably 20 ⁇ m or less, more preferably 15 ⁇ m or less, further preferably 12 ⁇ m or less, particularly preferably 10 ⁇ m or less. Most preferably, it is 5 ⁇ m or less. When the thickness of the photosensitive resin layer is 20 ⁇ m or less, it is advantageous in terms of thinning the entire photosensitive transfer material and improving the transmittance of the photosensitive resin layer.
  • the thickness of the photosensitive resin layer is preferably 1 ⁇ m or more, more preferably 2 ⁇ m or more, from the viewpoint of manufacturing suitability.
  • the thickness of the photosensitive resin layer is measured by the following method.
  • the arithmetic mean value of the thickness of the photosensitive resin layer measured at five randomly selected points was calculated, and the obtained value was calculated as the thickness of the photosensitive resin layer. Satoshi
  • the cross-sectional observation image in the thickness direction of the photosensitive resin layer can be obtained using a scanning electron microscope (SEM).
  • the minimum transmittance of the photosensitive resin layer at a wavelength of 400 nm to 700 nm is preferably 80% or more, more preferably 90% or more.
  • Examples of the method for measuring the minimum transmittance of the photosensitive resin layer include a method using a spectrophotometer [eg, MCPD-6800 manufactured by Otsuka Electronics Co., Ltd.].
  • the method for forming the photosensitive resin layer is not particularly limited, and a known method can be applied.
  • Examples of the photosensitive resin layer include a method in which a coating solution for forming a photosensitive resin layer containing each of the above-mentioned components is applied onto an object to be coated and dried.
  • the coating method is not particularly limited, and a known coating method can be applied. Examples of the coating method include slit coating, spin coating, curtain coating, inkjet coating and the like.
  • the drying temperature is not particularly limited and can be appropriately set depending on the type of volatile components such as a solvent.
  • the drying temperature can be set to, for example, 60°C to 120°C.
  • the photosensitive resin layer-forming coating liquid can be prepared, for example, by mixing the above-mentioned components and a solvent in an arbitrary ratio.
  • the solvent is not particularly limited, and a known solvent can be applied.
  • the solvent include the ester compounds, ether compounds, and ketone compounds described below.
  • the ester compound include ethyl acetate, propyl acetate, isobutyl acetate, sec-butyl acetate, t-butyl acetate, isopropyl acetate, n-butyl acetate, 1-methoxy-2-propyl acetate and the like.
  • the ether compound include diisopropyl ether, 1,4-dioxane, 1,2-dimethoxyethane, 1,3-dioxolane, propylene glycol dimethyl ether, propylene glycol monoethyl ether and the like.
  • ketone compound examples include methyl n-butyl ketone, methyl ethyl ketone, methyl isobutyl ketone, diethyl ketone, methyl n-propyl ketone, and methyl isopropyl ketone.
  • the solvent contained in the coating liquid for forming the photosensitive resin layer does not need to be completely removed.
  • the photosensitive resin layer preferably contains no solvent, or more than 0% by mass and 1% by mass or less with respect to the total mass of the photosensitive resin layer, and does not contain a solvent or is photosensitive. It is more preferable that it is more than 0% by mass and 0.5% by mass or less with respect to the total mass of the functional resin layer.
  • the solid content concentration of the coating liquid for forming the photosensitive resin layer is not particularly limited.
  • the solid content concentration of the coating liquid for forming the photosensitive resin layer is preferably 1% by mass to 40% by mass, and more preferably 5% by mass to 30% by mass, from the viewpoint of coating suitability.
  • the “solid content concentration of the photosensitive resin layer-forming coating liquid” means a volatile component such as a solvent from the photosensitive resin layer-forming coating liquid with respect to the total mass of the photosensitive resin layer-forming coating liquid. It means the ratio of the removed residue.
  • the photosensitive transfer material of the present disclosure has a layer containing silver nanowires (that is, a silver nanowire layer).
  • the silver nanowire layer can function as a so-called conductive layer after transfer.
  • silver nanowire examples of the shape of the silver nanowire include a columnar shape, a rectangular parallelepiped shape, and a columnar shape having a polygonal cross section.
  • the silver nanowires preferably have at least one of a columnar shape and a columnar shape having a polygonal cross section.
  • the cross-sectional shape of the silver nanowire can be observed using, for example, a transmission electron microscope (TEM).
  • the diameter (so-called minor axis length) of the silver nanowire is not particularly limited, but for example, from the viewpoint of transparency, it is preferably 50 nm or less, more preferably 35 nm or less, and 20 nm or less. More preferable.
  • the lower limit of the diameter of the silver nanowire is preferably 5 nm or more, for example, from the viewpoint of oxidation resistance and durability.
  • the length (so-called major axis length) of the silver nanowire is not particularly limited, but for example, from the viewpoint of conductivity, it is preferably 5 ⁇ m or more, more preferably 10 ⁇ m or more, and more preferably 30 ⁇ m or more. Is more preferable.
  • the upper limit of the length of the silver nanowire is preferably 1 mm or less, for example, from the viewpoint of suppressing the formation of aggregates in the manufacturing process.
  • the diameter and length of the silver nanowire can be measured using, for example, a transmission electron microscope (TEM) or an optical microscope. Specifically, the diameter and the length of 300 randomly selected silver nanowires are measured from the silver nanowires magnified and observed using a transmission electron microscope (TEM) or an optical microscope. The measured values are arithmetically averaged, and the obtained values are used as the diameter and length of the silver nanowire.
  • TEM transmission electron microscope
  • optical microscope optical microscope
  • the content of the silver nanowires in the silver nanowire layer is not particularly limited, but for example, from the viewpoint of transparency and conductivity, it is 1% by mass to 99% by mass with respect to the total mass of the silver nanowire layer. Is preferred, and more preferably 10% by mass to 95% by mass.
  • the silver nanowire layer may include a binder (also referred to as “matrix”), if necessary.
  • the binder is a solid material in which silver nanowires are dispersed or embedded.
  • the binder can protect the silver nanowires from harmful environmental factors such as corrosion and abrasion.
  • binder examples include polymer materials and inorganic materials.
  • a light transmissive material is preferable.
  • polymer material examples include (meth)acrylic resin [for example, poly(methyl methacrylate)], polyester [for example, polyethylene terephthalate (PET)], polycarbonate, polyimide, polyamide, polyolefin (for example, polypropylene), polynorbornene, and cellulose.
  • a compound, polyvinyl alcohol (PVA), polyvinyl pyrrolidone, etc. are mentioned.
  • the cellulose compound include hydroxypropylmethyl cellulose (HPMC), hydroxyethyl cellulose (HEC), methyl cellulose (MC), hydroxypropyl cellulose (HPC), carboxymethyl cellulose (CMC) and the like.
  • the polymer material may be a conductive polymer material. Examples of the conductive polymer material include polyaniline and polythiophene.
  • inorganic materials examples include silica, mullite and alumina.
  • the silver nanowire layer contains a binder, it may contain only one kind of binder or two or more kinds of binder.
  • the content of the binder in the silver nanowire layer is preferably 1% by mass to 99% by mass, and preferably 5% by mass to 80% by mass, based on the total mass of the silver nanowire layer. More preferably, it is mass %.
  • the thickness of the silver nanowire layer is not particularly limited, but for example, from the viewpoint of transparency and conductivity, it is preferably 1 nm to 400 nm, more preferably 10 nm to 200 nm.
  • the thickness of the silver nanowire layer is measured by the following method.
  • the arithmetic mean value of the thickness of the silver nanowire layer measured at five randomly selected points was calculated, and the obtained value was calculated as the thickness of the silver nanowire layer. Satoshi
  • the cross-sectional observation image in the thickness direction of the silver nanowire layer can be obtained using a scanning electron microscope (SEM).
  • the minimum transmittance of the silver nanowire layer at a wavelength of 400 nm to 700 nm is preferably 80% or more, and more preferably 90% or more.
  • Examples of the method for measuring the minimum transmittance of the silver nanowire layer include a method using a spectrophotometer [eg, MCPD-6800 manufactured by Otsuka Electronics Co., Ltd.].
  • the method for producing the silver nanowire is not particularly limited, and a known method can be applied.
  • a method for producing a silver nanowire for example, in a water-based solvent containing at least a halogen compound and a reducing agent, a step of adding a silver complex solution and heating at a temperature of 150° C. or lower, and, if necessary, Examples thereof include a method including a step of desalting.
  • the halogen compound is not particularly limited as long as it is a compound containing bromine, chlorine or iodine.
  • the halogen compound include alkali halides such as sodium bromide, sodium chloride, sodium iodide, potassium iodide, potassium bromide and potassium chloride.
  • alkali halides such as sodium bromide, sodium chloride, sodium iodide, potassium iodide, potassium bromide and potassium chloride.
  • HTAB hexadecyl-trimethylammonium bromide
  • HTAC hexadecyl-trimethylammonium chloride
  • metal borohydride salts such as sodium borohydride and potassium borohydride; lithium aluminum hydride, potassium aluminum hydride, cesium aluminum hydride, beryllium aluminum hydride, magnesium aluminum hydride, aluminum hydride
  • Aluminum hydride salts such as calcium; sodium sulfite, hydrazine compound, dextrin, hydroquinone, hydroxylamine, citric acid or its salt, succinic acid or its salt, ascorbic acid or its salt, etc.; diethylaminoethanol, ethanolamine, propanolamine, tritium Alkanolamines such as ethanolamine and dimethylaminopropanol; Aliphatic amines such as propylamine, butylamine, dipropyleneamine, ethylenediamine and triethylenepentamine; Heterocyclic amines such as piperidine, pyrrolidine, N-methylpyrrolidine and morpholine; Aniline , N-methylaniline, toluidine
  • Examples of the ligand of the silver complex include CN-, SCN-, SO 3 2- , thiourea, ammonia and the like.
  • a silver ammonia complex is preferable.
  • the heating temperature is preferably 150° C. or lower, more preferably 20° C. to 130° C., further preferably 30° C. to 100° C., particularly preferably 40° C. to 90° C.
  • the desalting treatment can be performed by a method such as ultrafiltration, dialysis, gel filtration, decantation, and centrifugation after forming the silver nanowires.
  • the method for forming the silver nanowire layer is not particularly limited, and a known method can be applied.
  • a method of forming the silver nanowire layer for example, a method of applying a coating solution for forming a silver nanowire layer containing silver nanowires onto an object to be coated and drying the coating solution can be mentioned.
  • the coating liquid for forming the silver nanowire layer can be prepared, for example, by mixing the silver nanowire and the solvent at an arbitrary ratio.
  • Water is mainly used as the solvent, and an organic solvent miscible with water may be used in combination at a ratio of 80% by volume or less with respect to the total amount of the solvent.
  • an alcohol compound having a boiling point of 50° C. to 250° C., more preferably 55° C. to 200° C. is preferable.
  • Alcohol compounds include methanol, ethanol, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol 200, polyethylene glycol 300, glycerin, propylene glycol, dipropylene glycol, 1,3-propanediol, 1,2-butanediol, 1 1,4-butanediol, 1,5-pentanediol, 1-ethoxy-2-propanol, ethanolamine, diethanolamine, 2-(2-aminoethoxy)ethanol, 2-dimethylaminoisopropanol and the like can be mentioned.
  • the content of silver nanowires in the coating liquid for silver nanowire layer formation is preferably 0.1% by mass to 99% by mass, based on the total mass of the coating liquid for silver nanowire layer formation, and 0.3 It is more preferable that the content is from 95% by mass to 95% by mass.
  • the coating method is not particularly limited, and a known coating method can be applied. Examples of the coating method include slit coating, spin coating, curtain coating, inkjet coating and the like.
  • the drying temperature is not particularly limited and can be appropriately set depending on the type of volatile components such as a solvent.
  • the drying temperature can be set to, for example, 60°C to 120°C.
  • the photosensitive transfer material of the present disclosure has a thermosetting resin layer.
  • the thermosetting resin layer is soluble in a developing solution before the thermosetting and can be patterned by being selectively dissolved, and after the thermosetting, the photosensitive resin layer or a cured product of the photosensitive resin layer. It is difficult to be peeled off even after the step of removing, and has both patterning suitability and peeling resistance.
  • the thermosetting resin layer preferably does not have photocurability.
  • the thermosetting resin layer preferably contains a compound having a functional group that forms a bond by thermal reaction.
  • the functional group that forms a bond by thermal reaction include a (block) isocyanate group, an epoxy group, an oxetane group, a hydroxymethyl group, an alkoxymethyl group, and an oxazoline group.
  • the “(block)isocyanate group” is a concept that includes both an isocyanate group and a blocked isocyanate group.
  • the thermosetting resin layer is preferably a layer that is cured by the reaction of a functional group that forms a bond by a thermal reaction with a functional group having active hydrogen to form a crosslinked structure.
  • the thermosetting resin layer has (1) a functional group that forms a bond by a thermal reaction and active hydrogen. It is preferable to include at least one of a compound having a functional group, and (2) a combination of a compound having a functional group that forms a bond by thermal reaction and a compound having a functional group having active hydrogen.
  • Examples of the functional group having active hydrogen include a hydroxyl group, a carboxy group, a thiol group, an amino group and a phenol group.
  • thermosetting resin layer preferably has the functional groups in the combinations shown in (A) to (D) below.
  • A A combination of a (block) isocyanate group and at least one functional group selected from the group consisting of a hydroxyl group, a carboxy group, and an amino group.
  • B A combination of at least one of an epoxy group and an oxetane group and a carboxy group.
  • C A combination of at least one of a hydroxymethyl group and an alkoxymethyl group and at least one of a hydroxyl group and a carboxy group.
  • D A combination of an oxazoline group and a carboxy group.
  • a combination of a functional group forming a bond by a thermal reaction and a functional group having active hydrogen from the viewpoint of stability over time and curability, a combination of a blocked isocyanate group and at least one of a hydroxyl group and a carboxy group is more preferable. A combination of a blocked isocyanate group and a hydroxyl group is more preferable. The blocked isocyanate group and the hydroxyl group form a urethane bond by a thermal reaction.
  • the temperature of the thermal reaction is preferably 100°C to 180°C, more preferably 110°C to 160°C, and further preferably 120°C to 150°C.
  • the thermosetting resin layer is cured in the step of drying the coating film of the coating liquid for forming the thermosetting resin layer, which is performed when forming the thermosetting resin layer. Without doing so, the thermosetting resin layer can be efficiently thermoset in the thermosetting step after the developing step.
  • the thermosetting resin layer preferably contains a blocked isocyanate compound.
  • the blocked isocyanate compound is a compound having a blocked isocyanate group.
  • the “blocked isocyanate group” is usually protected by blocking the isocyanate group with a blocking agent (so-called mask) to suppress the reactivity of the isocyanate group, but deprotects when heated, By a group is meant an active isocyanate group.
  • the “blocked isocyanate compound” means a compound having a blocked isocyanate group as described above.
  • the blocked isocyanate group has a partial structure represented by the following formula.
  • X represents a structure obtained by removing a hydrogen atom from the blocking agent.
  • the blocking agent include ketoxime compounds, amide compounds, nitrogen-containing heterocyclic compounds, active methylene compounds and the like.
  • the nitrogen-containing heterocyclic compound is preferably a compound having a pyrazole structure, a compound having an imidazole structure, or the like.
  • the blocked isocyanate group in which X is a ketoxime group is preferably a group represented by the following formula.
  • R 101 and R 102 each independently represent an alkyl group or an aryl group. R 101 and R 102 may combine with each other to form a ring structure. R 101 and R 102 are preferably a methyl group or an ethyl group.
  • blocked isocyanate group in which X is an amide group (so-called amide blocked isocyanate group) and the blocked isocyanate group in which X is an imide group (so-called imide blocked isocyanate group)
  • groups represented by the following formulas are preferable.
  • R 103 represents a substituent
  • R 105 represents an alkyl group
  • n1 represents an integer of 0 to 3.
  • the substituent represented by R 103 is preferably an alkyl group, an alkoxy group, or a halogen atom.
  • the blocked isocyanate group in which X is a nitrogen-containing heterocycle (so-called nitrogen-containing heterocycle blocked isocyanate group), a group represented by the following formula is preferable.
  • R 103 represents a substituent
  • n1 represents an integer of 0 to 3.
  • the substituent represented by R 103 is preferably an alkyl group, and more preferably an alkyl group having 1 to 4 carbon atoms.
  • nitrogen-containing heterocyclic blocked isocyanate group a dimethylpyrazole blocked isocyanate group is more preferable.
  • the blocked isocyanate group in which X is an active methylene group is preferably a group represented by the following formula.
  • R 104 and R 106 each independently represent an alkyl group or an alkoxy group. R 104 and R 106 may combine with each other to form a ring structure.
  • the blocked isocyanate compound preferably reacts at the heating temperature in the thermosetting process described below. From this point of view, the dissociation temperature of the blocked isocyanate compound is preferably 100° C. to 180° C., more preferably 110° C. to 160° C., and further preferably 120° C. to 150° C.
  • blocked isocyanate compounds and their dissociation temperatures are shown below.
  • Dimethylpyrazole blocked isocyanate compound (dissociation temperature: 100°C to 120°C)
  • active methylene blocked isocyanate compound (dissociation temperature: 100°C to 120°C)
  • ketoxime blocked isocyanate compound (dissociation temperature: 130°C to 150°C)
  • ⁇ - Caprolactam-blocked isocyanate compound dissociation temperature: 160°C to 180°C.
  • the blocked isocyanate compound from the viewpoint of thermal reactivity and stability, at least one compound selected from the group consisting of a dimethylpyrazole blocked isocyanate compound, an active methylene blocked isocyanate compound, and a ketoxime blocked isocyanate compound. Ketoxime blocked isocyanate compounds are more preferred.
  • the dissociation temperature of the blocked isocyanate compound in the present disclosure means "the temperature of the endothermic peak associated with the deprotection reaction of the blocked isocyanate when measured by DSC (Differential scanning calorimetry) using a differential scanning calorimeter". To do.
  • a differential scanning calorimeter for example, a differential scanning calorimeter (model: DSC6200) manufactured by Seiko Instruments Inc. can be preferably used. However, the differential scanning calorimeter is not limited to this.
  • the number of blocked isocyanate groups in the blocked isocyanate compound is not particularly limited, but for example, from the viewpoint of curability, it is preferable to have two or more blocked isocyanate groups in one molecule, and to have three or more blocked isocyanate groups. Is more preferable.
  • the functional group concentration of the blocked isocyanate group in the blocked isocyanate compound is preferably 0.3 mmol/g or more, more preferably 0.5 mmol or more, further preferably 1 mmol/g or more, 2 mmol/g The above is particularly preferable.
  • the upper limit of the functional group concentration of the blocked isocyanate group in the blocked isocyanate compound is not particularly limited, but is preferably 6 mmol/g or less, for example.
  • the functional group concentration of the blocked isocyanate group in the thermosetting resin layer is preferably 0.1 mmol/g or more, more preferably 0.3 mmol/g or more, further preferably 1 mmol/g or more. , 1.5 mmol/g or more is particularly preferable.
  • the functional group concentration of the blocked isocyanate group in the thermosetting resin layer is 0.1 mmol/g or more, the thermosetting property of the thermosetting resin layer is further improved, and the cured product of the thermosetting resin layer is formed. Since the resistance to peeling from the substrate is further increased, the conductive pattern tends to be more difficult to peel from the substrate.
  • the upper limit of the functional group concentration of the blocked isocyanate group in the thermosetting resin layer is not particularly limited, but is preferably 6 mmol/g or less from the viewpoint of developability and solvent solubility, for example.
  • the functional group concentration of the blocked isocyanate group in the thermosetting resin layer is represented by the product of the functional group concentration of the blocked isocyanate group of the blocked isocyanate compound and the mass content of the blocked isocyanate compound in the thermosetting resin layer.
  • the thermosetting resin layer contains two or more blocked isocyanate compounds, it is represented by the sum of the functional group concentrations in the thermosetting resin layer calculated from the respective blocked isocyanate compounds.
  • the blocked isocyanate compound preferably has at least one of a hydroxyl group and an acid group.
  • thermosetting resin layer contains a blocked isocyanate compound
  • thermosetting resin layer further contains a compound having at least one of a hydroxyl group and an acid group other than the blocked isocyanate compound.
  • thermosetting resin layer has a hydroxyl group
  • thermosetting property of the thermosetting resin layer is further improved, and the resistance to peeling of the cured product of the thermosetting resin layer from the substrate is further increased. Therefore, the conductive pattern tends to be more difficult to peel off.
  • thermosetting resin layer has a hydroxyl group
  • the thermosetting resin layer contains a blocked isocyanate compound having a hydroxyl group, and (2) the thermosetting resin layer does not have a hydroxyl group.
  • thermosetting resin layer contains a blocked isocyanate compound having a hydroxyl group and a compound having a hydroxyl group.
  • thermosetting resin layer has an acid group
  • the developability of the thermosetting resin layer is further improved, so that the development residue tends to be more suppressed.
  • thermosetting resin layer has an acid group
  • the thermosetting resin layer contains a blocked isocyanate compound having an acid group
  • the thermosetting resin layer has an acid group. Examples thereof include a block isocyanate compound not having it and a compound having an acid group, and a case where (3) the thermosetting resin layer contains a block isocyanate compound having an acid group and a compound having an acid group.
  • the acid group examples include a carboxy group, a sulfonamide group, a sulfonimide group, a phenol group and the like. Among these, a carboxy group is preferable as the acid group.
  • the functional group concentration of the hydroxyl group in the thermosetting resin layer is preferably 0.1 mmol/g or more, more preferably 0.3 mmol/g or more, 0 More preferably, it is 0.5 mmol/g or more.
  • the functional group concentration of the hydroxyl group in the thermosetting resin layer is 0.1 mmol/g or more, the thermosetting property of the thermosetting resin layer is further improved, and the cured product of the thermosetting resin layer is formed from the substrate. Since the peeling resistance of 1 is further increased, the conductive pattern tends to be more difficult to peel from the substrate.
  • the upper limit of the functional group concentration of hydroxyl groups in the thermosetting resin layer is not particularly limited, but is preferably 3 mmol/g or less from the viewpoint of developability and solvent solubility, for example.
  • the functional group concentration of the hydroxyl group in the thermosetting resin layer is represented by the product of the functional group concentration of the hydroxyl group of the compound having a hydroxyl group and the mass content of the compound having a hydroxyl group in the thermosetting resin layer.
  • the thermosetting resin layer contains two or more kinds of compounds having a hydroxyl group, it is represented by the sum of the functional group concentrations in the thermosetting resin layer calculated from the respective compounds having a hydroxyl group.
  • the functional group concentration of the acid group in the thermosetting resin layer (also referred to as “acid value”; the same applies below) is 0.05 mmol/g to 5 mmol/g. It is preferably 0.1 mmol/g to 3 mmol/g, more preferably 0.2 mmol/g to 2 mmol/g.
  • the functional group concentration of the acid group in the thermosetting resin layer is within the above range, the developability of the thermosetting resin layer is further improved, so that the development residue tends to be more suppressed.
  • the functional group concentration of the acid group in the thermosetting resin layer is represented by the product of the functional group concentration of the acid group of the compound having an acid group and the mass content of the compound having an acid group in the thermosetting resin layer. Be done.
  • the thermosetting resin layer contains two or more compounds having an acid group, it is represented by the sum of the functional group concentrations in the thermosetting resin layer calculated from the compounds having an acid group.
  • the blocked isocyanate compound may be a low molecular weight compound or a high molecular weight compound, but is preferably a high molecular weight compound from the viewpoint of reaction efficiency and suppression of precipitation.
  • the blocked isocyanate compound is a polymer compound
  • the blocked isocyanate compound is preferably a polymer, more preferably a polymer having a (meth)acrylic monomer as a repeating unit, and is represented by the following formula BR-1.
  • a polymer having a repeating unit represented by the formula: BR-2 is more preferable, and a polymer having a repeating unit represented by the following formula BR-2 is particularly preferable.
  • the “(meth)acrylic monomer” means a monomer having a (meth)acryloyl group.
  • X represents a structure in which a hydrogen atom is removed from the blocking agent
  • Z 1 represents a hydrogen atom or a methyl group.
  • R 101 and R 102 each independently represent an alkyl group or an aryl group. R 101 and R 102 may combine with each other to form a ring structure.
  • Z 1 represents a hydrogen atom or a methyl group.
  • R 101 and R 102 are preferably a methyl group or an ethyl group.
  • the content of the repeating unit represented by BR-1 in the polymer having the repeating unit represented by the formula BR-1 is preferably 10 mol% to 100 mol% with respect to the total repeating units of the polymer, and 20 mol. % To 80 mol% is more preferable, and 30 mol% to 80 mol% is further preferable.
  • the polymer having the repeating unit represented by the formula BR-1 preferably has at least one of a hydroxyl group and an acid group.
  • the polymer has a repeating unit having a hydroxyl group and an acid group (preferably a carboxy group) in addition to the repeating unit represented by the formula BR-1 and the repeating unit represented by the formula BR-1. And at least one repeating unit of the repeating units having.
  • the polymer has a repeating unit having a hydroxyl group and an acid group (preferably a carboxy group) in addition to the repeating unit represented by the formula BR-1 and the repeating unit represented by the formula BR-1. And both repeating units of the repeating unit having.
  • the repeating unit having a hydroxyl group is preferably a repeating unit derived from hydroxyalkyl(meth)acrylate.
  • the repeating unit having an acid group is preferably a repeating unit derived from (meth)acrylic acid.
  • the polymer having the repeating unit represented by the formula BR-1 may further have another repeating unit copolymerizable with the repeating unit represented by the formula BR-1.
  • the other repeating unit is not particularly limited, and examples thereof include a repeating unit derived from an alkyl(meth)acrylate, a repeating unit derived from an aralkyl(meth)acrylate, and a repeating unit derived from styrene.
  • the total content of repeating units derived from acrylic acid and repeating units derived from acrylic acid ester is 30 mol% to 100 mol% based on all repeating units of the polymer. Is preferable, and more preferably 50 mol% to 100 mol %.
  • the weight average molecular weight of the blocked isocyanate compound is not particularly limited, but is preferably 2,000 to 100,000, more preferably 3,000 to 50,000, More preferably, it is 4,000 to 30,000.
  • the weight average molecular weight of the blocked isocyanate compound is a polystyrene equivalent weight average molecular weight measured by the method described above (that is, GPC).
  • the blocked isocyanate compound is a polymer compound
  • the blocked isocyanate compound is preferably a polymer represented by the following formula.
  • Z 1 represents a hydrogen atom or a methyl group.
  • the blocked isocyanate compound is a low molecular weight compound
  • the blocked isocyanate compound is preferably a compound represented by the following formula.
  • X 1 represents a structure obtained by removing a hydrogen atom from the blocking agent.
  • X 1 has a structure obtained by removing a hydrogen atom from the blocking agent, or a hydrophilic group (preferably a polyalkylene glycol group). ), and at least one of a plurality of X 1 s represents a structure in which a hydrogen atom is removed from the blocking agent.
  • the compound having at least one of a hydroxyl group and an acid group may be a low molecular weight compound or a high molecular weight compound, but is preferably a high molecular weight compound.
  • the polymer compound is preferably a polymer.
  • the low molecular weight compound having a hydroxyl group a compound having two or more hydroxyl groups is preferable, and a compound having 3 to 8 hydroxyl groups is more preferable.
  • examples of such compounds include polyols such as trimethylolethane, trimethylolpropane, glycerin, pentaerythritol, dipentaerythritol, and ditrimethylolethane.
  • the polymer has at least one repeating unit having a repeating unit having a hydroxyl group and a repeating unit having an acid group (preferably a carboxy group).
  • the polymer has both a repeating unit having a hydroxyl group and a repeating unit having an acid group (preferably a carboxy group).
  • the repeating unit having a hydroxyl group is preferably a repeating unit derived from hydroxyalkyl(meth)acrylate.
  • the repeating unit having an acid group (preferably a carboxy group) is preferably a repeating unit derived from (meth)acrylic acid.
  • the polymer having at least one of a hydroxyl group and an acid group may further have a repeating unit having a hydroxyl group or another repeating unit copolymerizable with the repeating unit having an acid group (preferably a carboxy group).
  • the other repeating unit is not particularly limited, and examples thereof include a repeating unit derived from an alkyl(meth)acrylate, a repeating unit derived from an aralkyl(meth)acrylate, and a repeating unit derived from styrene.
  • the polymer having at least one of a hydroxyl group and an acid group has a total content of repeating units derived from acrylic acid and repeating units derived from acrylic acid ester of 30 mol% with respect to all repeating units of the polymer. It is preferably ⁇ 100 mol %, and more preferably 50 mol% to 100 mol %.
  • the weight average molecular weight of the polymer having at least one of a hydroxyl group and an acid group is not particularly limited, but is preferably 2,000 to 100,000, more preferably 3,000 to 80,000, and It is more preferably 000 to 50,000.
  • the weight average molecular weight of the polymer having at least one of a hydroxyl group and an acid group is a polystyrene equivalent weight average molecular weight measured by the method described above (that is, GPC).
  • the polymer having at least one of a hydroxyl group and an acid group is preferably a polymer represented by the following formula.
  • Z 1 represents a hydrogen atom or a methyl group.
  • the thermosetting resin layer may have at least one of an epoxy group and an oxetane group as a functional group that forms a bond by thermal reaction.
  • the thermosetting resin layer preferably contains at least one of an epoxy group and an oxetane group in a mode including a compound having at least one of an epoxy group and an oxetane group.
  • Examples of the compound having an epoxy group include low molecular weight compounds such as glycidyl ether compounds and polycarboxylic acid glycidyl ester compounds, and polymers having a repeating unit having an epoxy group in its side chain.
  • the repeating unit having an epoxy group in the side chain is preferably a repeating unit derived from glycidyl (meth)acrylate.
  • thermosetting resin layer contains a polymer having both a repeating unit having an epoxy group and a repeating unit having a carboxy group.
  • the thermosetting resin layer may have at least one of a hydroxymethyl group and an alkoxymethyl group as a functional group that forms a bond by thermal reaction.
  • the thermosetting resin layer preferably contains at least one of a hydroxymethyl group and an alkoxymethyl group in a mode including a compound having at least one of a hydroxymethyl group and an alkoxymethyl group.
  • a compound having at least one of a hydroxymethyl group and an alkoxymethyl group a low-molecular compound such as hydroxymethylmelamine, alkoxymethylmelamine, alkoxymethylglycolurea, alkoxymethylbenzoguanamine, and hydroxymethyl-substituted phenol, derived from N-alkoxymethylacrylamide
  • a polymer having a repeating unit of is preferable from the viewpoint of curability.
  • thermosetting resin layer contains a polymer having a repeating unit derived from N-alkoxymethylacrylamide, a repeating unit having a hydroxyl group, and a repeating unit having a carboxy group.
  • thermosetting resin layer may contain a corrosion inhibitor.
  • the thermosetting resin layer contains a corrosion inhibitor, the silver nanowires are prevented from being corroded, so that durability can be improved.
  • the corrosion inhibitor has the same meaning as the corrosion inhibitor described in “Positive Photosensitive Resin Layer”, and the preferred examples are also the same, so the description thereof is omitted here.
  • thermosetting resin layer When the thermosetting resin layer contains a corrosion inhibitor, it may contain only one type of corrosion inhibitor or may contain two or more types of corrosion inhibitors.
  • the content of the corrosion inhibitor in the thermosetting resin layer is 0.001% by mass to 5% by mass based on the total mass of the thermosetting resin layer. It is preferably 0.005% by mass to 3% by mass.
  • thermosetting resin layer may contain a surfactant.
  • the surfactant has the same meaning as the surfactant described in “Positive-type photosensitive resin layer”, and the preferred examples are also the same, and therefore the description thereof is omitted here.
  • thermosetting resin layer may contain only one type of surfactant, or may contain two or more types of surfactant.
  • the content ratio of the surfactant in the thermosetting resin layer is 0. 0 with respect to the total mass of the thermosetting resin layer from the viewpoint of the film thickness uniformity.
  • the amount is preferably 05% by mass to 10% by mass, and more preferably 0.05% by mass to 5% by mass.
  • thermosetting resin layer may contain components other than the above components (hereinafter, also referred to as “other components”).
  • Other components are not particularly limited and can be appropriately selected depending on the purpose and the like.
  • Other components include a polymerization inhibitor, an ultraviolet absorber, a development accelerator, a coloring agent and the like.
  • the thickness of the thermosetting resin layer is not particularly limited and is, for example, preferably 1 nm to 10,000 nm, more preferably 1 nm to 5,000 nm, further preferably 1 nm to 1,000 nm. It is particularly preferably 1 nm to 300 nm, and most preferably 20 nm to 100 nm.
  • the cured resin layer that is, the thermosetting resin layer
  • the thickness of the thermosetting resin layer is measured by the following method.
  • the arithmetic mean value of the thickness of the thermosetting resin layer measured at five randomly selected points was calculated, and the obtained value was used as the thermosetting resin.
  • the layer thickness is obtained using a scanning electron microscope (SEM).
  • the minimum transmittance of the thermosetting resin layer at a wavelength of 400 nm to 700 nm is preferably 80% or more, more preferably 90% or more.
  • Examples of the method for measuring the minimum transmittance of the thermosetting resin layer include a method using a spectrophotometer [eg, MCPD-6800 manufactured by Otsuka Electronics Co., Ltd.].
  • thermosetting resin layer The contact resistance of the thermosetting resin layer is preferably 200 ⁇ or less, more preferably 1 ⁇ to 200 ⁇ , and more preferably 1 ⁇ to, from the viewpoint of the conductivity of the cured resin layer (that is, the thermosetting resin layer). It is more preferably 100 ⁇ , and particularly preferably 1 ⁇ to 50 ⁇ .
  • the contact resistance of the thermosetting resin layer is measured by the TLM (Transmission Line Model) method.
  • the specific measuring method is as follows. Seven copper electrodes (thickness: 300 nm, width: 500 ⁇ m) arranged on a substrate (for example, a cycloolefin polymer film) in parallel and independently at intervals of 2 mm, 4 mm, 6 mm, 8 mm, 12 mm, and 20 mm. ) Is formed. Next, one photosensitive transfer material was pasted on the seven copper electrodes to produce a test body having a structure in which a silver nanowire layer was laminated on the copper electrodes via a thermosetting resin layer. To do.
  • the silver nanowire layer is arranged so as to cross the seven copper electrodes, and the angle formed by each copper electrode and the silver nanowire layer is 90°.
  • the contact resistance of the thermosetting resin layer is obtained by plotting the relationship between the resistance (vertical axis) and the distance (horizontal axis) between the copper electrodes.
  • a resistivity meter (trade name: Loresta-GP, manufactured by Mitsubishi Chemical Analytech Co., Ltd.) can be used.
  • the measuring device is not limited to this.
  • thermosetting resin layer The glass transition temperature of the thermosetting resin layer is preferably ⁇ 50° C. to 100° C., and more preferably ⁇ 30° C. to 80° C., from the viewpoint of coating properties and adhesiveness when it is bonded to a substrate. , -10°C to 50°C is more preferable.
  • the glass transition temperature of the thermosetting resin layer is the thermosetting resin layer formed by applying the thermosetting resin layer forming coating solution to the substrate and drying the solvent at a temperature at which the thermosetting resin layer does not cure. , DSC (Differential scanning calorimetry) analysis using a differential scanning calorimeter.
  • thermosetting resin layer a compound having a different glass transition temperature is appropriately selected as a compound (block isocyanate compound, compound having a hydroxyl group, compound having an acid group, etc.) contained in the thermosetting resin layer. Can be adjusted.
  • thermosetting resin layer (Method of forming thermosetting resin layer)
  • the method for forming the thermosetting resin layer is not particularly limited, and a known method can be applied.
  • examples of the thermosetting resin layer include a method in which a coating liquid for forming a thermosetting resin layer containing each of the above-mentioned components is applied onto an object to be coated and dried.
  • the coating method is not particularly limited, and a known coating method can be applied. Examples of the coating method include slit coating, spin coating, curtain coating, inkjet coating and the like.
  • the drying temperature is not particularly limited and can be appropriately set depending on the type of volatile components such as a solvent.
  • the drying temperature can be set to, for example, 60°C to 120°C.
  • thermosetting resin layer-forming coating liquid can be prepared, for example, by mixing the above-mentioned components and a solvent in an arbitrary ratio.
  • the solvent is not particularly limited, and a known solvent can be used.
  • the solvent has the same meaning as the solvent described in “Method for forming photosensitive resin layer”, and the preferred examples are also the same, and therefore the description thereof is omitted here.
  • thermosetting resin layer the solvent contained in the coating liquid for forming the thermosetting resin layer does not need to be completely removed.
  • the thermosetting resin layer contains no solvent, or preferably contains more than 0 mass% and 1 mass% or less of the total mass of the thermosetting resin layer and contains no solvent, or More preferably, it is more than 0% by mass and 0.5% by mass or less based on the total mass of the thermosetting resin layer.
  • the solid content concentration of the thermosetting resin layer-forming coating liquid is not particularly limited. From the viewpoint of coating suitability, the solid content concentration of the thermosetting resin layer forming coating liquid is preferably 0.1% by mass to 30% by mass, and 0.5% by mass to 20% by mass. More preferable.
  • the “solid content concentration of the thermosetting resin layer-forming coating liquid” refers to volatilization of a solvent or the like from the thermosetting resin layer-forming coating liquid with respect to the total mass of the thermosetting resin layer-forming coating liquid. It means the ratio of the residue excluding the sex components.
  • the photosensitive transfer material of the present disclosure may have a protective film on the surface of the thermosetting resin layer opposite to the silver nanowire layer side.
  • the protective film include polyethylene terephthalate film, polypropylene film, polystyrene film, polycarbonate film and the like.
  • the protective film is described in paragraphs [0083] to [0087] and [0093] of JP 2006-259138 A, for example. These descriptions are incorporated herein by reference.
  • the method for producing a patterned substrate of the present disclosure is the above-described photosensitive transfer material and the step of attaching the substrate (hereinafter, also referred to as “attaching step”), and the photosensitive resin layer in the photosensitive transfer material.
  • Pattern exposure hereinafter, also referred to as "exposure step”
  • developing step a step of developing the photosensitive transfer material that has undergone the pattern exposure to form a pattern
  • thermally curing the thermosetting resin layer hereinafter, also referred to as “thermosetting step” is included in this order.
  • the method for producing a patterned substrate according to the present disclosure includes a bonding step, an exposure step, a developing step, and a thermosetting step in this order, and therefore, a patterned substrate in which the conductive pattern is difficult to peel off from the substrate is produced.
  • the method for manufacturing a patterned substrate according to the present disclosure includes the above-described photosensitive transfer material and a step of bonding the substrates (that is, a bonding step).
  • the photosensitive transfer material in the method for manufacturing a patterned substrate according to the present disclosure is as described in the above-mentioned “Photosensitive transfer material”, and the preferred embodiment is also the same, and therefore the description thereof is omitted here.
  • the photosensitive resin layer in the photosensitive transfer material is preferably a positive photosensitive resin layer from the viewpoint of resolution.
  • the substrate may be a substrate such as glass, silicon, or a film itself, or may be a substrate provided with an optional layer such as a conductive layer on the substrate such as glass, silicon, or film, if necessary. May be.
  • the substrate further has a conductive layer, the substrate preferably has a conductive layer on the base material.
  • the base material is preferably a glass base material or a film base material, more preferably a film base material, and further preferably a resin film.
  • the base material is preferably transparent.
  • the transparent substrate is described, for example, in JP 2010-86684 A, JP 2010-152809 A and JP 2010-257492 A. These descriptions are incorporated herein by reference.
  • the refractive index of the base material is preferably 1.50 to 1.52.
  • tempered glass represented by Corning's gorilla glass
  • a film base material it is preferable to use a base material having small optical distortion and a base material having high transparency.
  • the material of the resin film includes polyethylene terephthalate (PET), polyethylene naphthalate, polycarbonate, triacetyl cellulose, cycloolefin polymer and the like.
  • Examples of the conductive layer include general circuit wiring and any conductive layer used for touch panel wiring. Examples of the conductive layer include a metal layer and a conductive metal oxide layer. In the present disclosure, “conductive” means that the volume resistivity is less than 1 ⁇ 10 6 ⁇ cm. The volume resistivity is preferably less than 1 ⁇ 10 4 ⁇ cm.
  • the material of the metal layer examples include Al (aluminum), Zn (zinc), Cu (copper), Fe (iron), Ni (nickel), Cr (chrome), Mo (molybdenum), and the like.
  • the metal forming the metal layer may be a single metal consisting of one kind of metal element, a metal mixture containing two or more kinds of metal elements, or an alloy containing at least one kind of metal element. It may be.
  • the conductive metal oxide forming the conductive metal oxide layer examples include ITO (Indium Tin Oxide), IZO (Indium Zinc Oxide), and SiO 2 .
  • the conductive layer is preferably at least one kind of layer selected from the group consisting of a metal layer and a conductive metal oxide layer, more preferably a metal layer, from the viewpoint of conductivity and fine wire forming property, and a copper layer. More preferably, it is a layer.
  • the conductive layer is preferably an electrode pattern corresponding to the sensor of the visual recognition part used in the capacitive touch panel or a wiring of the peripheral extraction part.
  • the photosensitive transfer material and the substrate are bonded by bringing the thermosetting resin layer in the photosensitive transfer material into contact with the substrate.
  • the lamination of the photosensitive transfer material and the substrate can be performed using a known laminator such as a vacuum laminator and an auto cut laminator.
  • the laminating temperature is not particularly limited.
  • the laminating temperature is preferably 80° C. to 150° C., more preferably 90° C. to 150° C., and further preferably 100° C. to 150° C.
  • the laminating temperature refers to the temperature of the rubber roller.
  • the substrate temperature during lamination is not particularly limited.
  • the substrate temperature during lamination may be, for example, 10° C. to 150° C., preferably 20° C. to 150° C., and more preferably 30° C. to 150° C.
  • the substrate temperature during lamination is preferably 10°C to 80°C, more preferably 20°C to 60°C, and further preferably 30°C to 50°C. preferable.
  • the linear pressure during lamination is not particularly limited.
  • the linear pressure during lamination is preferably 0.5 N/cm to 20 N/cm, more preferably 1 N/cm to 10 N/cm, and further preferably 1 N/cm to 5 N/cm.
  • the conveying speed during laminating is preferably 0.5 m/min to 5 m/min, more preferably 1.5 m/min to 3 m/min.
  • the method for producing a patterned substrate according to the present disclosure includes a step of pattern-exposing the photosensitive resin layer in the photosensitive transfer material (that is, an exposure step).
  • the photosensitive resin layer in the photosensitive transfer material is pattern-exposed to form an exposed portion and a non-exposed portion on the photosensitive resin layer.
  • the exposed photosensitive resin layer in the photosensitive transfer material when the photosensitive resin layer in the photosensitive transfer material is a positive type, the exposed photosensitive resin layer (so-called exposed portion) has increased solubility in the developing solution due to polarity change.
  • the photosensitive resin layer in the photosensitive transfer material is a negative type, the exposed photosensitive resin layer (so-called unexposed portion) is cured.
  • the pattern exposure method may be exposure through a mask (also called “photomask”) or digital exposure using a laser or the like.
  • the light source for exposure is not particularly limited.
  • the light source for exposure can be appropriately selected depending on the components contained in the photosensitive resin layer.
  • examples of the light source include a light source capable of irradiating light (for example, 365 nm or 405 nm) in a wavelength range in which the exposed portion can be dissolved in the developing solution.
  • examples of the light source include a light source capable of irradiating with light in a wavelength range in which the exposed portion can be cured (for example, 365 nm or 405 nm).
  • Specific examples of the light source include various lasers, light emitting diodes (LEDs), ultrahigh pressure mercury lamps, high pressure mercury lamps, metal halide lamps and the like.
  • Exposure is preferably 5mJ / cm 2 ⁇ 200mJ / cm 2, more preferably 10mJ / cm 2 ⁇ 200mJ / cm 2.
  • the photosensitive resin layer may be pattern-exposed after the temporary support is peeled off from the photosensitive transfer material attached to the substrate, and the photosensitive resin layer may be patterned while leaving the temporary support. You may expose.
  • the method for manufacturing a patterned substrate of the present disclosure includes a step of developing the photosensitive transfer material that has undergone the pattern exposure to form a pattern (that is, a developing step).
  • the developing step when the photosensitive resin layer in the photosensitive transfer material is a positive type, a pattern can be formed by removing the exposed portion of the photosensitive transfer material with a developing solution.
  • the photosensitive resin layer in the photosensitive transfer material is a negative type, the pattern can be formed by removing the non-exposed portion of the photosensitive transfer material with a developing solution.
  • the silver nanowire layer and the thermosetting resin layer are also developed using the pattern of the photosensitive resin layer as a mask, the silver nanowire layer and the thermosetting resin layer can be simultaneously formed with a pattern.
  • the developer is not particularly limited and, for example, a known developer such as the developer described in JP-A-5-72724 can be used.
  • the developer is preferably an alkaline aqueous solution.
  • alkaline compound that can be contained in the alkaline aqueous solution, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, Examples thereof include tetrabutylammonium hydroxide and choline (2-hydroxyethyltrimethylammonium hydroxide).
  • the pH of the alkaline aqueous solution at 25° C. is preferably 8 to 13, more preferably 9 to 12, and even more preferably 10 to 12.
  • the content of the alkaline compound in the alkaline aqueous solution is preferably 0.1% by mass to 5% by mass, and more preferably 0.1% by mass to 3% by mass, based on the total mass of the alkaline aqueous solution.
  • the liquid temperature of the developer is preferably 20°C to 40°C.
  • development methods include paddle development, shower development, shower and spin development, and dip development.
  • JP 2006-23696 A the description in paragraphs [0035] to [0051] of JP 2006-23696 A can be referred to.
  • thermosetting step The method for manufacturing a patterned substrate according to the present disclosure includes a step of thermally curing the thermosetting resin layer in the photosensitive transfer material described above (that is, a thermosetting step).
  • thermosetting resin layer is thermoset.
  • the heating temperature and heating time for thermosetting the thermosetting resin layer are not particularly limited as long as the thermosetting resin layer can be thermoset, and may be appropriately set according to the components contained in the thermosetting resin layer.
  • the heating temperature is preferably 100°C to 180°C, more preferably 110°C to 160°C, and further preferably 120°C to 150°C. When the heating temperature is within the above range, the thermosetting resin layer can be thermoset more efficiently.
  • the heating time is preferably 0.1 minutes to 120 minutes, more preferably 0.5 minutes to 60 minutes, and further preferably 1 minute to 30 minutes. When the heating time is within the above range, discoloration and deformation of the substrate due to heating hardly occur.
  • the heating method is not particularly limited, and a known heating method can be applied.
  • Examples of the heating method include a method of heating by contacting with a heat source such as a hot plate, a method of heating in a heating atmosphere using an oven, and a method of heating with warm air, an infrared heater or the like.
  • the method for manufacturing a circuit board according to the present disclosure includes a step of bonding the above-mentioned photosensitive transfer material and the substrate (bonding step), and a step of pattern-exposing the photosensitive resin layer in the photosensitive transfer material (exposure step). ), a step of developing the photosensitive transfer material that has undergone the pattern exposure to form a pattern (developing step), a step of thermally curing the thermosetting resin layer (thermosetting step), and The step of removing the cured product of the photosensitive resin layer or the photosensitive resin layer (hereinafter, also referred to as "removal step”) is included in this order.
  • the method for manufacturing a circuit board according to the present disclosure includes a bonding step, an exposure step, a developing step, and a thermosetting step in this order, so that the conductive pattern is peeled off from the board even after the removal step. It is possible to manufacture a circuit board that is difficult to manufacture.
  • the bonding step, the exposure step, the development step, and the heat curing step in the circuit board manufacturing method of the present disclosure are the bonding step, the exposure step, the development step, and the heat curing in the above-mentioned “method for manufacturing a patterned substrate”.
  • the steps are synonymous with each other, and the preferred embodiments are also the same, and therefore the description thereof is omitted here.
  • the circuit board manufacturing method of the present disclosure includes a step (removing step) of removing the photosensitive resin layer or the cured product of the photosensitive resin layer in the pattern formed in the developing step.
  • removing step the photosensitive resin layer or a cured product of the photosensitive resin layer in the pattern formed in the developing step
  • the "photosensitive resin layer or a cured product of the photosensitive resin layer in the pattern formed in the developing step” is also referred to as "removed layer”.
  • the photosensitive resin layer or the cured product of the photosensitive resin layer in the pattern is usually formed on the outermost layer of the pattern (that is, among the layers constituting the pattern, the layer arranged at the position farthest from the substrate). It is arranged.
  • a cured product of the photosensitive resin layer for example, a cured product of a negative photosensitive resin layer can be mentioned.
  • the cured product of the negative photosensitive resin layer is formed, for example, by exposing the negative photosensitive resin layer in the exposure step.
  • a method of removing the layer to be removed for example, a method of removing the layer to be removed by chemical treatment can be mentioned, and a method using a removing liquid is preferable.
  • the substrate having the layer to be removed is placed in the removal liquid under stirring at preferably 30° C. to 80° C., more preferably 50° C. to 80° C. for 1 minute to 30 minutes A method of dipping for a minute may be mentioned.
  • the removing liquid is preferably a removing liquid containing 30% by mass or more of water, more preferably a removing liquid containing 50% by mass or more of water, and further preferably a removing liquid containing 70% by mass or more of water.
  • the removing liquid is an inorganic alkali component such as sodium hydroxide, potassium hydroxide or sodium carbonate, or an organic alkali such as a primary amine compound, a secondary amine compound, a tertiary amine compound or a quaternary ammonium salt compound. It is preferable to include components.
  • the content of the alkali component is preferably 0.01% by mass to 20% by mass, and more preferably 0.1% by mass to 10% by mass, based on the total mass of the removing liquid. More preferable.
  • the method for manufacturing a circuit board according to the present disclosure may include steps (so-called other steps) other than the bonding step, the exposure step, the developing step, the thermosetting step, and the removing step.
  • steps other steps
  • a process of exposing the entire surface of the pattern formed through the developing process before the removal process (hereinafter, also referred to as “entire surface exposure process”) can be mentioned.
  • the circuit board manufacturing method of the present disclosure may include a step of exposing the entire surface of the pattern formed through the developing step (entire surface exposing step) before the removing step.
  • the solubility of the photosensitive resin layer in the removal liquid can be further improved.
  • the exposure amount in the overall exposure step is preferably 5mJ / cm 2 ⁇ 1,000mJ / cm 2, more preferably 10mJ / cm 2 ⁇ 800mJ / cm 2, 100mJ / More preferably, it is from cm 2 to 500 mJ/cm 2 .
  • the above-mentioned removal step may be performed after the whole surface exposure step, if necessary.
  • the laminate of the present disclosure includes a substrate, a layer containing a resin obtained by thermosetting (hereinafter, also referred to as “thermosetting resin layer”), and a layer containing silver nanowires (silver nanowire layer).
  • thermosetting resin layer a resin obtained by thermosetting
  • silver nanowire layer a layer containing silver nanowires
  • the laminate of the present disclosure has the substrate, the thermosetting resin layer, and the silver nanowire layer in this order, it is difficult for the conductive pattern formed by the silver nanowire layer to be peeled from the substrate.
  • the laminate of the present disclosure since it has a substrate, a thermosetting resin layer, and a silver nanowire layer in this order, the sheet resistance value increases even when exposed to a humid heat environment. It is possible to realize a circuit board that is difficult to perform and has excellent durability.
  • FIG. 2 is a schematic cross-sectional view showing an example of the layer structure of the laminate of the present disclosure.
  • the laminated body 200 illustrated in FIG. 2 includes the substrate 50, the thermosetting resin layer 40B, and the silver nanowire layer 30 in this order.
  • thermosetting resin layer is a layer obtained by curing the thermosetting resin layer that is the transfer layer, and the silver nanowire layer is the transfer layer.
  • transfer layer means a layer formed by transfer.
  • the laminated body of the present disclosure has a substrate.
  • the substrate in the laminated body of the present disclosure has the same meaning as the substrate described in the above-mentioned “method for manufacturing a patterned substrate”, and the preferred embodiment is also the same, and therefore the description thereof is omitted here.
  • thermosetting resin layer The laminate of the present disclosure has a layer containing a resin obtained by thermosetting (that is, a thermosetting resin layer).
  • the thermosetting resin layer is a layer containing a resin obtained by thermosetting.
  • the heat-cured resin is a cured product of the components described in the above-mentioned "thermosetting resin layer”. Since the thermosetting resin layer is a layer containing a resin that is thermoset, it is difficult to peel from the substrate. The conductive pattern tends to be more difficult to peel from the substrate.
  • the heat-cured resin is preferably a crosslinked resin having a urethane bond. It can be confirmed by a known method [for example, IR (infrared spectroscopy) analysis] that the heat-cured resin has a urethane bond.
  • thermosetting resin layer may contain only one kind of thermosetting resin, or may contain two or more kinds.
  • the content of the thermosetting resin in the thermosetting resin layer is preferably 50% by mass to 100% by mass, and 70% by mass to 100% by mass based on the total mass of the thermosetting resin layer. Is more preferable, and 90% by mass to 100% by mass is further preferable.
  • the content of the thermosetting resin in the thermosetting resin layer is within the above range, it tends to be more difficult to peel from the substrate. Further, even when exposed to a moist heat environment, it is possible to form a circuit board in which the sheet resistance value is less likely to increase and the durability is superior.
  • the thickness of the thermosetting resin layer is not particularly limited and is, for example, preferably 1 nm to 10,000 nm, more preferably 1 nm to 5,000 nm, further preferably 1 nm to 1,000 nm. Particularly preferably, it is 1 nm to 300 nm, and most preferably 20 nm to 100 nm.
  • the thickness of the thermosetting resin layer is within the above range, the thermosetting resin layer tends to be more difficult to peel from the substrate. Further, even when exposed to a moist heat environment, it is possible to form a circuit board in which the sheet resistance value is less likely to increase and the durability is superior.
  • the thickness of the thermosetting resin layer is measured by the following method.
  • the arithmetic mean value of the thickness of the thermosetting resin layer measured at five randomly selected points is calculated, and the obtained value is calculated as the thickness of the thermosetting resin layer. Satoshi
  • the cross-sectional observation image in the thickness direction of the thermosetting resin layer can be obtained using a scanning electron microscope (SEM).
  • the contact resistance of the thermosetting resin layer is preferably 200 ⁇ or less, more preferably 1 ⁇ to 200 ⁇ , more preferably 1 ⁇ to 100 ⁇ , and more preferably 1 ⁇ to 50 ⁇ . More preferable.
  • the contact resistance of the thermosetting resin layer is measured by the TLM (Transmission Line Model) method.
  • the specific method is as follows. Seven copper electrodes (thickness: 300 nm, width: 500 ⁇ m) arranged on a substrate (for example, a cycloolefin polymer film) in parallel and independently at intervals of 2 mm, 4 mm, 6 mm, 8 mm, 12 mm, and 20 mm. ) Is formed. Next, after bonding one photosensitive transfer material on the seven copper electrodes, the thermosetting resin layer is thermally cured by heating, so that the silver nano-particles are formed on the copper electrodes via the thermosetting resin layer. A test body having a structure in which wire layers are laminated is produced.
  • the silver nanowire layer is arranged so as to cross the seven copper electrodes, and the angle formed by each copper electrode and the silver nanowire layer is 90°.
  • the contact resistance of the thermosetting resin layer is obtained by plotting the relationship between the resistance (vertical axis) and the distance (horizontal axis) between the copper electrodes.
  • the laminate of the present disclosure has a layer containing silver nanowires (that is, a silver nanowire layer).
  • the silver nanowire layer in the layered product of the present disclosure has the same meaning as the silver nanowire layer described in the above section “Photosensitive transfer material”, and the preferred embodiment is also the same, and therefore the description thereof is omitted here.
  • Method for manufacturing laminated body The method for producing the laminate of the present disclosure is not particularly limited, and a known method can be applied.
  • the method for manufacturing the laminated body of the present disclosure for example, the methods described in the above-mentioned “method for manufacturing patterned substrate” and “method for manufacturing circuit board” can be applied.
  • the touch panel of the present disclosure has the laminated body of the present disclosure. Since the touch panel of the present disclosure has the laminated body of the present disclosure, the conductive pattern formed by the silver nanowire layer is difficult to peel off from the substrate. Further, since the touch panel of the present disclosure has the laminated body of the present disclosure, the sheet resistance value does not easily increase even when exposed to a humid heat environment, and the durability is excellent.
  • the layered product in the touch panel of the present disclosure has the same meaning as the layered product described in the section “Layered product” described above, and the preferred embodiment is also the same, and thus the description thereof is omitted here.
  • the touch panel of the present disclosure when the laminated body is used as a circuit board, it is preferable that a part of the region including the thermosetting resin layer and the silver nanowire layer in the laminated body be patterned.
  • the detection method in the touch panel of the present disclosure includes a resistance film method, a capacitance method, an ultrasonic method, an electromagnetic induction method, an optical method, and the like.
  • the capacitance method is preferable as the detection method.
  • a so-called in-cell type for example, those described in FIGS. 5, 6, 7, and 8 of JP 2012-517051 A
  • a so-called on-cell type for example, JP2013-168125A
  • OGS One Glass Solution
  • TOL Touch-on-Lens
  • GG Garnier-on-Lens
  • the manufacturing method of the touch panel of the present disclosure includes the manufacturing method of the circuit board of the present disclosure described above. That is, the manufacturing method of the circuit board of the present disclosure can be applied to the manufacturing method of the touch panel of the present disclosure.
  • the method of manufacturing the circuit board in the method of manufacturing the touch panel of the present disclosure has the same meaning as the method of manufacturing the circuit board described in the above-mentioned “method of manufacturing a circuit board”, and preferable aspects are also the same. The description is omitted.
  • FIG. 3 shows an example of a mask pattern used in the touch panel manufacturing method of the present disclosure.
  • the pattern A shown in FIG. 3 can be used when pattern-exposing a positive photosensitive resin layer.
  • the solid line portion SL and the gray portion G are light-shielding portions, and the dotted line portion DL is a virtual alignment alignment frame.
  • the touch panel manufacturing method of the present disclosure for example, the positive photosensitive resin layer is exposed through the mask having the pattern A shown in FIG. 3 to form a pattern corresponding to the solid line portion SL and the gray portion G.
  • a touch panel on which circuit wiring is formed can be manufactured.
  • the weight average molecular weight of the resin is the weight average molecular weight determined in terms of polystyrene by gel permeation chromatography (GPC).
  • the glass transition temperature of the thermosetting resin layer is the glass transition temperature obtained by the method described above.
  • TEM transmission electron microscope
  • An additive solution G was prepared by dissolving 5 g of glucose powder in 1400 mL of pure water.
  • additive solution H was prepared by dissolving 5 g of HTAB (hexadecyl-trimethylammonium bromide) powder in 275 mL of pure water.
  • an ultrafiltration membrane [trade name: Microza (registered trademark) UF module SIP1013, molecular weight cutoff: 6,000, manufactured by Asahi Kasei Co., Ltd.], a magnet pump, and a stainless steel cup were used. Ultrafiltration was performed using an ultrafiltration device connected using a tube. Specifically, the cooled liquid was put into a stainless steel cup, and a magnet pump was operated to perform ultrafiltration. When the filtrate from the ultrafiltration membrane reached 50 mL, 950 mL of pure water was added to the stainless cup for washing. After repeating this washing 10 times, concentration was performed until the amount of the liquid became 50 mL.
  • the concentrated liquid was diluted with a mixed liquid of pure water and methanol (volume ratio of pure water and methanol: 60/40) to obtain a silver nanowire layer forming coating liquid.
  • the coating liquid for forming the silver nanowire layer was applied to the cycloolefin polymer film.
  • the coating amount of the coating liquid for forming the silver nanowire layer was such that the wet film thickness was 20 ⁇ m.
  • the sheet resistance of the silver nanowire layer after drying was 60 ⁇ / ⁇ .
  • a non-contact type eddy current type resistance measuring instrument [trade name: EC-80P, manufactured by Napson Corporation] was used to measure the sheet resistance.
  • the silver nanowire contained in the coating liquid for forming the silver nanowire layer had a diameter of 17 nm and a length of 35 ⁇ m.
  • thermosetting resin layer [Preparation of coating liquid for forming thermosetting resin layer] ⁇ Materials A-1 to A-4> The components were mixed so as to have the composition shown in Table 1 to prepare materials A-1 to A-4 which are coating liquids for forming a thermosetting resin layer.
  • Comparative material B-1 which is a non-thermosetting resin layer forming coating liquid (so-called resin layer forming coating liquid having no thermosetting property) were prepared by mixing the components so as to have the composition shown in Table 1. did.
  • Comparative material B-2 Each component was mixed so as to have the composition shown in Table 2 to prepare Comparative Material B-2 which is a non-thermosetting resin layer forming coating liquid (so-called resin layer forming coating liquid having no thermosetting property). did.
  • the compounds N1 to N5 which are the binder polymers shown in Tables 1 and 2, are the compounds shown below.
  • the numerical value written together with each structural unit in the compounds N1 to N5 represents the content ratio (molar ratio) of each structural unit.
  • Compound N1 a resin having the structure shown below [weight average molecular weight: 21,000, acid value: 0.5 mmol/g, hydroxyl functional group concentration: 2.8 mmol/g, glass transition temperature: -5°C]
  • Compound N2 Resin having the structure shown below [weight average molecular weight: 5,500, acid value: 1.0 mmol/g, functional group concentration of blocked isocyanate group: 4.1 mmol/g, glass transition temperature: 20°C]
  • Compound N3 Resin having a structure shown below [weight average molecular weight: 23,000, acid value: 0.5 mmol/g, functional group concentration of blocked isocyanate group: 2.5 mmol/g, functional group concentration of hydroxyl group: 0.5 mmol /G, glass transition temperature: -1°C]
  • Compound N4 Resin having the structure shown below [weight average molecular weight: 12,000, acid value: 32 mgKOH/g]
  • Compound N5 Resin having the structure shown below [weight average molecular weight: 10,000, acid value: 47 mgKOH/g]
  • thermosetting resin layer The glass transition temperature of the thermosetting resin layer formed by using the materials A-5 to A-8 which are the coating liquid for forming the thermosetting resin layer was measured.
  • the specific method is as follows. Each of the materials A-5 to A-8 was spin-coated on a glass substrate under the conditions of 500 rpm and 20 seconds to form a coating film. Then, the formed coating film was dried at 100° C. for 1 minute using a hot plate to obtain a thermosetting resin layer. When the obtained thermosetting resin layer was scraped and analyzed by DSC (Differential scanning calorimetry), the glass transition temperature of the thermosetting resin layer was in the range of -10°C to 50°C. A differential scanning calorimeter (model: DSC6200) manufactured by Seiko Instruments Inc. was used for the DSC analysis.
  • Compound D which is a polymer shown in Table 3, is a compound shown below.
  • the numerical value written together with each structural unit in the compound D represents the content ratio (molar ratio) of each structural unit.
  • Compound D Resin having the structure shown below [weight average molecular weight: 25,000]
  • Compound E which is a photoacid generator shown in Table 3, is the compound shown below.
  • Compound B which is the binder polymer described in Table 4, is the compound shown below.
  • the numerical value written together with each structural unit in the compound B represents the content ratio (molar ratio) of each structural unit.
  • Compound B Resin having the structure shown below [weight average molecular weight: 20,000, acid value: 95 mgKOH/g]
  • the coating liquid for forming the silver nanowire layer was applied onto the positive photosensitive resin layer using a slit-shaped nozzle at an application amount such that the wet film thickness was 20 ⁇ m to form a coating film.
  • the coating film was dried at a drying temperature of 100° C. to form a silver nanowire layer (that is, a layer containing silver nanowires).
  • the formed silver nanowire layer had a thickness of 100 nm.
  • thermosetting resin layer that is, any of materials A-1 to A-8) or non-thermosetting selected according to the description in Table 5
  • a comparative material that is, comparative material B-1 or B-2 which is a coating liquid for forming a functional resin layer was applied to form a coating film.
  • the coating amounts of the materials A-1 to A-8 and the comparative materials B-1 and B-2 were such that the thickness of the layer after drying was the thickness shown in Table 5.
  • the coating film was dried at a drying temperature of 100° C. to form a thermosetting resin layer or a non-thermosetting resin layer.
  • a protective film [trade name: Lumirror (registered trademark) 16KS40, polyethylene terephthalate film, thickness: 16 ⁇ m, manufactured by Toray Industries, Inc.] was pressure-bonded onto the thermosetting resin layer or the non-thermosetting resin layer. ..
  • the photosensitive transfer materials of Examples 1 to 4 and Examples 9 to 12 and Comparative Examples 1 and 3 were prepared.
  • thermosetting property selected according to the description in Table 5 using a slit nozzle On the protective film [trade name: Lumirror (registered trademark) 16KS40, polyethylene terephthalate film, thickness: 16 ⁇ m, manufactured by Toray Industries, Inc.], a thermosetting property selected according to the description in Table 5 using a slit nozzle.
  • a material that is a coating liquid for forming a resin layer that is, any of materials A-1 to A-8) or a comparative material that is a coating liquid for forming a non-thermosetting resin layer (that is, comparative material B-1 or B- 2) was applied to form a coating film.
  • the coating amounts of the materials A-1 to A-8 and the comparative materials B-1 and B-2 were such that the thickness of the layer after drying was the thickness shown in Table 5.
  • the coating film was dried at a drying temperature of 100° C. to form a thermosetting resin layer or a non-thermosetting resin layer.
  • a coating liquid for forming a silver nanowire layer is applied onto the thermosetting resin layer or the non-thermosetting resin layer using a slit-shaped nozzle in an application amount such that a wet film thickness is 20 ⁇ m, and then applied.
  • a film was formed.
  • the coating film was dried at a drying temperature of 100° C. to form a silver nanowire layer (that is, a layer containing silver nanowires).
  • the formed silver nanowire layer had a thickness of 100 nm.
  • the material BN-1 which is a coating liquid for forming a negative photosensitive resin layer was coated on the silver nanowire layer to form a coating film.
  • the coating amount of the material BN-1 was such that the thickness of the layer after drying was 3 ⁇ m.
  • the coating film was dried at a drying temperature of 100° C. to form a negative photosensitive resin layer.
  • a temporary support [trade name: Lumirror (registered trademark) 16KS40, polyethylene terephthalate film, thickness: 16 ⁇ m, manufactured by Toray Industries, Inc.] was pressure-bonded onto the negative photosensitive resin layer to form Example 5. 8 to Examples 13 to 16 and Comparative Examples 2 and 4 were prepared.
  • a multilayer body was prepared according to the following procedure.
  • the photosensitive transfer material from which the protective film has been peeled off is attached to a transparent film substrate (cycloolefin polymer film, thickness: 38 ⁇ m, refractive index: 1.53) (hereinafter referred to as “laminating” in this paragraph).
  • a multi-layer body was obtained.
  • the lamination process was performed using a vacuum laminator manufactured by MCK Co., Ltd. under the conditions of the transparent film substrate temperature: 40° C., the rubber roller temperature: 100° C., the linear pressure: 3 N/cm, and the conveying speed: 2 m/min. went.
  • the laminating process the surface exposed by peeling the protective film from the photosensitive transfer material was brought into contact with the surface of the transparent film substrate.
  • a transparent electrode pattern film was produced according to the following procedure using the above-mentioned multilayer bodies produced by using the photosensitive transfer materials of Examples 1 to 4 and Examples 9 to 12 and Comparative Examples 1 and 3.
  • a proximity type exposure machine manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.
  • the exposure mask quartz exposure mask having a transparent electrode forming pattern
  • the temporary support is brought into close contact with each other, and the temporary support is provided.
  • the positive photosensitive resin layer was pattern-exposed through the body with an exposure amount of 100 mJ/cm 2 (i-line). After the temporary support was peeled off, development treatment was carried out at 32° C.
  • thermosetting resin layer or the non-thermosetting resin layer, the silver nanowire layer, and the photosensitive resin layer were patterned.
  • air was blown to the transparent film substrate from which the residue was removed to remove the moisture on the transparent film substrate, and then heat treatment was performed at 145° C. for 10 minutes to obtain a patterned substrate.
  • the exposure amount of 400 mJ/cm 2 (i-line) was applied to the positive type photosensitivity remaining on the patterned substrate.
  • the positive photosensitive resin layer is removed by treatment with a 1% by mass aqueous solution of sodium carbonate at 32° C. for 60 seconds, and a transparent electrode having a patterned silver nanowire layer A pattern film (so-called circuit board) was produced.
  • the change in sheet resistance before and after the wet heat test was evaluated according to the following evaluation criteria. If the evaluation result was "A” or "B", it was judged to be within the practically acceptable range. In the following evaluation criteria, “A” indicates the case where the durability is the best, and “C” indicates the case where the durability is the worst.
  • thermosetting resin layer was measured by the TLM (Transmission Line Model) method.
  • the specific method is as follows. Seven coppers arranged on the substrate (cycloolefin polymer film, thickness: 38 ⁇ m, refractive index: 1.53) at intervals of 2 mm, 4 mm, 6 mm, 8 mm, 12 mm, and 20 mm in parallel and independently of each other. An electrode (thickness: 300 nm, width: 500 ⁇ m) was formed. Next, the photosensitive transfer materials of Examples 1 to 8 from which the protective film was peeled off were adhered to the seven copper electrodes, respectively, to form a silver nanowire layer on the copper electrodes via a thermosetting resin layer.
  • a test body having a laminated structure was prepared.
  • the silver nanowire layer was arranged so as to cross the seven copper electrodes, and the angle formed by each copper electrode and the silver nanowire layer was 90°.
  • the contact resistance of the thermosetting resin layer was obtained by plotting the relationship between the resistance (vertical axis) and the distance (horizontal axis) between the copper electrodes.
  • a resistivity meter [trade name: Loresta GP, manufactured by Mitsubishi Chemical Analytech Co., Ltd.] was used to measure the resistance between the copper electrodes.
  • the contact resistance of the thermosetting resin layer of each of the photosensitive transfer materials of Examples 1 to 8 was 200 ⁇ or less.
  • the sample was subjected to a heat treatment at 145° C. for 10 minutes to cure the thermosetting resin layer, and the contact resistance was measured in the same manner.
  • the contact resistance of each of the layers containing the resin was 200 ⁇ or less.
  • the photosensitive materials of Comparative Examples 1 to 4 having a temporary support, a photosensitive resin layer, a silver nanowire layer, and a non-thermosetting resin layer (that is, a resin layer having no thermosetting property) in this order. It was confirmed that the conductive pattern formed by using the conductive transfer material was more easily peeled from the substrate than the conductive patterns formed by using the photosensitive transfer materials of Examples 1 to 16. In addition, the transparent electrode pattern films produced using the photosensitive transfer materials of Comparative Examples 1 to 4 were more durable than the transparent electrode pattern films produced using the photosensitive transfer materials of Examples 1 to 16. It was confirmed that it was inferior in sex.

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Abstract

L'invention concerne un matériau de transfert photosensible ayant un support temporaire, une couche de résine photosensible, une couche de nanofil d'argent contenant un nanofil d'argent et une couche de résine thermodurcissable, dans cet ordre ; un stratifié ; un panneau tactile ; un procédé de production d'un substrat à motifs ; un procédé de production d'une carte de circuit imprimé ; et un procédé de production d'un panneau tactile.
PCT/JP2019/042577 2018-12-27 2019-10-30 Matériau de transfert photosensible, stratifié, panneau tactile, procédé de production de substrat à motifs, procédé de production de carte de circuit imprimé et procédé de production de panneau tactile WO2020137144A1 (fr)

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JP2010251186A (ja) * 2009-04-17 2010-11-04 Hitachi Chem Co Ltd 導電性転写フィルム及びそれを用いた導電性パターンの形成方法
WO2011155412A1 (fr) * 2010-06-07 2011-12-15 日立化成工業株式会社 Composition de résine photosensible, élément photosensible comprenant la composition, procédé de formation d'un septum pour un dispositif d'affichage d'image, procédé de fabrication d'un dispositif d'affichage d'image et dispositif d'affichage d'image
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