WO2021033451A1 - 感光性転写部材、回路配線の製造方法、タッチパネルの製造方法 - Google Patents

感光性転写部材、回路配線の製造方法、タッチパネルの製造方法 Download PDF

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Publication number
WO2021033451A1
WO2021033451A1 PCT/JP2020/026806 JP2020026806W WO2021033451A1 WO 2021033451 A1 WO2021033451 A1 WO 2021033451A1 JP 2020026806 W JP2020026806 W JP 2020026806W WO 2021033451 A1 WO2021033451 A1 WO 2021033451A1
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Prior art keywords
resin layer
photosensitive resin
photosensitive
layer
transfer member
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Ceased
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PCT/JP2020/026806
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English (en)
French (fr)
Japanese (ja)
Inventor
一真 両角
隆志 有冨
藤本　進二
知樹 松田
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Fujifilm Corp
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Fujifilm Corp
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Priority to CN202080058305.1A priority Critical patent/CN114270262A/zh
Priority to JP2021540663A priority patent/JP7649746B2/ja
Publication of WO2021033451A1 publication Critical patent/WO2021033451A1/ja
Anticipated expiration legal-status Critical
Priority to JP2024023774A priority patent/JP2024063054A/ja
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06—Hydrocarbons
    • C08F212/08—Styrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F257/00—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00
    • C08F257/02—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00 on to polymers of styrene or alkyl-substituted styrenes
    • 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
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • 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
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • G—PHYSICS
    • G06—COMPUTING OR CALCULATING; 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
    • 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
    • H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
    • H05K3/06—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding the conductive material being removed chemically or electrolytically, e.g. by photo-etch process

Definitions

  • the present invention relates to a method for manufacturing a photosensitive transfer member, a circuit wiring, and a method for manufacturing a touch panel.
  • a display device organic electroluminescence (EL) display device, liquid crystal display device, etc.
  • a touch panel such as a capacitance type input device
  • the electrode pattern corresponding to the sensor of the visual recognition part, the peripheral wiring part, and the wiring of the take-out wiring part are wired.
  • the conductive layer pattern such as is provided inside the touch panel.
  • a layer (photosensitive layer) of a photosensitive resin composition is provided on a substrate by using a photosensitive transfer member. A method of exposing the photosensitive layer through a mask having a desired pattern and then developing the photosensitive layer is widely adopted.
  • Patent Document 1 in a pattern forming material having a cushion layer and a photosensitive layer in this order on a support, the photosensitive layer contains a fluorescent whitening agent as a sensitizer, and the photosensitive layer is exposed and developed.
  • a pattern-forming material is described in which the minimum energy of light used for exposure in is specified.
  • the means for solving the above problems include the following aspects.
  • the polymerizable compound B1 having two ethylenically unsaturated groups, and the content of the structural unit derived from styrene with respect to the total mass of the polymer A is more than 40% by mass
  • the arithmetic mean roughness Ra value of the surface of the cover film in contact with the photosensitive resin layer is 0.05 ⁇ m or less.
  • the photosensitive transfer member according to any one of [1] to [11] and the substrate having the conductive layer are brought into contact with the surface of the photosensitive resin layer on the side not facing the temporary support.
  • a method for producing a resin pattern which comprises a step of bonding the photosensitive resin layers together, a step of pattern-exposing the photosensitive resin layer, and a step of developing the exposed photosensitive resin layer to form a resin pattern.
  • the photosensitive transfer member according to any one of [1] to [11] has at least one selected from the group consisting of an alkylene glycol ether solvent and an alkylene glycol ether acetate solvent on the surface of the temporary support.
  • the step of drying the coating film of the thermoplastic resin composition to form the thermoplastic resin layer and the process of forming the thermoplastic resin layer on the surface of the thermoplastic resin layer are carried out with water and a water-mixable organic solvent.
  • the intermediate layer composition containing at least one selected from the group consisting of the step of drying the coating film of the intermediate layer composition to form the intermediate layer, and the step of forming the intermediate layer, and the polymer A on the surface of the intermediate layer.
  • the coating film of the photosensitive resin composition is applied.
  • the method for producing a resin pattern according to [12] which is a photosensitive transfer member produced by a production method including a step of drying to form a photosensitive resin layer.
  • a conductive layer in a region where the resin pattern is not arranged is provided.
  • a method of manufacturing a circuit wiring which includes a step of etching.
  • a conductive layer in a region where the resin pattern is not arranged is formed.
  • a method for manufacturing a touch panel which comprises a step of forming wiring for a touch panel by etching.
  • the present invention it is possible to provide a photosensitive transfer member capable of producing a resin pattern having better resolution. Further, according to the present invention, it is possible to provide a method for manufacturing a circuit wiring and a method for manufacturing a touch panel.
  • the notation that does not describe substitution and non-substitution includes those having no substituent as well as those having a substituent.
  • alkyl group includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
  • (meth) acrylic acid represents both acrylic acid and methacrylic acid, or one of them
  • (meth) acrylate” represents both or one of acrylate and methacrylate.
  • the chemical structural formula in the present specification may be described by a simplified structural formula in which a hydrogen atom is omitted.
  • the amount (content, etc.) of each component means the total amount (total content, etc.) of the plurality of substances, unless otherwise specified, when a plurality of substances contained in each component are present.
  • the numerical range represented by using “-” means a range including the numerical values before and after "-" as the lower limit value and the upper limit value.
  • “% by mass” and “% by weight” are synonymous, and “parts by mass” and “parts by weight” are synonymous.
  • the term “process” does not mean only an independent process, and even if it cannot be clearly distinguished from other processes, the term “process” is used as long as the process achieves the intended purpose. included.
  • the term “exposure” includes not only exposure using light but also drawing using particle beams such as electron beams and ion beams, unless otherwise specified.
  • the light used for exposure includes, for example, the emission line spectrum of a mercury lamp, far ultraviolet rays typified by an excimer laser, extreme ultraviolet rays (EUV (Extreme ultraviolet lithography) light), and active rays (active energy rays) such as X rays. ).
  • the weight average molecular weight (Mw) and the number average molecular weight (Mn) use columns of TSKgel GMHxL, TSKgel G4000HxL, and TSKgel G2000HxL (all trade names manufactured by Toso Co., Ltd.). It is a molecular weight converted by detecting a compound in a THF (tetrahydrofuran) solvent with a differential refractometer by a gel permeation chromatography (GPC) analyzer, and using polystyrene as a standard substance. In the present specification, a combination of two or more preferred embodiments is a more preferred embodiment.
  • the photosensitive transfer member according to the present invention includes at least a temporary support and a photosensitive resin layer.
  • the temporary support and the photosensitive resin layer may be directly laminated without interposing another layer, or may be laminated through another layer. Further, another layer may be laminated on the surface of the photosensitive resin layer opposite to the surface facing the temporary support. Examples of the layer other than the temporary support and the photosensitive resin layer include a thermoplastic resin layer, an intermediate layer, and a cover film.
  • the photosensitive transfer member according to the present invention includes a temporary support.
  • the temporary support is a support that supports a photosensitive resin layer or a laminate containing a photosensitive resin layer and is removable.
  • the temporary support preferably has light transmission property from the viewpoint of enabling exposure of the photosensitive resin layer through the temporary support when pattern-exposing the photosensitive resin layer.
  • “having light transmittance” means that the transmittance of light of the wavelength used for pattern exposure is 50% or more.
  • the temporary support preferably has a light transmittance of 60% or more, preferably 70% or more, at a wavelength (more preferably 365 nm) used for pattern exposure. Is more preferable.
  • the transmittance of the layer included in the photosensitive transfer member refers to the light emitted through the layer with respect to the intensity of the incident light when the light is incident in the direction perpendicular to the main surface of the layer (thickness direction). It is a ratio of the intensity of light emission, and is measured using MCPD Series manufactured by Otsuka Electronics Co., Ltd.
  • Examples of the material constituting the temporary support include a glass substrate, a resin film and paper, and a resin film is preferable from the viewpoint of strength, flexibility and light transmission.
  • Examples of the resin film include polyethylene terephthalate (PET: polyethylene terephthalate) film, cellulose triacetate film, polystyrene film and polycarbonate film. Among them, PET film is preferable, and biaxially stretched PET film is more preferable.
  • the thickness (layer thickness) of the temporary support is not particularly limited, and the strength as the support, the flexibility required for bonding to the circuit wiring forming substrate, and the light required in the first exposure step. From the viewpoint of transparency, it may be selected according to the material.
  • the thickness of the temporary support is preferably in the range of 5 to 100 ⁇ m, and more preferably in the range of 10 to 50 ⁇ m from the viewpoint of ease of handling and versatility.
  • the film used as the temporary support has no deformation such as wrinkles or scratches.
  • the number of fine particles, foreign substances, and defects contained in the temporary support is small.
  • the total number of fine particles, foreign substances and defects having a diameter of 1 ⁇ m or more is preferably 50 pieces / 10 mm 2 or less, more preferably 10 pieces / 10 mm 2 or less, and 3 pieces / 10 mm 2 or less. More preferably, 0 pieces / 10 mm 2 is particularly preferable.
  • Preferred embodiments of the provisional support include, for example, paragraphs 0017 to 0018 of JP2014-085643), paragraphs 0019 to 0026 of JP2016-0273363, and paragraphs of International Publication No. 2012/081680.
  • 0041 to 0057, paragraphs 0029 to 0040 of WO 2018/179370 are mentioned, and the contents of these publications are incorporated herein by reference.
  • the photosensitive transfer member according to the present invention includes a photosensitive resin layer.
  • the photosensitive resin layer used in the present invention has a layer thickness of 8 ⁇ m or less, a polymer A having a structural unit derived from styrene, and a polymerizable compound B1 having an aromatic ring and two ethylenically unsaturated groups. And contains. Further, the mass ratio of the content of the polymerizable compound B1 to the content of the polymerizable compound B having a polymerizable group and the content of the structural unit derived from styrene in the polymer A exceeds a predetermined amount is determined. It is more than a fixed amount.
  • the present inventors have found that a resin pattern having better resolution can be produced by using a photosensitive transfer member having the above structure.
  • the photosensitive resin layer contains a predetermined amount of the polymer A and a predetermined amount of the polymerizable compound B1
  • the content of the aromatic ring in the photosensitive resin layer is increased. It is presumed that the resolution of the resin pattern is improved because the swelling of the photosensitive resin layer during development is suppressed.
  • the photosensitive resin layer is preferably a negative photosensitive resin layer in which the solubility of the exposed portion in the developing solution is reduced by exposure and the non-exposed portion is removed by development.
  • the photosensitive resin layer is not limited to the negative photosensitive resin layer, and even if the photosensitive resin layer is a positive photosensitive resin layer in which the solubility of the exposed portion in the developing solution is improved by exposure and the exposed portion is removed by development. Good.
  • the polymer A has a structural unit derived from styrene, and the content of the structural unit derived from styrene with respect to the total mass of the polymer A (hereinafter, also referred to as “styrene content”) is more than 40% by mass. ..
  • the polymer A may be composed of only the structural unit derived from styrene, or may have a structural unit other than the structural unit derived from styrene. That is, the upper limit of the styrene content of the polymer A is not particularly limited, and the styrene content may be 100% by mass or less.
  • the styrene content of the polymer A is more excellent in the resolution of the resin pattern formed by suppressing the swelling of the photosensitive resin layer by the developing solution (hereinafter, also simply referred to as “resolution”). Therefore, 50% by mass or more is preferable.
  • the styrene content of the polymer A is preferably 70% by mass or less, more preferably 60% by mass or less, because the resin pattern is excellent in peelability from the substrate (hereinafter, also simply referred to as “peeling property”).
  • the polymer A may have a structural unit derived from a polymerizable monomer other than styrene that can be polymerized with styrene.
  • the polymer A preferably has a structural unit having an acid group from the viewpoint of excellent developability.
  • the acid group include a carboxy group, a sulfo group, a phosphoric acid group and a phosphonic acid group.
  • the polymer A preferably has a structural unit having a carboxy group, and more preferably has a structural unit derived from (meth) acrylic acid.
  • the content of the constituent unit having an acid group (more preferably, the constituent unit derived from (meth) acrylic acid) in the polymer A is preferably 10 to 40% by mass, preferably 20 to 30% by mass, based on the total mass of the polymer A. More preferably by mass.
  • the polymer A preferably further has a structural unit derived from the (meth) acrylic acid ester from the viewpoint of excellent compatibility.
  • the (meth) acrylic acid ester include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, and (meth) acrylic.
  • examples thereof include (meth) acrylic acid alkyl esters having an alkyl group having 1 to 8 carbon atoms such as hexyl acid, heptyl (meth) acrylate, octyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate.
  • (meth) acrylic acid ester a (meth) acrylic acid alkyl ester having an alkyl group having 1 to 4 carbon atoms is preferable, and methyl (meth) acrylate or ethyl (meth) acrylate is more preferable.
  • the polymer A may have one type of structural unit derived from the (meth) acrylic acid ester alone, or may have two or more types.
  • the content of the structural unit derived from the (meth) acrylic acid ester in the polymer A is preferably 5 to 40% by mass, more preferably 10 to 30% by mass, based on the total mass of the polymer A.
  • the polymer A preferably has both a structural unit derived from (meth) acrylic acid and a structural unit derived from (meth) acrylic acid ester.
  • the total content of the structural unit derived from (meth) acrylic acid and the structural unit derived from (meth) acrylic acid ester is 60% by mass or less, which is more excellent in resolution and therefore less than 50% by mass. Is preferable.
  • the method for producing the polymer A is not particularly limited, and for example, the polymer A is produced by a known method of radically polymerizing styrene and a polymerizable monomer other than styrene, which is an optional component, in the presence of a polymerization initiator. do it.
  • the polymerization method at this time include a bulk polymerization method, a suspension polymerization method, an emulsion polymerization method and a solution polymerization method.
  • the acid value of the polymer A is preferably 220 mgKOH / g or less, more preferably less than 200 mgKOH / g, and more preferably 190 mgKOH / g, from the viewpoint of better resolution by suppressing the swelling of the photosensitive resin layer due to the developing solution. Less than is more preferred.
  • the lower limit of the acid value of the polymer A is not particularly limited, but from the viewpoint of more excellent developability, 60 mgKOH / g or more is preferable, 155 mgKOH / g or more is more preferable, and 170 mgKOH / g or more is further preferable.
  • the acid value is the mass [mg] of potassium hydroxide required to neutralize 1 g of the sample, and the unit is described as mgKOH / g in the present specification.
  • the acid value can be calculated, for example, from the average content of acid groups in the compound.
  • the acid value of the polymer A may be adjusted according to the type of the structural unit constituting the polymer A and the content of the structural unit containing an acid group.
  • the weight average molecular weight (Mw) of the polymer A is preferably 1,000 or more, more preferably 10,000 to 100,000, and even more preferably 20,000 to 50,000.
  • the photosensitive resin layer may contain one type of polymer A alone, or may contain two or more types of polymer A.
  • the content of the polymer A in the photosensitive resin layer is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, and 30 to 70% by mass with respect to the total mass of the photosensitive resin layer from the viewpoint of photosensitive. % Is more preferable.
  • the photosensitive resin layer contains a polymerizable compound B having a polymerizable group.
  • a part or all of the polymerizable compound B contained in the photosensitive resin layer is the polymerizable compound B1 described later.
  • the "polymerizable compound” means a compound that polymerizes under the action of a polymerization initiator described later, and is different from the resin A described above.
  • the polymerizable group contained in the polymerizable compound B is not particularly limited as long as it is a group involved in the polymerization reaction, and for example, an ethylenically unsaturated group such as a vinyl group, an acryloyl group, a methacryloyl group, a styryl group and a maleimide group can be used. Groups having; and groups having cationically polymerizable groups such as epoxy groups and oxetane groups can be mentioned. As the polymerizable group, a group having an ethylenically unsaturated group is preferable, and an acryloyl group or a metaacryloyl group is more preferable.
  • a compound having one or more ethylenically unsaturated groups is preferable in that the photosensitive resin layer is more photosensitive, and two or more in one molecule.
  • a compound having an ethylenically unsaturated group is more preferable.
  • the number of ethylenically unsaturated groups contained in one molecule of the ethylenically unsaturated compound is preferably 6 or less, more preferably 3 or less, and 2 or less in terms of excellent resolution and peelability. More preferred.
  • the photosensitive resin layer is bifunctional or trifunctional having two or three ethylenically unsaturated groups in one molecule in that the photosensitive resin layer has a better balance of photosensitivity, resolution and peelability. It is preferable to contain an ethylenically unsaturated compound, and more preferably to contain a bifunctional ethylenically unsaturated compound having two ethylenically unsaturated groups in one molecule.
  • the content of the bifunctional ethylenically unsaturated compound in the photosensitive resin layer with respect to the content of the polymerizable compound B is preferably 60% by mass or more, more preferably more than 70% by mass, and 90% by mass from the viewpoint of excellent peelability. % Or more is more preferable.
  • the upper limit is not particularly limited and may be 100% by mass. That is, all the polymerizable compounds B contained in the photosensitive resin layer may be bifunctional ethylenically unsaturated compounds. Further, as the ethylenically unsaturated compound, a (meth) acrylate compound having a (meth) acryloyl group as a polymerizable group is preferable.
  • the photosensitive resin layer according to the present invention contains an aromatic ring and a polymerizable compound B1 having two ethylenically unsaturated groups.
  • the polymerizable compound B1 is a bifunctional ethylenically unsaturated compound having one or more aromatic rings in one molecule among the above-mentioned polymerizable compounds B.
  • the mass ratio of the content of the polymerizable compound B1 to the content of the polymerizable compound B in the photosensitive resin layer according to the present invention is 55% by mass or more.
  • the content of the polymerizable compound B1 in the photosensitive resin layer with respect to the content of the polymerizable compound B is preferably more than 60% by mass, more preferably more than 70% by mass, and more preferably 80% by mass from the viewpoint of better resolution. Super is more preferred.
  • the upper limit is not particularly limited, but from the viewpoint of peelability, 99% by mass or less is preferable, and 95% by mass or less is more preferable.
  • aromatic ring contained in the polymerizable compound B1 examples include aromatic hydrocarbon rings such as benzene ring, naphthalene ring and anthracene ring, thiophene ring, furan ring, pyrrole ring, imidazole ring, triazole ring and pyridine ring. Heterocycles and fused rings thereof are mentioned, and aromatic hydrocarbon rings are preferable, and benzene rings are more preferable.
  • the aromatic ring may have a substituent.
  • the polymerizable compound B1 may have only one aromatic ring, or may have two or more aromatic rings.
  • the polymerizable compound B1 preferably has a bisphenol structure from the viewpoint of improving the resolution by suppressing the swelling of the photosensitive resin layer due to the developing solution.
  • the bisphenol structure include a bisphenol A structure derived from bisphenol A (2,2-bis (4-hydroxyphenyl) propane) and a bisphenol derived from bisphenol F (2,2-bis (4-hydroxyphenyl) methane).
  • examples thereof include an F structure and a bisphenol B structure derived from bisphenol B (2,2-bis (4-hydroxyphenyl) butane), and a bisphenol A structure is preferable.
  • Examples of the polymerizable compound B1 having a bisphenol structure include a compound having a bisphenol structure and two polymerizable groups (preferably (meth) acryloyl groups) bonded to both ends of the bisphenol structure. Both ends of the bisphenol structure and the two polymerizable groups may be directly bonded or may be bonded via one or more alkyleneoxy groups. As the alkyleneoxy group added to both ends of the bisphenol structure, an ethyleneoxy group or a propyleneoxy group is preferable, and an ethyleneoxy group is more preferable.
  • the number of alkyleneoxy groups added to the bisphenol structure is not particularly limited, but is preferably 4 to 16 per molecule, more preferably 6 to 14.
  • the polymerizable compound B1 having a bisphenol structure is described in paragraphs 0072 to 0080 of JP-A-2016-224162, and the contents described in this publication are incorporated in the present specification.
  • the polymerizable compound B1 a bifunctional ethylenically unsaturated compound having a bisphenol A structure is preferable, and 2,2-bis (4-((meth) acryloxypolyalkoxy) phenyl) propane is more preferable.
  • 2,2-bis (4-((meth) acryloxipolyalkoxy) phenyl) propane examples include 2,2-bis (4- (methacryloxydiethoxy) phenyl) propane (FA-324M, Hitachi Chemical Co., Ltd.).
  • the polymerizable compound B1 may be used alone or in combination of two or more.
  • the content of the polymerizable compound B1 in the photosensitive resin layer is preferably 10% by mass or more, more preferably 20% by mass or more, based on the total mass of the photosensitive resin layer, from the viewpoint of more excellent resolution.
  • the upper limit is not particularly limited, but is preferably 70% by mass or less, more preferably 60% by mass or less, from the viewpoint of transferability and edge fusion (a phenomenon in which the photosensitive resin exudes from the end of the transfer member).
  • the photosensitive resin layer may contain a polymerizable compound B other than the above-mentioned polymerizable compound B1.
  • the polymerizable compound B other than the polymerizable compound B1 is not particularly limited and may be appropriately selected from known compounds.
  • a compound having one ethylenically unsaturated group in one molecule monoofunctional ethylenically unsaturated compound
  • a bifunctional ethylenically unsaturated compound having no aromatic ring and a trifunctional or higher ethylenically unsaturated compound. Examples include compounds.
  • Examples of the monofunctional ethylenically unsaturated compound include ethyl (meth) acrylate, ethylhexyl (meth) acrylate, 2- (meth) acryloyloxyethyl succinate, polyethylene glycol mono (meth) acrylate, and polypropylene glycol mono (meth) acrylate. , And phenoxyethyl (meth) acrylate.
  • Examples of the bifunctional ethylenically unsaturated compound having no aromatic ring include alkylene glycol di (meth) acrylate, polyalkylene glycol di (meth) acrylate, urethane di (meth) acrylate, and trimethylolpropane diacrylate. Be done.
  • Examples of the alkylene glycol di (meth) acrylate include tricyclodecanedimethanol diacrylate (A-DCP, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) and tricyclodecanedimethanol dimethacrylate (DCP, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.).
  • 1,9-Nonandiol diacrylate (A-NOD-N, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), 1,6-Hexanediol diacrylate (A-HD-N, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.)
  • Ethylene glycol dimethacrylate 1,10-decanediol diacrylate
  • neopentyl glycol di (meth) acrylate examples of the polyalkylene glycol di (meth) acrylate include polyethylene glycol di (meth) acrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, and polypropylene glycol di (meth) acrylate.
  • Examples of the urethane di (meth) acrylate include propylene oxide-modified urethane di (meth) acrylate, and ethylene oxide and propylene oxide-modified urethane di (meth) acrylate.
  • Examples of commercially available products include 8UX-015A (manufactured by Taisei Fine Chemical Industry Co., Ltd.), UA-32P (manufactured by Shin Nakamura Chemical Industry Co., Ltd.), and UA-1100H (manufactured by Shin Nakamura Chemical Industry Co., Ltd.). Can be mentioned.
  • Examples of the trifunctional or higher functional ethylenically unsaturated compound include dipentaerythritol (tri / tetra / penta / hexa) (meth) acrylate, pentaerythritol (tri / tetra) (meth) acrylate, and trimethylolpropane tri (meth).
  • Examples thereof include acrylates, trimethylolpropane tetra (meth) acrylates, trimethylolethanetri (meth) acrylates, tri (meth) acrylates of isocyanurates, glycerintri (meth) acrylates, and modified alkylene oxides thereof.
  • (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 that includes tri (meth) acrylate and tetra (meth) acrylate.
  • alkylene oxide-modified product of the trifunctional or higher-functional ethylenically unsaturated compound examples include caprolactone-modified (meth) acrylate compound (KAYARAD (registered trademark) DPCA-20 manufactured by Nippon Kayaku Co., Ltd. and A manufactured by Shin Nakamura Chemical Industry Co., Ltd. -9300-1CL, etc.), alkylene oxide-modified (meth) acrylate compound (KAYARAD RP-1040 manufactured by Nippon Kayaku Co., Ltd., ATM-35E and A-9300 manufactured by Shin Nakamura Chemical Industry Co., Ltd., EBECRYL manufactured by Daicel Ornex Co., Ltd.
  • KAYARAD registered trademark
  • DPCA-20 manufactured by Nippon Kayaku Co., Ltd. and A manufactured by Shin Nakamura Chemical Industry Co., Ltd. -9300-1CL, etc.
  • alkylene oxide-modified (meth) acrylate compound alkylene oxide-modified (meth) acrylate compound
  • the polymerizable compound B other than the polymerizable compound B1 the polymerizable compound having an acid group described in paragraphs 0025 to 0030 of JP-A-2004-239942 may be used.
  • the polymerizable compound B may be used alone or in combination of two or more.
  • the content of the polymerizable compound B in the photosensitive resin layer is preferably 10 to 70% by mass, more preferably 20 to 60% by mass, still more preferably 20 to 50% by mass, based on the total mass of the photosensitive resin layer.
  • the weight average molecular weight (Mw) of the polymerizable compound B containing the polymerizable compound B1 is preferably 200 to 3,000, more preferably 280 to 2,200, and even more preferably 300 to 2,200.
  • the photosensitive resin layer may contain components other than the polymer A and the polymerizable compound B.
  • the photosensitive resin layer preferably contains a photopolymerization initiator.
  • the photopolymerization initiator is a compound that initiates the polymerization of a polymerizable compound by receiving active light such as ultraviolet rays, visible light, and X-rays.
  • the photopolymerization initiator is not particularly limited, and a known photopolymerization initiator can be used. Examples of the photopolymerization initiator include a photoradical polymerization initiator and a photocationic polymerization initiator, and a photoradical polymerization initiator is preferable.
  • Examples of the photoradical polymerization initiator include a photopolymerization initiator having an oxime ester structure, a photopolymerization initiator having an ⁇ -aminoalkylphenone structure, a photopolymerization initiator having an ⁇ -hydroxyalkylphenone structure, and an acylphosphine oxide. Examples thereof include a photopolymerization initiator having a structure and a photopolymerization initiator having an N-phenylglycine structure.
  • the photosensitive resin layer contains 2,4,5-triarylimidazole dimer as a photoradical polymerization initiator from the viewpoints of photosensitivity, visibility of exposed and non-exposed areas, and resolution. It is preferable to contain at least one selected from the group consisting of the derivatives.
  • the two 2,4,5-triarylimidazole structures in the 2,4,5-triarylimidazole dimer and its derivatives may be the same or different.
  • Derivatives of the 2,4,5-triarylimidazole dimer include, for example, 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4,5-di.
  • the photoradical polymerization initiator for example, the polymerization initiator described in paragraphs 0031 to 0042 of JP2011-0957116 and paragraphs 0064 to 0081 of JP2015-014783 may be used.
  • photoradical polymerization initiator examples include ethyl dimethylaminobenzoate (DBE, CAS No. 10287-53-3), benzoin methyl ether, anisyl (p, p'-dimethoxybenzyl), and TAZ-110 (trade name:).
  • Midori Kagaku Co., Ltd. benzophenone, TAZ-111 (trade name: Midori Kagaku Co., Ltd.), IrgacureOXE01, OXE02, OXE03 (BASF), Omnirad 651 and 369 (trade name: IGM Resins BV) , And 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetraphenyl-1,2'-biimidazole (manufactured by Tokyo Kasei Kogyo Co., Ltd.).
  • photoradical polymerization initiators examples include 1- [4- (phenylthio)] -1,2-octanedione-2- (O-benzoyloxime) (trade name: IRGACURE (registered trademark) OXE-01.
  • a photocationic polymerization initiator is a compound that generates an acid by receiving active light.
  • a compound that generates an acid in response to an active light having a wavelength of 300 nm or more is preferable, and a compound that generates an acid in response to an active light having a wavelength of 300 to 450 nm is more preferable. Is not restricted.
  • a photocationic polymerization initiator that is not directly sensitive to active light having a wavelength of 300 nm or more is also a sensitizer if it is a compound that is sensitive to active light having a wavelength of 300 nm or more and generates an acid when used in combination with a sensitizer.
  • a photocationic polymerization initiator that generates an acid having a pKa of 4 or less is preferable, a photocationic polymerization initiator that generates an acid having a pKa of 3 or less is more preferable, and an acid having a pKa of 2 or less is used.
  • the generated photocationic polymerization initiator is more preferred.
  • the lower limit of pKa is not particularly defined, but is preferably -10.0 or higher, for example.
  • Examples of the photocationic polymerization initiator include an ionic photocationic polymerization initiator and a nonionic photocationic polymerization initiator.
  • Examples of the ionic photocationic polymerization initiator include onium salt compounds such as diaryliodonium salt compounds and triarylsulfonium salt compounds, and quaternary ammonium salt compounds.
  • the ionic photocationic polymerization initiator described in paragraphs 0114 to 0133 of JP-A-2014-085643 may be used.
  • nonionic photocationic polymerization initiator examples include trichloromethyl-s-triazine compounds, diazomethane compounds, imide sulfonate compounds, and oxime sulfonate compounds.
  • trichloromethyl-s-triazine compound the diazomethane compound and the imide sulfonate compound
  • the compounds described in paragraphs 0083 to 0088 of JP2011-221494 may be used.
  • the oxime sulfonate compound the compounds described in paragraphs 0084 to 0088 of International Publication No. 2018/179640 may be used.
  • the photosensitive resin layer preferably contains a photoradical polymerization initiator, and more preferably contains at least one selected from the group consisting of 2,4,5-triarylimidazole dimers and derivatives thereof. ..
  • the photosensitive resin layer may contain one type of photopolymerization initiator alone or two or more types.
  • the content of the photopolymerization initiator in the photosensitive resin layer is not particularly limited, but is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, based on the total mass of the photosensitive resin layer. It is more preferably 0% by mass or more.
  • the upper limit is not particularly limited, but is preferably 10% by mass or less, more preferably 5% by mass or less, based on the total mass of the photosensitive resin layer.
  • the photosensitive resin layer has a maximum absorption wavelength of 450 nm or more in the wavelength range of 400 to 780 nm at the time of color development from the viewpoints of visibility of exposed and non-exposed areas, pattern visibility after development, and resolution.
  • a dye also simply referred to as "dye N"
  • the detailed mechanism is unknown, but the adhesion to the adjacent layer (for example, the temporary support and the intermediate layer) is improved, and the resolution is more excellent.
  • the term "the maximum absorption wavelength changes depending on an acid, base or radical” means that the dye in a color-developing state is decolorized by an acid, base or radical, and the dye in a decolorized state is an acid. It may mean any aspect of a mode in which a color is developed by a base or a radical, or a mode in which a dye in a colored state changes to a colored state of another hue.
  • the dye N may be a compound that changes from the decolorized state by exposure to develop a color, or may be a compound that changes from the decolorized state by exposure to decolorize.
  • the dye may change the state of color development or decolorization due to the generation and action of acids, bases or radicals in the photosensitive resin layer by exposure, and the state in the photosensitive resin layer by the acids, bases or radicals. It may be a dye whose color development or decolorization state changes by changing (for example, pH). Further, it may be a dye that changes its color-developing or decolorizing state by directly receiving an acid, a base or a radical as a stimulus without exposure.
  • the dye N is preferably a dye whose maximum absorption wavelength is changed by an acid or a radical, and more preferably a dye whose maximum absorption wavelength is changed by a radical.
  • the photosensitive resin layer may contain both a dye whose maximum absorption wavelength is changed by radicals as dye N and a photoradical polymerization initiator from the viewpoint of visibility and resolution of exposed and unexposed parts. preferable.
  • the dye N is preferably a dye that develops color by an acid, a base, or a radical.
  • a photoradical polymerization initiator, a photocationic polymerization initiator (photoacid generator) or a photobase generator is added to the photosensitive resin layer, and the photoradical polymerization initiator is added after exposure.
  • a radical-reactive dye, an acid-reactive dye or a base-reactive dye for example, a leuco dye
  • a radical-reactive dye, an acid-reactive dye or a base-reactive dye for example, a leuco dye
  • the dye N preferably has a maximum absorption wavelength of 550 nm or more in the wavelength range of 400 to 780 nm at the time of color development, more preferably 550 to 700 nm. It is more preferably about 650 nm. Further, the dye N may have only one maximum absorption wavelength in the wavelength range of 400 to 780 nm at the time of color development, or may have two or more. When the dye N has two or more maximum absorption wavelengths in the wavelength range of 400 to 780 nm at the time of color development, the maximum absorption wavelength having the highest absorbance among the two or more maximum absorption wavelengths may be 450 nm or more.
  • the maximum absorption wavelength of the dye N is transmitted by a solution containing the dye N (liquid temperature 25 ° C.) in the range of 400 to 780 nm using a spectrophotometer: UV3100 (manufactured by Shimadzu Corporation) in an atmospheric atmosphere. It is obtained by measuring the spectrum and detecting the wavelength at which the light intensity becomes the minimum (maximum absorption wavelength).
  • Examples of the dye that develops or decolorizes by exposure include leuco compounds.
  • Examples of dyes that are decolorized by exposure include leuco compounds, diarylmethane dyes, oxazine dyes, xanthene dyes, iminonaphthoquinone dyes, azomethine dyes and anthraquinone dyes.
  • As the dye N a leuco compound is preferable from the viewpoint of visibility of the exposed portion and the non-exposed portion.
  • the leuco compound examples include a leuco compound having a triarylmethane skeleton (triarylmethane dye), a leuco compound having a spiropyran skeleton (spiropylan dye), a leuco compound having a fluorane skeleton (fluorane dye), and a diarylmethane skeleton.
  • Leuco compounds diarylmethane dyes
  • leuco compounds having a rhodamine lactam skeleton (rodamine lactam dyes)
  • leuco compounds having an indolylphthalide skeleton indolylphthalide dyes
  • leukooramine skeletons examples include a leuco compound having a triarylmethane skeleton (triarylmethane dye), a leuco compound having a spiropyran skeleton (spiropylan dye), a leuco compound having a fluorane skeleton (fluorane dye), and a
  • leuco compounds having leuco compounds include leuco auramine dyes.
  • leuco auramine dyes include leuco compounds having leuco compounds (leuco auramine dyes).
  • a triarylmethane dye or a fluorane dye is preferable, and a leuco compound having a triphenylmethane skeleton (triphenylmethane dye) or a fluorane dye is more preferable.
  • the leuco compound preferably has a lactone ring, a surujin ring, or a sultone ring from the viewpoint of visibility of the exposed portion and the non-exposed portion.
  • the lactone ring, sultin ring, or sulton ring of the leuco compound is reacted with the radical generated from the photoradical polymerization initiator or the acid generated from the photocationic polymerization initiator to change the leuco compound into a ring-closed state.
  • the color can be decolorized or the leuco compound can be changed to an open ring state to develop a color.
  • the leuco compound preferably has a lactone ring, a sultone ring, or a sultone ring, and the lactone ring, the sultone ring, or the sultone ring is opened by a radical or an acid to develop a color.
  • a compound in which the lactone ring is opened to develop color is more preferable.
  • Examples of the dye N include the following dyes and leuco compounds. Specific examples of dyes among dyes N include brilliant green, ethyl violet, methyl green, crystal violet, basic fucsin, methyl violet 2B, quinaldine red, rose bengal, methanyl yellow, timol sulfophthalene, xylenol blue, and methyl.
  • leuco compound among the dyes N include p, p', p "-hexamethyltriaminotriphenylmethane (leucocrystal violet), Pergascript Blue SRB (manufactured by Ciba Geigy), crystal violet lactone, and malakite green lactone.
  • the dye N is preferably a dye whose maximum absorption wavelength is changed by radicals from the viewpoints of visibility of exposed and unexposed areas, pattern visibility after development, and resolution, and is a dye that develops color by radicals. Is more preferable.
  • As the dye N leuco crystal violet, crystal violet lactone, or Victoria pure blue-naphthalene sulfonate is preferable.
  • the dye N may be used alone or in combination of two or more.
  • the content of the dye N is 0.1% by mass or more with respect to the total mass of the photosensitive resin layer from the viewpoints of visibility of the exposed and non-exposed areas, pattern visibility after development, and resolution.
  • 0.1 to 10% by mass is more preferable, 0.1 to 5% by mass is further preferable, and 0.1 to 1% by mass is particularly preferable.
  • the content of the dye N means the content of the dye when all of the dye N contained in the photosensitive resin layer is in a colored state.
  • a method for quantifying the content of dye N will be described by taking a dye that develops color by radicals as an example.
  • a solution in which 0.001 g and 0.01 g of the dye are dissolved in 100 mL of methyl ethyl ketone is prepared.
  • a photoradical polymerization initiator Irgacre OXE01 (trade name, BASF Japan Ltd.) is added to each of the obtained solutions, and radicals are generated by irradiating with light of 365 nm to bring all the dyes into a colored state.
  • the absorbance of each solution having a liquid temperature of 25 ° C. is measured using a spectrophotometer (UV3100, manufactured by Shimadzu Corporation), and a calibration curve is prepared.
  • UV3100 UV3100, manufactured by Shimadzu Corporation
  • the absorbance of the solution in which all the dyes are colored is measured by the same method as above except that 3 g of the photosensitive resin layer is dissolved in methyl ethyl ketone instead of the dye. From the absorbance of the obtained solution containing the photosensitive resin layer, the content of the dye contained in the photosensitive resin layer is calculated based on the calibration curve.
  • the photosensitive resin layer preferably contains a surfactant from the viewpoint of thickness uniformity.
  • the surfactant include anionic surfactants, cationic surfactants, nonionic (nonionic) surfactants, and amphoteric surfactants, and nonionic surfactants are preferable.
  • nonionic surfactant examples include a polyoxyethylene higher alkyl ether compound, a polyoxyethylene higher alkylphenyl ether compound, a higher fatty acid diester compound of polyoxyethylene glycol, a silicone-based nonionic surfactant, and a fluorine-based nonionic compound.
  • examples include sex surfactants.
  • the photosensitive resin layer preferably contains a fluorine-based nonionic surfactant from the viewpoint of being more excellent in resolution. It is considered that the photosensitive resin layer contains a fluorine-based nonionic surfactant to suppress the penetration of the etching solution into the photosensitive resin layer and reduce the side etching. Examples of commercially available products of the fluorine-based nonionic surfactant include Megafuck F-551, F-552 and F-554 (all manufactured by DIC Corporation).
  • surfactant examples include the surfactant described in paragraphs 0120 to 0125 of International Publication No. 2018/179640, the surfactant described in paragraph 0017 of Japanese Patent No. 45027884, and JP-A-2009-237362. Surfactants described in paragraphs 0060 to 0071 of the publication can also be used.
  • the photosensitive resin layer may contain one type of surfactant alone or two or more types.
  • the content of the surfactant is preferably 0.001 to 10% by mass, more preferably 0.01 to 3% by mass, based on the total mass of the photosensitive resin layer.
  • the photosensitive resin layer may contain known additives, if necessary.
  • the additive include a polymerization inhibitor, a sensitizer, a plasticizer, a heterocyclic compound, a resin other than the polymer A, and a solvent.
  • the photosensitive resin layer may contain a polymerization inhibitor.
  • the polymerization inhibitor include the thermal polymerization inhibitor described in paragraph 0018 of Japanese Patent No. 4502784. Of these, phenothiazine, phenothiazine or 4-methoxyphenol is preferable.
  • the photosensitive resin layer may contain one type of polymerization inhibitor alone or two or more types.
  • the content of the polymerization inhibitor is preferably 0.01 to 3% by mass, preferably 0.01 to 1% by mass, based on the total mass of the photosensitive resin layer. More preferably, 0.01 to 0.8% by mass is further preferable.
  • the photosensitive resin layer may contain a sensitizer.
  • the sensitizer is not particularly limited, and known sensitizers, dyes and pigments can be used.
  • Examples of the sensitizer include dialkylaminobenzophenone compounds, pyrazoline compounds, anthracene compounds, coumarin compounds, xanthone compounds, thioxanthone compounds, acridone compounds, oxazole compounds, benzoxazole compounds, thiazole compounds, benzothiazole compounds, and triazole compounds (for example, 1,2,4-triazole), stillben compounds, triazine compounds, thiophene compounds, naphthalimide compounds, triarylamine compounds, and aminoaclydin compounds.
  • the photosensitive resin layer may contain one kind of sensitizer alone or two or more kinds.
  • the content of the sensitizer can be appropriately selected depending on the purpose, but from the viewpoint of improving the sensitivity to the light source and improving the curing rate by balancing the polymerization rate and the chain transfer. Therefore, it is preferably 0.01 to 5% by mass, more preferably 0.05 to 1% by mass, based on the total mass of the photosensitive resin layer.
  • the photosensitive resin layer may contain at least one selected from the group consisting of plasticizers and heterocyclic compounds.
  • plasticizers and heterocyclic compounds include the compounds described in paragraphs 097 to 0103 and 0111 to 0118 of WO 2018/179640.
  • the photosensitive resin layer may contain a resin other than the polymer A. That is, the photosensitive resin layer may contain a resin having a styrene content of 40% by mass or less.
  • Resins other than polymer A include acrylic resin, styrene-acrylic copolymer (however, styrene content is 40% by mass or less), polyurethane resin, polyvinyl alcohol, polyvinyl formal, polyamide resin, polyester resin, polyamide. Examples thereof include resins, epoxy resins, polyacetal resins, polyhydroxystyrene resins, polyimide resins, polybenzoxazole resins, polysiloxane resins, polyethyleneimines, polyallylamines, and polyalkylene glycols.
  • the photosensitive resin layer may contain a solvent.
  • the solvent may remain in the photosensitive resin layer.
  • the photosensitive resin layer includes metal oxide particles, antioxidants, dispersants, acid growth agents, development accelerators, conductive fibers, thermal radical polymerization initiators, thermal acid generators, ultraviolet absorbers, and thickeners. , Crosslinking agents, and known additives such as organic or inorganic precipitation inhibitors may be further contained. Additives contained in the photosensitive resin layer are described in paragraphs 0165 to 0184 of JP-A-2014-085643, and the contents of this publication are incorporated in the present specification.
  • the layer thickness of the photosensitive resin layer is 8 ⁇ m or less. As a result, the developability of the photosensitive resin layer is improved, and the resolvability can be improved. From the viewpoint of excellent resolution and peelability, the thickness of the photosensitive resin layer is preferably 6 ⁇ m or less, more preferably less than 5 ⁇ m, and even more preferably 4 ⁇ m or less.
  • the lower limit is not particularly limited, but 0.8 ⁇ m or more is preferable, and 2 ⁇ m or more is more preferable, from the viewpoint of being excellent in visibility of the exposed portion and the non-exposed portion and adhesion to the adjacent layer.
  • the layer thickness of each layer included in the photosensitive transfer member is based on an observation image obtained by observing a cross section in a direction perpendicular to the main surface of the photosensitive transfer member with a scanning electron microscope (SEM). It is measured by measuring the thickness of each layer at 10 points or more and calculating the average value thereof.
  • SEM scanning electron microscope
  • the transmittance of light having a wavelength of 365 nm in the photosensitive resin layer is preferably 10% or more, more preferably 30% or more, still more preferably 50% or more.
  • the upper limit is not particularly limited, but is preferably 99.9% or less.
  • the method for forming the photosensitive resin layer is not particularly limited as long as it is a method capable of forming a layer containing the above components.
  • a method for forming the photosensitive resin layer for example, a photosensitive resin composition containing the polymer A, the polymerizable compound B1 and a solvent is prepared, and the photosensitive resin composition is applied to the surface of the temporary support to make the photosensitive resin layer photosensitive. Examples thereof include a method of forming by drying a coating film of a sex resin composition.
  • Examples of the photosensitive resin composition used for forming the photosensitive resin layer include a composition containing a polymer A, a polymerizable compound B1, the above-mentioned optional components and a solvent.
  • the photosensitive resin composition preferably contains a solvent in order to adjust the viscosity of the photosensitive resin composition and facilitate the formation of the photosensitive resin layer.
  • the solvent contained in the photosensitive resin composition is not particularly limited as long as the polymer A, the polymerizable compound B1 and the above optional components can be dissolved or dispersed, and known solvents can be used.
  • the solvent include an alkylene glycol ether solvent, an alkylene glycol ether acetate solvent, an alcohol solvent (methanol, ethanol, etc.), a ketone solvent (acetone, methyl ethyl ketone, etc.), an aromatic hydrocarbon solvent (toluene, etc.), and an aprotonic polar solvent.
  • the photosensitive resin composition is selected from the group consisting of an alkylene glycol ether solvent and an alkylene glycol ether acetate solvent. It is preferable to contain at least one of them.
  • a mixed solvent containing at least one selected from the group consisting of an alkylene glycol ether solvent and an alkylene glycol ether acetate solvent and at least one selected from the group consisting of a ketone solvent and a cyclic ether solvent is more preferable.
  • a mixed solvent containing at least one selected from the group consisting of a glycol ether solvent and an alkylene glycol ether acetate solvent, a ketone solvent, and at least three cyclic ether solvents is more preferable.
  • alkylene glycol ether solvent examples include ethylene glycol monoalkyl ether, ethylene glycol dialkyl ether, propylene glycol monoalkyl ether, propylene glycol dialkyl ether, diethylene glycol dialkyl ether, dipropylene glycol monoalkyl ether and dipropylene glycol dialkyl ether. ..
  • alkylene glycol ether acetate solvent examples include ethylene glycol monoalkyl ether acetate, propylene glycol monoalkyl ether acetate, diethylene glycol monoalkyl ether acetate and dipropylene glycol monoalkyl ether acetate.
  • the solvent described in paragraphs 0092 to 0094 of International Publication No. 2018/179640 and the solvent described in paragraph 0014 of JP-A-2018-177789 may be used. Incorporated herein.
  • the photosensitive resin composition may contain one type of solvent alone, or may contain two or more types of solvent.
  • the content of the solvent when the thermoplastic resin composition is applied is preferably 50 to 1,900 parts by mass, more preferably 100 to 900 parts by mass, based on 100 parts by mass of the total solid content in the thermoplastic resin composition. ..
  • the method for preparing the photosensitive resin composition is not particularly limited.
  • a photosensitive resin composition is prepared by preparing a solution in which each component is dissolved in the above solvent in advance and mixing the obtained solution in a predetermined ratio. There is a method of preparing.
  • the photosensitive resin composition is preferably filtered using a filter having a pore size of 0.2 to 30 ⁇ m before forming the photosensitive resin layer.
  • the method for applying the photosensitive resin composition is not particularly limited, and the photosensitive resin composition may be applied by a known method. Examples of the coating method include slit coating, spin coating, curtain coating and inkjet coating. Further, the photosensitive resin layer may be formed by applying the photosensitive resin composition on a cover film described later and drying it.
  • the photosensitive transfer member may include a thermoplastic resin layer.
  • the photosensitive transfer member preferably includes a thermoplastic resin layer between the temporary support and the photosensitive resin layer.
  • the thermoplastic resin layer contains an alkali-soluble resin as the thermoplastic resin.
  • alkali-soluble means that the solubility of sodium carbonate in 100 g of a 1 mass% aqueous solution is 0.1 g or more at 22 degreeC.
  • alkali-soluble resin include acrylic resin, polystyrene resin, styrene-acrylic copolymer, polyurethane resin, polyvinyl alcohol, polyvinyl formal, polyamide resin, polyester resin, polyamide resin, epoxy resin, polyacetal resin, and polyhydroxystyrene resin.
  • examples thereof include polyimide resins, polybenzoxazole resins, polysiloxane resins, polyethyleneimines, polyallylamines and polyalkylene glycols.
  • an acrylic resin is preferable from the viewpoint of developability and adhesion to an adjacent layer.
  • the acrylic resin was selected from the group consisting of a structural unit derived from (meth) acrylic acid, a structural unit derived from (meth) acrylic acid ester, and a structural unit derived from (meth) acrylic acid amide. It means a resin having at least one structural unit.
  • the acrylic resin the total content of the structural unit derived from (meth) acrylic acid, the structural unit derived from (meth) acrylic acid ester, and the structural unit derived from (meth) acrylic acid amide is that of the acrylic resin. It is preferably 50% by mass or more with respect to the total mass.
  • the total content of the structural unit derived from (meth) acrylic acid and the structural unit derived from (meth) acrylic acid ester is preferably 30 to 100% by mass with respect to the total mass of the acrylic resin, and is preferably 50. More preferably, it is ⁇ 100% by mass.
  • the alkali-soluble resin is preferably a polymer having an acid group.
  • the acid group include a carboxy group, a sulfo group, a phosphoric acid group and a phosphonic acid group, and a carboxy group is preferable.
  • the alkali-soluble resin is more preferably an alkali-soluble resin having an acid value of 60 mgKOH / g or more, and further preferably a carboxy group-containing acrylic resin having an acid value of 60 mgKOH / g or more.
  • the upper limit of the acid value of the alkali-soluble resin is not particularly limited, but is preferably 200 mgKOH / g or less, and more preferably 150 mgKOH / g or less.
  • the carboxy group-containing acrylic resin having an acid value of 60 mgKOH / g or more is not particularly limited, and can be appropriately selected from known resins and used.
  • alkali-soluble resins which are carboxy group-containing acrylic resins having an acid value of 60 mgKOH / g or more, described in paragraphs 0033 to 0052 of JP2010-237589A.
  • Acrylic resin can be mentioned.
  • the copolymerization ratio of the structural unit having a carboxy group in the carboxy group-containing acrylic resin is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, and 12 to 30% by mass with respect to the total mass of the acrylic resin. Is more preferable.
  • an acrylic resin having a structural unit derived from (meth) acrylic acid is particularly preferable from the viewpoint of developability and adhesion to an adjacent layer.
  • the alkali-soluble resin may have a reactive group.
  • the reactive group may be any addition-polymerizable group, and an ethylenically unsaturated group; a polycondensable group such as a hydroxy group and a carboxy group; a polyadditive reactive group such as an epoxy group and a (block) isocyanate group may be used. Can be mentioned.
  • the weight average molecular weight (Mw) of the alkali-soluble resin is preferably 1,000 or more, more preferably 10,000 to 100,000, and even more preferably 20,000 to 50,000.
  • the thermoplastic resin layer may contain one kind of alkali-soluble resin alone or two or more kinds.
  • the content of the alkali-soluble resin is preferably 10 to 99% by mass, more preferably 20 to 90% by mass, based on the total mass of the thermoplastic resin layer from the viewpoint of developability and adhesion to the adjacent layer. It is more preferably 40 to 80% by mass, and particularly preferably 50 to 70% by mass.
  • the thermoplastic resin layer contains a dye (also simply referred to as "dye B") having a maximum absorption wavelength of 450 nm or more in the wavelength range of 400 to 780 nm at the time of color development and whose maximum absorption wavelength is changed by an acid, a base, or a radical. It is preferable to do so.
  • the preferred embodiment of the dye B is the same as the preferred embodiment of the dye N except for the points described later.
  • the dye B is preferably a dye whose maximum absorption wavelength is changed by an acid or radical, and more preferably a dye whose maximum absorption wavelength is changed by an acid, from the viewpoint of visibility and resolution of exposed and unexposed areas. .. From the viewpoint of visibility and resolution of the exposed and unexposed areas, the thermoplastic layer contains both a dye whose maximum absorption wavelength changes depending on the acid as the dye B and a compound that generates an acid by light, which will be described later. It is preferable to contain it.
  • the dye B may be used alone or in combination of two or more.
  • the content of the dye B is preferably 0.2% by mass or more, more preferably 0.2 to 6% by mass, based on the total mass of the thermoplastic resin layer from the viewpoint of visibility of the exposed part and the non-exposed part. , 0.2 to 5% by mass, more preferably 0.25 to 3.0% by mass.
  • the content of the dye B means the content of the dye when all the dyes B contained in the thermoplastic resin layer are in a colored state.
  • the method for quantifying the content of the dye B will be described below by taking a dye that develops color by radicals as an example.
  • a solution in which 0.001 g and 0.01 g of the dye are dissolved in 100 mL of methyl ethyl ketone is prepared.
  • a photoradical polymerization initiator Irgacure OXE01 (trade name, BASF Japan Ltd.) is added to each of the obtained solutions, and radicals are generated by irradiating with light of 365 nm to bring all the dyes into a colored state.
  • the absorbance of each solution having a liquid temperature of 25 ° C. is measured using a spectrophotometer (UV3100, manufactured by Shimadzu Corporation), and a calibration curve is prepared.
  • UV3100 UV3100, manufactured by Shimadzu Corporation
  • the absorbance of the solution in which all the dyes are colored is measured by the same method as above except that 0.1 g of the thermoplastic resin layer is dissolved in methyl ethyl ketone instead of the dye. From the absorbance of the obtained solution containing the thermoplastic resin layer, the amount of the dye contained in the thermoplastic resin layer is calculated based on the calibration curve.
  • the thermoplastic resin layer may contain a compound (also simply referred to as “compound C”) that generates an acid, a base or a radical by light.
  • a compound that generates an acid, a base, or a radical by receiving active light such as ultraviolet rays and visible light is preferable.
  • known photoacid generators, photobase generators, and photoradical polymerization initiators (photoradical generators) can be used. Of these, a photoacid generator is preferable.
  • thermoplastic resin layer preferably contains a photoacid generator.
  • the photoacid generator include a photocationic polymerization initiator that may be contained in the above-mentioned photosensitive resin layer, and the preferred embodiments are the same except for the points described below.
  • the photoacid generator preferably contains at least one compound selected from the group consisting of an onium salt compound and an oxime sulfonate compound from the viewpoint of sensitivity and resolution, and preferably contains sensitivity, resolution and resolution. From the viewpoint of adhesion, it is more preferable to contain an oxime sulfonate compound. Further, as the photoacid generator, a photoacid generator having the following structure is also preferable.
  • thermoplastic resin layer may contain a photoradical polymerization initiator (photoradical polymerization initiator).
  • photoradical polymerization initiator include a photoradical polymerization initiator that may be contained in the photosensitive resin layer described above, and the preferred embodiment is also the same.
  • thermoplastic resin layer may contain a photobase generator.
  • the photobase generator is not particularly limited as long as it is a known photobase generator, and for example, 2-nitrobenzylcyclohexylcarbamate, triphenylmethanol, O-carbamoyl hydroxylamide, O-carbamoyloxime, [[(2,2).
  • the thermoplastic resin layer may contain the compound C alone or in combination of two or more.
  • the content of compound C is preferably 0.1 to 10% by mass, preferably 0.5 to 5% by mass, based on the total mass of the thermoplastic resin layer from the viewpoint of visibility and resolution of the exposed and unexposed areas. More preferably by mass.
  • the thermoplastic resin layer preferably contains a plasticizer from the viewpoint of resolution, adhesion to adjacent layers, and developability.
  • the plasticizer preferably has a smaller molecular weight (weight average molecular weight (Mw) in the case of an oligomer or polymer) than the alkali-soluble resin.
  • the molecular weight of the plasticizer (weight average molecular weight (Mw)) is preferably 200 to 2,000.
  • the plasticizer is not particularly limited as long as it is a compound that is compatible with the alkali-soluble resin and exhibits plasticity, but from the viewpoint of imparting plasticity, a plasticizer having an alkyleneoxy group in the molecule is preferable, and a polyalkylene glycol compound is more preferable. preferable.
  • the alkyleneoxy group contained in the plasticizer more preferably has a polyethyleneoxy structure or a polypropyleneoxy structure.
  • the plasticizer preferably contains a (meth) acrylate compound from the viewpoint of resolution and storage stability.
  • the alkali-soluble resin is an acrylic resin and the plasticizer contains a (meth) acrylate compound.
  • the (meth) acrylate compound used as a plasticizer include the (meth) acrylate compound described as the polymerizable compound B contained in the photosensitive resin layer described above.
  • both the thermoplastic resin layer and the photosensitive resin layer contain the same (meth) acrylate compound. .. This is because the thermoplastic resin layer and the photosensitive resin layer contain the same (meth) acrylate compound, respectively, so that the diffusion of components between the layers is suppressed and the storage stability is improved.
  • the thermoplastic resin layer contains a (meth) acrylate compound as a plasticizer
  • the (meth) acrylate compound used as a plasticizer is a polyfunctional compound having two or more (meth) acryloyl groups in one molecule from the viewpoints of resolution, adhesion to adjacent layers, and developability.
  • a (meth) acrylate compound is preferred.
  • a (meth) acrylate compound having an acid group or a urethane (meth) acrylate compound is also preferable.
  • the thermoplastic resin layer may contain one type of plasticizer alone, or may contain two or more types of plasticizer.
  • the content of the plasticizer is preferably 1 to 70% by mass, more preferably 10 to 60% by mass, based on the total mass of the thermoplastic resin layer from the viewpoint of resolution, adhesion to adjacent layers, and developability. It is preferable, and more preferably 20 to 50% by mass.
  • the thermoplastic resin layer preferably contains a surfactant from the viewpoint of thickness uniformity.
  • the surfactant include surfactants that may be contained in the above-mentioned photosensitive resin layer, and the preferred embodiment is the same.
  • the thermoplastic resin layer may contain one type of surfactant alone or two or more types.
  • the content of the surfactant is preferably 0.001 to 10% by mass, more preferably 0.01 to 3% by mass, based on the total mass of the thermoplastic resin layer.
  • the thermoplastic resin layer may contain a sensitizer.
  • the sensitizer is not particularly limited, and examples thereof include a sensitizer that may be contained in the above-mentioned photosensitive resin layer.
  • the thermoplastic resin layer may contain one type of sensitizer alone or two or more types.
  • the content of the sensitizer can be appropriately selected depending on the purpose, but from the viewpoint of improving the sensitivity to the light source and the visibility of the exposed and non-exposed areas, 0.01 to 0.01 to the total mass of the thermoplastic resin layer.
  • the range of 5% by mass is preferable, and the range of 0.05 to 1% by mass is more preferable.
  • thermoplastic resin layer may contain known additives, if necessary. Further, the thermoplastic resin layer is described in paragraphs 0189 to 0193 of JP-A-2014-085643, and the contents described in this publication are incorporated in the present specification.
  • the layer thickness of the thermoplastic resin layer is not particularly limited, but is preferably 1 ⁇ m or more, more preferably 2 ⁇ m or more, from the viewpoint of adhesion to adjacent layers.
  • the upper limit is not particularly limited, but from the viewpoint of developability and resolution, 20 ⁇ m or less is preferable, 10 ⁇ m or less is more preferable, and 5 ⁇ m or less is further preferable.
  • the method for forming the thermoplastic resin layer is not particularly limited as long as it is a method capable of forming a layer containing the above components.
  • a method for forming the thermoplastic resin layer for example, a thermoplastic resin composition containing the above components and a solvent is prepared, the thermoplastic resin composition is applied to the surface of the temporary support, and the thermoplastic resin composition is formed. Examples thereof include a method of forming the coating film by drying.
  • the thermoplastic resin composition preferably contains a solvent in order to adjust the viscosity of the thermoplastic resin composition and facilitate the formation of the thermoplastic resin layer.
  • the solvent contained in the thermoplastic resin composition is not particularly limited as long as the above-mentioned components contained in the thermoplastic resin layer can be dissolved or dispersed.
  • Examples of the solvent contained in the thermoplastic resin composition include solvents that may be contained in the above-mentioned photosensitive resin composition, and the preferred embodiment is also the same.
  • the solvent contained in the thermoplastic resin composition may be one kind alone or two or more kinds.
  • the content of the solvent when the thermoplastic resin composition is applied is preferably 50 to 1,900 parts by mass, more preferably 100 to 900 parts by mass, based on 100 parts by mass of the total solid content in the thermoplastic resin composition. ..
  • thermoplastic resin composition and the formation of the thermoplastic resin layer may be carried out according to the above-mentioned method for preparing the photosensitive resin composition and the method for forming the photosensitive resin layer.
  • a solution in which each component contained in the thermoplastic resin layer is dissolved in the above solvent is prepared in advance, and the obtained solution is mixed at a predetermined ratio to prepare a thermoplastic resin composition, which is then obtained.
  • the obtained thermoplastic resin composition is applied to the surface of the temporary support, and the coating film of the thermoplastic resin composition is dried to form the thermoplastic resin layer.
  • the thermoplastic resin layer may be formed on the surface of the intermediate layer.
  • the photosensitive transfer member preferably includes an intermediate layer between the thermoplastic resin layer and the photosensitive resin layer.
  • the intermediate layer is preferably a water-soluble layer from the viewpoint of developability and suppressing mixing of components during application of the plurality of layers and storage after application.
  • water-soluble means that the solubility in 100 g of water having a liquid temperature of 22 ° C. and pH 7.0 is 0.1 g or more.
  • the intermediate layer examples include an oxygen blocking layer having an oxygen blocking function, which is described as a “separation layer” in JP-A-5-07724.
  • the intermediate layer is an oxygen blocking layer, the sensitivity at the time of exposure is improved, the time load of the exposure machine is reduced, and the productivity is improved, which is preferable.
  • the oxygen blocking layer used as the intermediate layer may be appropriately selected from known layers such as the layers described in the above publication. Of these, an oxygen blocking layer that exhibits low oxygen permeability and is dispersed or dissolved in water or an alkaline aqueous solution (1% by mass aqueous solution of sodium carbonate at 22 ° C.) is preferable.
  • the intermediate layer preferably contains a resin.
  • the resin contained in the intermediate layer include polyvinyl alcohol-based resin, polyvinylpyrrolidone-based resin, cellulose-based resin, acrylamide-based resin, polyethylene oxide-based resin, gelatin, vinyl ether-based resin, polyamide resin, and their common weights. Examples include resins such as coalescence.
  • a water-soluble resin is preferable.
  • the resin contained in the intermediate layer contains the polymer A contained in the photosensitive resin layer and the thermoplastic resin (alkali soluble) contained in the thermoplastic resin layer from the viewpoint of suppressing the mixing of the components between the plurality of layers. It is preferable that the resin is different from any of the resins).
  • the intermediate layer preferably contains polyvinyl alcohol from the viewpoint of oxygen blocking property and suppressing mixing of components during application of the plurality of layers and storage after application, and contains both polyvinyl alcohol and polyvinylpyrrolidone. It is more preferable to contain it.
  • the intermediate layer may contain the above resin alone or in combination of two or more.
  • the content of the resin in the intermediate layer is not particularly limited, but is based on the total mass of the intermediate layer from the viewpoint of oxygen blocking property and suppressing mixing of components when the plurality of layers are applied and stored after application. , 50 to 100% by mass, more preferably 70 to 100% by mass, further preferably 80 to 100% by mass, and particularly preferably 90 to 100% by mass.
  • the intermediate layer may contain an additive such as a surfactant, if necessary.
  • the layer thickness of the intermediate layer is not particularly limited, but is preferably 0.1 to 5 ⁇ m, more preferably 0.5 to 3 ⁇ m.
  • the thickness of the intermediate layer is within the above range, the oxygen blocking property is not deteriorated, the mixing of the components at the time of applying the plurality of layers and at the time of storage after application can be suppressed, and the intermediate during development. This is because the increase in the layer removal time can be suppressed.
  • the method for forming the intermediate layer is not particularly limited, and for example, an intermediate layer composition containing the above resin and any additive is prepared and applied to the surface of the thermoplastic resin layer or the photosensitive resin layer to form the intermediate layer composition.
  • examples thereof include a method of forming an intermediate layer by drying a coating film of an object.
  • the intermediate layer composition preferably contains a solvent in order to adjust the viscosity of the thermoplastic resin composition and facilitate the formation of the thermoplastic resin layer.
  • the solvent contained in the intermediate layer composition is not particularly limited as long as the above resin can be dissolved or dispersed, and at least one selected from the group consisting of water and a water-miscible organic solvent is preferable, and water or water or water is preferable.
  • a mixed solvent of water and a water-miscible organic solvent is more preferable.
  • the water-miscible organic solvent include alcohols having 1 to 3 carbon atoms, acetone, ethylene glycol and glycerin, and alcohols having 1 to 3 carbon atoms are preferable, and methanol or ethanol is more preferable.
  • the photosensitive transfer member preferably includes a cover film that is in contact with a surface of the photosensitive resin layer that does not face the temporary support.
  • a cover film that is in contact with a surface of the photosensitive resin layer that does not face the temporary support.
  • first surface the surface of the photosensitive resin layer facing the temporary support
  • second surface the surface opposite to the first surface
  • Examples of the material constituting the cover film include a resin film and paper, and a resin film is preferable from the viewpoint of strength and flexibility.
  • Examples of the resin film include a polyethylene film, a polypropylene film, a polyethylene terephthalate film, a cellulose triacetate film, a polystyrene film, and a polycarbonate film. Of these, polyethylene film, polypropylene film, or polyethylene terephthalate film is preferable.
  • the thickness (layer thickness) of the cover film is not particularly limited, but is preferably 5 to 100 ⁇ m, more preferably 10 to 50 ⁇ m.
  • the arithmetic mean roughness Ra value of the surface of the cover film in contact with the photosensitive resin layer (hereinafter, also simply referred to as “the surface of the cover film”) is preferably 0.3 ⁇ m or less from the viewpoint of excellent resolution. It is more preferably 1 ⁇ m or less, and further preferably 0.05 ⁇ m or less. It is considered that when the Ra value on the surface of the cover film is within the above range, the uniformity of the layer thickness of the photosensitive resin layer and the formed resin pattern is improved.
  • the lower limit of the Ra value on the surface of the cover film is not particularly limited, but is preferably 0.001 ⁇ m or more.
  • the Ra value on the surface of the cover film is measured by the following method. Using a three-dimensional optical profiler (New View7300, manufactured by Zygo), the surface of the cover film is measured under the following conditions to obtain a surface profile of the optical film. As the measurement / analysis software, Microscope Application of MetroPro ver 8.3.2 is used. Next, the Surface Map screen is displayed with the above analysis software, and histogram data is obtained in the Surface Map screen. From the obtained histogram data, the arithmetic mean roughness is calculated to obtain the Ra value of the surface of the cover film. When the cover film is attached to the photosensitive transfer member, the cover film may be peeled off from the photosensitive transfer member, and the Ra value of the surface on the peeled side may be measured.
  • the photosensitive transfer member may include a layer other than the above-mentioned layer (hereinafter, also referred to as “other layer”).
  • Other layers include, for example, a contrast enhancement layer.
  • the contrast enhancement layer is described in paragraph 0134 of WO 2018/179640. Further, other layers are described in paragraphs 0194 to 0196 of JP-A-2014-085643. The contents of these publications are incorporated herein.
  • the method for producing the photosensitive transfer member according to the present disclosure is not particularly limited, and a known production method, for example, a known method for forming each layer can be used.
  • a method for manufacturing a photosensitive transfer member according to the present disclosure will be described with reference to FIG.
  • the photosensitive transfer member according to the present disclosure is not limited to the one having the configuration shown in FIG.
  • FIG. 1 is a schematic view showing an example of the configuration of the photosensitive transfer member according to the present disclosure.
  • the photosensitive transfer member 100 shown in FIG. 1 has a structure in which a temporary support 10, a thermoplastic resin layer 12, an intermediate layer 14, a photosensitive resin layer 16, and a cover film 18 are laminated in this order.
  • the thermoplastic resin layer is formed by applying the thermoplastic resin composition to the surface of the temporary support 10 and then drying the coating film of the thermoplastic resin composition. 12 is formed, the intermediate layer composition is applied to the surface of the thermoplastic resin layer 12, and then the coating film of the intermediate layer composition is dried to form the intermediate layer 14, and the surface of the intermediate layer 14 is formed.
  • a method including a step of applying a photosensitive resin composition containing the polymer A and the polymerizable compound B1 and then drying the coating film of the photosensitive resin composition to form the photosensitive resin layer 16 can be mentioned.
  • thermoplastic resin composition containing at least one selected from the group consisting of an alkylene glycol ether solvent and an alkylene glycol ether acetate solvent, and a water- and water-mixable organic solvent.
  • a photosensitive resin containing at least one selected from the group consisting of an intermediate layer composition containing at least one of the above, polymer A, polymerizable compound B1, and an alkylene glycol ether solvent and an alkylene glycol ether acetate solvent. It is preferable to use with the composition.
  • thermoplastic resin layer 12 the components contained in the thermoplastic resin layer 12 during the application of the intermediate layer composition to the surface of the thermoplastic resin layer 12 and / or the storage period of the laminate having the coating film of the intermediate layer composition.
  • a laminate having a coating film of the photosensitive resin composition on the surface of the intermediate layer 14 and / or a coating film of the photosensitive resin composition which can suppress mixing with the components contained in the intermediate layer 14.
  • mixing of the component contained in the intermediate layer 14 and the component contained in the photosensitive resin layer 16 can be suppressed.
  • the photosensitive transfer member 100 is manufactured by pressing the cover film 18 against the photosensitive resin layer 16 of the laminate manufactured by the above manufacturing method.
  • the method for manufacturing the photosensitive transfer member according to the present disclosure includes a step of providing a cover film 18 so as to be in contact with the second surface of the photosensitive resin layer 16, thereby including a temporary support 10, a thermoplastic resin layer 12, and an intermediate. It is preferable to manufacture the photosensitive transfer member 100 including the layer 14, the photosensitive resin layer 16 and the cover film 18.
  • the photosensitive transfer member 100 in the form of a roll may be manufactured and stored by winding the photosensitive transfer member 100.
  • the roll-type photosensitive transfer member can be provided as it is in the process of bonding with a substrate in a roll-to-roll method described later.
  • the method for producing the resin pattern is not particularly limited as long as it is the method for producing the resin pattern using the above-mentioned photosensitive transfer member.
  • a method for producing a resin pattern a photosensitive transfer member and a substrate (preferably a conductive substrate) are placed on a second surface of the photosensitive resin layer, that is, a surface on a side not facing the temporary support. (Hereinafter referred to as "bonding step"), a step of pattern-exposing the photosensitive resin layer (hereinafter also referred to as "exposure step”), and developing the exposed photosensitive resin layer.
  • a method including a step of forming a resin pattern hereinafter, also referred to as a “development step” in this order is preferable.
  • the method for manufacturing the circuit wiring is not particularly limited as long as it is the method for manufacturing the circuit wiring using the above-mentioned photosensitive transfer member.
  • the circuit wiring is manufactured in a region where the resin pattern is not arranged in the laminated body in which the substrate, the conductive layer, and the resin pattern manufactured by using the above-mentioned photosensitive transfer member are laminated in this order.
  • a method including a step of etching the conductive layer (hereinafter, also referred to as an “etching step”) is preferable, and a resin pattern manufactured by a manufacturing method including the bonding step, the exposure step, and the developing step is used. If so, it is more preferable.
  • etching step a method including a step of etching the conductive layer
  • the method for producing the resin pattern preferably includes a bonding step.
  • the bonding step it is preferable that the substrate (or the conductive layer when the conductive layer is provided on the surface of the substrate) is brought into contact with the second surface of the photosensitive resin layer, and the photosensitive transfer member and the substrate are pressure-bonded. ..
  • the adhesion between the second surface of the photosensitive resin layer and the substrate is improved, it is suitable as an etching resist when etching the patterned photosensitive resin layer conductive layer after exposure and development. Can be used.
  • the cover film may be removed from the surface of the photosensitive resin layer and then bonded. Further, in the bonding step, a layer other than the cover film (for example, a high refractive index layer and / or a low refractive index layer) is further formed on the surface of the photosensitive resin layer on the side where the photosensitive transfer member does not face the temporary support. When provided, the surface of the photosensitive resin layer on the side not having the temporary support and the substrate are bonded to each other via the layer.
  • a layer other than the cover film for example, a high refractive index layer and / or a low refractive index layer
  • the method of crimping the substrate and the photosensitive transfer member is not particularly limited, and a known transfer method and laminating method can be used.
  • the bonding of the photosensitive transfer member to the substrate is preferably performed by stacking the substrate on the second surface side of the photosensitive resin layer and applying pressure and heating by means such as a roll.
  • a known laminator such as a laminator, a vacuum laminator, and an auto-cut laminator capable of further increasing productivity can be used.
  • the resin pattern manufacturing method including the bonding step and the circuit wiring manufacturing method are preferably performed by a roll-to-roll method.
  • the roll-to-roll method will be described below.
  • the roll-to-roll method is a structure in which a substrate that can be wound and unwound is used as the substrate, and the substrate or the substrate is included before any of the steps included in the resin pattern manufacturing method or the circuit wiring manufacturing method. Includes a step of unwinding a body (also referred to as a "unwinding step”) and a step of winding up a structure including a base material or a substrate (also referred to as a "winding step”) after any of the steps.
  • the unwinding method in the unwinding step and the winding method in the winding step are not particularly limited, and a known method may be used in the manufacturing method to which the roll-to-roll method is applied.
  • a known substrate may be used, but a substrate having a conductive layer is preferable, and it is more preferable to have a conductive layer on the surface of the substrate. ..
  • the substrate may have any layer other than the conductive layer, if necessary.
  • the base material constituting the substrate examples include glass, silicon and film.
  • the base material constituting the substrate is preferably transparent.
  • transparent means that the transmittance of light having a wavelength of 400 to 700 nm is 80% or more.
  • the refractive index of the base material constituting the substrate is preferably 1.50 to 1.52.
  • the transparent glass base material examples include tempered glass represented by Corning's gorilla glass. Further, as the transparent glass substrate, the materials used in JP-A-2010-086644, JP-A-2010-152809 and JP-A-2010-257492 can be used.
  • a film base material When a film base material is used as the base material, it is preferable to use a film base material having low optical distortion and / or high transparency.
  • a film substrate examples include polyethylene terephthalate (PET), polyethylene naphthalate, polycarbonate, triacetyl cellulose and cycloolefin polymers.
  • the base material of the substrate a film base material is preferable when it is manufactured by the roll-to-roll method. Further, when a circuit wiring for a touch panel is manufactured by a roll-to-roll method, it is preferable that the base material is a sheet-like resin composition.
  • Examples of the conductive layer included in the substrate include known conductive layers used for circuit wiring or touch panel wiring.
  • As the conductive layer at least one layer selected from the group consisting of a metal layer, a conductive metal oxide layer, a graphene layer, a carbon nanotube layer and a conductive polymer layer is preferable from the viewpoint of conductivity and fine wire forming property.
  • a metal layer is more preferable, and a copper layer or a silver layer is further preferable.
  • the substrate may have one conductive layer alone, or may have two or more conductive layers. When having two or more conductive layers, it is preferable to have conductive layers made of different materials.
  • Examples of the material of the conductive layer include metals and conductive metal oxides.
  • Examples of the metal include Al, Zn, Cu, Fe, Ni, Cr, Mo, Ag and Au.
  • Examples of the conductive metal oxide include ITO (Indium Tin Oxide), IZO (Indium Zinc Oxide) and SiO 2 .
  • conductive means that the volume resistivity is less than 1 ⁇ 10 6 ⁇ cm.
  • the volume resistivity of the conductive metal oxide is preferably less than 1 ⁇ 10 4 ⁇ cm.
  • At least one conductive layer among the plurality of conductive layers contains a conductive metal oxide.
  • the conductive layer an electrode pattern corresponding to a sensor of a visual recognition portion used in a capacitive touch panel or wiring of a peripheral extraction portion is preferable.
  • the method for producing the resin pattern preferably includes a step (exposure step) of pattern-exposing the photosensitive resin layer after the bonding step.
  • the electrode pattern and / or the portion of the take-out wiring of the touch panel includes a thin wire having a width of 20 ⁇ m or less, and more preferably a thin wire having a width of 10 ⁇ m or less.
  • the light source used for exposure can be appropriately selected and used as long as it is a light source that irradiates the photosensitive resin layer with light having a wavelength that allows exposure (for example, 365 nm or 405 nm).
  • a light source that irradiates the photosensitive resin layer with light having a wavelength that allows exposure for example, 365 nm or 405 nm.
  • Specific examples thereof include ultra-high pressure mercury lamps, high pressure mercury lamps, metal halide lamps and LEDs (Light Emitting Diodes).
  • the exposure amount is preferably 5 ⁇ 200mJ / cm 2, more preferably 10 ⁇ 100mJ / cm 2.
  • the temporary support may be peeled off from the photosensitive resin layer and then pattern-exposed, or the temporary support may be peeled off after pattern-exposure through the temporary support.
  • the pattern exposure may be an exposure through a mask or a direct exposure using an exposure means such as a laser.
  • the method for producing a resin pattern preferably includes, after the above-mentioned exposure step, a step (development step) of developing the exposed photosensitive resin layer to form a resin pattern.
  • a step (development step) of developing the exposed photosensitive resin layer to form a resin pattern When the photosensitive transfer member has a thermoplastic resin and an intermediate layer, the thermoplastic resin layer and the intermediate layer in the non-exposed portion are also removed together with the photosensitive resin layer in the non-exposed portion in the developing step. Further, in the developing step, the thermoplastic resin layer and the intermediate layer of the exposed portion may also be removed in a form of being dissolved or dispersed in the developing solution.
  • the developing solution is not particularly limited as long as the non-image portion (non-exposed portion) of the photosensitive resin layer can be removed.
  • a known developing solution such as the developing solution described in JP-A-5-07724 can be used. Can be used.
  • the developer may contain a water-soluble organic solvent and / or a surfactant.
  • the developing solution described in paragraph 0194 of International Publication No. 2015/093271 is also preferable.
  • the development method is not particularly limited, and may be any of paddle development, shower development, shower and spin development, and dip development.
  • Shower development is a development process for removing a non-exposed portion by spraying a developing solution on the photosensitive resin layer after exposure by a shower. After the developing step, it is preferable to spray the cleaning agent with a shower and rub with a brush to remove the developing residue.
  • the temperature of the developing solution is not particularly limited, but is preferably 20 to 40 ° C.
  • a substrate, a conductive layer, and a resin pattern are laminated in this order. It is preferable to include a step (etching step) of etching the conductive layer in the region where the resin pattern is not arranged in the laminated body.
  • the resin pattern formed from the photosensitive resin layer is used as an etching resist, and the conductive layer is etched.
  • a method of etching treatment a known method can be applied, and for example, the method described in paragraphs 0209 to 0210 of JP2017-120435A and the method described in paragraphs 0048 to 0054 of JP2010-152155A. Examples thereof include a wet etching method in which the material is immersed in an etching solution, and a dry etching method such as plasma etching.
  • an acidic or alkaline etching solution may be appropriately selected according to the etching target.
  • the acidic etching solution include an aqueous solution of an acidic component alone selected from hydrochloric acid, sulfuric acid, nitric acid, acetic acid, hydrofluoric acid, oxalic acid and phosphoric acid, an acidic component, ferric chloride, ammonium fluoride and Examples thereof include a mixed aqueous solution with a salt selected from potassium permanganate.
  • the acidic component may be a component in which a plurality of acidic components are combined.
  • an aqueous solution of an alkaline component alone selected from sodium hydroxide, potassium hydroxide, ammonia, an organic amine, and a salt of an organic amine (tetramethylammonium hydroxide, etc.), and an alkaline component and a salt. Examples thereof include a mixed aqueous solution with (potassium hydroxide, etc.).
  • the alkaline component may be a component in which a plurality of alkaline components are combined.
  • the removing step is not particularly limited and can be performed as needed, but it is preferably performed after the etching step.
  • the method for removing the remaining resin pattern is not particularly limited, and examples thereof include a method for removing by chemical treatment, and a method for removing with a removing liquid is preferable.
  • a method for removing the photosensitive resin layer a substrate having a residual resin pattern is immersed in a stirring liquid having a liquid temperature of preferably 30 to 80 ° C., more preferably 50 to 80 ° C. for 1 to 30 minutes. There is a way to do it.
  • the removing solution examples include a removing solution in which an inorganic alkaline component or an organic alkaline component is dissolved in water, dimethyl sulfoxide, N-methylpyrrolidone, or a mixed solution thereof.
  • the inorganic alkaline component examples include sodium hydroxide and potassium hydroxide.
  • the organic alkali component examples include a primary amine compound, a secondary amine compound, a tertiary amine compound and a quaternary ammonium salt compound.
  • the removing liquid may be used and removed by a known method such as a spray method, a shower method and a paddle method.
  • the circuit wiring manufacturing method may include any process (other process) other than the above-mentioned process.
  • the following steps can be mentioned, but the steps are not limited to these steps.
  • examples of the exposure step, the developing step, and other steps applicable to the method for manufacturing the circuit wiring include the steps described in paragraphs 0035 to 0051 of JP-A-2006-023696.
  • the method for producing the resin pattern preferably includes a step of peeling the cover film from the photosensitive transfer member.
  • the method of peeling the cover film is not limited, and a known method can be applied.
  • the method for manufacturing the circuit wiring may include a step of reducing the visible light reflectance of a part or all of the plurality of conductive layers of the base material.
  • the treatment for reducing the visible light reflectance include an oxidation treatment.
  • the visible light reflectance of the conductive layer can be reduced by oxidizing copper to copper oxide and blackening the conductive layer.
  • the treatment for lowering the visible light reflectance is described in paragraphs 0017 to 0025 of JP-A-2014-150118 and paragraphs 0041, 0042, 0048 and 0058 of JP-A-2013-206315. , The contents of these publications are incorporated herein by reference.
  • the method for manufacturing a circuit wiring preferably includes a step of forming an insulating film on the surface of the circuit wiring and a step of forming a new conductive layer on the surface of the insulating film.
  • a second electrode pattern insulated from the first electrode pattern can be formed.
  • the step of forming the insulating film is not particularly limited, and examples thereof include a known method of forming a permanent film.
  • an insulating film having a desired pattern may be formed by photolithography using a photosensitive material having an insulating property.
  • the step of forming the new conductive layer on the insulating film is not particularly limited, and for example, a new conductive layer having a desired pattern may be formed by photolithography using a photosensitive material having conductivity.
  • a substrate having a plurality of conductive layers on both surfaces of the base material it is also preferable to use a substrate having a plurality of conductive layers on both surfaces of the base material, and to form circuits sequentially or simultaneously on the conductive layers formed on both surfaces of the base material.
  • a circuit wiring for a touch panel in which a first conductive pattern is formed on one surface of a base material and a second conductive pattern is formed on the other surface. It is also preferable to form the touch panel circuit wiring having such a configuration from both sides of the base material by roll-to-roll.
  • the circuit wiring manufactured by the method of manufacturing the circuit wiring can be applied to various devices.
  • Examples of the device provided with the circuit wiring manufactured by the above manufacturing method include an input device, a touch panel is preferable, and a capacitance type touch panel is more preferable.
  • the input device can be applied to a display device such as an organic EL display device and a liquid crystal display device.
  • the method for manufacturing the touch panel is not particularly limited as long as it is the method for manufacturing the touch panel using the above-mentioned photosensitive transfer member.
  • a method for manufacturing a touch panel in a laminate in which a substrate, a conductive layer, and a resin pattern manufactured by using the above-mentioned photosensitive transfer member are laminated in this order, the conductivity is in a region where the resin pattern is not arranged.
  • a method including a step of forming a touch panel wiring by etching a layer is preferable, and a resin pattern manufactured by a manufacturing method including the bonding step, the exposure step, and the developing step is used. , More preferred.
  • each step in the touch panel manufacturing method and the embodiment such as the order in which each step is performed are as described in the above-mentioned "Circuit wiring manufacturing method", and the preferred embodiments are also the same.
  • the method for manufacturing the touch panel a known method for manufacturing the touch panel may be referred to except that the wiring for the touch panel is formed by the above method.
  • the touch panel manufacturing method may include any process (other process) other than those described above.
  • FIGS. 2 and 3 An example of a mask pattern used in manufacturing a touch panel is shown in FIGS. 2 and 3.
  • SL and G are non-image parts (light-shielding parts)
  • DL is a virtual representation of the alignment frame.
  • a touch panel in which a circuit wiring having a pattern A corresponding to SL and G is formed is manufactured. it can. Specifically, it can be produced by the method shown in FIG. 1 of International Publication No. 2016/190405.
  • G is a portion where a transparent electrode (touch panel electrode) is formed
  • SL is a portion where wiring of a peripheral take-out portion is formed.
  • a touch panel having at least touch panel wiring is manufactured.
  • the touch panel preferably has a transparent substrate, electrodes, and an insulating layer or a protective layer.
  • Examples of the detection method on the touch panel include known methods such as a resistive film method, a capacitance method, an ultrasonic method, an electromagnetic induction method, and an optical method. Above all, the capacitance method is preferable.
  • the touch panel type includes a so-called in-cell type (for example, those shown in FIGS. 5, 6, 7, and 8 of JP-A-2012-517501), a so-called on-cell type (for example, JP-A-2013-168125).
  • in-cell type for example, those shown in FIGS. 5, 6, 7, and 8 of JP-A-2012-517501
  • on-cell type for example, JP-A-2013-168125.
  • the ones shown in FIG. 19 and those shown in FIGS. 1 and 5 of JP2012-081020A eg, Japanese Patent Application Laid-Open No. 2012
  • OGS One Glass Solution
  • TOR Touch-on-Lens
  • Polymer A-1 was synthesized according to the following method. In the method for synthesizing polymer A-1, the following abbreviations represent the following compounds, respectively.
  • St Styrene (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
  • MAA Methacrylic acid (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
  • MMA Methyl methacrylate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
  • V-601 2,2'-azobis (isobutyric acid) dimethyl (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., polymerization initiator)
  • PGMEA Propylene glycol monomethyl ether acetate
  • PGMEA 116.5 parts was placed in a three-necked flask, and the temperature was raised to 90 ° C. in a nitrogen atmosphere.
  • St 52.0 parts
  • Polymers A-2 to A-9 were synthesized according to the method for synthesizing polymer A-1, except that the type and amount of the monomers used for synthesizing the polymer were changed as shown in Table 1 below.
  • a composition containing 30.0% by mass of the coalesced A-2 to A-9 was obtained.
  • the unit of the amount of each monomer shown in Table 1 is mass%.
  • Table 1 shows the acid values (unit: mgKOH / g) of the obtained polymers A-1 to A-9.
  • B-1 NK ester BPE-500 (2,2-bis (4- (methacryloxypentaethoxy) phenyl) propane, manufactured by Shin Nakamura Chemical Industry Co., Ltd.)
  • B-2 Aronix M-270 (polypropylene glycol diacrylate, manufactured by Toagosei Co., Ltd.)
  • B-3 NK ester A-TMPT (trimethylolpropane triacrylate, manufactured by Shin Nakamura Chemical Industry Co., Ltd.)
  • B-4 UA306H (Pentaerythritol triacrylate hexamethylene diisocyanate urethane prepolymer, manufactured by Kyoeisha Chemical Co., Ltd.)
  • B-6 SR494NS (Ethoxylation (4) Pentaerythritol Tetraacryl
  • C-1 B-CIM (photoradical polymerization initiator, 2- (2-chlorophenyl) -4,5-diphenylimidazole dimer, manufactured by Hampford)
  • C-2 EAB-F (photoradical polymerization initiator (sensitizer), 4,4'-bis (diethylamino) benzophenone, manufactured by Tokyo Kasei Co., Ltd.)
  • E-1 Mega Fvck F552 (manufactured by DIC Corporation)
  • E-2 Mega Fvck F551 (manufactured by DIC Corporation)
  • ⁇ Intermediate layer composition> The following components were mixed to prepare an intermediate layer composition.
  • -Ion-exchanged water 38.12 parts-Methanol (manufactured by Mitsubishi Gas Chemical Company, Inc.): 57.17 parts-Clarepovar PVA-205 (polyvinyl alcohol, manufactured by Kuraray Co., Ltd.): 3.22 parts-Polyvinylpyrrolidone K -30 (manufactured by Nippon Catalyst Co., Ltd.): 1.49 parts, Megafuck F-444 (fluorine-based nonionic surfactant, manufactured by DIC Co., Ltd.): 0.0015 parts
  • thermoplastic resin composition The following components were mixed to prepare a thermoplastic resin composition.
  • ⁇ Copolymer of benzyl methacrylate, methacrylic acid and acrylic acid solid content concentration 30.0%, Mw30000, acid value 153 mgKOH / g): 42.85 parts
  • ⁇ NK ester A-DCP tricyclodecanedimethanol diacrylate, Shin-Nakamura Chemical Industry Co., Ltd.
  • 8UX-015A polyfunctional urethane acrylate compound, manufactured by Taisei Fine Chemical Co., Ltd.
  • Aronix TO-2349 polyfunctional acrylate having a carboxy group
  • Compound manufactured by Toa Synthesis Co., Ltd .
  • 0.77 parts-Compound having the structure shown below photoacid generator, compound synthesized according to the method described in paragraph 0227 of JP2013-047765A
  • ⁇ E-1 0.03 parts ⁇ MEK (manufactured by Sankyo Chemical Co., Ltd.): 39.50 parts ⁇ PGMEA (manufactured by Showa Denko Co., Ltd.): 9.51 parts
  • a PET film having a thickness of 30 ⁇ m was prepared as a temporary support.
  • the above thermoplastic resin composition was applied to the surface of the temporary support using a slit-shaped nozzle so that the coating width was 1.0 m and the layer thickness after drying was 4.0 ⁇ m.
  • the coating film of the formed thermoplastic resin composition was dried at 80 ° C. for 40 seconds to form a thermoplastic resin layer.
  • the above intermediate layer composition was applied to the surface of the formed thermoplastic resin layer using a slit-shaped nozzle so that the coating width was 1.0 m and the layer thickness after drying was 1.2 ⁇ m.
  • the coating film of the intermediate layer composition was dried at 80 ° C. for 40 seconds to form an intermediate layer.
  • the photosensitive resin composition RC-1 was applied to the surface of the formed intermediate layer using a slit-shaped nozzle so that the coating width was 1.0 m and the layer thickness after drying was 3.0 ⁇ m.
  • the coating film of the photosensitive resin composition RC-1 was dried at 80 ° C. for 40 seconds to form a photosensitive resin layer.
  • a PET film manufactured by Toray Industries, Inc., Lumirror 16QS62, arithmetic average roughness (Ra value) 0.02 ⁇ m
  • the obtained photosensitive transfer member was wound up to prepare a roll-shaped photosensitive transfer member.
  • the Ra value of the cover film was measured by the following method. Using a three-dimensional optical profiler (New View7300, manufactured by Zygo), the surface of the cover film was measured under the following conditions to obtain a surface profile of the cover film. As the measurement / analysis software, Microscope Application of MetroPro ver 8.3.2 was used. Next, the Surface Map screen was displayed with the above software, and histogram data was obtained in the Surface Map screen. From the obtained histogram data, the arithmetic mean roughness (Ra value) of the surface of the cover film was calculated.
  • a value arithmetic mean roughness
  • a PET substrate with a copper layer was produced by forming a copper layer having a thickness of 200 nm on a polyethylene terephthalate (PET) film having a thickness of 100 ⁇ m by a sputtering method.
  • PET polyethylene terephthalate
  • the photosensitive resin layer was exposed by irradiating an ultra-high pressure mercury lamp (exposure main wavelength: 365 nm) from the temporary support side of the obtained laminate via a photomask.
  • the ratio of the widths of the transmission region and the light-shielding region is 1: 1 and the line width (and space width) changes stepwise from 1 ⁇ m to 20 ⁇ m every 1 ⁇ m. It had a line and space pattern.
  • the photosensitive resin layer has a line width of a line-and-space pattern and a line width of a resin pattern formed by exposure by irradiation light passing through a region where the space width is 20 ⁇ m. The amount of exposure to light was adjusted.
  • the laminate was shower-developed for 30 seconds using a 1.0% sodium carbonate aqueous solution having a liquid temperature of 25 ° C.
  • a 1.0% sodium carbonate aqueous solution having a liquid temperature of 25 ° C.
  • the minimum line width (hereinafter also referred to as "resolution") of the line width of the resin pattern in which the cured photosensitive resin layer does not peel off at the line portion and there is no residue of the photosensitive resin layer is determined, and the resin pattern is determined.
  • the resolution of was evaluated based on the following criteria. 5: Resolution is 4 ⁇ m or less 4: Resolution is 5 ⁇ m or 6 ⁇ m 3: Resolution is 7 ⁇ m or 8 ⁇ m 2: Resolution is 9 ⁇ m or 10 ⁇ m 1: The resolution is 11 ⁇ m or more. The higher the score, the better the resolution.
  • the resolution is preferably 3 or more.
  • the PET substrate with a copper layer is subjected to the method described in the above (evaluation of resolution).
  • a resin pattern was formed on the surface of the copper layer.
  • the obtained resin pattern had a line-and-space pattern having a duty ratio of 1: 1 and a line width of 10 ⁇ m.
  • the laminate having the above resin pattern was immersed in a stripping solution at 40 ° C. (KP-301 manufactured by Kanto Chemical Co., Inc.), and the stripping solution was stirred at 100 rpm.
  • the time required for the resin pattern to completely peel off from the surface of the copper layer after the start of immersion of the laminate in the stripping liquid was measured, and the peelability of the resin pattern was evaluated based on the following criteria. 5: Peeling time within 0.5 minutes 4: Peeling time over 0.5 minutes and within 1 minute 3: Peeling time over 1 minute and within 2 minutes 2: Peeling time over 2 minutes and within 5 minutes 1: Peeling time More than 5 minutes
  • the peelability is preferably 3 or more.
  • the lamination having the resin pattern was performed according to the method described in Example 1. The body was made.
  • the “layer thickness” column of the "photosensitive resin layer” in Table 3 indicates the layer thickness (unit: ⁇ m) of the photosensitive resin layer included in the photosensitive transfer member.
  • the “transmittance” column of the "photosensitive resin layer” in Table 3 shows the transmittance of light having a wavelength of 365 nm passing through the photosensitive resin layer.
  • the “Cover film” column in Table 3 indicates that the following cover film was used in the production of the photosensitive transfer member.
  • CF-1 Lumirror 16QS62 (manufactured by Toray Industries, Inc., PET film, Ra value: 0.02 ⁇ m)
  • CF-2 Lumirror 16FB40 (manufactured by Toray Industries, Inc., PET film, Ra value: 0.05 ⁇ m)
  • CF-3 Alfan E501 (manufactured by Oji F-Tex Co., Ltd., PET film, Ra value: 0.138 ⁇ m)
  • the layer thickness of the photosensitive resin layer is preferably less than 5 ⁇ m from the viewpoint of better resolution of the resin pattern and peelability of the resin pattern from the substrate (comparison between Example 2 and Example 7). ..
  • the styrene content is preferably 50% by mass or more (comparison between Examples 3 and 9 and Example 7) from the viewpoint of more excellent resolution of the resin pattern. Further, it was confirmed that the styrene content is preferably 70% by mass or less (comparison between Example 10 and Example 11) and more preferably 60% by mass or less from the viewpoint of more excellent peelability of the resin pattern from the substrate. (Comparison between Example 11 and Example 7).
  • the acid value of the polymer A is preferably less than 200 mgKOH / g from the viewpoint of more excellent resolution of the resin pattern (comparison between Examples 4 and 7). Further, the acid value of the polymer A is preferably 155 mgKOH / g or more (comparison between Example 5 and Example 6) from the viewpoint of more excellent resolution of the resin pattern and peelability from the substrate, and the substrate of the resin pattern. It was confirmed that the acid value of the polymer A is more preferably 170 mgKOH / g or more from the viewpoint of further excellent peelability from the polymer (comparison between Example 5 and Example 7).
  • the ratio 1 (mass ratio of the content of the polymerizable compound B1 to the total content of the polymerizable compound B) is preferably more than 60% by mass (Examples 12 and 12). (Comparison with 13), it was confirmed that more than 70% by mass was more preferable (comparison between Example 7 and Example 12). It was confirmed that the ratio 1 (mass ratio of the content of the polymerizable compound B1 to the total content of the polymerizable compound B) is preferably 99% by mass or less from the viewpoint of more excellent peelability of the resin pattern from the substrate. (Comparison between Example 7 and Example 19).
  • the content of the bifunctional ethylenically unsaturated compound with respect to the content of the polymerizable compound B is preferably more than 70% by mass from the viewpoint of more excellent peelability of the resin pattern from the substrate (Example 7 and). Comparison of 12 with Examples 16-18).
  • the photosensitive resin layer contains a fluorine-based nonionic surfactant from the viewpoint of better resolution of the resin pattern (comparison between Example 7 and Example 8).
  • the arithmetic mean roughness Ra value of the surface of the cover film in contact with the photosensitive resin layer is preferably 0.1 ⁇ m or less because the resolution of the resin pattern is more excellent (Examples 7 and 15). comparison).
  • Example 101 An ITO having a thickness of 150 nm is formed by sputtering on a PET substrate having a thickness of 100 ⁇ m as a second conductive layer, and a copper layer having a thickness of 200 nm as a first conductive layer is formed therein by a vacuum vapor deposition method. The film was formed and used as a circuit forming substrate. After peeling the cover film from the photosensitive transfer member obtained in Example 1, the photosensitive transfer member and the substrate are bonded to each other with the photosensitive resin layer in contact with the copper layer (laminate roll temperature 100 ° C.). , Linear pressure 0.8 MPa, linear velocity 3.0 m / min.), A laminate was prepared.
  • the temporary support was peeled off from the laminated body, developed and washed with water to obtain a pattern A (resin pattern).
  • the copper layer in the region where the pattern A is not arranged is etched with a copper etching solution (Cu-02 manufactured by Kanto Chemical Co., Ltd.), and then the ITO etching solution (ITO-02 manufactured by Kanto Chemical Co., Ltd.) is used. ) was used to etch the ITO layer in the region where the resin pattern was not arranged to obtain a substrate in which both copper and ITO were drawn in the pattern A.
  • Example 2 Another photosensitive transfer member obtained in Example 1 was prepared, and after the cover film was peeled off, the photosensitive transfer member and the laminate in which the resist (cured photosensitive resin layer) remained were combined with each other. It was reattached under the same conditions as above.
  • the photosensitive resin layer included in the laminated body was subjected to pattern exposure via the temporary support using a photomask provided with the pattern B shown in FIG. 3 without peeling the temporary support.
  • a high-pressure mercury lamp having i-line (365 nm) as the main exposure wavelength was used.
  • the temporary support was peeled off from the laminated body, developed and washed with water to obtain a pattern B (resin pattern).

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JP2022154008A (ja) * 2021-03-30 2022-10-13 三菱ケミカル株式会社 電気触覚デバイス及び触覚デバイス用部材
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