WO2022044963A1 - 転写フィルム、積層体の製造方法、回路配線の製造方法、電子デバイスの製造方法 - Google Patents

転写フィルム、積層体の製造方法、回路配線の製造方法、電子デバイスの製造方法 Download PDF

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Publication number
WO2022044963A1
WO2022044963A1 PCT/JP2021/030399 JP2021030399W WO2022044963A1 WO 2022044963 A1 WO2022044963 A1 WO 2022044963A1 JP 2021030399 W JP2021030399 W JP 2021030399W WO 2022044963 A1 WO2022044963 A1 WO 2022044963A1
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Prior art keywords
resin composition
composition layer
group
preferable
transfer film
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PCT/JP2021/030399
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English (en)
French (fr)
Japanese (ja)
Inventor
悟 山田
寛 野副
一真 両角
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Fujifilm Corp
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Fujifilm Corp
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Priority to JP2022544522A priority Critical patent/JP7682185B2/ja
Priority to CN202180050843.0A priority patent/CN115884875B/zh
Publication of WO2022044963A1 publication Critical patent/WO2022044963A1/ja
Priority to US18/170,591 priority patent/US20230194988A1/en
Anticipated expiration legal-status Critical
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
    • 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
    • G03F1/00—Originals for photomechanical production of textured or patterned surfaces, e.g., masks, photo-masks, reticles; Mask blanks or pellicles therefor; Containers specially adapted therefor; Preparation thereof
    • G03F1/68—Preparation processes not covered by groups G03F1/20 - G03F1/50
    • G03F1/80—Etching
    • 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
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • 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
    • G03F7/0047—Photosensitive materials characterised by additives for obtaining a metallic or ceramic pattern, e.g. by firing
    • 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
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G03F7/0382—Macromolecular compounds which are rendered insoluble or differentially wettable the macromolecular compound being present in a chemically amplified negative photoresist composition
    • 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
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • 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
    • G03F7/20—Exposure; Apparatus therefor
    • G03F7/2002—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image
    • G03F7/2004—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image characterised by the use of a particular light source, e.g. fluorescent lamps or deep UV light
    • 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
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/34—Imagewise removal by selective transfer, e.g. peeling away
    • 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
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P72/00—Handling or holding of wafers, substrates or devices during manufacture or treatment thereof
    • H10P72/70—Handling or holding of wafers, substrates or devices during manufacture or treatment thereof for supporting or gripping
    • H10P72/74—Handling or holding of wafers, substrates or devices during manufacture or treatment thereof for supporting or gripping using temporarily an auxiliary support

Definitions

  • the present invention relates to a transfer film, a method for manufacturing a laminate, a method for manufacturing a circuit wiring, and a method for manufacturing an electronic device.
  • Patent Document 1 discloses a transfer film containing a copolymer having a predetermined fluoroalkyl group.
  • the present inventor examined a transfer film as disclosed in Patent Document 1, it was found that the pattern obtained after exposure and development was liable to have an appearance defect. Specifically, the pattern is easily peeled off or residue is easily generated during pattern formation, and a high-resolution pattern cannot be obtained.
  • the pattern contains a pigment, the density unevenness is large, and there are many defects on the surface of the pattern. Can be mentioned.
  • the pattern is easily peeled off or residue is easily generated at the time of pattern formation, and a high-resolution pattern cannot be obtained, the density unevenness is large when the pattern contains a pigment, and the surface of the pattern is defective. It is also said that the ability to suppress at least one of the many cases is less likely to cause poor appearance of the pattern.
  • Another object of the present invention is to provide a transfer film in which the appearance of the pattern is less likely to be poor. Another object of the present invention is to provide a method for manufacturing a laminated body, a method for manufacturing a circuit wiring, and a method for manufacturing an electronic device regarding the transfer film.
  • the resin composition layer is made of resin, It includes a block composed of a structural unit X having a group represented by the formula (A) described later or a group represented by the formula (B) described later, and a block composed of a structural unit Y having a poly (oxyalkylene) group.
  • the resin is an alkali-soluble resin, The transfer film according to any one of [1] to [5], wherein the resin composition layer further contains a polymerizable compound.
  • the resin is a resin having a structural unit having an acid group protected by an acid-degradable group.
  • the substrate is brought into contact with the surface of the transfer film according to any one of [1] to [12] on the opposite side of the temporary support, and the transfer film and the substrate are bonded to each other with a transfer film.
  • the bonding process to obtain the substrate and An exposure process for pattern exposure of the resin composition layer and A developing step of developing an exposed resin composition layer to form a resin pattern Further, a method for manufacturing a laminated body, which comprises a peeling step of peeling a temporary support from a substrate with a transfer film between a bonding step and an exposure step, or between an exposure step and a developing step.
  • the present invention it is possible to provide a transfer film in which the appearance of the pattern is less likely to deteriorate. Further, it is possible to provide a method for manufacturing a laminated body, a method for manufacturing a circuit wiring, and a method for manufacturing an electronic device regarding the transfer film.
  • the present invention will be described in detail.
  • the description of the constituent elements described below may be based on the representative embodiments of the present invention, but the present invention is not limited to such embodiments.
  • 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.
  • the bonding direction of the divalent group (for example, —CO—O—) described is not particularly limited.
  • (meth) acrylate represents acrylate and methacrylate.
  • (Meta) acrylic acid represents acrylic acid and methacrylic acid.
  • the (meth) acryloyl group represents a meta-acryloyl group or an acryloyl group.
  • the notation that does not describe substitution or non-substitution includes a group having a substituent as well as a group having no substituent.
  • the "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).
  • the "organic group” in the present specification means a group containing at least one carbon atom.
  • the type of the substituent, the position of the substituent, and the number of the substituents when "may have a substituent" are not particularly limited.
  • the number of substituents may be, for example, one, two, three, or more. Further, it may be non-replacement.
  • the substituent include a monovalent non-metal atomic group excluding a hydrogen atom, and for example, it can be selected from the following substituent group T.
  • the substituent T includes a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom; an alkoxy group such as a methoxy group, an ethoxy group and a tert-butoxy group; and an aryloxy group such as a phenoxy group and a p-tolyloxy group.
  • a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom
  • an alkoxy group such as a methoxy group, an ethoxy group and a tert-butoxy group
  • an aryloxy group such as a phenoxy group and a p-tolyloxy group.
  • alkoxycarbonyl group such as methoxycarbonyl group, butoxycarbonyl group, and phenoxycarbonyl group
  • acyloxy group such as acetoxy group, propionyloxy group, and benzoyloxy group
  • acyl groups such as metoxaryl groups; alkylsulfanyl groups such as methylsulfanyl and tert-butylsulfanyl groups; arylsulfanyl groups such as phenylsulfanyl and p-tolylsulfonyl groups; alkyl groups; cycloalkyl groups; aryl groups; hetero Aryl group; hydroxyl group; carboxy group; formyl group; sulfo group; cyano group; alkylaminocarbonyl group; arylaminocarbonyl group; sulfonamide group; silyl group; amino group; monoalkylamino group; dialkylamino group; arylamino group; In addition, these combinations can be mentioned.
  • the weight average molecular weight (Mw) and the number average molecular weight (Mn) are values calculated by gel permeation chromatography (GPC) in terms of polystyrene. GPC is measured under the following conditions.
  • THF Tetrahydrofuran
  • EcoSEC HLC-8320GPC manufactured by Tosoh Corporation
  • TSKgel SuperHZM-H TSKgel SuperHZ4000
  • TSKgel SuperHZ200 manufactured by Tosoh Corporation
  • the molecular weight of a compound having a molecular weight distribution is the weight average molecular weight (Mw).
  • the room temperature is 25 ° C. unless otherwise specified.
  • alkali-soluble means that the solubility of sodium carbonate in 100 g of a 1% by mass aqueous solution at 22 ° C. is 0.1 g or more.
  • water-soluble means that the solubility in 100 g of water having a liquid temperature of 22 ° C. and a pH of 7.0 is 0.1 g or more.
  • the layer thickness (thickness) of each layer provided in the transfer film or the like is determined by observing a cross section in a direction perpendicular to the main surface of the layer (film) with a scanning electron microscope (SEM). It is measured by measuring the thickness of each layer at 10 points or more based on the obtained observation image and calculating the average value thereof.
  • the transfer film has a temporary support and a resin composition layer arranged on the temporary support, and the resin composition layer is a resin and a group represented by the formula (A) or a group represented by the formula (B).
  • a block copolymer containing a block composed of a structural unit X having a represented group and a block composed of a structural unit Y having a poly (oxyalkylene) group (hereinafter, also simply referred to as "block copolymer”). as well as, It includes at least one compound selected from the group consisting of the compound represented by the formula (1) (hereinafter, also referred to as “compound (1)”).
  • the present inventors infer as follows.
  • the appearance of the above-mentioned pattern may be poor.
  • the appearance defect of the above pattern may occur more remarkably.
  • the present inventors have found that the above-mentioned problem is caused by air bubbles (pores) in the resin composition layer.
  • the group consisting of a predetermined block copolymer and compound (1) having a group represented by the formula (A) or a group represented by the formula (B) and a poly (oxyalkylene) group from the group consisting of a predetermined block copolymer and compound (1) having a group represented by the formula (A) or a group represented by the formula (B) and a poly (oxyalkylene) group.
  • each of the above groups in the resin composition layer containing at least one selected compound suppresses the generation of the above-mentioned bubbles (pores) and suppresses the appearance deterioration of the pattern.
  • the effect of the present invention is more excellent when the appearance defect of the pattern is less likely to occur.
  • the temporary support and one or more resin composition layers described later may be directly laminated without interposing another layer, or may be laminated via another layer. Further, another layer may be laminated on the surface of the resin composition layer having one or more layers opposite to the surface facing the temporary support. Another layer may be present between the one or more resin composition layers. That is, the transfer film preferably has one or more resin composition layers, and more preferably has two or more resin composition layers. In the transfer film, of the one or more layers (for example, 1 to 5 layers) of the resin composition layer, at least one layer may be the resin composition layer of the present invention, and more than half of the layers may be the resin composition of the present invention. It may be a layer, or all layers may be the resin composition layer of the present invention. It is also preferable that the transfer film contains at least one layer of the photosensitive resin composition described later. The photosensitive resin composition layer may be a colored resin composition layer.
  • the transfer film has a temporary support.
  • the temporary support is a support that supports and can be peeled off from the resin composition layer described later or the laminate containing the resin composition layer.
  • the temporary support preferably has light transmission property from the viewpoint of enabling exposure through the temporary support when pattern-exposing the resin composition layer.
  • “having light transmittance” means that the transmittance of light of the wavelength used for pattern exposure is 50% or more.
  • the transmittance of light having a wavelength (more preferably 365 nm) used for pattern exposure is preferably 60% or more, more preferably 70% or more.
  • the transmittance of the layer included in the transfer film is the emission 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 intensity 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) film, cellulose triacetate film, polystyrene film and polycarbonate film. Among them, a PET film is preferable, and a 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 are not particularly limited. From the viewpoint of transparency, it may be selected according to the material.
  • the thickness of the temporary support is preferably 5 to 100 ⁇ m, more preferably 10 to 50 ⁇ m, still more preferably 10 to 20 ⁇ m, and particularly preferably 10 to 16 ⁇ m from the viewpoint of ease of handling and versatility.
  • the film used as the temporary support is free from deformation such as wrinkles, scratches, defects and the like.
  • the number of fine particles, foreign substances, defects, precipitates and the like contained in the temporary support is small.
  • the number of fine particles, foreign matter and / or 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, further preferably 3 pieces / 10 mm 2 or less, and 0 pieces / 10 mm 2 . Especially preferable.
  • Preferred embodiments of the provisional support include, for example, paragraphs [0017] to [0018] of JP-A-2014-085643, paragraphs [0019]-[0026] of JP-A-2016-0273363, and International Publication No. 2012 /.
  • the resin composition layer of the present invention contains a resin and at least one compound selected from the group consisting of block copolymers and compound (1).
  • the mode of the resin composition layer may be, for example, a photosensitive resin composition layer, a thermoplastic resin composition layer, a colored resin composition layer, and / or a water-soluble resin composition layer, which will be described later.
  • the components that can be contained in each resin composition layer in each embodiment will be described. It should be noted that the component described as a component of the resin composition layer of one embodiment does not mean that it is allowed to be contained only when the resin composition layer is in that aspect, and as a component of the resin composition layer of another aspect. Can also be used.
  • the component described as a component of the photosensitive resin composition layer may be used as a component other than the photosensitive resin composition layer.
  • the resin composition layer contains a resin.
  • the above resin is a component different from the block copolymer described later.
  • the properties and / or characteristics of the resin are not limited and can be appropriately selected according to the use of the resin composition layer. The details of the resin will be described later according to each form of the resin composition layer.
  • the block copolymer has a block (block segment) consisting of a structural unit X having a group represented by the formula (A) or a group represented by the formula (B), and a poly (oxyalkylene) group. Includes a block (block segment) consisting of the unit Y.
  • a block copolymer is a polymer having a molecular structure in which a plurality of types of blocks are linked, and each block is a chain formed by linking constituent units.
  • the block structure of the block copolymer is not particularly limited, and examples thereof include block structures a to e represented by the formulas (a) to (e).
  • Equations (a) (A)-(B) In the formula (a), A represents a block composed of the structural unit X, and B represents a block composed of the structural unit Y.
  • the block structure a represented by the formula (a) is a block structure (AB type) in which a block composed of the constituent unit X and a block composed of the constituent unit Y are connected.
  • A represents a block composed of the structural unit X
  • B represents a block composed of the structural unit Y.
  • the block structure b represented by the formula (b) is a block structure (BAB type) in which a block composed of the constituent unit Y is connected to both ends of the block composed of the constituent unit X.
  • Equation (c) (B)-(A)-(C) A represents a block composed of the constituent unit X
  • B represents a block composed of the constituent unit Y
  • C represents a block composed of the constituent unit X and a constituent unit different from the constituent unit Y.
  • a block composed of the constituent unit Y, a block composed of the constituent unit X, and a block composed of a constituent unit X different from the constituent unit X and the constituent unit Y are arranged in this order. It is a connected block structure (BAC type).
  • A represents a block composed of the constituent unit X
  • B represents a block composed of the constituent unit Y
  • C represents a block composed of the constituent unit X and the first constituent unit different from the constituent unit Y
  • D represents a block composed of a constituent unit X, a constituent unit Y, and a second constituent unit different from the first constituent unit.
  • the block structure d represented by the formula (d) is a block composed of the constituent unit Y, a block composed of the constituent unit X, a block composed of the first constituent unit different from the constituent unit X and the constituent unit Y, and a constituent unit.
  • a block structure (BACD type) in which X, a structural unit Y, and a block composed of a second structural unit different from the first structural unit are connected in this order is shown.
  • Equation (e) (A)-(B)-(A)-(B)
  • A represents a block composed of the structural unit X
  • B represents a block composed of the structural unit Y.
  • the block structure e represented by the formula (e) is a block structure in which a block composed of the constituent unit X and a block composed of the constituent unit Y are alternately connected a plurality of times.
  • the block structure the block structures a to c are preferable, the block structure a or c is more preferable, and the block structure a is further preferable.
  • the number of types of blocks contained in the block structure is 2 or more, preferably 2 to 10, more preferably 2 to 5, further preferably 2 to 3, and particularly preferably 2 from the viewpoint of solubility.
  • the structural unit X has a group represented by the formula (A) or a group represented by the formula (B). Among them, the structural unit X preferably has a group represented by the formula (A) in that the effect of the present invention is more excellent.
  • m and n each independently represent an integer of 1 to 3.
  • m an integer of 2 to 3 is preferable, and 2 is more preferable.
  • n an integer of 2 to 3 is preferable, and 3 is more preferable.
  • * Represents the bond position.
  • the number of groups represented by the formula (A) of the structural unit X is preferably 1 to 3, and more preferably 1.
  • L 1 represents an oxygen atom or an alkylene group.
  • the alkylene group represented by L 1 may be linear or branched.
  • the number of carbon atoms of the alkylene group represented by L 1 is preferably 1 to 10, more preferably 1 to 6, further preferably 1 to 3, and particularly preferably 1 to 2.
  • the alkylene group represented by L 1 may have a substituent.
  • the substituent is not particularly limited, and examples thereof include the substituents exemplified in the substituent group T.
  • L 1 an oxygen atom or an alkylene group having 1 to 2 carbon atoms is preferable, and an oxygen atom is more preferable.
  • the number of groups represented by the formula (B) of the structural unit X is preferably 1 to 3, and more preferably 1.
  • the structural unit X the structural unit represented by the formula (C) is preferable.
  • R represents a hydrogen atom or a substituent.
  • the substituent represented by R is not particularly limited, and examples thereof include the substituents exemplified in the substituent group T, and an alkyl group having 1 to 6 carbon atoms is preferable.
  • L represents a single bond or a divalent linking group. Examples of the divalent linking group include -O-, -CO-, -S-, -SO 2- , -NR X- ( RX represents a hydrogen atom or a substituent), an alkylene group, and an alkenylene.
  • Examples thereof include a group, an alkynylene group, an aromatic ring group, an alicyclic group, and a group combining these (for example, -CO-O-, -CO-O-alkylene group, etc.).
  • Examples of the substituent represented by RX include the substituents exemplified in the substituent group T, and an alkyl group having 1 to 2 carbon atoms is preferable.
  • the alkylene group, alkenylene group, alkynylene group, aromatic ring group, and alicyclic group may further have a substituent.
  • Examples of the substituent include the substituents exemplified in the substituent group T.
  • the alkylene group, alkenylene group, and alkynylene group may be linear or branched.
  • the carbon number of the alkylene group is preferably 1 to 20, more preferably 1 to 10, and even more preferably 1 to 5.
  • the carbon number of the alkenylene group and the alkynylene group is preferably 2 to 20, more preferably 2 to 10, and even more preferably 2 to 5.
  • Z represents a group represented by the formula (A) or a group represented by the formula (B).
  • the group represented by the above formula (A) and the group represented by the formula (B) are the groups represented by the formula (A) and the formula (B) of the above-mentioned block copolymer, respectively. It has the same meaning as the group represented, and the preferred range is also the same.
  • the structural unit X may be used alone or in combination of two or more.
  • the lower limit of the content of the constituent unit X is more than 0 mol%, preferably 1 mol% or more, more preferably 10 mol% or more, more preferably 30 mol%, based on the number of moles of all the constituent units of the block copolymer. More preferably, mol% or more, and particularly preferably 40 mol% or more.
  • the upper limit is less than 100 mol%, preferably 90 mol% or less, more preferably 80 mol% or less, still more preferably 60 mol% or less.
  • the structural unit Y has a poly (oxyalkylene) group.
  • the structural unit Y is not particularly limited, but preferably has a group represented by the formula (PAL1).
  • AL represents an alkylene group.
  • the alkylene group may be linear or branched.
  • the number of carbon atoms of the alkylene group represented by AL is preferably 1 to 10, more preferably 1 to 6, further preferably 2 to 4, and particularly preferably 2 to 3.
  • nAL represents a number of 2 or more, preferably 2 to 100, more preferably 4 to 20, further preferably 4 to 15, and particularly preferably 4 to 12.
  • the ALs having nALs may be the same or different from each other, and it is preferable that they represent the same structure.
  • the alkylene group represented by AL may have a substituent.
  • the substituent is not particularly limited, and examples thereof include the substituents exemplified in the substituent group T.
  • the structural unit Y preferably has a poly (oxyalkylene) group in the side chain, more preferably has a group represented by the formula (PAL1) in the side chain, and is represented by the formula (PAL2). It is more preferably a structural unit derived from a monomer.
  • R 1 represents a hydrogen atom or a methyl group.
  • a hydrogen atom is preferable as R1 .
  • Y represents an oxygen atom, a sulfur atom, or -N (R 2 )-.
  • R 2 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
  • the alkyl group having 1 to 4 carbon atoms represented by R2 may be linear, branched or cyclic.
  • R2 a hydrogen atom or an alkyl group having 1 to 2 carbon atoms is preferable, and an alkyl group having 1 to 2 carbon atoms is more preferable.
  • Y an oxygen atom or a sulfur atom is preferable, and an oxygen atom is more preferable.
  • R 3 represents a hydrogen atom or a substituent.
  • the substituent represented by R 3 is not particularly limited, and examples thereof include the substituents exemplified in the substituent group T, and an alkyl group having 1 to 6 carbon atoms is preferable.
  • a hydrogen atom is preferable as R3 .
  • AL and nAL in the formula (PAL2) are synonymous with AL and nAL in the above-mentioned formula (PAL1), respectively, and the preferred embodiments are also the same.
  • the structural unit Y may be used alone or in combination of two or more.
  • the lower limit of the content of the constituent unit Y is more than 0 mol%, preferably 1 mol% or more, more preferably 10 mol% or more, more preferably 30 mol%, based on the number of moles of all the constituent units of the block copolymer. More preferably, mol% or more, and particularly preferably 40 mol% or more.
  • the upper limit is less than 100 mol%, preferably 90 mol% or less, and more preferably 60 mol% or less.
  • the block copolymer may have other structural units in addition to the structural unit X and the structural unit Y.
  • a structural unit selected from the group consisting of a structural unit derived from (meth) acrylic acid ester and a structural unit derived from (meth) acrylic acid is preferable.
  • the (meth) acrylic acid ester include (meth) acrylic acid alkyl esters having an alkyl group having 1 to 18 carbon atoms. Specifically, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate. , And stearyl (meth) acrylate and the like. Of these, lauryl (meth) acrylate is preferable.
  • the other structural units may be used alone or in combination of two or more.
  • As the lower limit of the content of other structural units 1 mol% or more is preferable, 10 mol% or more is more preferable, and 20 mol% or more is further preferable with respect to the number of moles of all the structural units of the block copolymer. ..
  • the upper limit is preferably 90 mol% or less, more preferably 60 mol% or less, still more preferably 40 mol% or less.
  • block copolymers will be exemplified, but the block copolymers in the present invention are not limited thereto.
  • the lower limit of the weight average molecular weight of the block copolymer 1,000 or more is preferable, 1,500 or more is more preferable, 2,000 or more is further preferable, and 5,000 or more is particularly preferable.
  • the upper limit thereof is preferably 100,000 or less, more preferably 50,000 or less, and even more preferably 20,000 or less.
  • the number average molecular weight (Mn) of the block copolymer is preferably 1,000 to 40,000, more preferably 2,000 to 20,000, further preferably 5,000 to 15,000, and 7,000 to 12 000 is particularly preferred.
  • the dispersity (Mw / Mn) of the block copolymer is preferably 1.00 to 12.00, more preferably 1.00 to 11.00, further preferably 1.00 to 10.00, and 1.00 to 1.00 to 10.00. 5.00 is particularly preferable, and 1.00 to 2.00 is most preferable.
  • the block copolymer may be used alone or in combination of two or more.
  • the content of the block copolymer is preferably 0.001 to 10.00% by mass, more preferably 0.01 to 3.00% by mass, and 0.02 to 1. 00% by mass is more preferable, and 0.10 to 1.00% by mass is particularly preferable.
  • the polymerization method of the block copolymer is not particularly limited, and examples thereof include known polymerization methods.
  • Examples of the method for polymerizing block copolymers include living radical polymerization, living cationic polymerization, and living anionic polymerization.
  • Examples of the living radical polymerization, the living cationic polymerization, and the living anionic polymerization include "Precision Radical Polymerization Guidebook (Aldrich)" (URL: http://www.sigmaaldrich.com/japan/materialscience/polymer-science/crp).
  • the compound (1) is a compound represented by the formula (1).
  • Z represents a group represented by the formula (A) or a group represented by the formula (B).
  • the group represented by the above formula (A) and the group represented by the above formula (B) are the group represented by the above formula (A) and the group represented by the formula (B), respectively. It has the same meaning as the group represented by, and the preferable range is also the same.
  • L 2 represents a single bond or a divalent linking group.
  • the divalent linking group represented by L 2 include -O-, -CO-, -S-, -SO 2- , and -NR X- ( RX represents a hydrogen atom or a substituent. ), An alkylene group, an alkenylene group, an alkynylene group, an aromatic ring group, an alicyclic group, and a group combining these.
  • RX represents a hydrogen atom or a substituent.
  • the substituent represented by RX include the substituents exemplified in the substituent group T, and an alkyl group having 1 to 2 carbon atoms is preferable.
  • the alkylene group, the alkenylene group, the alkynylene group, the aromatic ring group, and the alicyclic group may further have a substituent.
  • the substituent include the substituents exemplified in the substituent group T. Among them, as the substituent, a halogen atom is preferable, and a fluorine atom is more preferable.
  • the alkylene group, the alkenylene group, and the alkynylene group may be linear or branched.
  • the carbon number of the alkylene group is preferably 1 to 20, more preferably 1 to 10, and even more preferably 1 to 5.
  • the carbon number of the alkenylene group and the alkynylene group is preferably 2 to 20, more preferably 2 to 10, and even more preferably 2 to 5.
  • L 2 when Z is a group represented by the formula (A), —O— is preferable, and when Z is a group represented by the formula (B), a single bond is preferable.
  • W represents a group containing a poly (oxyalkylene) group.
  • W is not particularly limited as long as it is a group containing a poly (oxyalkylene) group.
  • a monovalent organic group containing a poly (oxyalkylene) group is preferable, a group containing a group represented by the above-mentioned formula (PAL1) is more preferable, and a group represented by the formula (2) is more preferable. Is more preferable.
  • Equation (2) *-(AL-O-) nAL -R 3
  • the definitions of AL, R3 and nAL in the formula (2) are the same as the definitions of each group in the above-mentioned formula (PAL2). * Represents the bond position.
  • the upper limit of the molecular weight of the compound (1) is preferably 3,000 or less, more preferably 2,000 or less.
  • the compound (1) may be used alone or in combination of two or more.
  • the content of the compound (1) is preferably 0.001 to 10.00% by mass, more preferably 0.01 to 3.00% by mass, and 0.02 to 1. 00% by mass is more preferable.
  • the resin composition layer may contain other components in addition to the resin, the block copolymer, and the compound (1).
  • Other components include polymerizable compounds, polymerization initiators, dyes, heat-crosslinkable compounds, additives, plasticizers, sensitizers, pigments, and compounds that generate acids, bases, or radicals with light. Can be mentioned. Details of the other components will be described later in each form of the resin composition layer.
  • the resin composition layer may be a photosensitive resin composition layer.
  • a pattern can be formed on the transferred object by transferring the photosensitive resin composition layer onto the transferred object and then exposing and developing the photosensitive resin composition layer.
  • the photosensitive resin composition layer may be a positive type or a negative type.
  • the positive photosensitive composition layer is a photosensitive composition layer in which the exposed portion becomes highly soluble in a developing solution due to exposure.
  • the negative photosensitive composition layer is a photosensitive composition layer in which the exposed portion is less soluble in a developing solution due to exposure. Above all, it is preferable to use a negative photosensitive composition layer.
  • the photosensitive composition layer is a negative photosensitive composition layer, the formed pattern corresponds to a protective film.
  • the photosensitive resin composition layer preferably further contains an alkali-soluble resin and a polymerizable compound in addition to the block copolymer and the compound (1) described above.
  • the photosensitive resin composition layer is a resin having a structural unit having an acid group protected by an acid-degradable group described later, in addition to the block copolymer and the compound (1) described above, and a resin described later. It is also preferable to include a photoacid generator.
  • a transfer film having a photosensitive resin composition layer may be used to obtain a pattern such as wiring included in a touch panel.
  • a display device organic electroluminescence (EL) display device, liquid crystal display device, etc.
  • a conductive layer pattern such as wiring is provided inside the touch panel.
  • a photosensitive resin composition layer is provided on a substrate using a transfer film or the like, and the photosensitive resin composition layer is exposed to the photosensitive resin composition layer via a mask having a desired pattern. After that, the method of developing is widely adopted.
  • the components that can be contained in the photosensitive resin composition layer will be described.
  • the photosensitive resin composition layer may contain an alkali-soluble resin (hereinafter, also referred to as “polymer P”).
  • the alkali-soluble resin corresponds to the resin contained in the resin composition layer described above.
  • the acid value of the polymer P is preferably 220 mgKOH / g or less, more preferably less than 200 mgKOH / g, and 190 mgKOH from the viewpoint of better resolution by suppressing the swelling of the photosensitive resin composition layer by the developing solution. Less than / g is more preferable.
  • the lower limit of the acid value of the polymer P is not particularly limited, but from the viewpoint of better developability, 60 mgKOH / g or more is preferable, 80 mgKOH / g or more is more preferable, and 90 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 P may be adjusted according to the type of the structural unit constituting the polymer P and the content of the structural unit containing the acid group.
  • the weight average molecular weight of the polymer P is preferably 5,000 to 500,000. When the weight average molecular weight is 500,000 or less, it is preferable from the viewpoint of improving resolution and developability.
  • the weight average molecular weight is more preferably 100,000 or less, further preferably 60,000 or less.
  • the weight average molecular weight is 5,000 or more, the properties of the developed aggregate and the properties of the unexposed film such as the edge fuse property and the cut chip property when the laminate has the photosensitive resin composition layer are deteriorated. It is preferable from the viewpoint of control.
  • the weight average molecular weight is more preferably 10,000 or more, further preferably 20,000 or more, and particularly preferably 30,000 or more.
  • the edge fuse property refers to the degree of ease with which the photosensitive resin composition layer protrudes from the end face of the roll when the laminate is wound into a roll as a laminate having the photosensitive resin composition layer.
  • the cut chip property refers to the degree of ease of chip flying when the unexposed film is cut with a cutter. When this chip adheres to the upper surface or the like of a laminate having a photosensitive resin composition layer, it is transferred to a mask in a later exposure step or the like, which causes a defective product.
  • the dispersity of the polymer P is preferably 1.0 to 6.0, more preferably 1.0 to 5.0, still more preferably 1.0 to 4.0, and particularly preferably 1.0 to 3.0. ..
  • the photosensitive resin composition layer contains a structural unit based on a monomer having an aromatic hydrocarbon group from the viewpoint of suppressing line width thickening and deterioration of resolution when the focal position is deviated during exposure.
  • aromatic hydrocarbon groups include substituted or unsubstituted phenyl groups and substituted or unsubstituted aralkyl groups.
  • the content of the structural unit derived from the monomer having an aromatic hydrocarbon group in the polymer P is preferably 20.0% by mass or more, more preferably 30.0% by mass or more, based on the total mass of the polymer P. ..
  • the upper limit is not particularly limited, but is preferably 95.0% by mass or less, and more preferably 85.0% by mass or less.
  • the average value of the content of the constituent units derived from the monomer having an aromatic hydrocarbon group is within the above range.
  • the monomer having an aromatic hydrocarbon group examples include a monomer having an aralkyl group, styrene, and a polymerizable styrene derivative (for example, methyl styrene, vinyl toluene, tert-butoxy styrene, acetoxy styrene, 4-vinyl benzoic acid). , Styrene dimer, styrene trimmer, etc.). Of these, a monomer having an aralkyl group or styrene is preferable.
  • the content of the structural unit derived from styrene is 20.0 to 70.
  • the total mass of the polymer P 0% by mass is preferable, 25.0 to 65.0% by mass is more preferable, 30.0 to 60.0% by mass is further preferable, and 30.0 to 55.0% by mass is particularly preferable.
  • aralkyl group examples include a substituted or unsubstituted phenylalkyl group (excluding a benzyl group), a substituted or unsubstituted benzyl group and the like, and a substituted or unsubstituted benzyl group is preferable.
  • Examples of the monomer having a phenylalkyl group include phenylethyl (meth) acrylate and the like.
  • Examples of the monomer having a benzyl group include (meth) acrylate having a benzyl group, for example, benzyl (meth) acrylate and chlorobenzyl (meth) acrylate; a vinyl monomer having a benzyl group, for example, vinylbenzyl chloride, and Vinyl benzyl alcohol can be mentioned. Of these, benzyl (meth) acrylate is preferable.
  • the content of the structural unit derived from the benzyl (meth) acrylate is based on the total mass of the polymer P. 50.0 to 95.0% by mass is preferable, 60.0 to 90.0% by mass is more preferable, 70.0 to 90.0% by mass is further preferable, and 75.0 to 90.0% by mass is preferable. Especially preferable.
  • the polymer P containing a structural unit derived from a monomer having an aromatic hydrocarbon group is a monomer having an aromatic hydrocarbon group, at least one of the first monomers described later, and / or a second monomer described later. It is preferably obtained by polymerizing with at least one kind.
  • the polymer P containing no structural unit derived from a monomer having an aromatic hydrocarbon group is preferably obtained by polymerizing at least one of the first monomers described later, and at least one of the first monomers. It is more preferable to obtain it by copolymerizing with at least one of the second monomers described later.
  • the first monomer is a monomer having a carboxy group in the molecule.
  • the first monomer include (meth) acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, 4-vinylbenzoic acid, maleic acid anhydride, maleic acid semi-ester and the like. Of these, (meth) acrylic acid is preferable.
  • the content of the structural unit derived from the first monomer in the polymer P is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, and 15 to 30% by mass with respect to the total mass of the polymer P. Is more preferable. It is preferable that the content is 5% by mass or more from the viewpoint of exhibiting good developability, controlling edge fuseability, and the like. It is preferable that the content is 50% by mass or less from the viewpoint of high resolution of the resist pattern and the shape of the resist pattern, and further from the viewpoint of chemical resistance of the resist pattern.
  • the second monomer is a monomer that is non-acidic and has at least one polymerizable unsaturated group in the molecule.
  • Examples of the second monomer include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, and tert.
  • -(Meta) acrylates such as butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate; vinyl acetate Such as vinyl alcohol esters; as well as (meth) acrylonitrile.
  • methyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, or n-butyl (meth) acrylate is preferable, and methyl (meth) acrylate is more preferable.
  • the content of the structural unit derived from the second monomer in the polymer P is preferably 5 to 60% by mass, more preferably 15 to 50% by mass, and 17 to 45% by mass with respect to the total mass of the polymer P. Is more preferable.
  • the polymer P contains a structural unit derived from a monomer having an aralkyl group and / or a structural unit derived from styrene
  • a copolymer containing a constituent unit derived from methacrylic acid, a constituent unit derived from benzyl methacrylate, and a constituent unit derived from styrene, a constituent unit derived from methacrylic acid, a constituent unit derived from methyl methacrylate, and benzyl methacrylate a copolymer containing a constituent unit derived from methacrylic acid, a constituent unit derived from benzyl methacrylate, and a constituent unit derived from styrene.
  • a copolymer or the like containing a structural unit derived from it and a structural unit derived from styrene is preferable.
  • the polymer P contains 25 to 55% by mass of a structural unit derived from a monomer having an aromatic hydrocarbon group, 20 to 35% by mass of a structural unit derived from the first monomer, and a second monomer. It is preferably a polymer containing 15 to 45% by mass of the derived structural unit.
  • the polymer preferably contains 70 to 90% by mass of a structural unit derived from a monomer having an aromatic hydrocarbon group and 10 to 25% by mass of a structural unit derived from the first monomer. ..
  • the polymer P may have a branched structure and / or an alicyclic structure in the side chain. Further, the polymer P may have a linear structure in the side chain. Introducing a branched structure and / or an alicyclic structure into the side chain of the polymer P by using a monomer having a group having a branched structure in the side chain or a monomer containing a group having an alicyclic structure in the side chain. Can be done.
  • the group having an alicyclic structure may be monocyclic or polycyclic. Specific examples of the monomer containing a group having a branched structure in the side chain include (meth) acrylic acid i-propyl and (meth) acrylic acid i-.
  • i-propyl (meth) acrylate, i-butyl (meth) acrylate, or t-butyl methacrylate are preferable, and i-propyl methacrylate or t-butyl methacrylate is more preferable.
  • Examples of the alicyclic structure include a monocyclic alicyclic structure and a polycyclic alicyclic structure, and a polycyclic alicyclic structure is preferable.
  • Specific examples of the monomer containing a group having an alicyclic structure in the side chain include (meth) acrylate having an alicyclic hydrocarbon group having 5 to 20 carbon atoms. More specific examples include (meth) acrylic acid (bicyclo [2.2.1] heptyl-2), (meth) acrylic acid-1-adamantyl, (meth) acrylic acid-2-adamantyl, (meth).
  • Fentyl acrylate, 1-mentyl (meth) acrylate, or tricyclodecane (meth) acrylate is preferred, cyclohexyl (meth) acrylate, (nor) bornyl (nor) acrylate, isobornyl (meth) acrylate, -2-adamantyl (meth) acrylate or tricyclodecane (meth) acrylate is more preferred.
  • the polymer P may be used alone or in combination of two or more.
  • two kinds of polymers P containing a structural unit derived from a monomer having an aromatic hydrocarbon group may be mixed and used, or a configuration derived from a monomer having an aromatic hydrocarbon group may be used.
  • the content of the polymer P containing the structural unit derived from the monomer having an aromatic hydrocarbon group is preferably 50% by mass or more, more preferably 70% by mass or more, based on the total mass of the polymer P. It is preferable, 80% by mass or more is more preferable, and 90% by mass or more is particularly preferable.
  • the upper limit is not particularly limited, and is preferably 100% by mass or less.
  • the synthesis of the polymer P is carried out by diluting the above-mentioned one or more monomers with a solvent such as acetone, methyl ethyl ketone and isopropanol, and a radical polymerization initiator such as benzoyl peroxide and azoisobutyronitrile. Is preferably added in an appropriate amount and heated and stirred. In some cases, a part of the mixture is added dropwise to the reaction solution for synthesis. After completion of the reaction, a solvent may be further added to adjust the concentration to a desired level.
  • a solvent may be further added to adjust the concentration to a desired level.
  • the synthesis means bulk polymerization, suspension polymerization, or emulsion polymerization may be used in addition to solution polymerization.
  • the glass transition temperature Tg of the polymer P is preferably 30 to 135 ° C.
  • the Tg of the polymer P is preferably 130 ° C. or lower, more preferably 120 ° C. or lower, and particularly preferably 110 ° C. or lower.
  • the polymer P having a Tg of 30 ° C. or higher from the viewpoint of improving the edge fuse resistance.
  • the Tg of the polymer P is more preferably 40 ° C. or higher, further preferably 50 ° C. or higher, particularly preferably 60 ° C. or higher, and most preferably 70 ° C. or higher.
  • the photosensitive resin composition layer may contain other resins other than those described above.
  • Other resins include acrylic resin, styrene-acrylic copolymer, polyurethane resin, polyvinyl alcohol, polyvinyl formal, polyamide resin, polyester resin, polyamide resin, epoxy resin, polyacetal resin, polyhydroxystyrene resin, polyimide resin, and poly. Examples thereof include benzoxazole resin, polysiloxane resin, polyethyleneimine, polyallylamine, and polyalkylene glycol.
  • the alkali-soluble resin described in the description of the thermoplastic resin composition layer described later may be used.
  • the content of the polymer P is preferably 10.00 to 90.00% by mass, more preferably 20.00 to 80.00% by mass, and 20.00 to 70 with respect to the total mass of the photosensitive resin composition layer. .00% by mass is more preferable, and 20.00 to 60.00% by mass is particularly preferable. It is preferable that the content of the polymer P is 90.00% by mass or less from the viewpoint of controlling the developing time. On the other hand, it is preferable that the content of the polymer P is 10.00% by mass or more from the viewpoint of improving the edge fuse resistance.
  • the photosensitive resin composition layer preferably contains a resin having an acid group protected by an acid-degradable group.
  • the resin having an acid group protected by an acid-degradable group corresponds to the resin contained in the above-mentioned resin composition layer.
  • the resin having an acid group protected by the acid-degradable group is a polymer having a structural unit having an acid group protected by an acid-degradable group (hereinafter, also referred to as “constituent unit A”) (hereinafter, “polymer”). It is also referred to as "A").
  • the positive photosensitive resin composition layer may contain another polymer in addition to the polymer having the structural unit A.
  • the polymer having the structural unit A and other polymers are collectively referred to as "polymer component".
  • the structural unit A having an acid group protected by an acid-degradable group in the polymer A undergoes a deprotection reaction to become an acid group due to the action of a catalytic amount of an acidic substance generated by exposure, and the developer becomes a developer. Can be developed by.
  • preferred embodiments of the structural unit A will be described.
  • the photosensitive resin composition layer may further contain a polymer other than the polymer having a structural unit having an acid group protected by an acid-degradable group. Further, it is preferable that all the polymers contained in the polymer components are polymers having at least a structural unit having an acid group described later. Further, the photosensitive resin composition layer may further contain a polymer other than these.
  • the above-mentioned polymer component in the present specification is not particularly limited, and is meant to include other polymers added as needed.
  • an addition polymerization type resin is preferable, and a polymer having a structural unit derived from (meth) acrylic acid or an ester thereof is more preferable.
  • the structural unit other than the structural unit derived from (meth) acrylic acid or an ester thereof may have, for example, a structural unit derived from styrene and a structural unit derived from a vinyl compound.
  • the photosensitive resin composition layer contains a polymer having a structural unit A1 represented by the formula (A1) described later as the structural unit A as a polymer component from the viewpoint of solubility in a developing solution and transferability.
  • the polymer component it is preferable to include the polymer A having the structural unit A1 represented by the formula (A1) described later as the structural unit A and having a glass transition temperature of 90 ° C. or lower.
  • the structural unit A has the structural unit A1 represented by the following formula (A1) and the structural unit B having an acid group described later, and the glass transition temperature is 90 ° C. or lower. It is more preferable to include the coalescence A.
  • the structural unit A is a structural unit having an acid group protected by an acid-degradable group.
  • the acid group protected by the acid-degradable group include known acid groups and acid-degradable groups.
  • the acid group include a carboxy group and a phenolic hydroxyl group.
  • the acid group protected by the acid-degradable group include a group protected by a group represented by the formula (A1), a tetrahydropyranyl ester group, and a group relatively easily decomposed by an acid.
  • Acetal functional groups such as tetrahydrofuranyl ester groups, groups that are relatively difficult to decompose with acids (eg, tertiary alkyl groups such as tert-butyl ester groups, and tertiary alkyl carbonates such as tert-butyl carbonate groups). Basics, etc.).
  • the acid-degradable group is preferably a group having a structure protected by an acetal-based functional group.
  • the structural unit A the structural units A1 to A4 described later are preferable, the structural units A2 or A4 are more preferable, and the structural unit A2 is further preferable.
  • the structural unit A1 represented by the following formula (A1) is also preferable from the viewpoint of sensitivity and resolution.
  • R 31 and R 32 each independently represent a hydrogen atom, an alkyl group, or an aryl group, and at least one of R 31 and R 32 represents an alkyl group or an aryl group.
  • R 31 or R 32 is an alkyl group
  • the R 31 and R 32 are preferably an alkyl group having 1 to 10 carbon atoms.
  • R 31 or R 32 is an aryl group
  • a phenyl group is preferable as R 31 and R 32 .
  • R 31 and R 32 hydrogen atoms or alkyl groups having 1 to 4 carbon atoms are preferable, respectively.
  • R 33 represents an alkyl group or an aryl group, and R 31 or R 32 and R 33 may be linked to form a cyclic ether.
  • the number of ring members of the cyclic ether is not particularly limited, but is preferably 5 to 6, and more preferably 5.
  • R 33 an alkyl group having 1 to 10 carbon atoms is preferable, and an alkyl group having 1 to 6 carbon atoms is more preferable.
  • the alkyl group and aryl group represented by R 31 to R 33 may have a substituent.
  • the substituent is not particularly limited, and examples thereof include the substituents exemplified in the substituent group T.
  • R 34 represents a hydrogen atom or a methyl group.
  • a hydrogen atom is preferable from the viewpoint that the Tg of the polymer A can be made lower.
  • the content of the structural unit in which R 34 is a hydrogen atom is preferably 20% by mass or more with respect to the total amount of the structural unit A1 contained in the polymer A.
  • the upper limit is not particularly limited, and is preferably 100% by mass or less.
  • the content (content ratio: mass ratio) of the structural unit in which R 34 is a hydrogen atom should be confirmed by the intensity ratio of the peak intensity calculated by a conventional method from 13 C-nuclear magnetic resonance spectrum (NMR) measurement. Can be done.
  • X 0 represents a single bond or an arylene group.
  • X 0 a single bond is preferable.
  • the arylene group may have a substituent.
  • the substituent is not particularly limited, and examples thereof include the substituents exemplified in the substituent group T.
  • R 34 represents a hydrogen atom or a methyl group.
  • R 34 has the same meaning as R 34 in the above-mentioned formula (A1), and the preferable range is also the same.
  • R 35 to R 41 each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. As R 35 to R 41 , a hydrogen atom is preferable.
  • R 34 represents a hydrogen atom or a methyl group.
  • RB1 to RB4 have the same meaning as R31 to R34 in the above-mentioned formula (A1), respectively, and the preferable range is also the same.
  • XB represents a single bond or a divalent linking group.
  • the alkylene group may be linear, branched or cyclic. Further, the alkylene group may have a substituent. The substituent is not particularly limited, and examples thereof include the substituents exemplified in the substituent group T.
  • the alkylene group preferably has 1 to 10 carbon atoms, and more preferably 1 to 4 carbon atoms.
  • RN represents an alkyl group or a hydrogen atom
  • an alkyl group or a hydrogen atom having 1 to 4 carbon atoms is preferable, and a hydrogen atom is more preferable.
  • a single bond is preferable as XB .
  • the group containing RB1 to RB3 and XB are bonded to each other at the para position.
  • RB12 represents a substituent.
  • an alkyl group or a halogen atom is preferable.
  • the alkyl group preferably has 1 to 10 carbon atoms, and more preferably 1 to 4 carbon atoms.
  • n represents an integer from 0 to 4. As n, 0 to 1 is preferable, and 0 is more preferable.
  • RB4 to RB11 are synonymous with R 34 to R 41 in the formula (A2), respectively, and the preferable range is also the same.
  • RB12 and n are synonymous with RB12 and n in the formula (A3), respectively, and the preferable range is also the same.
  • RB4 represents a hydrogen atom or a methyl group.
  • the structural unit A may be used alone or in combination of two or more.
  • the content of the structural unit A is preferably 20.0% by mass or more, more preferably 20.0 to 90.0% by mass, and 30.0 to 70.0% by mass with respect to the total mass of the polymer A. Is more preferable.
  • the content of the monomer derived from the structural unit A is preferably 5.0 to 80.0% by mass, more preferably 10 to 80% by mass, and 30 to 70% by mass with respect to the total mass of the polymer A. % Is more preferable.
  • the polymer A may contain a structural unit B having an acid group.
  • the structural unit B is, for example, a structural unit containing an acid group that is not protected by an acid-degradable group, that is, an acid group that does not have a protecting group.
  • the structural unit B include the structural units of the alkali-soluble resin described above.
  • the structural unit B may be used alone or in combination of two or more.
  • the content of the structural unit B is preferably 0.1 to 20.0% by mass, more preferably 0.5 to 15.0% by mass, and 1 to 10.0% by mass with respect to the total mass of the polymer A. % Is more preferable.
  • the polymer A may contain other structural units (hereinafter, also referred to as “constituent unit C”) in addition to the above-mentioned structural units A to B.
  • Examples of the monomer forming the structural unit C include styrenes, (meth) acrylic acid alkyl esters, (meth) acrylic acid cyclic alkyl esters, (meth) acrylic acid aryl esters, unsaturated dicarboxylic acid diesters, and bicyclounsaturated compounds.
  • constituent unit C examples include styrene, tert-butoxystyrene, methylstyrene, ⁇ -methylstyrene, acetoxystyrene, methoxystyrene, ethoxystyrene, chlorostyrene, methyl vinylbenzoate, and ethyl vinylbenzoate, (meth).
  • a structural unit formed by polymerizing benzyl acrylate, isobornyl (meth) acrylate, acrylonitrile, mono (meth) acrylate of ethylene glycol monoacetate, and the like can be mentioned. Further, the compounds described in paragraphs [0021] to [0024] of JP-A-2004-246623 are also mentioned.
  • the structural unit C a structural unit having an aromatic ring or a structural unit having an aliphatic cyclic skeleton is preferable.
  • the monomers forming the above-mentioned structural unit include styrene, tert-butoxystyrene, methylstyrene, ⁇ -methylstyrene, dicyclopentanyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, and benzyl ( Meta) acrylate can be mentioned.
  • the structural unit C a structural unit derived from cyclohexyl (meth) acrylate is preferable.
  • a (meth) acrylic acid alkyl ester is preferable, and a (meth) acrylic acid alkyl ester having an alkyl group having 4 to 12 carbon atoms is more preferable.
  • Specific examples thereof include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate.
  • the structural unit C may be used alone or in combination of two or more.
  • the content of the structural unit C is preferably 70.0% by mass or less, more preferably 60.0% by mass or less, still more preferably 50.0% by mass or less, based on the total mass of the polymer A.
  • As the lower limit value 0% by mass or more is preferable, 1.0% by mass or more is more preferable, and 5.0% by mass or more is further preferable. Within the above range, the resolution and adhesion are further improved.
  • the polymer A contains the structural unit having the ester of the acid group in the structural unit B as the structural unit C also optimizes the solubility in the developing solution and the physical properties of the photosensitive resin composition layer. Preferred from the point of view.
  • the polymer A preferably contains a structural unit having a carboxylic acid group as the structural unit B, and further preferably contains a structural unit C containing a carboxylic acid ester group as a copolymerization component, and methyl (meth) acrylate.
  • a polymer A containing the structural unit B derived from the above and the structural unit C derived from cyclohexyl (meth) acrylate and / or ethyl (meth) acrylate is more preferable.
  • the glass transition temperature (Tg) of the polymer A is preferably 90 ° C. or lower.
  • the Tg is more preferably 60 ° C. or lower, and even more preferably 40 ° C. or lower.
  • the lower limit of Tg is not particularly limited, but is preferably ⁇ 20 ° C. or higher, more preferably ⁇ 10 ° C. or higher.
  • the glass transition temperature of the polymer A can be measured using differential scanning calorimetry (DSC). The specific measuring method was carried out according to the method described in JISK7121 (1987) or JISK6240 (2011). As the glass transition temperature in the present specification, the extrapolated glass transition start temperature (hereinafter, also referred to as “Tig”) is used.
  • DSC differential scanning calorimetry
  • the molecular weight of the polymer A is preferably 60,000 or less, more preferably 2,000 to 60,000, still more preferably 3,000 to 50,000.
  • the weight average molecular weight of the polymer A can be measured by the above-mentioned GPC (gel permeation chromatography).
  • the dispersity (Mw / Mn) of the polymer A is preferably 1.0 to 5.0, more preferably 1.05 to 3.5.
  • the method for producing the polymer A is not particularly limited, and a known method may be used.
  • a polymerization initiator is used in an organic solvent containing a monomer for forming the structural unit A1, a monomer for forming the structural unit B having an acid group, and a monomer for forming the structural unit C. It can be synthesized by polymerizing.
  • the photosensitive resin composition layer may contain other polymers in addition to the polymer A.
  • the content of the other polymer is preferably 50% by mass or less, more preferably 30% by mass or less, based on the total mass of the photosensitive resin composition layer. It is preferably 20% by mass or less, more preferably 20% by mass or less.
  • the lower limit is not particularly limited, but it is often 0% by mass or more.
  • Examples of other polymers include polyhydroxystyrene. Specific examples include SMA1000P, SMA2000P, SMA3000P, SMA1440F, SMA17352P, SMA2625P, and SMA3840F (all manufactured by Sartmer), ARUFONUC-3000, ARUFONUC-3510, ARUFONUC-3900, ARUFONUC-3910, ARUF. Examples thereof include ARUFONUC-3080 (above, manufactured by Toagosei Co., Ltd.), and Jonclyl690, Jonclyl678, Jonclyl67, and Jonclyl586 (above, manufactured by BASF).
  • the polymer A may be used alone or in combination of two or more.
  • the content of the polymer A is preferably 50.00 to 99.99% by mass, more preferably 70.00 to 98.00% by mass, based on the total mass of the photosensitive resin composition layer.
  • the photosensitive resin composition layer may contain a photoacid generator.
  • the photoacid generator include photoacid generators that may be contained in the thermoplastic resin composition layer described later, and the preferred embodiments are the same.
  • the photoacid generator may be used alone or in combination of two or more.
  • the content of the photoacid generator is preferably 0.1 to 30.0% by mass, more preferably 1.0 to 20.0% by mass, and 5.0 to 5.0 to the total mass of the photosensitive resin composition layer. 15.0% by mass is more preferable.
  • the photosensitive resin composition layer may contain a polymerizable compound having a polymerizable group.
  • a polymerizable compound means a compound different from the above-mentioned block copolymer, compound (1), and polymer P.
  • the polymerizable group of the polymerizable compound 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 a cationically polymerizable group such as an epoxy group and an oxetane group 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, and two or more in one molecule, because the photosensitive resin composition layer is more excellent in photosensitivity.
  • 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.
  • a bifunctional or trifunctional ethylenically unsaturated molecule having two or three ethylenically unsaturated groups in a better balance of photosensitivity, resolution and releasability of the photosensitive resin composition layer It is preferable to contain a 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 with respect to the total mass of the polymerizable compound is preferably 20% by mass or more, preferably more than 40% by mass, from the viewpoint of excellent peelability with respect to the total mass of the photosensitive resin composition layer. More preferably, 55% by mass or more is further preferable.
  • the upper limit is not particularly limited and may be 100% by mass or less. That is, all the polymerizable compounds 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 composition layer preferably contains a polymerizable compound B1 having an aromatic ring and 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 total mass of the polymerizable compound in the photosensitive resin composition layer is preferably 40% by mass or more, more preferably 50% by mass or more, from the viewpoint of better resolution. , 55% by mass or more is more preferable, and 60% by mass or more is particularly preferable.
  • the upper limit is not particularly limited, but from the viewpoint of peelability, for example, it is 100% by mass or less, preferably 99% by mass or less, more preferably 95% by mass or less, further preferably 90% by mass or less, and 85% by mass or less. Especially 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 composition 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 oxyalkylene groups. As the oxyalkylene group added to both ends of the bisphenol structure, an oxyethylene group or an oxypropylene group is preferable, and an oxyethylene group is more preferable.
  • the number of oxyalkylene 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) acryloxypolyalkoxy) phenyl) propane examples include 2,2-bis (4- (methacryloxydiethoxy) phenyl) propane (FA-324M, Hitachi Chemical Co., Ltd.).
  • polymerizable compound B1 a compound represented by the following general formula (B1) is also preferable.
  • R 1 and R 2 independently represent a hydrogen atom or a methyl group, respectively.
  • A represents C 2 H 4 .
  • B represents C 3 H 6 .
  • n1 and n3 are independently integers of 1 to 39, and n1 + n3 are integers of 2 to 40.
  • n2 and n4 are independently integers of 0 to 29, and n2 + n4 are integers of 0 to 30.
  • the sequence of constituent units of-(AO)-and-(BO)- may be random or block. In the case of a block, either ⁇ (A—O) ⁇ or ⁇ (BO) ⁇ may be on the bisphenyl group side.
  • n1 + n2 + n3 + n4 is preferably an integer of 2 to 20, more preferably an integer of 2 to 16, and even more preferably an integer of 4 to 12. Further, n2 + n4 is preferably an integer of 0 to 10, more preferably an integer of 0 to 4, further preferably an integer of 0 to 2, and particularly preferably 0.
  • the polymerizable compound B1 may be used alone or in combination of two or more.
  • the content of the polymerizable compound B1 is preferably 10% by mass or more, more preferably 20% by mass or more, based on the total mass of the photosensitive resin composition layer, from the viewpoint of better resolution.
  • the upper limit is not particularly limited, but from the viewpoint of transferability and edge fusion (a phenomenon in which the photosensitive resin exudes from the end of the transfer member), 70% by mass or less is preferable, and 60% by mass or less is more preferable.
  • the photosensitive resin composition layer may contain a polymerizable compound other than the above-mentioned polymerizable compound B1.
  • the polymerizable compound 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.), tricyclodecanedimethanol dimethacrylate (DCP, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), and the like.
  • 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, and neopentyl glycol di (meth) acrylate.
  • 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.).
  • 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, isocyanuric acid tri (meth) acrylates, glycerintri (meth) acrylates, and alkylene oxide-modified products 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.
  • the photosensitive resin composition layer preferably contains the above-mentioned polymerizable compound B1 and a trifunctional or higher ethylenically unsaturated compound, and the above-mentioned polymerizable compound B1 and two or more types of trifunctional or higher ethylene. It is more preferable to contain a sex unsaturated compound.
  • the photosensitive resin composition preferably contains the above-mentioned polymerizable compound B1 and two or more trifunctional ethylenically unsaturated compounds.
  • alkylene oxide-modified product of the trifunctional or higher ethylenically unsaturated compound examples include caprolactone-modified (meth) acrylate compound (KAYARAD (registered trademark) DPCA-20 manufactured by Nippon Kayaku Co., Ltd. and A-9300-1CL manufactured by Shin-Nakamura Chemical Industry Co., Ltd.).
  • KAYARAD registered trademark
  • DPCA-20 Nippon Kayaku Co., Ltd.
  • A-9300-1CL manufactured by Shin-Nakamura Chemical Industry Co., Ltd.
  • 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 (registered trademark) 135 manufactured by Daicel Ornex Co., Ltd., etc.), Acrylate glycerin triacrylate (A-GLY-9E manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), Aronix (registered trademark) TO-2349 (manufactured by Toa Synthetic Co., Ltd.), Aronix M-520 (manufactured by Toa Synthetic Co., Ltd.), and Aronix M. -510 (manufactured by Toa Synthetic Co., Ltd.) can be mentioned.
  • a polymerizable compound having an acid group (carboxy group or the like) may be used.
  • the acid group may form an acid anhydride group.
  • Polymerizable compounds having an acid group include Aronix (registered trademark) TO-2349 (manufactured by Toagosei), Aronix (registered trademark) M-520 (manufactured by Toagosei), and Aronix (registered trademark) M-510. (Manufactured by Toagosei Co., Ltd.) can be mentioned.
  • the polymerizable compound having an acid group for example, the polymerizable compound having an acid group described in paragraphs [0025] to [0030] of JP-A-2004-239942 may be used.
  • the molecular weight (weight average molecular weight when having a molecular weight distribution) of the polymerizable compound (including the polymerizable compound B1) is preferably 200 to 3,000, more preferably 280 to 2,200, and preferably 300 to 2,200. More preferred.
  • the polymerizable compound may be used alone or in combination of two or more.
  • the content of the polymerizable compound is preferably 1 to 70% by mass, more preferably 5 to 70% by mass, further preferably 20 to 70% by mass, and 40 to 60% by mass with respect to the total mass of the photosensitive resin composition layer. % Is particularly preferable.
  • the photosensitive resin composition layer may contain a polymerization initiator.
  • the polymerization initiator is selected according to the type of the polymerization reaction, and examples thereof include a thermal polymerization initiator and a photopolymerization initiator.
  • the polymerization initiator may be a radical polymerization initiator or a cationic polymerization initiator.
  • the photosensitive resin composition 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 composition layer contains 2,4,5-triarylimidazole dimer as a photoradical polymerization initiator from the viewpoints of photosensitive, visibility of exposed and unexposed areas, and resolution. It preferably contains at least one selected from the group consisting of the body and its 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.
  • 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:).
  • the photocationic polymerization initiator (photoacid generator) is a compound that generates an acid by receiving active light rays.
  • the photocationic polymerization initiator is preferably a compound that is sensitive to active light having a wavelength of 300 nm or more, preferably 300 to 450 nm, and generates an acid, but its chemical structure is not limited.
  • a photocationic polymerization initiator that is not directly sensitive to active light with a wavelength of 300 nm or more is also a sensitizer if it is a compound that is sensitive to active light with a wavelength of 300 nm or more and generates an acid when used in combination with a sensitizer. Can be preferably used in combination with.
  • 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 particularly 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 salts and triarylsulfonium salts, and quaternary ammonium salts.
  • 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-triazines, diazomethane compounds, imide sulfonate compounds, and oxime sulfonate compounds.
  • trichloromethyl-s-triazines, 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 examples include the photoacid generator described in the description of the thermoplastic resin composition layer described later and the colored resin composition layer described later.
  • the photosensitive resin composition 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 polymerization initiator may be used alone or in combination of two or more.
  • the content of the polymerization initiator (preferably a photopolymerization initiator) 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 composition layer. It is preferable, and 1.0% by mass or more is more preferable.
  • the upper limit is not particularly limited, but is preferably 20% by mass or less, more preferably 15% by mass or less, still more preferably 10% by mass or less, and particularly preferably 5% by mass or less, based on the total mass of the photosensitive resin composition layer.
  • the photosensitive resin composition 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 unexposed areas, pattern visibility after development, and resolution. It is also preferable to include a dye (also referred to as "dye N") whose maximum absorption wavelength is changed by an acid, a base, or a radical. When the dye N is contained, 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 better.
  • the term "the maximum absorption wavelength is changed by an acid, a base or a radical” means that the dye in a color-developing state is decolorized by an acid, a base or a 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 color-developing state changes to a color-developing state of another hue.
  • the dye N may be a compound that changes its color from the decolorized state by exposure and may be a compound that changes its color from the decolorized state by exposure.
  • a dye may be a dye in which an acid, a base or a radical is generated in the photosensitive resin composition layer by exposure and the state of color development or decolorization is changed by the action, and the photosensitive resin composition is formed by the acid, the base or the radical. It may be a dye whose color development or decolorization state changes by changing the state (for example, pH) in the material layer. Further, it may be a dye that changes its color development or decolorization state by directly receiving an acid, a base or a radical as a stimulus without going through 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, from the viewpoint of visibility and resolution of the exposed part and the non-exposed part. ..
  • the photosensitive resin composition layer contains 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. Is 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 composition layer, and photoradical polymerization is initiated 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 ⁇ 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 the transmission spectrum of the 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. Is measured and the wavelength at which the intensity of light is minimized (maximum absorption wavelength) is detected.
  • Examples of the dye that develops or decolorizes by exposure include leuco compounds.
  • Examples of the dye that is decolorized by exposure include a leuco compound, a diarylmethane dye, an oxadin dye, a xanthene dye, an iminonaphthoquinone dye, an azomethin dye, and an anthraquinone dye.
  • 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 leuco auramine-based dyes
  • triarylmethane-based dyes or fluorane-based dyes are preferable, and leuco compounds (triphenylmethane-based dyes) or fluorane-based dyes having a triphenylmethane skeleton are 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 closed ring state.
  • the color can be decolorized by allowing the compound to be decolorized, or the leuco compound can be changed to the ring-opened state to develop the color.
  • the leuco compound has a lactone ring, a sultone ring, or a sultone ring, and a compound in which the lactone ring, the sultone ring, or the sultone ring is opened by a radical or an acid to develop color is preferable, and the leuco compound has a lactone ring.
  • a compound in which the lactone ring is opened by a radical or an acid to develop a 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 fuchsin, methyl violet 2B, quinaldine red, rose bengal, methanyl yellow, timol sulfophthaline, 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, brilliant green, 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 with respect to the total mass of the photosensitive resin composition layer from the viewpoints of visibility of the exposed portion and the non-exposed portion, pattern visibility after development, and resolution.
  • the above is preferable, 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 total mass of the photosensitive resin composition 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 of the dye is dissolved and a solution in which 0.01 g of the dye is dissolved are prepared in 100 mL of methyl ethyl ketone.
  • Irgacure OXE01 (trade name, manufactured by BASF Japan Ltd.), a photoradical polymerization initiator, 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. Then, in an atmospheric atmosphere, 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. Next, 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 composition layer is dissolved in methyl ethyl ketone instead of the dye. From the absorbance of the obtained solution containing the photosensitive resin composition layer, the content of the dye with respect to the total mass of the photosensitive resin composition layer is calculated based on the calibration curve.
  • the photosensitive resin composition layer preferably contains a heat-crosslinkable compound from the viewpoint of the strength of the obtained cured film and the adhesiveness of the obtained uncured film.
  • the heat-crosslinkable compound having an ethylenically unsaturated group described later is not treated as a polymerizable compound, but is treated as a heat-crosslinkable compound.
  • the heat-crosslinkable compound include a methylol compound and a blocked isocyanate compound. Of these, a blocked isocyanate compound is preferable from the viewpoint of the strength of the obtained cured film and the adhesiveness of the obtained uncured film.
  • the blocked isocyanate compound reacts with a hydroxy group and a carboxy group, for example, when the resin and / or the polymerizable compound has at least one of the hydroxy group and the carboxy group, the hydrophilicity of the formed film decreases.
  • the blocked isocyanate compound refers to "a compound having a structure in which the isocyanate group of isocyanate is protected (so-called masked) with a blocking agent".
  • the dissociation temperature of the blocked isocyanate compound is not particularly limited, but is preferably 100 to 160 ° C, more preferably 130 to 150 ° C.
  • the dissociation temperature of the blocked isocyanate means "the temperature of the endothermic peak associated with the deprotection reaction of the blocked isocyanate when measured by DSC (Differential scanning calorimetry) analysis using a differential scanning calorimeter".
  • DSC Different scanning calorimeter
  • a differential scanning calorimeter model: DSC6200 manufactured by Seiko Instruments Co., Ltd. can be preferably used.
  • the differential scanning calorimeter is not limited to this.
  • the blocking agent having a dissociation temperature of 100 to 160 ° C. for example, at least one selected from oxime compounds is preferable from the viewpoint of storage stability.
  • the blocked isocyanate compound preferably has an isocyanurate structure, for example, from the viewpoint of improving the brittleness of the membrane and improving the adhesion to the transferred body.
  • the blocked isocyanate compound having an isocyanurate structure can be obtained, for example, by subjecting hexamethylene diisocyanate to isocyanurate to protect it.
  • a compound having an oxime structure using an oxime compound as a blocking agent is more likely to have a dissociation temperature in a preferable range than a compound having no oxime structure, and has less development residue. It is preferable from the viewpoint of easy operation.
  • the blocked isocyanate compound may have a polymerizable group.
  • the polymerizable group is not particularly limited, and a known polymerizable group can be used, and a radically polymerizable group is preferable.
  • the polymerizable group include a (meth) acryloxy group, a (meth) acrylamide group, an ethylenically unsaturated group such as a styryl group, and a group having an epoxy group such as a glycidyl group.
  • an ethylenically unsaturated group is preferable
  • a (meth) acryloxy group is more preferable
  • an acryloxy group is further preferable.
  • blocked isocyanate compound a commercially available product can be used.
  • examples of commercially available blocked isocyanate compounds include Karenz (registered trademark) AOI-BM, Karenz (registered trademark) MOI-BM, Karenz (registered trademark) MOI-BP (all manufactured by Showa Denko KK), and block type.
  • examples thereof include the Duranate series (for example, Duranate (registered trademark) TPA-B80E, Duranate (registered trademark) WT32-B75P, etc., manufactured by Asahi Kasei Chemicals Co., Ltd.).
  • the blocked isocyanate compound a compound having the following structure can also be used.
  • the heat-crosslinkable compound may be used alone or in combination of two or more.
  • the content of the heat-crosslinkable compound is preferably 1 to 50% by mass, more preferably 5 to 30% by mass, based on the total mass of the photosensitive resin composition layer.
  • the photosensitive resin composition layer may contain known additives in addition to the above components, if necessary.
  • the additive include a radical polymerization inhibitor, a sensitizer, a plasticizer, a heterocyclic compound (triazole, etc.), benzotriazoles, carboxybenzotriazoles, pyridines (isonicotinamide, etc.), a purine base (adenine, etc.). ), And a surfactant.
  • Each additive may be used alone or in combination of two or more.
  • radical polymerization inhibitor examples include the thermal polymerization inhibitor described in paragraph [0018] of Japanese Patent No. 4502784. Of these, phenothiazine, phenoxazine, or 4-methoxyphenol is preferable.
  • examples of other radical polymerization inhibitors include naphthylamine, cuprous chloride, nitrosophenylhydroxyamine aluminum salt, diphenylnitrosamine and the like. It is preferable to use a nitrosophenylhydroxyamine aluminum salt as a radical polymerization inhibitor so as not to impair the sensitivity of the photosensitive resin composition layer.
  • benzotriazoles include 1,2,3-benzotriazole, 1-chloro-1,2,3-benzotriazole, bis (N-2-ethylhexyl) aminomethylene-1,2,3-benzotriazole, and the like. Examples thereof include bis (N-2-ethylhexyl) aminomethylene-1,2,3-triltriazole and bis (N-2-hydroxyethyl) aminomethylene-1,2,3-benzotriazole.
  • carboxybenzotriazoles examples include 4-carboxy-1,2,3-benzotriazole, 5-carboxy-1,2,3-benzotriazole, and N- (N, N-di-2-ethylhexyl) aminomethylene. Examples thereof include carboxybenzotriazole, N- (N, N-di-2-hydroxyethyl) aminomethylenecarboxybenzotriazole, and N- (N, N-di-2-ethylhexyl) aminoethylenecarboxybenzotriazole.
  • a commercially available product such as CBT-1 (Johoku Chemical Industry Co., Ltd., trade name) can be used.
  • the total content of the radical polymerization inhibitor, benzotriazols, and carboxybenzotriazols is preferably 0.01 to 3% by mass when the total mass of the photosensitive resin composition layer is 100% by mass. , 0.05 to 1% by mass is more preferable. It is preferable that the content is 0.01% by mass or more from the viewpoint of imparting storage stability to the composition. On the other hand, it is preferable to make the content 3% by mass or less from the viewpoint of maintaining the sensitivity and suppressing the decolorization of the dye.
  • the sensitizer is not particularly limited, and known sensitizers, dyes and pigments can be used.
  • 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), stylben compounds, triazine compounds, thiophene compounds, naphthalimide compounds, triarylamine compounds, and aminoacridin compounds.
  • the content of the sensitizer can be appropriately selected depending on the purpose.
  • the content of the sensitizer is 0.01 to 5 mass with respect to the total mass of the photosensitive resin composition layer 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. % Is preferable, and 0.05 to 1% by mass is more preferable.
  • plasticizer and the heterocyclic compound examples include the compounds described in paragraphs [0907] to [0103] and [0111] to [0118] of International Publication No. 2018/179640.
  • the photosensitive resin composition comprises metal oxide particles, antioxidants, dispersants, acid growth agents, development accelerators, conductive fibers, UV absorbers, thickeners, cross-linking agents, and organic or inorganic precipitation prevention. It may further contain known additives such as agents. Examples of the additive contained in the photosensitive resin composition include the compounds 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 (thickness) of the photosensitive resin composition layer is not particularly limited, and is, for example, often 0.1 to 300 ⁇ m, preferably 0.2 to 100 ⁇ m, and more preferably 0.5 to 50 ⁇ m. 0.5 to 15 ⁇ m is more preferable, 0.5 to 10 ⁇ m is particularly preferable, and 0.5 to 8 ⁇ m is most preferable. As a result, the developability of the photosensitive resin composition layer is improved, and the resolvability can be improved. Further, in one embodiment, 0.5 to 5 ⁇ m is preferable, 0.5 to 4 ⁇ m is more preferable, and 0.5 to 3 ⁇ m is further preferable.
  • the transmittance of the light of the photosensitive resin composition layer at a wavelength of 365 nm 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 photosensitive resin composition layer may contain a predetermined amount of impurities.
  • impurities include sodium, potassium, magnesium, calcium, iron, manganese, copper, aluminum, titanium, chromium, cobalt, nickel, zinc, tin, halogen and ions thereof.
  • halide ions, sodium ions, and potassium ions are easily mixed as impurities, so the following content is preferable.
  • the upper limit of the content of impurities is preferably 80% by mass or less, more preferably 10% by mass or less, still more preferably 2% by mass or less, based on the total mass of the photosensitive resin composition layer.
  • the lower limit of the content is preferably 1 mass ppb or more, more preferably 0.1 mass ppm or more.
  • Impurities can be quantified by known methods such as ICP (Inductively Coupled Plasma) emission spectroscopy, atomic absorption spectroscopy, and ion chromatography.
  • ICP Inductively Coupled Plasma
  • the content of compounds such as benzene, formaldehyde, trichlorethylene, 1,3-butadiene, carbon tetrachloride, chloroform, N, N-dimethylformamide, N, N-dimethylacetamide, and hexane in the photosensitive resin composition layer is , Preferably less.
  • the upper limit of the content of these compounds is preferably 100 mass ppm or less, more preferably 20 mass ppm or less, still more preferably 4 mass ppm or less, based on the total mass of the photosensitive resin composition layer.
  • As the lower limit of the content 10 mass ppb or more is preferable, and 100 mass ppb or more is more preferable with respect to the total mass of the photosensitive resin composition layer.
  • the content of these compounds can be suppressed in the same manner as the above-mentioned metal impurities. Further, it can be quantified by a known measurement method.
  • the photosensitive resin composition layer may contain the residual monomers of the above-mentioned polymer P and each structural unit of the polymer A.
  • the content of the residual monomer is preferably 5,000 mass ppm or less, more preferably 2,000 mass ppm or less, based on the total mass of the polymer P or the polymer A from the viewpoint of patterning property and reliability. , 500 mass ppm or less is more preferable.
  • the lower limit is not particularly limited, but 1 mass ppm or more is preferable, and 10 mass ppm or more is more preferable with respect to the total mass of the polymer P or the polymer A.
  • the residual monomer of each structural unit of the polymer P or the polymer A is preferably 3,000 mass ppm or less, preferably 600 mass ppm or less, based on the total mass of the photosensitive resin composition layer from the viewpoint of patterning property and reliability. It is more preferably mass ppm or less, and even more preferably 100 mass ppm or less.
  • the lower limit is not particularly limited, but is preferably 0.1 mass ppm or more, and more preferably 1 mass ppm or more, with respect to the total mass of the photosensitive resin composition layer.
  • the amount of the residual monomer can be measured by a known method such as liquid chromatography and gas chromatography.
  • the resin composition layer may be a thermoplastic resin composition layer.
  • the thermoplastic resin composition layer is preferably formed between the temporary support and the resin composition layer, for example, in a transfer film having the temporary support and the resin composition layer.
  • the transfer film improves the followability to the substrate in the bonding process between the transfer film and the substrate, and the substrate and the transfer film. The mixing of air bubbles between the film and the film can be suppressed, and the adhesion to the adjacent layer (for example, a temporary support) can be improved.
  • the thermoplastic resin composition layer means an embodiment in which the alkali-soluble resin in the photosensitive resin composition layer is a thermoplastic resin.
  • the thermoplastic resin may be alkali-soluble. That is, it may be a resin exhibiting thermoplasticity and alkali solubility (hereinafter, also referred to as "alkali-soluble thermoplastic resin").
  • the thermoplastic resin composition layer may contain other thermoplastic resins in addition to the alkali-soluble thermoplastic resin.
  • alkali-soluble thermoplastic resin examples 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 polyhydroxy.
  • alkali-soluble thermoplastic resin examples 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 polyhydroxy.
  • examples thereof include styrene resin, polyimide resin, polybenzoxazole resin, polysiloxane resin, polyethyleneimine, polyallylamine, and polyalkylene glycol.
  • 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 the acrylic resin. It is preferably 30% by mass or more, more preferably 50% by mass or more, based on 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, preferably 50 to 100% by mass, based on the total mass of the acrylic resin. 100% by mass is more preferable.
  • the alkali-soluble thermoplastic 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 acid value of the alkali-soluble thermoplastic resin is preferably 60 mgKOH / g or more from the viewpoint of developability.
  • the upper limit of the acid value of the alkali-soluble thermoplastic resin is not particularly limited, but is preferably 300 mgKOH / g or less, more preferably 250 mgKOH / g or less, further preferably 200 mgKOH / g or less, and particularly preferably 150 mgKOH / g or less.
  • the alkali-soluble thermoplastic resin (preferably a 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.
  • an alkali-soluble resin which is an acrylic resin having a carboxy group having an acid value of 60 mgKOH / g or more
  • a paragraph of JP-A-2010-237589 [
  • an acrylic resin having a carboxy group having an acid value of 60 mgKOH / g or more can be mentioned.
  • the copolymerization ratio of the structural unit having a carboxy group in the acrylic resin having a carboxy group 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 thermoplastic 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 polyaddition 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 thermoplastic resin is preferably 1,000 or more, more preferably 10,000 to 100,000, still more preferably 20,000 to 50,000.
  • the alkali-soluble thermoplastic resin may be used alone or in combination of two or more.
  • the content of the alkali-soluble thermoplastic resin is preferably 10.00 to 99.00% by mass, preferably 10.00 to 99.00% by mass, based on the total mass of the thermoplastic resin composition layer from the viewpoint of developability and adhesion to the adjacent layer. It is more preferably 00 to 90.00% by mass, further preferably 40.00 to 80.00% by mass, and particularly preferably 50.00 to 75.00% by mass.
  • thermoplastic resin composition 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, and the maximum absorption wavelength is changed by an acid, a base, or a radical (also referred to simply as “dye B”). It is preferable to include.
  • the preferred embodiment of the dye B is the same as the preferred embodiment of the dye N described above, except for the points described later.
  • the dye B 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 an acid, from the viewpoint of visibility and resolution of the exposed part and the non-exposed part. ..
  • the thermoplastic resin composition layer is 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, from the viewpoint of visibility and resolution of the exposed part and the non-exposed part. It is preferable to include both of the above.
  • 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, preferably 0.2 to 6.0% by mass, based on the total mass of the thermoplastic resin composition layer from the viewpoint of visibility of the exposed portion and the non-exposed portion. Is more preferable, 0.2 to 5.0% by mass is further preferable, and 0.25 to 3.0% by mass is particularly preferable.
  • the content of the dye B means the content of the dye when all of the dye B contained in the thermoplastic resin composition layer is in a colored state.
  • a method for quantifying the content of dye B will be described by taking a dye that develops color by radicals as an example.
  • a solution in which 0.001 g of the dye is dissolved and a solution in which 0.01 g of the dye is dissolved are prepared in 100 mL of methyl ethyl ketone.
  • Irgacure OXE01 (trade name, manufactured by BASF Japan Ltd.), a photoradical polymerization initiator, 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 composition layer is dissolved in methyl ethyl ketone instead of the dye. From the absorbance of the obtained solution containing the thermoplastic resin composition layer, the amount of the dye with respect to the total mass of the thermoplastic resin composition layer is calculated based on the calibration curve.
  • the thermoplastic resin composition may contain a compound that generates an acid, a base, or a radical by light (hereinafter, also simply referred to as “Compound C”).
  • a compound that receives an active ray such as ultraviolet rays and visible rays to generate an acid, a base, or a radical is preferable.
  • a known photoacid generator, photobase generator, and photoradical polymerization initiator (photoradical generator) can be used. Of these, a photoacid generator is preferable.
  • Photoacid generator examples include a photocationic polymerization initiator which may be contained in the above-mentioned photosensitive resin composition layer, and preferred embodiments are also 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 adhesion. From the viewpoint of sex, 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.
  • photo-radical polymerization initiator examples include a photo-radical polymerization initiator which may be contained in the above-mentioned photosensitive resin composition layer, and the preferred embodiment is also the same.
  • the photobase generator is not particularly limited as long as it is a known photobase generator, and for example, 2-nitrobenzylcyclohexylcarbamate, triphenylmethanol, O-carbamoylhydroxylamide, O-carbamoyloxime, [[(2, 6-Dinitrobenzyl) oxy] carbonyl] cyclohexylamine, bis [[(2-nitrobenzyl) oxy] carbonyl] hexane 1,6-diamine, 4- (methylthiobenzoyl) -1-methyl-1-morpholinoetan, (4) -Morholinobenzoyl) -1-benzyl-1-dimethylaminopropane, N- (2-nitrobenzyloxycarbonyl) pyrrolidine, hexaammine cobalt (III) tris (triphenylmethylborate), 2-benzyl-2-dimethylamino- 1- (4-morpholinophenyl) -butanone,
  • Compound C may be used alone or in combination of two or more.
  • the content of the compound C is preferably 0.1 to 10% by mass, preferably 0.5 to 10% by mass, based on the total mass of the thermoplastic resin composition layer from the viewpoint of visibility and resolution of the exposed and non-exposed areas. 5% by mass is more preferable.
  • the thermoplastic resin composition layer preferably contains a plasticizer from the viewpoint of adhesion to adjacent layers, resolvability, and developability.
  • the plasticizer preferably has a smaller molecular weight (oligomer or polymer, weight average molecular weight when it has a molecular weight distribution) than the alkali-soluble resin.
  • the molecular weight (weight average molecular weight) of the plasticizer is preferably 200 to 2,000.
  • the plasticizer is not particularly limited as long as it is a compound that develops plasticity by being compatible with an alkali-soluble thermoplastic resin, but from the viewpoint of imparting plasticity, the plasticizer preferably has an oxyalkylene group in the molecule, and is poly.
  • An alkylene glycol compound is more preferred.
  • the oxyalkylene group contained in the plasticizer is more preferably having a polyethylene oxy structure or a polypropylene oxy 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 the plasticizer include the (meth) acrylate compound described as the polymerizable compound contained in the above-mentioned photosensitive resin composition layer.
  • the thermoplastic resin composition layer and the photosensitive resin composition layer are both the same (meth) acrylate compound. It is preferable to include. This is because the thermoplastic resin composition layer and the photosensitive resin composition layer contain the same (meth) acrylate compound, so that the diffusion of components between the layers is suppressed and the storage stability is improved.
  • the thermoplastic resin composition layer contains a (meth) acrylate compound as a plasticizer
  • the (meth) acrylate compound is also contained in the exposed portion after exposure from the viewpoint of adhesion between the thermoplastic resin composition layer and the adjacent layer. It is preferable not to polymerize.
  • the (meth) acrylate compound used as a plasticizer includes two or more (meth) acrylate compounds in one molecule from the viewpoints of resolution of the thermoplastic resin composition layer, adhesion to adjacent layers, and developability. )
  • a polyfunctional (meth) acrylate compound having an acryloyl group is preferable.
  • a (meth) acrylate compound having an acid group or a urethane (meth) acrylate compound is also preferable.
  • the plasticizer may be used alone or in combination of two or more.
  • the content of the plasticizer is 1 to 70% by mass with respect to the total mass of the thermoplastic resin composition layer from the viewpoint of the resolution of the thermoplastic resin composition layer, the adhesion to the adjacent layer, and the developability. It is preferable, 10 to 60% by mass is more preferable, and 15 to 50% by mass is further preferable.
  • the thermoplastic resin composition 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 composition layer.
  • the sensitizer may be used alone or in combination of two or more.
  • 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 portion and the non-exposed portion, 0. It is preferably 01 to 5% by mass, more preferably 0.05 to 1% by mass.
  • thermoplastic resin composition layer may contain known additives, if necessary. Further, the thermoplastic resin composition 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 composition 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 resolvability, 20 ⁇ m or less is preferable, 10 ⁇ m or less is more preferable, and 8 ⁇ m or less is further preferable.
  • the thermoplastic resin composition layer may contain a predetermined amount of impurities.
  • the impurities are not particularly limited, and examples thereof include impurities that may be contained in the above-mentioned photosensitive resin composition layer, and the preferred range is also the same.
  • the thermoplastic resin composition layer may contain residual monomers of each structural unit of the above-mentioned alkali-soluble thermoplastic resin.
  • the preferable range of the content of the residual monomer is the same as the content of the residual monomer that may be contained in the photosensitive resin composition layer described above.
  • the resin composition layer may be a colored resin composition layer.
  • the liquid crystal display window of electronic devices may be equipped with a cover glass having a black frame-shaped light-shielding layer formed on the peripheral edge of the back surface of a transparent glass substrate or the like in order to protect the liquid crystal display window. be.
  • a colored resin composition layer can be used to form such a light-shielding layer.
  • the colored resin composition layer contains a pigment.
  • the colored resin composition layer is a colored resin composition containing a resin (for example, polymer P and polymer A, etc.), a polymerizable compound, and a block copolymer and / or compound (1), as well as a pigment. It may be a physical layer.
  • the colored resin composition layer further contains a polymerization initiator. It is also preferable to include it.
  • a pigment may be further added to each of the above-mentioned resin composition layers to form a colored resin composition layer.
  • a pigment or a pigment dispersion
  • the layer can be used as a colored resin composition layer. That is, the above-mentioned photosensitive resin composition layer may be used as a photosensitive resin composition layer which is a colored resin composition layer.
  • each of the above-mentioned resin composition layers may be used as a colored resin composition layer to which a pigment is added.
  • the above-mentioned photosensitive resin composition layer may be a colored resin composition layer containing a pigment as described above. That is, the above-mentioned photosensitive resin composition layer may be a photosensitive resin composition layer which is a colored resin composition layer.
  • the pigment contained in the colored resin composition layer may be appropriately selected according to a desired hue, and can be selected from black pigments, white pigments, and chromatic pigments other than black and white. Among them, when forming a black pattern, a black pigment is preferably selected as the pigment.
  • the black pigment a known black pigment (organic pigment, inorganic pigment, etc.) can be appropriately selected as long as the effect of the present invention is not impaired.
  • carbon black, titanium oxide, titanium carbide, iron oxide, titanium oxide, graphite and the like are preferably mentioned as the black pigment from the viewpoint of optical density, and carbon black is particularly preferable.
  • carbon black from the viewpoint of surface resistance, carbon black having at least a part of the surface coated with a resin is preferable.
  • the black pigment (preferably carbon black) is preferably used in the form of a pigment dispersion.
  • the dispersion liquid may be prepared by adding a mixture obtained by previously mixing a black pigment and a pigment dispersant to an organic solvent (or vehicle) and dispersing it with a disperser.
  • the pigment dispersant may be selected depending on the pigment and the solvent, and for example, a commercially available dispersant can be used.
  • the vehicle refers to a portion of the medium in which the pigment is dispersed when the pigment is dispersed, and is a liquid, a binder component that holds the black pigment in a dispersed state, and a solvent component that dissolves and dilutes the binder component. (Organic solvent) and.
  • the disperser is not particularly limited, and examples thereof include known dispersers such as a kneader, a roll mill, an attritor, a super mill, a dissolver, a homomixer, and a sand mill. Further, it may be finely pulverized by mechanical grinding using frictional force.
  • disperser and fine pulverization the description of "Encyclopedia of Pigments" (Kunizo Asakura, First Edition, Asakura Shoten, 2000, 438, 310) can be referred to.
  • the particle size of the black pigment is preferably 0.001 to 0.1 ⁇ m, more preferably 0.01 to 0.08 ⁇ m in terms of number average particle size.
  • the particle size refers to the diameter of the circle when the area of the pigment particles is obtained from the photographic image of the pigment particles taken with an electronic microscope and the circle having the same area as the area of the pigment particles is considered, and the number average particle size. Is an average value obtained by obtaining the above particle size for any 100 particles and averaging the obtained 100 particle sizes.
  • the white pigment described in paragraphs [0015] and [0114] of JP-A-2005-007765 can be used as the white pigment.
  • the white pigments as the inorganic pigment, titanium oxide, zinc oxide, lithopone, light calcium carbonate, white carbon, aluminum oxide, aluminum hydroxide, or barium sulfate is preferable, and titanium oxide or oxidation is preferable. Zinc is more preferred, and titanium oxide is even more preferred.
  • rutile-type or anatase-type titanium oxide is more preferable, and rutile-type titanium oxide is particularly preferable.
  • the surface of titanium oxide may be treated with silica, alumina, titania, zirconia, or an organic substance, or may be subjected to two or more treatments.
  • the catalytic activity of titanium oxide is suppressed, and heat resistance, fading and the like are improved.
  • at least one of alumina treatment and zirconia treatment is preferable as the surface treatment of the surface of titanium oxide, and both alumina treatment and zirconia treatment are particularly preferable. ..
  • the colored resin composition layer further contains a chromatic pigment other than the black pigment and the white pigment.
  • a chromatic pigment is contained, it is desirable that the chromatic pigment is well dispersed in the colored resin layer, and from this viewpoint, the particle size is preferably 0.1 ⁇ m or less, more preferably 0.08 ⁇ m or less.
  • chromatic pigments include Victoria Pure Blue BO (Color Index (hereinafter CI) 42595), Auramine (CI41000), Fat Black HB (CI26150), and Monolite.
  • Pigment Red 180 C.I. I. Pigment Red 192, C.I. I. Pigment Red 215, C.I. I. Pigment Green 7, C.I. I. Pigment Blue 15: 1, C.I. I. Pigment Blue 15: 4, C.I. I. Pigment Blue 22, C.I. I. Pigment Blue 60, C.I. I. Pigment Blue 64 and C.I. I. Pigment Violet 23. Above all, C.I. I. Pigment Red 177 is preferred.
  • the content of the pigment is preferably more than 3% by mass and 40% by mass or less, more preferably more than 3% by mass and 35% by mass or less, and more than 5% by mass and 35% by mass or less with respect to the total mass of the colored resin composition layer. More preferably, 10 to 35% by mass is particularly preferable.
  • a pigment other than the black pigment (white pigment and chromatic pigment) is contained, it is preferably 30% by mass or less, more preferably 1 to 20% by mass, still more preferably 3 to 15% by mass with respect to the black pigment.
  • the layer thickness (thickness) of the colored resin composition layer is often 0.1 to 300 ⁇ m, preferably 0.2 to 100 ⁇ m, more preferably 0.5 to 50 ⁇ m, still more preferably 0.5 to 15 ⁇ m. , 0.5 to 10 ⁇ m is particularly preferable, and 0.5 to 8 ⁇ m is most preferable.
  • the colored resin composition layer may contain a predetermined amount of impurities.
  • the impurities are not particularly limited, and examples thereof include impurities that may be contained in the above-mentioned photosensitive resin composition layer, and the preferred range is also the same.
  • the colored resin composition layer may contain a residual monomer of each structural unit of the above-mentioned resin (for example, polymer P, polymer A, alkali-soluble resin, etc.).
  • the preferable range of the content of the residual monomer is the same as the content of the residual monomer that may be contained in the photosensitive resin composition layer described above.
  • the resin composition layer may be a water-soluble resin composition layer.
  • the water-soluble resin composition layer is a resin composition layer containing a block copolymer and / or compound (1) and a water-soluble resin.
  • the resin that can be used as the water-soluble resin 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 both of these. Examples thereof include resins such as polymers.
  • this water-soluble resin is a resin contained in an adjacent layer (for example, a polymer) from the viewpoint of suppressing mixing of components between a plurality of layers. It is preferable that the resin is different from P, the polymer A, and the alkali-soluble thermoplastic resin.
  • the water-soluble resin composition layer preferably contains polyvinyl alcohol, and is preferably polyvinyl alcohol and polyvinylpyrrolidone, from the viewpoint of oxygen blocking property and suppressing mixing of components during application and storage after application. It is more preferable to include both of the above.
  • the water-soluble resin composition layer may be used alone or in combination of two or more.
  • the content of the water-soluble resin is not particularly limited, but from the viewpoint of oxygen blocking property and suppressing the mixing of components during application of a plurality of layers and storage after application, the total mass of the water-soluble resin composition layer.
  • 50.0% by mass or more and less than 100.0% by mass is preferable, 70.0% by mass or more and less than 100.0% by mass is more preferable, and 80.0% by mass or more and less than 100.0% by mass is further preferable.
  • 90.0% by mass or more and less than 100.0% by mass is particularly preferable.
  • the method for forming the water-soluble resin composition layer is not particularly limited, and can be, for example, the same as the method using a photosensitive resin composition.
  • the method for forming the intermediate layer is not particularly limited, and for example, the water-soluble resin composition is applied to the surface of the thermoplastic resin composition layer or the photosensitive resin composition layer.
  • a method of forming a water-soluble resin composition layer by drying a coating film of the water-soluble resin composition can be mentioned.
  • the layer thickness of the water-soluble resin composition layer is not particularly limited, but is preferably 0.1 to 5.0 ⁇ m, more preferably 0.5 to 3.0 ⁇ m.
  • the oxygen blocking property is not lowered, the mixing of the components can be suppressed when the plurality of layers are applied and when the layers are stored after application, and the mixture of the components can be suppressed. This is because it is possible to suppress an increase in the time for removing the water-soluble resin layer during development.
  • the water-soluble resin composition layer may contain a predetermined amount of impurities.
  • the impurities are not particularly limited, and examples thereof include impurities that may be contained in the above-mentioned photosensitive resin composition layer, and the preferred range is also the same.
  • the water-soluble resin composition layer may contain residual monomers of each structural unit of the above-mentioned resin (for example, water-soluble resin, polymer P, polymer A, alkali-soluble resin, etc.).
  • the preferable range of the content of the residual monomer is the same as the content of the residual monomer that may be contained in the photosensitive resin composition layer described above.
  • the resin composition layer is preferably, for example, a layer composed of only the components contained in the above-mentioned resin composition layer.
  • the resin composition layer of the present invention is contained in, for example, the above-mentioned photosensitive resin composition layer, thermoplastic resin composition layer, colored resin composition layer, and / or water-soluble resin composition layer. It is a layer consisting only of the components that are used.
  • the resin composition layer other than the present invention is, for example, in the above-mentioned photosensitive resin composition layer, thermoplastic resin composition layer, colored resin composition layer, and / or water-soluble resin composition layer, each of the above-mentioned resins. Examples thereof include a resin composition layer composed of components other than the components contained in the composition layer.
  • the transfer film preferably has a cover film in contact with a surface of each resin composition layer that does not face the temporary support.
  • the surface of the composition layer facing the temporary support is also referred to as a “first surface”, and the surface opposite to the first surface is also referred to as a “second 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 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 each resin composition layer (hereinafter, also simply referred to as “the surface of the cover film”) is preferably 0.3 ⁇ m or less because it is superior in resolution. 1 ⁇ m or less is more preferable, and 0.05 ⁇ m or less is further preferable. It is considered that the Ra value on the surface of the cover film is in the above range to improve the uniformity of the layer thickness of the formed resin pattern.
  • the lower limit of the Ra value on the surface of the cover film is not particularly limited, but 0.001 ⁇ m or more is preferable.
  • 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 the surface profile of the optical film. As the measurement / analysis software, Microscope Application of MetroPro ver8.3.2 is used. Next, the Surface Map screen is displayed by the above analysis software, and the histogram data is obtained in the Surface Map screen. From the obtained histogram data, the arithmetic mean roughness is calculated, and the Ra value on the surface of the cover film is obtained. When the cover film is attached to the transfer film, the cover film may be peeled from the transfer film and the Ra value of the surface on the peeled side may be measured.
  • the method for producing the transfer film is not particularly limited, and a known production method, for example, a known method for forming each resin composition layer can be used.
  • a method for producing a transfer film will be described with reference to FIG. 1.
  • the transfer film is not limited to the one having the structure shown in FIG.
  • FIG. 1 is a schematic view showing an example of the configuration of a transfer film.
  • the transfer film 100 shown in FIG. 1 has a structure in which a temporary support 10, a thermoplastic resin composition layer 12, an intermediate layer 14, a photosensitive resin composition layer 16, and a cover film 18 are laminated in this order. Have.
  • the transfer film includes the intermediate layer 14, it is possible to suppress the mixing of the components when the plurality of layers are applied and when the transfer film is stored after the application.
  • the intermediate layer include an oxygen blocking layer having an oxygen blocking function, which is described as an “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 the known layers described in the above publications and the like.
  • 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 and the resin composition capable of forming the intermediate layer will be described in detail later.
  • the thermoplastic resin composition 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.
  • a method including a step of applying the photosensitive resin composition to the surface of the intermediate layer 14 and then drying the coating film of the photosensitive resin composition to form the photosensitive resin composition layer 16 can be mentioned.
  • the thermoplastic resin composition is a composition for forming the above-mentioned thermoplastic resin composition layer, and may contain the above-mentioned various components.
  • the thermoplastic resin composition may contain a solvent in order to improve the coatability.
  • the photosensitive resin composition is a composition for forming the above-mentioned photosensitive resin composition, and may contain various components described above.
  • the photosensitive resin composition may contain a solvent in order to improve the coatability.
  • the transfer film 100 is manufactured by pressure-bonding the cover film 18 to the photosensitive resin composition layer 16 of the laminate manufactured by the above-mentioned manufacturing method.
  • the method for producing a transfer film according to the present invention includes a step of providing a cover film 18 so as to be in contact with the second surface of the photosensitive resin composition layer 16, thereby providing a temporary support 10 and a thermoplastic resin composition layer 12. It is preferable to manufacture the transfer film 100 including the intermediate layer 14, the photosensitive resin composition layer 16, and the cover film 18. After manufacturing the transfer film 100 by the above-mentioned manufacturing method, the transfer film 100 may be wound up to prepare and store the transfer film in the form of a roll.
  • the roll-type transfer film can be provided as it is in the bonding process with the substrate in the roll-to-roll method described later.
  • thermoplastic resin composition layer and the photosensitive resin composition layer are both the resin composition layer of the present invention, but at least one of these is the resin composition layer of the present invention. Anything may be sufficient, and one type may be a resin composition layer other than the present invention (for example, a thermoplastic resin composition layer other than the present invention and / or a photosensitive resin composition layer other than the present invention).
  • thermoplastic resin composition layer 12 and the photosensitive resin composition layer 16 may be the resin composition layer of the present invention, and the other one is other than the present invention. It may be the resin composition layer of.
  • a water-soluble resin composition layer is preferable.
  • the aspect of the water-soluble resin composition layer is as described above.
  • the transfer film may have a refractive index adjusting layer.
  • the position of the refractive index adjusting layer is not particularly limited, but it is preferably arranged in contact with each resin composition layer.
  • the transfer film preferably has a temporary support, a photosensitive resin composition layer or a thermoplastic resin composition layer, and a refractive index adjusting layer in this order.
  • the transfer film further has the above-mentioned cover film, it may have a temporary support, a photosensitive resin composition layer or a thermoplastic resin composition layer, a refractive index adjusting layer, and a cover film in this order. preferable.
  • the refractive index adjusting layer As the refractive index adjusting layer, a known refractive index adjusting layer can be applied. Examples of the material contained in the refractive index adjusting layer include resin and particles.
  • the resin examples include resins that may be contained in the above-mentioned resin composition layer, and polymer P and / or water-soluble resins are preferable. Further, in the present specification, when the bending ratio adjusting layer contains, for example, a water-soluble resin, it also corresponds to the water-soluble resin composition layer.
  • the particles include zirconium oxide particles (ZrO 2 particles), niobium oxide particles (Nb 2 O 5 particles), titanium oxide particles (TiO 2 particles), and silicon dioxide particles (SiO 2 particles).
  • the refractive index adjusting layer preferably contains a metal oxidation inhibitor.
  • the metal oxidation inhibitor for example, a compound having an aromatic ring containing a nitrogen atom in the molecule is preferable.
  • the metal oxidation inhibitor include imidazole, benzimidazole, tetrazole, mercaptothiadiazole, and benzotriazole.
  • the refractive index of the refractive index adjusting layer is preferably 1.60 or more, more preferably 1.63 or more.
  • the upper limit of the refractive index of the refractive index adjusting layer is preferably 2.10 or less, and more preferably 1.85 or less.
  • the thickness of the refractive index adjusting layer is preferably 500 nm or less, more preferably 110 nm or less, still more preferably 100 nm or less.
  • the lower limit is not particularly limited, and is preferably 20 nm or more, and more preferably 50 nm or more.
  • the thickness of the refractive index adjusting layer is calculated as an average value of any five points measured by cross-sectional observation with a scanning electron microscope (SEM).
  • the refractive index adjusting layer may be a known refractive index adjusting layer, and examples thereof include the second resin layer disclosed in paragraphs [0200] to [0214] of JP-A-2020-091322.
  • thermoplastic resin composition layer (layer other than the temporary support and the cover film) constituting the transfer film having each of the above configurations, at least one of the thermoplastic resin layer and the photosensitive resin composition layer is the resin composition of the present invention. It is a layer. In each of the above configurations, it is also preferable that
  • the present invention also relates to a method for producing a laminate.
  • the method for producing the laminate is not particularly limited as long as it is the method for producing the laminate using the transfer film described above.
  • the substrate preferably a conductive substrate
  • the transfer film and the substrate are contacted.
  • a bonding step hereinafter, also referred to as “bonding step” for bonding a substrate with a transfer film by bonding with a conductive substrate
  • an exposure step hereinafter, “exposure step” for pattern-exposing the resin composition layer.
  • a development step of developing the exposed resin composition layer to form a resin pattern (hereinafter, also referred to as“ development step ”), and further, between the bonding step and the exposure step, or. , A method including a peeling step (hereinafter, also referred to as “peeling step”) of peeling the temporary support from the substrate with the transfer film is preferable between the exposure step and the developing step.
  • the resin composition layer to be exposed to the pattern may be one layer alone or may be composed of two or more layers, and at least one layer constituting the resin composition layer is the resin composition layer of the present invention. Further, the resin composition layer exposed to the pattern preferably contains at least one photosensitive resin composition layer (a photosensitive resin composition layer of the present invention or a photosensitive resin composition layer other than the present invention).
  • the photosensitive resin composition layer may be a colored resin composition layer.
  • 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 transfer film described above.
  • a resin pattern is arranged in a laminate in which a substrate, a conductive layer (conductive layer possessed by the substrate), and a resin pattern manufactured by using the above transfer film are laminated in this order.
  • a method including a step of etching a conductive layer in a region not covered (hereinafter, also referred to as an “etching step”) is preferable. That is, in the method of manufacturing the circuit wiring, the substrate having the conductive layer is brought into contact with the surface (composition layer) on the opposite side of the temporary support of the transfer film, and the transfer film and the substrate having the conductive layer are bonded together.
  • a bonding step of obtaining a substrate with a transfer film (hereinafter, also referred to as “bonding step”), an exposure step of pattern-exposing the resin composition layer (hereinafter, also referred to as “exposure step”), and an exposed resin.
  • a development step of developing a composition layer to form a resin pattern (hereinafter, also referred to as a “development step”) and a step of etching a conductive layer in a region where a resin pattern is not arranged (hereinafter, also referred to as an “etching step”).
  • peeling step in which the temporary support is peeled from the substrate with the transfer film between the bonding step and the exposure step, or between the exposure step and the developing step.
  • peeling step in which the temporary support is peeled from the substrate with the transfer film between the bonding step and the exposure step, or between the exposure step and the developing step.
  • the method for producing the laminate preferably includes a bonding step.
  • the substrate or the conductive layer if the conductive layer is provided on the surface of the substrate
  • the transfer film and the substrate are pressure-bonded.
  • the adhesion between the resin composition layer and the substrate is improved, it can be suitably used as an etching resist when etching the conductive layer using the resin pattern on which the pattern is formed after exposure and development. can.
  • the transfer film includes a cover film
  • the cover film may be removed from the surface of the transfer film and then bonded.
  • the method of crimping the substrate and the transfer film is not particularly limited, and a known transfer method and laminating method can be used.
  • the bonding of the transfer film to the substrate is preferably performed by stacking the substrate on the surface of the transfer film on the side opposite to the temporary support, 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 method for manufacturing the laminated body including the bonding step and the method for manufacturing the circuit wiring are performed by a roll-to-roll method.
  • the roll-to-roll method uses a substrate that can be wound up and unwound as a substrate, and includes the substrate or the substrate before any of the steps included in the manufacturing method of the laminate or the manufacturing method of the circuit wiring.
  • a step of unwinding the body hereinafter, also referred to as “unwinding step”
  • a step of winding up the structure including the base material or the substrate hereinafter, also referred to as “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 a film.
  • the substrate 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.
  • film substrates 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 the circuit wiring for the touch panel is manufactured by the 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 conductive layers used for general circuit wiring and 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 .
  • conductivity means that the volume resistivity is less than 1 ⁇ 106 ⁇ cm.
  • the volume resistivity of the conductive metal oxide is preferably less than 1 ⁇ 10 4 ⁇ cm.
  • a resin pattern is produced using a substrate having a plurality of conductive layers
  • the conductive layer an electrode pattern corresponding to the sensor of the visual recognition portion used in the capacitive touch panel or wiring of the peripheral extraction portion is preferable.
  • the method for producing the laminate preferably includes a step (exposure step) of pattern-exposing the resin composition layer after the laminating step.
  • the detailed arrangement and specific size of the pattern in the pattern exposure are not particularly limited. At least a part (preferably) of the pattern so as to improve the display quality of a display device (for example, a touch panel) having an input device having a circuit wiring manufactured by a circuit wiring manufacturing method and to reduce the area occupied by the take-out wiring.
  • the electrode pattern and / or the portion of the take-out wiring of the touch panel preferably contains a thin wire having a width of 20 ⁇ m or less, and more preferably contains 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 composition layer with light having a wavelength that allows exposure (for example, 365 nm or 405 nm).
  • a light source that irradiates the photosensitive resin composition 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 to 200 mJ / cm 2 , more preferably 10 to 100 mJ / cm 2 .
  • the peeling step is a step of peeling the temporary support from the substrate with the resin composition layer between the bonding step and the exposure step, or between the exposure step and the development step described later.
  • the peeling method is not particularly limited, and a mechanism similar to the cover film peeling mechanism described in paragraphs [0161] to [0162] of JP2010-072589 can be used. Therefore, in the exposure step, the temporary support may be peeled off from the resin composition layer and then the pattern exposure may be performed. Before the temporary support is peeled off, the pattern is exposed through the temporary support, and then the temporary support is exposed. May be peeled off.
  • the mask When the temporary support is peeled off before exposure, the mask may be exposed in contact with the resin composition layer, or may be exposed in close proximity without contact. When the temporary support is exposed without peeling, the mask may be exposed in contact with the temporary support, or may be exposed in close proximity without contact. In order to prevent mask contamination due to contact between the composition layer and the mask and to avoid the influence of foreign matter adhering to the mask on the exposure, it is preferable to perform pattern exposure without peeling the temporary support.
  • the exposure method is a contact exposure method in the case of contact exposure, a proximity exposure method in the case of a non-contact exposure method, a lens-based and mirror-based projection exposure method, and a direct exposure method using an exposure laser or the like. Can be selected and used as appropriate.
  • an exposure machine having an appropriate numerical aperture (NA) of the lens can be used according to the required resolving power and depth of focus.
  • NA numerical aperture
  • drawing may be performed directly on the photosensitive resin composition layer, or reduced projection exposure may be performed on the photosensitive resin composition layer via a lens. Further, the exposure may be performed not only in the atmosphere but also under reduced pressure or vacuum, or may be exposed by interposing a liquid such as water between the light source and the resin composition layer.
  • the method for producing the laminate preferably includes, after the above-mentioned exposure step, a step (development step) of developing the exposed resin composition layer to form a resin pattern.
  • a step (development step) of developing the exposed resin composition layer to form a resin pattern.
  • the resin composition layer contains a photosensitive resin composition layer (a photosensitive resin composition layer of the present invention or a photosensitive resin composition layer other than the present invention)
  • the resin composition layer undergoes a curing reaction according to the exposed pattern.
  • a cured film patterned cured film
  • only the non-exposed portion of the resin composition layer can be removed with a developing solution (alkali developing solution or the like).
  • the different resin composition layer is the same portion as the portion to be removed in the photosensitive resin composition layer. Only the portion may be removed, or the portion other than the portion to be removed in the photosensitive resin composition layer may be completely removed.
  • the transfer film has a thermoplastic resin composition layer and / or a water-soluble resin composition layer together with the photosensitive resin composition layer, the thermoplastic resin composition layer of the non-exposed portion in the developing step. And / or only the water-soluble resin composition layer may be removed together with the photosensitive resin composition layer in the non-exposed portion.
  • thermoplastic resin composition layer and / or the water-soluble resin composition layer in both the exposed portion and the non-exposed portion may be removed in a form of being dissolved or dispersed in the developing solution.
  • a part or all of the resin pattern may be a layer in which the resin composition layer of the present invention undergoes a change such as a curing reaction.
  • the resin composition layer of the transfer film contains the photosensitive resin composition layer of the present invention
  • a part or all of the resin pattern is a material obtained by the curing reaction of the photosensitive resin composition layer of the present invention. Is.
  • the layer in which the resin composition layer of the present invention undergoes a change such as a curing reaction may not be included. That is, the resin pattern obtained after development may consist only of a resin composition layer other than the present invention and / or a layer obtained by changing the curing reaction or the like of the resin composition other than the present invention.
  • the exposed resin composition layer can be developed in the developing step using an alkaline developer.
  • an alkaline developer for example, a known developer such as the developer described in JP-A-5-07724 can be used.
  • the alkaline developer may contain a water-soluble organic solvent and / or a surfactant.
  • the alkaline developer the developer described in paragraph [0194] of International Publication No. 2015/093271 is also preferable.
  • the content of the organic solvent in the alkaline developer is preferably 0% by mass or more and less than 90% by mass with respect to the total mass of the developer.
  • 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 developer onto the exposed resin composition layer with 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 liquid temperature of the developing solution is not particularly limited, but is preferably 20 to 40 ° C.
  • the circuit wiring is manufactured by a manufacturing method including a substrate, a conductive layer (conductive layer of the substrate), and a resin pattern (more preferably, the bonding step, the exposure step, and the developing step. 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 in which the resin pattern is laminated in this order.
  • the resin pattern formed from the resin composition layer is used as an etching resist, and the conductive layer is etched.
  • a method of etching treatment a known method can be applied. For example, the methods described in paragraphs [0209] to [0210] of JP-A-2017-120435, paragraphs [0048] to JP-A-2010-152155. Examples thereof include the method described in [0054], a wet etching method of immersing 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, and the 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.
  • the alkaline etching solution includes 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 permanganate, 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 resin composition 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 liquid examples include a removing liquid in which an inorganic alkaline component or an organic alkaline component is dissolved in water, dimethyl sulfoxide, N-methylpyrrolidone, or a mixed solution thereof.
  • examples of the inorganic alkaline component include sodium hydroxide and potassium hydroxide.
  • examples of the organic alkali component 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 method for manufacturing the circuit wiring 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 manufacturing the laminate and the method for manufacturing the circuit wiring include a step of peeling the cover film from the transfer film.
  • the method of peeling the cover film is not limited, and a known method can be applied.
  • the method for manufacturing a 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 base material has a conductive layer containing copper
  • the visible light reflectance of the conductive layer can be lowered by oxidizing copper to obtain copper oxide and blackening the conductive layer.
  • paragraphs [0017] to [0025] of JP-A-2014-150118, and paragraphs [0041] to [0042] and paragraphs [0048] of JP-A-2013-206315. ] And [0058], and the contents described in these publications are incorporated in the present specification.
  • 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 a circuit 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 present invention also relates to a method for manufacturing an electronic device.
  • the method for manufacturing the electronic device the method for manufacturing the electronic device using the transfer film described above is preferable.
  • the method for manufacturing an electronic device includes the above-mentioned method for manufacturing a laminate.
  • the electronic device include an input device and the like, and a touch panel is preferable.
  • the input device can be applied to a display device such as an organic electroluminescence display device and a liquid crystal display device.
  • a resin pattern is arranged in a laminate in which a substrate, a conductive layer (a conductive layer possessed by the substrate), and a resin pattern manufactured by using the above transfer film are laminated in this order.
  • a method including a step of forming wiring for a touch panel by etching a conductive layer in a non-existent region is also preferable, and a resin manufactured by a manufacturing method including the bonding step, the exposure step, and the developing step. The method using a pattern is more preferable.
  • the touch panel manufacturing method including the step of forming the touch panel wiring a specific embodiment of each step and an embodiment such as an order in which each step is performed will be described in the above-mentioned "Circuit wiring manufacturing method" section. This is the same as the above, and the preferred embodiment is also the same. Further, the touch panel manufacturing method including the step of forming the touch panel wiring may include any step (other steps) other than those described above. As a method for forming the touch panel wiring, the method shown in FIG. 1 of International Publication No. 2016/190405 can also be referred to.
  • 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 resistance film method, a capacitance method, an ultrasonic method, an electromagnetic induction method, and an optical method. Of these, the capacitance method is preferable.
  • a so-called in-cell type for example, those shown in FIGS. 5, 6, 7, and 8 of JP-A-2012-51751
  • a so-called on-cell type for example, the figure of JP-A-2013-168125.
  • OGS One Glass Solution
  • TOR Touch-on-Lens
  • JP2013 -The figure of JP-A-2013-164871
  • various out-cell types as-called GG, G1 and G2, GF, GF2, GF1, G1F, etc.
  • other configurations eg, those described in FIG. 2 of JP2013-164871). 6).
  • Examples of the touch panel include those described in paragraph [0229] of JP-A-2017-120345.
  • Compound A-2 was synthesized according to Example 3 of paragraph [0033] of CN10291135A. The average number of moles of propylene oxide added to the obtained compound A-2 was 3.
  • Block copolymer B-1 was synthesized according to Journal of Polymer Research, 2018, 25 (7), 1-7.
  • synthetic raw materials 1H, 1H, 2H, 2H-nonafluorohexyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.), polyethylene glycol monoacrylate (Blemmer AE-400 (average number of added moles of polyethylene glycol is 10, manufactured by Nichiyu Co., Ltd.)) , Methyl-2-bromo-2-methylpropanoate (manufactured by Tokyo Chemical Industry Co., Ltd.), 2,2'-bipyridine (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), Copper bromide (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) ) And PGMEA (propylene glycol monomethyl ether acetate, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.).
  • solid content concentration: 20% by mass As used herein, the term "solid content” means all components except solvents. In addition, if it is a component excluding a solvent, a liquid component is also regarded as a solid content.
  • ⁇ Block Copolymer B-2> As synthetic raw materials, 1H, 1H, 2H, 2H-nonafluorohexyl acrylate, 1H, 1H, 2H, 2H-nonafluorohexyl methacrylate (manufactured by Tokyo Kasei Kogyo Co., Ltd.) and polyethylene glycol monoacrylate (Blemmer AE-400 (polyethylene)) The average number of added moles of glycol is 10, manufactured by Nichiyu Co., Ltd.)) is changed to polyethylene glycol monoacrylate (Blemmer AE-200 (average number of added moles of polyethylene glycol is 4.5, manufactured by Nichiyu Co., Ltd.)). , PGMEA solution (solid content concentration 20% by mass) of block copolymer B-2 was obtained by the same procedure as the above-mentioned ⁇ block copolymer B-1>.
  • Block Copolymer B-3> As a synthetic raw material, 1H, 1H, 2H, 2H-nonafluorohexyl acrylate was changed to 1,1,1,3,3,3-hexafluoroisopropylacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.), except that the above-mentioned ⁇ A PGMEA solution (solid content concentration: 20% by mass) of block copolymer B-3 was obtained in the same procedure as for block copolymer B-1>.
  • the structures of the block copolymer obtained above and the comparative compound are shown below.
  • the numerical value added to the structural unit in the copolymer represents the content (mass%) of each structural unit with respect to the total mass of each copolymer.
  • Megafuck F444, F551, F552, and F555 are comparative compounds that do not fall under block copolymers and do not fall under compound (1).
  • the weight average molecular weight (Mw), number average molecular weight (Mn), and dispersity (Mw / Mn) of each block copolymer were as follows.
  • the weight average molecular weight (Mw) of the copolymer was determined by GPC (gel permeation chromatography (EcoSEC HLC-8320GPC (manufactured by Tosoh Corporation)) with a THF eluent, a flow rate of 0.35 ml / min, and a temperature of 40 ° C. It was calculated in terms of polystyrene under the measurement conditions.
  • GPC gel permeation chromatography
  • TSKgel SuperHZM-H TSKgel SuperHZ4000
  • TSKgel SuperHZ200 manufactured by Tosoh Corporation
  • ⁇ 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.)
  • BzMA Benzyl methacrylate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
  • AA Acrylic acid (manufactured by Tokyo Kasei Co., Ltd.)
  • -MAA-GMA glycidyl methacrylate adduct of methacrylic acid-CHMA: cyclohexyl methacrylate (manufactured by Mitsubishi Gas Chemical Company, Inc.)
  • AMA Allyl methacrylate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) -
  • PGMEA 116.5 parts was placed in a three-necked flask, and the temperature was raised to 90 ° C. under a nitrogen atmosphere.
  • a solution containing St (52.0 parts), MMA (19.0 parts), MAA (29.0 parts), V-601 (4.0 parts), and PGMEA (116.5 parts) was added to 90 ° C. It was added dropwise over 2 hours into the flask solution maintained at ⁇ 2 ° C. After completion of the dropping, the solution in the flask was stirred at 90 ° C. ⁇ 2 ° C. for 2 hours to obtain a solution containing the resin P-1 (solid content concentration 30.0% by mass).
  • methacrylic acid (107.1 g, manufactured by Mitsubishi Rayon Co., Ltd., trade name Acryester M), methyl methacrylate (5.46 g, manufactured by Mitsubishi Gas Chemical Company, trade name MMA), and cyclohexyl methacrylate.
  • methyl methacrylate (5.46 g, manufactured by Mitsubishi Gas Chemical Company, trade name MMA)
  • cyclohexyl methacrylate (231.42 g, manufactured by Mitsubishi Gas Chemical Company, Inc., trade name CHMA) was mixed and diluted with propylene glycol monomethyl ether acetate (60.0 g) to obtain a dropping liquid (1).
  • dimethyl 2,2'-azobis (2-methylpropionate) (9.637 g, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., trade name V-601) was added to propylene glycol monomethyl ether acetate (2).
  • V-601 dimethyl 2,2'-azobis (2-methylpropionate)
  • the dropping liquid (1) and the dropping liquid (2) were simultaneously added dropwise to the above-mentioned flask having a capacity of 2000 mL (specifically, a flask having a capacity of 2000 mL containing a liquid heated to 90 ° C.) over 3 hours. ..
  • V-601 (2.401 g) was added to the flask three times every hour.
  • reaction solution obtained in the flask was diluted with propylene glycol monomethyl ether acetate (178.66 g).
  • tetraethylammonium bromide 1.8 g, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.
  • hydroquinone monomethyl ether 0.8 g, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.
  • the temperature of the reaction solution was raised to 100 ° C.
  • glycidyl methacrylate 76.03 g, manufactured by NOF CORPORATION, trade name Blemmer G
  • the above reaction solution was reacted at 100 ° C. for 6 hours to obtain 1158 g of a solution of the resin P-5 (solid content concentration: 36.3% by mass).
  • the obtained resin P-5 had a weight average molecular weight of 27,000, a number average molecular weight of 15,000, and an acid value of 95 mgKOH / g.
  • the resin P-6 was synthesized with reference to the method for synthesizing the resin P-5.
  • the temperature of the contents of the flask was returned to room temperature, the contents of the flask were dropped into 2.7 L of agitated ion-exchanged water, and reprecipitation was carried out to obtain a suspension.
  • the suspension was filtered through a filter paper-drawn Nutche (Buchner funnel), and the filtrate was further washed with ion-exchanged water to obtain a wet powder. After drying by blowing air at 45 ° C., it was confirmed that the amount became constant, and a resin P-7 was obtained as a powder in a yield of 70%.
  • the amount of residual monomer in the powder measured by gas chromatography was less than 0.1% by mass with respect to the polymer solid content.
  • PGMEA (75.0 parts) was placed in a three-necked flask, and the temperature was raised to 90 ° C. under a nitrogen atmosphere.
  • ATHF 29.0 parts
  • MMA 35.0 parts
  • ethyl acrylate EA, 30.0 parts
  • cyclohexyl acrylate CHAI, 5.0 parts
  • methacrylic acid 1, 2 obtained above. 2,6,6-Pentamethyl-4-piperidyl (PMMPA, 1.0 part), V-601 (4.0 parts), and PGMEA (75.0 parts) were added to the solution at 90 ° C ⁇ 2 ° C. It was added dropwise over 2 hours into the three-necked flask solution maintained at. After completion of the dropping, the mixture was stirred at 90 ° C. ⁇ 2 ° C. for 2 hours to obtain a solution containing resin P-8 (solid content concentration 40.0% by mass).
  • Table 2 shows the type and mass ratio of each monomer used for synthesizing each resin, and the weight average molecular weight (Mw) of each resin.
  • Resins P-1 to P-7 correspond to alkali-soluble resins (polymer P), and resin P-8 is a resin having a structural unit having an acid group protected by an acid-degradable group (polymer A). Applicable.
  • the resins P-1 to P-6 and P-8 were all added to the resin composition in the form of a solution, and the resin P-7 was added to the resin composition in the form of a powder.
  • the unit of the amount of the monomer in Table 1 is mass%.
  • -P-4 to P-5 Alkaline-soluble resin described above-Acribase
  • FF187 Alkali-soluble thermoplastic resin (solid content concentration 40% by mass, solvent: PGMEA, manufactured by Fujikura Kasei Co., Ltd.)
  • BB-1 Dye, compound with the structure shown below
  • thermoplastic resin composition layer Block copolymer described above-PGMEA: Propylene glycol monomethyl ether acetate (manufactured by Showa Denko KK) ⁇ MEK: Methyl ethyl ketone (manufactured by Sankyo Chemical Co., Ltd.)
  • the "Average film thickness ( ⁇ m) of the thermoplastic resin composition layer” column is the average film thickness of the thermoplastic resin composition layer formed when the test was performed using the thermoplastic resin composition. Is shown.
  • each component is shown below.
  • -PVA 4-88LA Kuraray Poval 4-88LA (water-soluble resin), manufactured by Kuraray Co., Ltd.
  • -PVA 205 Kuraray Poval 205 (water-soluble resin), manufactured by Kuraray Co., Ltd.-Polyvinyl pyrrolidone: water-soluble resin, manufactured by Nippon Catalyst Co., Ltd.-A -1 to A-2:
  • -Megafuck F444 Comparative compound, manufactured by DIC Corporation-Ion-exchanged water-Methanol: Solvent, manufactured by Mitsubishi Gas Chemical Company
  • the "Average film thickness ( ⁇ m) of water-soluble resin composition layer" column is water-soluble. The average film thickness of the water-soluble resin composition layer formed when the test was performed using the sex resin composition is shown.
  • -P-1 to P-3 Alkaline-soluble resin described above-BPE-500: 2,2-bis (4-((meth) acryloxipentethoxy) phenyl) propane, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.
  • -BPE-200 2,2-Bis (4-((meth) acryloxidiethoxy) phenyl) propane, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.
  • ⁇ M-270 Polypropylene glycol diacrylate (n ⁇ 12), manufactured by Toa Synthetic Co., Ltd., A- TMPT: Trimethylol Propanetriacryllate, manufactured by Shin-Nakamura Chemical Industry, SR-454: ethoxylated (3) Trimethylol propanetriacrylate, SR-502: ethoxylated (9) Trimethylol propanetriacrylate, A-9300-CL1: caprolactone-modified (meth) acrylate compound manufactured by Alchema, B-CIM manufactured by Shin-Nakamura Chemical Industry Co., Ltd .: 2,2'-bis (2-chlorophenyl) -4,4', 5,5' -Tetraphenylbiimidazole, Hampton, SB-PI 701: 4,4'-bis (diethylamino) benzophenone, Sanyo Trading Co., Ltd., Leuco Crystal Violet: Tokyo Kasei Kogyo Co., Ltd., Brilliant Green: Tokyo Kasei Kog
  • ⁇ CBT-1 Carboxybenzotriazole, Johoku Chemical Co., Ltd.
  • TDP-G Phenothiazine, Kawaguchi Chemical Co., Ltd.
  • Irganox245 Hindered phenolic antioxidant, BASF Co., Ltd.
  • N- Nitrosophenyl hydroxylamine Aluminum salt Fujifilm Wako Junyaku Co., Ltd.
  • Fenidon Tokyo Kasei Kogyo Co., Ltd.
  • B-1 to B-3 Block copolymer described above
  • ⁇ Megafuck F552 Comparative compound, manufactured by DIC Co., Ltd.
  • R-1 Comparative compound described above-PGMEA: Propropylene glycol monomethyl ether acetate (manufactured by Showa Denko) ⁇ MEK: Methyl ethyl ketone (manufactured by Sankyo Chemical Co., Ltd.)
  • the "Average film thickness ( ⁇ m) of the photosensitive resin composition layer” column is the average film thickness of the photosensitive resin composition layer formed when the test was performed using the photosensitive resin composition. Is shown.
  • a polyethylene terephthalate film having a width of 1.0 m and a thickness of 16 ⁇ m so that the average thickness of the composition layer after drying is a specified thickness of the prepared thermoplastic resin composition 1 using a slit-shaped nozzle.
  • a 3m dry zone which was applied to the support, Lumirror 16KS40 (manufactured by Toray Co., Ltd.) and set to 80 ° C. and the film surface wind speed to be 3m / sec by adjusting the intake and exhaust volumes, took 60 seconds. It was passed through to obtain a laminate A having a temporary support and a thermoplastic resin composition layer.
  • the width is 1.0 m
  • the average film thickness of the water-soluble resin composition layer after drying is the specified film thickness.
  • a slit-shaped nozzle is used so that the width is 1.0 m and the average film thickness of the dried photosensitive resin composition layer is a specified film thickness.
  • the film was passed over a second to obtain the transfer film of Example 1 in which the photosensitive resin composition layer was formed on the water-soluble resin composition layer.
  • the obtained transfer film of Example 1 was a temporary support / thermoplastic resin composition layer (first layer) / water-soluble resin composition layer (second layer) / photosensitive resin composition layer (third layer). Each resin composition layer is provided in this order.
  • each transfer film was obtained by the same procedure as in Example 1 except that the resin composition layer was changed as shown in Table 6.
  • a copper layer having a thickness of 200 nm was provided on a polyethylene terephthalate (PET) film having a thickness of 100 ⁇ m by a sputtering method, and a PET substrate with a copper layer was prepared.
  • PET polyethylene terephthalate
  • a temporary support was provided under laminating conditions of a roll temperature of 100 ° C., a linear pressure of 1.0 MPa, and a linear velocity of 4.0 m / min.
  • the PET substrate with a copper layer was laminated on the transfer film by laminating the surface of the photosensitive resin composition layer of the outermost layer arranged above and the PET substrate with the copper layer.
  • the temporary support was peeled off and developed after exposure with an ultra-high pressure mercury lamp via a line and space pattern mask (duty ratio 1: 1, line width 20 ⁇ m). Development was carried out by shower development for 30 seconds using a 1.0% sodium carbonate aqueous solution at 25 ° C.
  • the exposure amount at which the resist line width was 20 ⁇ m was defined as the optimum exposure amount.
  • the minimum line width resolved by observing an arbitrary 1 cm 2 region of the line-and-space pattern formed at the optimum exposure amount with a scanning electron microscope (SEM) without peeling the resist pattern and forming a residue. was evaluated according to the following evaluation criteria. Evaluation A or B is a practically acceptable range.
  • Minimum line width is less than 5 ⁇ m
  • ⁇ 8UX-015A Urethane acrylate, Taisei 75% by mass PGMEA solution of KAYARAD DPHA manufactured by Fine Chemical Industry Co., Ltd .: 75% by mass propylene glycol monomethyl ether acetate solution of KAYARAD DPHA (trade name: manufactured by Nippon Kayaku Co., Ltd.).
  • the composition of KAYARAD DPHA is shown below.
  • the "Average film thickness ( ⁇ m) of the photosensitive resin composition layer" column is the average film thickness of the photosensitive resin composition layer formed when the test was performed using the photosensitive resin composition. Is shown.
  • the photosensitive resin compositions 6 to 10 correspond to the photosensitive resin compositions which are colored resin compositions.
  • Irgacure OXE-02 BASF, Etanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl]-, 1- (o-acetyloxime) -1,2,4-Triazole: manufactured by Tokyo Chemical Industry Co., Ltd.-B-1 to B-3: the above-mentioned block copolymer-Megafuck F555A: manufactured by DIC Co., Ltd.-R-1: the above-mentioned comparative compound-PGMEA: Propylene glycol monomethyl ether acetate (manufactured by Showa Denko) ⁇ MEK: Methyl ethyl ketone (manufactured by Sankyo Chemical Co., Ltd.)
  • each transfer film was prepared by the same procedure as in [Preparation of Transfer Film] in Examples 1 to 3 and Comparative Examples 1 and 2 described above, except that each resin composition was used.
  • a polyethylene terephthalate film (PET substrate) having a thickness of 100 ⁇ m was prepared. After unwinding the produced transfer film, the outermost photosensitive resin composition layer arranged on the temporary support under laminating conditions of a roll temperature of 100 ° C., a linear pressure of 1.0 MPa, and a linear velocity of 4.0 m / min. The PET substrate was laminated on the transfer film by laminating the surface of the (colored resin composition layer) and the PET substrate. Then, after exposure with an ultra-high pressure mercury lamp without peeling the temporary support, the temporary support was peeled and developed. Development was carried out by shower development for 30 seconds using a 1.0% sodium carbonate aqueous solution at 25 ° C.
  • Evaluation A or B is a practically acceptable range. (Evaluation criteria) A: No unevenness (very good) B: There is slight unevenness, but it is a level that does not bother you (good) C: Unevenness is seen, but practical level (normal) D: Uneven (slightly bad) E: There is strong unevenness (very bad)
  • each component is shown below.
  • -P-5 to P-6 the above-mentioned alkali-soluble resin-A-DCP: tricyclodecanedimethanol diacrylate, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.
  • -A-NOD-N 1,9-nonanediol diacrylate, new Nakamura Kagaku Kogyo Co., Ltd.
  • A-DPH Dipentaerythritol hexaacrylate, Shin-Nakamura Kagaku Kogyo Co., Ltd.
  • OXE-02 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl] etanone-1- (O-acetyloxime), manufactured by BASF, Omnirad 907: 2-methyl- 1- (4-Methylthiophenyl) -2-morpholinopropane-1-one, manufactured by BASF, Duranate TPA-B80E: the above-mentioned blocked isocyanate compound, Q-1 to Q-2: the above-mentioned blocked isocyanate compound, N- Phenylglycine: manufactured by Tokyo Kasei Kogyo Co., Ltd. ⁇ Benzoimidazole: manufactured by Tokyo Kasei Kogyo Co., Ltd.
  • each component is shown below.
  • -Nano-use OZS-30M ZrO 2 particles (containing tin oxide) methanol dispersion (nonvolatile content 30.5% by mass), manufactured by Nissan Chemical Industries, Ltd.-Ammonia water (25% by mass)
  • -P-7 Alkaline-soluble resin described above-Alfon UC-3920: Water-soluble resin, manufactured by Toagosei Co., Ltd.-Monomer having a carboxy group: Aronix TO-2349, manufactured by Toagosei Co., Ltd.-Benzotriazole BT-LX, Johoku Chemical Industry Co., Ltd.
  • each transfer film was prepared by the same procedure as in [Preparation of Transfer Film] in Examples 1 to 3 and Comparative Examples 1 and 2 described above, except that each resin composition was used.
  • a polyethylene terephthalate film (PET substrate) having a thickness of 100 ⁇ m was prepared. After unwinding the produced transfer film, the outermost layer (photosensitive) of the composition layer arranged on the temporary support under laminating conditions of a roll temperature of 100 ° C., a linear pressure of 1.0 MPa, and a linear velocity of 4.0 m / min. The PET substrate was laminated on the transfer film by laminating the surface of the resin composition layer) and the PET substrate. Then, after exposure with an ultra-high pressure mercury lamp without peeling the temporary support, the temporary support was peeled and developed. Development was carried out by shower development for 30 seconds using a 1.0% sodium carbonate aqueous solution at 25 ° C.
  • the exposure amount at which the resist line width was 20 ⁇ m was defined as the optimum exposure amount.
  • the surface of the cured film formed at the optimum exposure amount was visually observed in a region having a length of 10 m and a width of 1.5 m, and surface defects were evaluated according to the following evaluation criteria. Evaluation A or B is a practically acceptable range.
  • P-8 Resin having a structural unit having an acid group protected by the above-mentioned acid-degradable group.
  • the "Average film thickness ( ⁇ m) of the photosensitive resin composition layer” column indicates the average film thickness of the photosensitive resin composition layer formed when the test was performed using the photosensitive resin composition. Is shown.
  • a polyethylene terephthalate film having a width of 1.0 m and a thickness of 16 ⁇ m so that the average film thickness of the composition layer after drying is a specified film thickness of the prepared photosensitive resin composition 16 using a slit-shaped nozzle. It was applied to 16KS40 (manufactured by Toray Industries, Inc.) and passed through a 3m dry zone set at 100 ° C. and adjusted to have a film surface wind speed of 3m / sec over 60 seconds. The transfer film of Example 10 was obtained. In Examples 11 to 12 and Comparative Examples 7 to 8, each transfer film was obtained by the same procedure as in Example 10 except that the composition was changed to a thermoplastic resin composition as shown in Table 13.

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JP2011232709A (ja) * 2010-04-30 2011-11-17 Taiyo Holdings Co Ltd 硬化性樹脂組成物
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