Transfer film, method for manufacturing a laminate, method for manufacturing circuit wiring, method for manufacturing an electronic device

Abstract

The present invention provides a transfer film that is less likely to cause defective pattern appearance, a method for manufacturing a laminate, a method for manufacturing circuit wiring, and a method for manufacturing an electronic device. The transfer film of the present invention has a temporary support and a resin composition layer disposed on the temporary support. The resin composition layer contains: a resin; and at least one compound selected from a block copolymer and the compound represented by formula (1). The block copolymer contains: a block containing a structural unit X having a group represented by formula (A) or a group represented by formula (B), and a block containing a structural unit Y having a poly(oxyalkylene) group.

Description

Technical Field

[0001] The present invention relates to a method for manufacturing a transfer film, a laminate, a circuit wiring, and an electronic device.

[0002] From the viewpoint of reducing the number of processes for forming a pattern of a predetermined shape, a method is widely used in which a resin composition layer provided on an arbitrary substrate using a transfer film is exposed through a mask including a desired pattern and then developed.

[0003] For example, Patent Document 1 discloses a transfer film including a copolymer having a predetermined fluoroalkyl group.

[0004] Prior Art Documents

[0005] Patent Documents

[0006] Patent Document 1: International Publication No. 2017 / 057348 Summary of the Invention

[0007] Technical Problem to be Solved by the Invention

[0008] As a result of research on the transfer film disclosed in Patent Document 1 by the present inventors, it has been found that the pattern obtained after exposure and development is likely to have poor appearance. Specifically, the following cases can be cited: when forming a pattern, the pattern is likely to peel off or residues are likely to be generated, resulting in a pattern with low resolution; when the pattern contains a pigment, the concentration unevenness is large; and there are many defects on the surface of the pattern.

[0009] Hereinafter, in the present specification, when at least one of the following cases can be suppressed, it is also referred to as being less likely to have poor appearance of the pattern: when forming a pattern, the pattern is likely to peel off or residues are likely to be generated, resulting in a pattern with low resolution; when the pattern contains a pigment, the concentration unevenness is large; and there are many defects on the surface of the pattern.

[0010] Therefore, an object of the present invention is to provide a transfer film that is less likely to have poor appearance of the pattern. Another object is to provide a method for manufacturing a laminate, a method for manufacturing a circuit wiring, and a method for manufacturing an electronic device related to the above transfer film.

[0011] Means for Solving the Technical Problem

[0012] As a result of intensive research to solve the above problems, the present inventors have found that the above problems can be achieved by the following structure.

[0013] 〔1〕A transfer film having a temporary support and a resin composition layer disposed on the temporary support,

[0014] The resin composition layer contains: a resin; and

[0015] At least one compound selected from a block copolymer and the compound represented by formula (1), the block copolymer including: a block including a structural unit X including a group represented by formula (A) described below or a group represented by formula (B) described below, and a block including a structural unit Y including a poly(alkylene oxide) group.

[0016] 〔2〕The transfer film according to 〔1〕, wherein

[0017] The structural unit X and the compound represented by formula (1) have a group represented by formula (A).

[0018] 〔3〕The transfer film according to 〔1〕, wherein

[0019] The structural unit X and the compound represented by formula (1) have a group represented by formula (B).

[0020] 〔4〕The transfer film according to any one of 〔1〕 to 〔3〕, wherein

[0021] The molecular weight of the compound represented by formula (1) is 2000 or less.

[0022] 〔5〕The transfer film according to any one of 〔1〕 to 〔4〕, wherein

[0023] The weight-average molecular weight of the block copolymer is 5000 or more.

[0024] 〔6〕The transfer film according to any one of 〔1〕 to 〔5〕, wherein

[0025] The resin is an alkali-soluble resin,

[0026] The resin composition layer further contains a polymerizable compound.

[0027] 〔7〕The transfer film according to any one of 〔1〕 to 〔5〕, wherein

[0028] The resin is a resin having a structural unit having an acid group protected by an acid-decomposable group,

[0029] The resin composition layer further contains a photoacid generator.

[0030] 〔8〕The transfer film according to any one of 〔1〕 to 〔7〕, wherein

[0031] The resin composition layer is a water-soluble resin composition layer.

[0032] 〔9〕The transfer film according to 〔8〕, wherein

[0033] The water-soluble resin composition layer contains metal oxide particles.

[0034]

[10] The transfer film according to any one of [1] to [9], wherein

[0035] The resin composition layer is a thermoplastic resin composition layer.

[0036]

[11] The transfer film according to any one of [1] to

[10] , wherein

[0037] The resin composition layer further contains a pigment.

[0038] A transfer film, wherein

[0039] The transfer film according to any one of [1] to

[11] has two or more resin composition layers.

[0040]

[13] A method for manufacturing a laminate, comprising:

[0041] A bonding step of bringing a substrate into contact with a surface on the side opposite to the temporary support of the transfer film according to any one of [1] to

[12] , bonding the transfer film and the substrate, and obtaining a substrate with a transfer film;

[0042] An exposure step of performing pattern exposure on the composition layer;

[0043] A development step of developing the exposed resin composition layer to form a resin pattern; and

[0044] A peeling step of peeling the temporary support from the substrate with a transfer film between the bonding step and the exposure step or between the exposure step and the development step.

[0045]

[14] A method for manufacturing a circuit wiring, comprising:

[0046] A bonding step of bringing a substrate having a conductive layer into contact with a surface on the side opposite to the temporary support of the transfer film according to any one of [1] to

[12] , bonding the transfer film and the substrate having a conductive layer, and obtaining a substrate with a transfer film;

[0047] An exposure step of performing pattern exposure on the composition layer;

[0048] A development step of developing the exposed resin composition layer to form a resin pattern; and

[0049] An etching step of etching the conductive layer in a region where no resin pattern is disposed; and

[0050] A peeling step of peeling the temporary support from the substrate with a transfer film between the bonding step and the exposure step or between the exposure step and the development step.

[0051] 〔15〕A method for manufacturing an electronic device, which includes the method for manufacturing the laminate described in 〔13〕, wherein,

[0052] The electronic device includes a resin pattern as a cured film.

[0053] Advantages of the Invention

[0054] According to the present invention, it is possible to provide a transfer film that is less likely to cause defective appearance of the pattern. In addition, it is possible to provide a method for manufacturing a laminate, a method for manufacturing circuit wiring, and a method for manufacturing an electronic device related to the above transfer film. Description of the Drawings

[0055] Figure 1 It is a schematic diagram showing an example of the structure of the transfer film. Detailed Description of the Invention

[0056] Hereinafter, the present invention will be described in detail.

[0057] The description of the constituent elements described below is sometimes based on representative embodiments of the present invention, but the present invention is not limited to such embodiments.

[0058] In this specification, the numerical range represented by "~" means a range including the numerical values described before and after "~" as the lower limit value and the upper limit value.

[0059] In this specification, the bonding direction of the divalent group (for example, -CO-O-) marked is not particularly limited.

[0060] In this specification, (meth)acrylate means acrylate and methacrylate. (Meth)acrylic acid means acrylic acid and methacrylic acid. (Meth)acryloyl means methacryloyl or acryloyl.

[0061] Regarding the marking of the group (atomic group) in this specification, the marking of unsubstituted and substituted includes a group without a substituent, and also includes a group with a substituent. For example, "alkyl" includes not only an alkyl without a substituent (unsubstituted alkyl), but also an alkyl with a substituent (substituted alkyl). In addition, the "organic group" in this specification means a group containing at least one carbon atom.

[0062] In this specification, when "may have a substituent", the type, position, and number of the substituents are not particularly limited. The number of substituents can be, for example, 1, 2, 3, or more. And it can also be unsubstituted.

[0063] As an example of a substituent, a monovalent non-metal atomic group obtained by removing a hydrogen atom can be mentioned, for example, and it can be selected from the following substituent group T.

[0064] (Substituent T)

[0065] As the substituent T, halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom can be mentioned; alkoxy groups such as methoxy group, ethoxy group and tert-butoxy group; aryloxy groups such as phenoxy group and p-tolyloxy group; alkoxycarbonyl groups such as methoxycarbonyl group, butoxycarbonyl group and phenoxycarbonyl group; acyloxy groups such as acetoxy group, propionyloxy group and benzoyloxy group; acyl groups such as acetyl group, benzoyl group, isobutyryl group, acryloyl group, methacryloyl group and oxalyl group; alkylthio groups such as methylthio group and tert-butylthio group; arylthio groups such as phenylthio group and p-tolylthio group; alkyl group; cycloalkyl group; aryl group; heteroaryl group; hydroxyl group; carboxyl group; formyl group; sulfo group; cyano group; alkylaminocarbonyl group; arylaminocarbonyl group; sulfonamido group; silyl group; amino group; monoalkylamino group; dialkylamino group; arylamino group; and combinations thereof.

[0066] In this specification, unless otherwise specified, 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.

[0067] Regarding GPC, the measurement is carried out under the following conditions.

[0068] [Eluent] Tetrahydrofuran (THF)

[0069] [Apparatus name] EcoSEC HLC-8320GPC (manufactured by TOSOH CORPORATION)

[0070] [Column] TSKgel SuperHZM-H, TSKgel SuperHZ4000 and TSKgel SuperHZ200 (manufactured by TOSOHCORPORATION))

[0071] [Column temperature] 40 °C

[0072] [Flow rate] 0.35 mL / min

[0073] In this specification, unless otherwise specified, the molecular weight of the compound having a molecular weight distribution is the weight-average molecular weight (Mw).

[0074] In this specification, unless otherwise specified, room temperature is 25 °C.

[0075] In this specification, "alkali-soluble" means that the solubility of sodium carbonate in 100 g of a 1 mass% aqueous solution is 0.1 g or more at 22 °C.

[0076] In this specification, "water-soluble" means a solubility of 0.1 g or more in 100 g of water at pH 7.0 with a liquid temperature of 22°C.

[0077] In this specification, the layer thickness (film thickness) of each layer provided in a transfer film or the like is measured as follows: The cross-section in the direction perpendicular to the main surface of the layer (film) is observed by a scanning electron microscope (SEM: Scanning Electron Microscope), the thicknesses of 10 or more portions of each layer are measured based on the obtained observation image, and the average value thereof is calculated.

[0078] [Transfer film]

[0079] The transfer film has a temporary support and a resin composition layer disposed on the temporary support. The resin composition layer contains: a resin; and at least one compound selected from a block copolymer (hereinafter, also simply referred to as "block copolymer") and the compound represented by formula (1) (hereinafter, also referred to as "compound (1)"). The block copolymer contains: a block containing a structural unit X having a group represented by formula (A) or a group represented by formula (B) and a block containing a structural unit Y having a poly(oxyalkylene) group.

[0080] Although the mechanism of solving the problems of the present invention by this structure is not yet clear, the present inventors presume as follows.

[0081] In the transfer film of the prior art, sometimes the appearance of the above-mentioned pattern is defective. In particular, sometimes the appearance defect of the above-mentioned pattern is more significantly generated depending on the conditions at the time of forming the resin composition layer.

[0082] As a result of the present inventors' study on the cause, it was found that the above problem is caused by bubbles (voids) in the resin composition layer. In contrast, in the resin composition layer containing at least one compound selected from a predetermined block copolymer having a group represented by formula (A) or a group represented by formula (B) and a poly(oxyalkylene) group and compound (1), the generation of the above bubbles (voids) is suppressed by having the above respective groups, and it is presumed that the appearance defect of the pattern can be suppressed.

[0083] Hereinafter, in this specification, when the appearance defect of the pattern is less likely to occur, it is also referred to as that the effect of the present invention is more excellent.

[0084] In the transfer film, the temporary support and one or more resin composition layers described later may be directly laminated without passing through other layers, or may be laminated through other layers. And, other layers may be laminated on the side opposite to the surface of the one or more resin composition layers facing the temporary support. Other layers may also exist between the one or more resin composition layers.

[0085] That is, the transfer film preferably has one or more resin composition layers, and more preferably has two or more resin composition layers.

[0086] In the transfer film, as long as at least one layer among one or more (for example, 1 to 5 layers) of resin composition layers is the resin composition layer of the present invention, more than half of the layers can be the resin composition layer of the present invention, or all layers can be the resin composition layer of the present invention.

[0087] The transfer film also preferably contains at least one layer of the photosensitive resin composition layer described later. The above photosensitive resin composition layer can be a colored resin composition layer.

[0088] 〔Temporary support〕

[0089] The transfer film has a temporary support.

[0090] The temporary support is a support that supports the resin composition layer or the laminate including the resin composition layer described later and can be peeled off.

[0091] From the viewpoint of being able to perform exposure via the temporary support when pattern-exposing the resin composition layer, the temporary support preferably has translucency. In addition, in this specification, "having translucency" means that the transmittance of light with the wavelength used in pattern exposure is 50% or more.

[0092] Regarding the temporary support, from the viewpoint of improving exposure sensitivity, the transmittance of light with the wavelength (more preferably the wavelength of 365 nm) used in pattern exposure is preferably 60% or more, and more preferably 70% or more.

[0093] In addition, the transmittance of the layer included in the transfer film is the ratio of the intensity of the outgoing light that passes through the layer to the intensity of the incident light when light is incident in the direction perpendicular to the main surface of the layer (thickness direction), and is measured using MCPD Series manufactured by Otsuka Electronics Co., Ltd.

[0094] As the material constituting the temporary support, for example, a glass substrate, a resin film, and paper can be mentioned. From the viewpoints of strength, flexibility, and translucency, a resin film is preferred.

[0095] As the resin film, a polyethylene terephthalate (PET) film, a cellulose triacetate film, a polystyrene film, and a polycarbonate film can be mentioned. Among them, a PET film is preferred, and a biaxially stretched PET film is more preferred.

[0096] The thickness (layer thickness) of the temporary support is not particularly limited, and it can be selected according to the material in consideration of the strength as a support, the flexibility required for bonding to the substrate for forming circuit wiring, and the light transmittance required for the first exposure process.

[0097] The thickness of the temporary support is preferably 5 to 100 μm, more preferably 10 to 50 μm, further preferably 10 to 20 μm, and particularly preferably 10 to 16 μm from the viewpoints of ease of operation and versatility.

[0098] Moreover, it is preferable that there are no deformations such as wrinkles, scratches, and defects in the film used as the temporary support.

[0099] From the viewpoints of pattern formability during pattern exposure via the temporary support and the transparency of the temporary support, those with a smaller number of fine particles, foreign substances, defects, precipitates, etc. contained in the temporary support are preferred. The number of fine particles, foreign substances, and / or defects with a diameter of 1 μm or more is preferably 50 pieces / 10 mm 2 Hereinafter, more preferably 10 pieces / 10 mm 2 Hereinafter, further preferably 3 pieces / 10 mm 2 Hereinafter, particularly preferably 0 pieces / 10 mm 2 .

[0100] As a preferred embodiment of the temporary support, for example, it is described in paragraphs

[0017] to

[0018] of Japanese Patent Laid-Open No. 2014-085643, paragraphs

[0019] to

[0026] of Japanese Patent Laid-Open No. 2016-027363, paragraphs

[0041] to

[0057] of International Publication No. 2012 / 081680 A1, paragraphs

[0029] to

[0040] of International Publication No. 2018 / 179370 A1, and paragraphs

[0012] to

[0032] of Japanese Patent Laid-Open No. 2019-101405, and the contents of these publications are incorporated into this specification.

[0101] [Resin composition layer]

[0102] The resin composition layer of the present invention contains: a resin; and at least one compound selected from block copolymers and compound (1).

[0103] As an embodiment of the resin composition layer, for example, it can be a photosensitive resin composition layer, a thermoplastic resin composition layer, a colored resin composition layer, and / or a water-soluble resin composition layer described later.

[0104] Hereinafter, the components that can be contained in each resin composition layer in each embodiment will be described.

[0105] In addition, the components described as components of the resin composition layer in one embodiment are not only allowed to be included when the resin composition layer is in this embodiment, but can also be used as components of the resin composition layer in another embodiment. For example, the components described as components of the photosensitive resin composition layer can be used as components other than the photosensitive resin composition layer.

[0106] <Resin>

[0107] The resin composition layer contains a resin.

[0108] The above resin is a component different from the block copolymer described later.

[0109] There is no limitation on the properties and / or characteristics of the resin, and it can be appropriately selected according to the use of the resin composition layer. Regarding the details of the resin, they will be described separately below according to each form of the resin composition layer.

[0110] <Block copolymer>

[0111] The block copolymer contains: a block (block segment) containing a structural unit X having a group represented by formula (A) or a group represented by formula (B); and a block (block segment) containing a structural unit Y having a poly(oxyalkylene) group.

[0112] The block copolymer is a polymer having a molecular structure in which a plurality of blocks are linked, and each block is a chain formed by linking structural units.

[0113] The block structure of the block copolymer is not particularly limited. For example, block structures a to e represented by formulas (a) to (e) can be cited.

[0114] Formula (a) (A)-(B)

[0115] In formula (a), A represents a block containing structural unit X, and B represents a block containing structural unit Y.

[0116] The block structure a represented by formula (a) is a block structure (A-B type) formed by linking a block containing structural unit X and a block containing structural unit Y.

[0117] Formula (b) (B)-(A)-(B)

[0118] In formula (b), A represents a block containing structural unit X, and B represents a block containing structural unit Y.

[0119] The block structure b represented by formula (b) is a block structure (B-A-B type) formed by linking blocks containing structural unit Y to both ends of a block containing structural unit X.

[0120] Formula (c) (B)-(A)-(C)

[0121] In formula (c), A represents a block containing structural unit X, B represents a block containing structural unit Y, and C represents a block containing a structural unit different from structural units X and Y.

[0122] The block structure c represented by formula (c) is a block structure (B-A-C type) formed by sequentially connecting a block containing structural unit Y, a block containing structural unit X, and a block containing a structural unit different from structural units X and Y.

[0123] Formula (d) (B)-(A)-(C)-(D)

[0124] In formula (d), A represents a block containing structural unit X, B represents a block containing structural unit Y, C represents a block containing a first structural unit different from structural units X and Y, and D represents a block containing a second structural unit different from structural units X, Y, and the first structural unit.

[0125] The block structure d represented by formula (d) is a block structure (B-A-C-D type) formed by sequentially connecting a block containing structural unit Y, a block containing structural unit X, a block containing a first structural unit different from structural units X and Y, and a block containing a second structural unit different from structural units X, Y, and the first structural unit.

[0126] Formula (e) (A)-(B)-(A)-(B)

[0127] In formula (e), A represents a block containing structural unit X, and B represents a block containing structural unit Y.

[0128] The block structure e represented by formula (e) is a block structure formed by alternately connecting a block containing structural unit X and a block containing structural unit Y multiple times.

[0129] Among them, as the block structure, block structures a to c are preferred, block structure a or c is more preferred, and block structure a is further preferred.

[0130] Regarding the number of types of blocks in the block structure, from the perspective of solubility, it is 2 or more, preferably 2 to 10, more preferably 2 to 5, further preferably 2 to 3, and particularly preferably 2.

[0131] (Structural unit X)

[0132] Structural unit X has a group represented by formula (A) or a group represented by formula (B).

[0133] Among them, from the viewpoint of more excellent effects of the present invention, it is preferred that the structural unit X has a group represented by the formula (A).

[0134] Formula (A) *-(CH 2 ) m -(CF 2 ) n -CF 3

[0135] In the formula (A), m and n each independently represent an integer of 1 to 3.

[0136] As m, it is preferably an integer of 2 to 3, more preferably 2.

[0137] As n, it is preferably an integer of 2 to 3, more preferably 3.

[0138] * represents the bonding position.

[0139] As the number of the groups represented by the formula (A) that the structural unit X has, it is preferably 1 to 3, more preferably 1.

[0140] Formula (B) *-L 1 -CH(CF 3 )-CF 3

[0141] In the formula (B), L 1 represents an oxygen atom or an alkylene group.

[0142] As L 1 The represented alkylene group can be linear or branched.

[0143] As the number of carbon atoms of the alkylene group represented by L 1 it is preferably 1 to 10, more preferably 1 to 6, further preferably 1 to 3, and particularly preferably 1 to 2.

[0144] L 1 The represented alkylene group can have a substituent. There is no particular limitation on the substituent. For example, substituents exemplified in the substituent group T can be cited.

[0145] As L 1 it is preferably an oxygen atom or an alkylene group having 1 to 2 carbon atoms, more preferably an oxygen atom.

[0146] * represents the bonding position.

[0147] As the number of the groups represented by the formula (B) that the structural unit X has, it is preferably 1 to 3, more preferably 1.

[0148] As the structural unit X, it is preferably a structural unit represented by the formula (C).

[0149] [Chemical Formula 1]

[0150]

[0151] In formula (C), R represents a hydrogen atom or a substituent. The substituent represented by R is not particularly limited, and examples of the substituent include the substituents exemplified in the substituent group T, and an alkyl group having 1 to 6 carbon atoms is preferred.

[0152] L represents a single bond or a divalent linking group. As the divalent linking group, for example, -O-, -CO-, -S-, -SO 2 -, -NR X -(R X 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 formed by combining these (for example, -CO-O-, -CO-O-alkylene, etc.). As the substituent represented by the above R X Examples of the substituent include the substituents exemplified in the substituent group T, and an alkyl group having 1 to 2 carbon atoms is preferred.

[0153] The above alkylene group, alkenylene group, alkynylene group, aromatic ring group, and alicyclic group may further have a substituent. As the substituent, for example, the substituents exemplified in the substituent group T can be cited. As the substituent, among them, a halogen atom is preferred, and a fluorine atom is more preferred.

[0154] As the above alkylene group, alkenylene group, and alkynylene group, they can be linear or branched.

[0155] And, as the number of carbon atoms of the above alkylene group, it is preferably 1 to 20, more preferably 1 to 10, and further preferably 1 to 5.

[0156] And, as the number of carbon atoms of the above alkenylene group and alkynylene group, it is preferably 2 to 20, more preferably 2 to 10, and further preferably 2 to 5.

[0157] Z represents the group represented by formula (A) or the group represented by formula (B).

[0158] The group represented by the above formula (A) and the group represented by formula (B) have the same meanings as the group represented by formula (A) and the group represented by formula (B) possessed by the above block copolymer, and the preferred ranges are also the same.

[0159] The structural unit X can be used alone in one kind, or two or more kinds can be used.

[0160] As the lower limit value of the content of structural unit X, it exceeds 0 mol% relative to the total number of moles of all structural units of the block copolymer, preferably 1 mol% or more, more preferably 10 mol% or more, still more preferably 30 mol% or more, and particularly preferably 40 mol% or more. Further, as the upper limit value, it is less than 100 mol%, preferably 90 mol% or less, more preferably 80 mol% or less, still more preferably 60 mol% or less.

[0161] (Structural unit Y)

[0162] Structural unit Y has a poly(alkylene oxide) group.

[0163] As the structural unit Y, there is no particular limitation, and it preferably has a group represented by formula (PAL1).

[0164] [Chemical formula 2]

[0165]

[0166] In formula (PAL1), AL represents an alkylene group.

[0167] The above-mentioned alkylene group may be linear or branched. As the number of carbon atoms of the alkylene group represented by AL, it is preferably 1 to 10, more preferably 1 to 6, still more preferably 2 to 4, and particularly preferably 2 to 3.

[0168] nAL represents a number of 2 or more, preferably 2 to 100, more preferably 4 to 20, still more preferably 4 to 15, and particularly preferably 4 to 12.

[0169] The nAL ALs may be the same or different from each other, and preferably represent the same structure.

[0170] Further, the alkylene group represented by AL may have a substituent. There is no particular limitation on the substituent, and for example, substituents exemplified in substituent group T can be cited.

[0171] Among them, as AL, it is preferably -CH 2 CH 2 -, -CH 2 CH 2 CH 2 -, -CH(CH 3 )CH 2 - or -CH(CH 2 CH 3 )CH 2 -, more preferably -CH(CH 3 )CH 2 - or -CH 2 CH 2 -.

[0172] * indicates the bonding position.

[0173] As the structural unit Y, it is preferably a poly(alkylene oxide) group in the side chain, more preferably a group represented by the formula (PAL1) in the side chain, and further preferably a structural unit derived from the monomer represented by the formula (PAL2).

[0174] [Chemical formula 3]

[0175]

[0176] In the formula (PAL2), R 1 represents a hydrogen atom or a methyl group.

[0177] As R 1 , it is preferably a hydrogen atom.

[0178] Y represents an oxygen atom, a sulfur atom or -N(R 2 )-.

[0179] R 2 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

[0180] As the alkyl group having 1 to 4 carbon atoms represented by R 2 , it can be any of linear, branched and cyclic.

[0181] As R 2 , it is preferably a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, and more preferably an alkyl group having 1 to 2 carbon atoms.

[0182] As Y, it is preferably an oxygen atom or a sulfur atom, and more preferably an oxygen atom.

[0183] R 3 represents a hydrogen atom or a substituent.

[0184] As the substituent represented by R 3 , there is no particular limitation, and examples of the substituent include the substituents exemplified in the substituent group T, and it is preferably an alkyl group having 1 to 6 carbon atoms.

[0185] As R 3 , it is preferably a hydrogen atom.

[0186] AL and nAL in the formula (PAL2) have the same meanings as AL and nAL in the above formula (PAL1), and the preferred embodiments are also the same.

[0187] The water-soluble resin Y can be used alone in one kind or two or more kinds can be used.

[0188] As the lower limit value of the content of structural unit Y, it exceeds 0 mol% relative to the total number of moles of all structural units of the block copolymer, preferably 1 mol% or more, more preferably 10 mol% or more, still more preferably 30 mol% or more, and particularly preferably 40 mol% or more. Further, as the upper limit value, it is less than 100 mol%, preferably 90 mol% or less, more preferably 60 mol% or less.

[0189] (Other structural units)

[0190] In addition to structural unit X and structural unit Y, the block copolymer may have other structural units.

[0191] As the other structural units, preferred are structural units selected from structural units derived from (meth)acrylate and structural units derived from (meth)acrylate.

[0192] Examples of the above (meth)acrylate include (meth)acrylate alkyl esters having 1 to 18 carbon atoms in the alkyl group. Specifically, examples include methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, and stearyl (meth)acrylate. Among them, lauryl (meth)acrylate is preferred.

[0193] The other structural units may be used alone or in combination of two or more.

[0194] As the lower limit value of the content of the other structural units, relative to the total number of moles of all structural units of the block copolymer, it is preferably 1 mol% or more, more preferably 10 mol% or more, still more preferably 20 mol% or more. Further, as the upper limit value, it is preferably 90 mol% or less, more preferably 60 mol% or less, still more preferably 40 mol% or less.

[0195] Hereinafter, specific examples of the block copolymer are shown, but the block copolymer in the present invention is not limited to these.

[0196] [Chemical formula 4]

[0197]

[0198] As the lower limit value of the weight average molecular weight of the block copolymer, it is preferably 1,000 or more, more preferably 1,500 or more, still more preferably 2,000 or more, and particularly preferably 5,000 or more. Further, as the upper limit value, it is preferably 100,000 or less, more preferably 50,000 or less, still more preferably 20,000 or less.

[0199] The number average molecular weight (Mn) of the block copolymer is preferably from 1,000 to 40,000, more preferably from 2,000 to 20,000, still more preferably from 5,000 to 15,000, and particularly preferably from 7,000 to 12,000.

[0200] The dispersity (Mw / Mn) of the block copolymer is preferably from 1.00 to 12.00, more preferably from 1.00 to 11.00, still more preferably from 1.00 to 10.00, particularly preferably from 1.00 to 5.00, and most preferably from 1.00 to 2.00.

[0201] One type of the block copolymer may be used alone, or two or more types may be used.

[0202] The content of the block copolymer is preferably from 0.001 to 10.00% by mass, more preferably from 0.01 to 3.00% by mass, still more preferably from 0.02 to 1.00% by mass, and particularly preferably from 0.10 to 1.00% by mass based on the total mass of the resin composition layer.

[0203] There is no particular limitation on the polymerization method of the block copolymer, and known polymerization methods can be cited.

[0204] Examples of the polymerization method of the block copolymer include living radical polymerization, living cationic polymerization, and living anionic polymerization.

[0205] Examples of living radical polymerization, living cationic polymerization, and living anionic polymerization include "CRP Guide (Aldrich)" (URL: http: / / www.sigmaaldrich.com / japan / Materialscience / polymer-science / crp-guide.html), edited by Tsuyoshi Endo, written by Mitsuo Sawamoto et al., "Synthesis of Polymers (Part 1) - Radical Polymerization, Cationic Polymerization, Anionic Polymerization", Kodansha, 2010, p60, p105 - 108, p249 - 259, p381 - 386, and paragraphs

[0067] to

[0074] of International Publication No. 2017 / 014145, and these contents are incorporated herein.

[0206] <Compound (1)>

[0207] Compound (1) is a compound represented by formula (1).

[0208] Formula (1) Z-L 2 -W

[0209] In formula (1), Z represents a group represented by formula (A) or a group represented by formula (B).

[0210] The groups represented by the above formula (A) and the groups represented by the above formula (B) have the same meanings as the groups represented by formula (A) and formula (B) respectively possessed by the above block copolymer, and the preferred ranges are also the same.

[0211] L 2 represents a single bond or a divalent linking group,

[0212] As the divalent linking group represented by L 2 , for example, -O-, -CO-, -S-, -SO 2 -, -NR X -(R X represents a hydrogen atom or a substituent.) alkylene, alkenylene, alkynylene, aromatic ring group, alicyclic group, and groups formed by combining these can be cited. As the substituent represented by the above R X , for example, the substituents exemplified in the substituent group T can be cited, and an alkyl group having 1 to 2 carbon atoms is preferred.

[0213] The above alkylene, alkenylene, alkynylene, aromatic ring group, and alicyclic group may further have a substituent. As the substituent, for example, the substituents exemplified in the substituent group T can be cited. Among them, as the substituent, a halogen atom is preferred, and a fluorine atom is more preferred.

[0214] As the above alkylene, alkenylene, and alkynylene, they can be linear or branched.

[0215] And, as the number of carbon atoms of the above alkylene, preferably 1 to 20, more preferably 1 to 10, and further preferably 1 to 5.

[0216] And, as the number of carbon atoms of the above alkenylene and alkynylene, preferably 2 to 20, more preferably 2 to 10, and further preferably 2 to 5.

[0217] Among them, as L 2 , when Z is a group represented by formula (A), -O- is preferred, and when Z is a group represented by formula (B), a single bond is preferred.

[0218] W represents a group containing a poly(alkylene oxide) group.

[0219] As W, as long as it is a group containing a poly(alkylene oxide) group, there is no particular limitation.

[0220] Among them, as W, a monovalent organic group containing a poly(alkylene oxide) group is preferred, a group containing the group represented by the above formula (PAL1) is more preferred, and the group represented by formula (2) is further preferred.

[0221] Formula (2) *-(AL-O-) nAL -R 3

[0222] AL and R in Formula (2) 3 and the definitions of nAL are the same as those of the respective groups in the above Formula (PAL2). * indicates the bonding position.

[0223] Hereinafter, specific examples of Compound (1) are shown, but Compound (1) in the present invention is not limited to these.

[0224] [Chemical formula 5]

[0225]

[0226] As the lower limit of the molecular weight of Compound (1), it is preferably 100 or more, more preferably 500 or more. As the upper limit of the molecular weight of Compound (1), it is preferably 3,000 or less, more preferably 2,000 or less.

[0227] Compound (1) can be used alone or in two or more kinds.

[0228] The content of Compound (1) is preferably 0.001 to 10.00% by mass, more preferably 0.01 to 3.00% by mass, and further preferably 0.02 to 1.00% by mass relative to the total mass of the resin composition layer.

[0229] <Other components>

[0230] The resin composition layer may contain other components in addition to the resin, block copolymer, and Compound (1).

[0231] Examples of other components include polymerizable compounds, polymerization initiators, pigments, thermally crosslinkable compounds, additives, plasticizers, sensitizers, pigments, and compounds that generate acids, bases, or free radicals by light.

[0232] Details of other components will be described separately for each form of the resin composition layer below.

[0233] 〔Photosensitive resin composition layer〕

[0234] The resin composition layer can be a photosensitive resin composition layer.

[0235] After transferring the photosensitive resin composition layer onto the material to be transferred, a pattern can be formed on the material to be transferred by performing exposure and development.

[0236] As the photosensitive resin composition layer, it can be positive or negative.

[0237] The positive photosensitive composition layer is a photosensitive composition layer in which the solubility of the exposed portion in the developer is increased by exposure.

[0238] The negative photosensitive composition layer is a photosensitive composition layer in which the solubility of the exposed portion in the developer is decreased by exposure.

[0239] Among them, a negative photosensitive composition layer is preferably used. When the photosensitive composition layer is a negative photosensitive composition layer, the formed pattern corresponds to a protective film.

[0240] In addition to the above-mentioned block copolymer and compound (1), the photosensitive resin composition layer preferably further contains an alkali-soluble resin and a polymerizable compound.

[0241] Moreover, in addition to the above-mentioned block copolymer and compound (1), the photosensitive resin composition layer also preferably further contains a resin having a structural unit having an acid group protected by an acid-decomposable group to be described later, and a photoacid generator to be described later.

[0242] The transfer film having a photosensitive resin composition layer can be used to obtain a pattern such as wiring of a touch panel.

[0243] In a display device (such as an organic electroluminescence (EL) display device and a liquid crystal display device) having a touch panel such as a capacitive input device, an electrode pattern equivalent to a sensor of a visual recognition unit, a conductive layer pattern such as a peripheral wiring portion and a take-out wiring portion are provided inside the touch panel.

[0244] Generally, in order to form a patterned layer, a method is widely adopted in which a photosensitive resin composition layer is provided on a substrate using a transfer film or the like, and after the photosensitive resin composition layer is exposed through a mask having a desired pattern, development is performed.

[0245] Hereinafter, the components that the photosensitive resin composition layer can contain will be described.

[0246] <Alkali-soluble resin>

[0247] 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 above-mentioned resin composition layer.

[0248] From the viewpoint of more excellent resolution by suppressing the swelling of the photosensitive resin composition layer caused by the developer, the acid value of polymer P is preferably 220 mgKOH / g or less, more preferably less than 200 mgKOH / g, and further preferably less than 190 mgKOH / g.

[0249] The lower limit of the acid value of the polymer P is not particularly limited, but from the viewpoint of more excellent developability, it is preferably 60 mgKOH / g or more, more preferably 80 mgKOH / g or more, and further preferably 90 mgKOH / g or more.

[0250] In addition, the acid value is the mass [mg] of potassium hydroxide required to neutralize 1 g of the sample. In this specification, the unit is described as mgKOH / g. The acid value can be calculated, for example, from the average content of acid groups in the compound.

[0251] Regarding the acid value of the polymer P, it can be adjusted according to the types of structural units constituting the polymer P and the content of the structural units containing acid groups.

[0252] 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 preferred from the viewpoints of improving resolution and developability. The weight-average molecular weight is more preferably 100,000 or less, and further preferably 60,000 or less. On the other hand, when the weight-average molecular weight is 5,000 or more, it is preferred from the viewpoints of controlling the properties of the developed aggregates and the properties of the unexposed film such as the edge melting property and the wafer cutting property when it is a laminate having a photosensitive resin composition layer. 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 melting property refers to the degree to which the photosensitive resin composition layer easily overflows from the end face of the roll when wound into a roll as a laminate having a photosensitive resin composition layer. The wafer cutting property refers to the degree of easy flying of the wafer when cutting the unexposed film with a cutter. If the wafer adheres to the upper surface of the laminate having a photosensitive resin composition layer, etc., it may be transferred to the mask in the subsequent exposure process and become a defective product. The dispersity of the polymer P is preferably 1.0 to 6.0, more preferably 1.0 to 5.0, further preferably 1.0 to 4.0, and particularly preferably 1.0 to 3.0.

[0253] In the photosensitive resin composition layer, from the viewpoints of suppressing the thickening of the line width and the deterioration of the resolution due to the shift of the focus position during exposure, the polymer P preferably contains a structural unit based on a monomer having an aromatic hydrocarbon. In addition, as such an aromatic hydrocarbon, for example, a substituted or unsubstituted phenyl group and a substituted or unsubstituted aralkyl group can be cited.

[0254] The content of the structural unit derived from the monomer having an aromatic hydrocarbon in the polymer P is preferably 20.0% by mass or more, more preferably 30.0% by mass or more, relative to the total mass of the polymer P. As the upper limit, there is no particular limitation, but it is preferably 95.0% by mass or less, more preferably 85.0% by mass or less. In addition, in the case of containing a plurality of polymers P, the average value of the content of the structural unit derived from the monomer having an aromatic hydrocarbon is preferably within the above range.

[0255] Examples of the monomer having an aromatic hydrocarbon include monomers having an aralkyl group, styrene, and polymerizable styrene derivatives (for example, methylstyrene, vinyltoluene, tert-butoxystyrene, acetoxystyrene, 4-vinylbenzoic acid, styrene dimer, styrene trimer, etc.). Among them, monomers having an aralkyl group or styrene are preferred. In one embodiment, when the monomer having an aromatic hydrocarbon in the polymer P is styrene, the content of the structural unit derived from styrene is preferably 20.0 to 70.0% by mass, more preferably 25.0 to 65.0% by mass, further preferably 30.0 to 60.0% by mass, and particularly preferably 30.0 to 55.0% by mass, relative to the total mass of the polymer P.

[0256] Examples of the aralkyl group include substituted or unsubstituted phenylalkyl (excluding benzyl) and substituted or unsubstituted benzyl, etc., and substituted or unsubstituted benzyl is preferred.

[0257] Examples of the monomer having a phenylalkyl group include phenethyl (meth)acrylate, etc.

[0258] Examples of the monomer having a benzyl group include (meth)acrylate having a benzyl group, such as benzyl (meth)acrylate and chlorobenzyl (meth)acrylate, etc.; vinyl monomers having a benzyl group, such as vinylbenzyl chloride and benzyl alcohol. Among them, benzyl (meth)acrylate is preferred. In one embodiment, when the monomer having an aromatic hydrocarbon in the polymer P is derived from benzyl (meth)acrylate, the content of the structural unit derived from benzyl (meth)acrylate is preferably 50.0 to 95.0% by mass, more preferably 60.0 to 90.0% by mass, further preferably 70.0 to 90.0% by mass, and particularly preferably 75.0 to 90.0% by mass, relative to the total mass of the polymer P.

[0259] The polymer P preferably containing the structural unit derived from the monomer having an aromatic hydrocarbon is obtained by polymerizing at least one of the monomer having an aromatic hydrocarbon and at least one of the following first monomer and / or the following second monomer.

[0260] The polymer P that does not contain a structural unit derived from a monomer having an aromatic hydrocarbon is preferably obtained by polymerizing at least one of the following-described first monomers, and more preferably obtained by copolymerizing at least one of the first monomers with at least one of the following-described second monomers.

[0261] The first monomer is a monomer having a carboxyl group in the molecule.

[0262] Examples of the first monomer include (meth)acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, 4-vinylbenzoic acid, maleic anhydride, and maleic half esters. Among them, (meth)acrylic acid is preferred.

[0263] 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 still more preferably 15 to 30% by mass, based on the total mass of the polymer P.

[0264] From the viewpoints of exhibiting good developability and controlling edge fusibility, etc., it is preferred that the above content be 5% by mass or more. From the viewpoints of the high resolution and edge shape of the resist pattern, and further from the viewpoint of the chemical resistance of the resist pattern, it is preferred that the above content be 50% by mass or less.

[0265] The second monomer is non-acidic and is a monomer having at least one polymerizable unsaturated group in the molecule.

[0266] Examples of the second monomer include (meth)acrylic acid esters such as (meth)methyl acrylate, (meth)ethyl acrylate, (meth)n-propyl acrylate, (meth)isopropyl acrylate, (meth)n-butyl acrylate, (meth)isobutyl acrylate, (meth)tert-butyl acrylate, (meth)2-hydroxyethyl acrylate, (meth)2-hydroxypropyl acrylate, (meth)cyclohexyl acrylate, and (meth)2-ethylhexyl acrylate; esters of vinyl alcohol such as vinyl acetate; and (meth)acrylonitrile. Among them, (meth)methyl acrylate, (meth)2-ethylhexyl acrylate, or (meth)n-butyl acrylate is preferred, and (meth)methyl acrylate is more preferred.

[0267] 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 still more preferably 17 to 45% by mass, based on the total mass of the polymer P.

[0268] When the polymer P contains structural units derived from monomers having an aralkyl group and / or structural units derived from styrene, it is preferable from the viewpoint of suppressing the thickening of the line width and the deterioration of the resolution due to the shift of the focal position during exposure. For example, a copolymer containing structural units derived from methacrylic acid, structural units derived from benzyl methacrylate, and structural units derived from styrene, a copolymer containing structural units derived from methacrylic acid, structural units derived from methyl methacrylate, structural units derived from benzyl methacrylate, and structural units derived from styrene, etc. are preferable.

[0269] In one embodiment, the polymer P is preferably a polymer containing 25 to 55% by mass of structural units derived from monomers having an aromatic hydrocarbon, 20 to 35% by mass of structural units derived from the first monomer, and 15 to 45% by mass of structural units derived from the second monomer. And, in another embodiment, a polymer containing 70 to 90% by mass of structural units derived from monomers having an aromatic hydrocarbon and 10 to 25% by mass of structural units derived from the first monomer is preferable.

[0270] The polymer P may have a branched structure and / or an alicyclic structure in the side chain. And, the polymer P may have a straight-chain structure in the side chain. By using a monomer containing a group having a branched structure in the side chain or a monomer containing a group having an alicyclic structure in the side chain, a branched structure and / or an alicyclic structure can be introduced into the side chain of the polymer P. The group having an alicyclic structure may be monocyclic or polycyclic.

[0271] Specific examples of the monomer containing a group having a branched structure in the side chain include isopropyl (meth)acrylate, isobutyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, isoamyl (meth)acrylate, tert-amyl (meth)acrylate, sec-isoamyl (meth)acrylate, 2-octyl (meth)acrylate, 3-octyl (meth)acrylate, and tert-octyl (meth)acrylate. Among these, isopropyl (meth)acrylate, isobutyl (meth)acrylate, or tert-butyl methacrylate is preferable, and isopropyl (meth)acrylate or tert-butyl methacrylate is more preferable.

[0272] As the alicyclic structure, a monocyclic alicyclic structure and a polycyclic alicyclic structure can be cited, and a polycyclic alicyclic structure is preferable.

[0273] As specific examples of the monomer containing a group having an alicyclic structure in the side chain, (meth)acrylates having an alicyclic hydrocarbon group with 5 to 20 carbon atoms can be cited. As more specific examples, (meth)acrylic acid (bicyclo[2.2.1]heptan-2-yl), 1-adamantyl (meth)acrylate, 2-adamantyl (meth)acrylate, 3-methyl-1-adamantyl (meth)acrylate, 3,5-dimethyl-1-adamantyl (meth)acrylate, 3-ethyladamantyl (meth)acrylate, 3-methyl-5-ethyl-1-adamantyl (meth)acrylate, 3,5,8-triethyl-1-adamantyl (meth)acrylate, 3,5-dimethyl-8-ethyl-1-adamantyl (meth)acrylate, 2-methyl-2-adamantyl (meth)acrylate, 2-ethyl-2-adamantyl (meth)acrylate, 3-hydroxy-1-adamantyl (meth)acrylate, octahydro-4,7-mentanoindene-5-yl (meth)acrylate, octahydro-4,7-menthanol-1-ylmethyl (meth)acrylate, 1-menthyl (meth)acrylate, tricyclodecane (meth)acrylate, 3-hydroxy-2,6,6-trimethyl-bicyclo[3.1.1]heptyl (meth)acrylate, 3,7,7-trimethyl-4-hydroxy-bicyclo[4.1.0]heptyl (meth)acrylate, (norbornanyl) (meth)acrylate, isobornyl (meth)acrylate, fenchyl (meth)acrylate, 2,2,5-trimethylcyclohexyl (meth)acrylate, cyclohexyl (meth)acrylate, etc. Among them, cyclohexyl (meth)acrylate, (norbornanyl) (meth)acrylate, isobornyl (meth)acrylate, 1-adamantyl (meth)acrylate, 2-adamantyl (meth)acrylate, fenchyl (meth)acrylate, 1-menthyl (meth)acrylate or tricyclodecane (meth)acrylate is preferable, and cyclohexyl (meth)acrylate, (norbornanyl) (meth)acrylate, isobornyl (meth)acrylate, 2-adamantyl (meth)acrylate or tricyclodecane (meth)acrylate is more preferable.

[0274] The polymer P can be used alone as one kind, or two or more kinds can be used.

[0275] In the case of using two or more types, it is preferable to use a mixture of two polymers P each containing a structural unit derived from a monomer having an aromatic hydrocarbon, or to use a mixture of a polymer P containing a structural unit derived from a monomer having an aromatic hydrocarbon and a polymer P not containing a structural unit derived from a monomer having an aromatic hydrocarbon. In the latter case, the content of the polymer P containing a structural unit derived from a monomer having an aromatic hydrocarbon is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 80% by mass or more, and particularly preferably 90% by mass or more, with respect to the total mass of the polymer P. The upper limit is not particularly limited and is preferably 100% by mass or less.

[0276] Regarding the synthesis of the polymer P, it is preferably carried out by adding an appropriate amount of a radical polymerization initiator such as benzoyl peroxide and azobisisobutyronitrile to a solution obtained by diluting the above-mentioned single or plural monomers with a solvent such as acetone, methyl ethyl ketone, and isopropyl alcohol, and then heating and stirring. Sometimes, a part of the mixture is added dropwise to the reaction solution while carrying out the synthesis. Sometimes, after the reaction is completed, a solvent is further added to adjust to a desired concentration. As the synthesis method, in addition to solution polymerization, bulk polymerization, suspension polymerization, or emulsion polymerization can also be used.

[0277] The glass transition temperature Tg of the polymer P is preferably 30 to 135°C. By using a polymer P having a Tg of 135°C or lower, it is possible to suppress the thickening of the line width and the deterioration of the resolution when the focus position shifts during exposure. From this viewpoint, the Tg of the polymer P is more preferably 130°C or lower, still more preferably 120°C or lower, and particularly preferably 110°C or lower. Also, from the viewpoint of improving the edge melting resistance, it is preferable to use a polymer P having a Tg of 30°C or higher. From this viewpoint, the Tg of the polymer P is more preferably 40°C or higher, still more preferably 50°C or higher, particularly preferably 60°C or higher, and most preferably 70°C or higher.

[0278] The photosensitive resin composition layer may contain other resins in addition to the above.

[0279] Examples of other resins include acrylic resins, styrene-acrylic copolymers, polyurethane resins, polyvinyl alcohol, polyvinyl formal, polyamide resins, polyester resins, polyamide resins, epoxy resins, polyacetal resins, polyhydroxystyrene resins, polyimide resins, polybenzoxazole resins, siloxane resins, polyethyleneimine, polyallylamine, and polyalkylene glycols.

[0280] As the polymer P, the alkali-soluble resin described in the description of the thermoplastic resin composition layer below can be used.

[0281] The content of polymer P is preferably 10.00 to 90.00% by mass, more preferably 20.00 to 80.00% by mass, still more preferably 20.00 to 70.00% by mass, and particularly preferably 20.00 to 60.00% by mass, based on the total mass of the photosensitive resin composition layer. From the viewpoint of controlling the development time, it is preferable that the content of polymer P is 90.00% by mass or less. On the other hand, from the viewpoint of improving the edge melting resistance, it is preferable that the content of polymer P is 10.00% by mass or more.

[0282] <Resin having a structural unit with an acid group protected by an acid-decomposable group>

[0283] When the photosensitive resin composition layer is a positive photosensitive resin composition layer, it is preferable that the photosensitive resin composition layer contains a resin having an acid group protected by an acid-decomposable group. The resin having an acid group protected by an acid-decomposable group corresponds to the resin contained in the above resin composition layer.

[0284] The resin having an acid group protected by the above acid-decomposable group is preferably a polymer (hereinafter, also referred to as "polymer A") having a structural unit with an acid group protected by an acid-decomposable group (hereinafter, also referred to as "structural unit A").

[0285] In addition, the above positive photosensitive resin composition layer may contain other polymers in addition to the polymer having structural unit A. In the present specification, the polymer having structural unit A and other polymers are collectively referred to as "polymer components".

[0286] By the action of an acidic substance in a catalytic amount generated by exposure of the above polymer A, the structural unit A having an acid group protected by an acid-decomposable group in polymer A undergoes a deprotection reaction to become an acid group, thereby enabling development with a developer.

[0287] Hereinafter, preferred embodiments of structural unit A will be described.

[0288] The above photosensitive resin composition layer may further contain a polymer other than the polymer having a structural unit with an acid group protected by an acid-decomposable group.

[0289] In addition, it is preferable that all the polymers contained in the above polymer components are polymers each having at least a structural unit with an acid group described below.

[0290] In addition, the above photosensitive resin composition layer may further contain polymers other than these. The above polymer components in the present specification are not particularly limited and are polymer components containing other polymers added as needed.

[0291] As the polymer A, an addition polymerization type resin is preferred, and a polymer having a structural unit derived from (meth)acrylic acid or its ester is more preferred. In addition, structural units other than the structural unit derived from (meth)acrylic acid or its ester may have, for example, a structural unit derived from styrene and a structural unit derived from a vinyl compound.

[0292] From the viewpoints of solubility in a developer and transferability, the photosensitive resin composition layer preferably contains, as the above structural unit A, a polymer having a structural unit A1 represented by the following formula (A1) as a polymer component, preferably contains, as the above structural unit A, a polymer A having a structural unit A1 represented by the following formula (A1) and a glass transition temperature of 90°C or lower as a polymer component, and more preferably contains, as the above structural unit A, a polymer A having a structural unit A1 represented by the following formula (A1) and a structural unit B having an acid group described later and a glass transition temperature of 90°C or lower as a polymer component.

[0293] (Structural unit A)

[0294] The structural unit A is a structural unit having an acid group protected by an acid-decomposable group.

[0295] As the acid group protected by an acid-decomposable group, known acid groups and acid-decomposable groups can be cited.

[0296] As the acid group, for example, a carboxyl group and a phenolic hydroxyl group can be cited. And, as the acid group protected by an acid-decomposable group, for example, a group that is relatively easily decomposed by an acid (for example, an ester group protected by a group represented by the formula (A1), an acetal-based functional group such as a tetrahydropyranyl ester group and a tetrahydrofuranyl ester group, etc.), a group that is relatively difficult to be decomposed by an acid (for example, a tertiary alkyl group such as a tert-butyl ester group and a tertiary alkyl carbonate group such as a tert-butyl carbonate group, etc.) can be cited.

[0297] Among them, as the above acid-decomposable group, a group having a structure protected by an acetal-based functional group is preferred.

[0298] As the structural unit A, the following structural units A1 to A4 are preferred, the structural unit A2 or A4 is more preferred, and the structural unit A2 is further preferred.

[0299] - Structural unit A1 -

[0300] As the structural unit A having an acid group protected by the above acid-decomposable group, from the viewpoints of sensitivity and resolution, the structural unit A1 represented by the following formula (A1) is also preferred.

[0301] [Chemical formula 6]

[0302]

[0303] In formula (A1), 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.

[0304] When R 31 or R 32 is an alkyl group, as R 31 and R 32 , it is preferably an alkyl group having 1 to 10 carbon atoms. When R 31 or R 32 is an aryl group, as R 31 and R 32 , it is preferably a phenyl group. As R 31 and R 32 , they are preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, respectively.

[0305] R 33 represents an alkyl group or an aryl group, and R 31 or R 32 and R 33 can be linked to form a cyclic ether.

[0306] There is no particular limitation on the number of ring members of the above cyclic ether, and it is preferably 5 to 6, more preferably 5.

[0307] As R 33 , it is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms.

[0308] The alkyl group and aryl group represented by R 31 to R 33 can have substituents. There is no particular limitation on the substituents. For example, substituents exemplified in the substituent group T can be mentioned.

[0309] R 34 represents a hydrogen atom or a methyl group.

[0310] As R 34 , from the viewpoint of being able to obtain a lower Tg of polymer A, it is preferably a hydrogen atom.

[0311] The content of the structural unit in which R 34 is a hydrogen atom is preferably 20% by mass or more relative to the total amount of the structural unit A1 contained in polymer A. The upper limit is not particularly limited and is preferably 100% by mass or less.

[0312] In addition, the content (content ratio: mass ratio) of the structural unit in which R 34 is a hydrogen atom can be determined by 13Confirmed by C-nuclear magnetic resonance spectroscopy (NMR) measurement and the intensity ratio of the peak intensities calculated by conventional methods.

[0313] X 0 Represents a single bond or an arylene group.

[0314] As X 0 , preferably a single bond.

[0315] The above arylene group may have substituents. There is no particular limitation on the substituents. For example, the substituents exemplified in the substituent group T can be cited.

[0316] - Structural unit A2-

[0317] [Chemical formula 7]

[0318]

[0319] In formula (A2), R 34 Represents a hydrogen atom or a methyl group.

[0320] In formula (A2), R 34 Has the same meaning as R 34 in the above formula (A1), and the preferred ranges are also the same.

[0321] R 35 ~R 41 Each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

[0322] As R 35 ~R 41 , preferably a hydrogen atom.

[0323] Specific examples of structural units A1 to A2 are shown.

[0324] In addition, hereinafter, R 34 Represents a hydrogen atom or a methyl group.

[0325] [Chemical formula 8]

[0326]

[0327] - Structural unit A3-

[0328] [Chemical formula 9]

[0329]

[0330] In formula (A3), R B1 ~R B4 Each has the same meaning as R 31 ~R 34 in the above formula (A1), and the preferred ranges are also the same.

[0331] X B represents a single bond or a divalent linking group.

[0332] As X B the divalent linking group represented, examples thereof include an alkylene group, -C(=O)O-, -C(=O)NR N , -O- and combinations thereof.

[0333] The above-mentioned alkylene group may be linear, branched or cyclic.

[0334] Moreover, the above-mentioned alkylene group may have a substituent. There is no particular limitation on the substituent. For example, substituents exemplified in the substituent group T may be mentioned.

[0335] The number of carbon atoms of the above-mentioned alkylene group is preferably 1 to 10, more preferably 1 to 4.

[0336] X B When -C(=O)O- is included, it is preferred that the carbon atom contained in -C(=O)O- is directly bonded to the carbon atom to which R B4 is bonded. X B When -C(=O)NR N - is included, it is preferred that the carbon atom contained in -C(=O)NR N - is directly bonded to the carbon atom to which R B4 is bonded.

[0337] R N represents an alkyl group or a hydrogen atom, preferably an alkyl group having 1 to 4 carbon atoms or a hydrogen atom, more preferably a hydrogen atom.

[0338] Among them, as X B , a single bond is preferred.

[0339] It is preferred that the group containing R B1 to R B3 is para-bonded to X B to each other.

[0340] R B12 represents a substituent.

[0341] As R B12 , an alkyl group or a halogen atom is preferred.

[0342] The number of carbon atoms of the above-mentioned alkyl group is preferably 1 to 10, more preferably 1 to 4.

[0343] N represents an integer of 0 to 4.

[0344] As n, 0 to 1 is preferred, and 0 is more preferred.

[0345] - Structural unit A4-

[0346] [Chemical formula 10]

[0347]

[0348] In formula (A4), R B4 ~R B11 has the same meaning as R 34 ~R 41 in formula (A2), and the preferred ranges are also the same.

[0349] Moreover, in formula (A4), R B12 and n have the same meaning as R B12 and n in formula (A3), and the preferred ranges are also the same.

[0350] As a specific example of structural unit A4, the following structural units can be exemplified.

[0351] In addition, R B4 represents a hydrogen atom or a methyl group.

[0352] [Chemical formula 11]

[0353]

[0354] The water-soluble resin A can be used alone in one kind, or two or more kinds can be used.

[0355] As the content of structural unit A, it is preferably 20.0% by mass or more, more preferably 20.0 - 90.0% by mass, and further preferably 30.0 - 70.0% by mass with respect to the total mass of polymer A.

[0356] Moreover, as the content of the monomer derived from structural unit A, it is preferably 5.0 - 80.0% by mass, more preferably 10 - 80% by mass, and further preferably 30 - 70% by mass with respect to the total mass of polymer A.

[0357] (Structural unit B)

[0358] Polymer A may contain a structural unit B having an acid group.

[0359] Structural unit B is, for example, an acid group not protected by an acid-decomposable group, that is, a structural unit containing an acid group without a protecting group. By polymer A containing structural unit B, the following can be achieved: good sensitivity during pattern formation, easy dissolution in an alkaline developer during the development process after pattern exposure, and shortening of the development time.

[0360] As structural unit B, the structural units possessed by the above-mentioned alkali-soluble resins can be cited.

[0361] The structural unit B can be used alone in one kind or two or more kinds can be used.

[0362] As the content of the structural unit B, it is preferably 0.1 to 20.0% by mass, more preferably 0.5 to 15.0% by mass, and still more preferably 1 to 10.0% by mass, relative to the total mass of the polymer A.

[0363] (Other structural units)

[0364] In addition to the above structural units A to B, the polymer A may contain other structural units (hereinafter, also referred to as "structural unit C").

[0365] As the monomer for forming the structural unit C, for example, styrenes, (meth)acrylic acid alkyl esters, (meth)acrylic acid cyclic alkyl esters, (meth)acrylic acid aryl esters, unsaturated dicarboxylic acid diesters, bicyclic unsaturated compounds, maleimide compounds, unsaturated aromatic compounds, conjugated diene compounds, unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, unsaturated dicarboxylic anhydrides, groups having an aliphatic cyclic skeleton, and other unsaturated compounds can be cited.

[0366] Various properties of the polymer A can be adjusted by using the structural unit C and adjusting either the type or the content. In particular, by appropriately using the structural unit C, the Tg of the polymer A can be easily adjusted to 90°C or lower.

[0367] Specific examples of the structural unit C include structural units formed by polymerizing styrene, tert-butoxystyrene, methylstyrene, α-methylstyrene, acetoxystyrene, methoxystyrene, ethoxystyrene, chlorostyrene, methyl vinylbenzoate, ethyl vinylbenzoate, (meth)acrylic acid methyl ester, (meth)acrylic acid ethyl ester, (meth)acrylic acid n-propyl ester, (meth)acrylic acid isopropyl ester, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, benzyl (meth)acrylate, isobornyl (meth)acrylate, acrylonitrile, and ethylene glycol monoacetoacetate mono(meth)acrylate.

[0368] In addition, the compounds described in paragraphs

[0021] to

[0024] of JP-A-2004-264623 can also be cited.

[0369] As the structural unit C, a structural unit having an aromatic ring or a structural unit having an aliphatic cyclic skeleton is preferred.

[0370] As the monomer for forming the above structural unit, for example, styrene, tert-butoxystyrene, methylstyrene, α-methylstyrene, dicyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, and benzyl (meth)acrylate can be cited.

[0371] Among them, as the structural unit C, a structural unit derived from cyclohexyl (meth)acrylate is preferably used.

[0372] In addition, as the monomer for forming the structural unit C, for example, an alkyl (meth)acrylate is also preferably used, and an alkyl (meth)acrylate having an alkyl group with 4 to 12 carbon atoms is more preferably used. Specifically, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate can be mentioned.

[0373] The structural unit C can be used alone or in combination of two or more.

[0374] With respect to the total mass of the polymer A, the content of the structural unit C is preferably 70.0% by mass or less, more preferably 60.0% by mass or less, and further preferably 50.0% by mass or less. As the lower limit value, 0% by mass or more is preferably used, more preferably 1.0% by mass or more, and further preferably 5.0% by mass or more. In the above range, the resolution and adhesion are further improved.

[0375] From the viewpoints of solubility in the developer and optimization of the physical properties of the above-mentioned photosensitive resin composition layer, it is preferred that the polymer A contains a structural unit having an ester of the acid group in the above-mentioned structural unit B as the structural unit C.

[0376] Among them, the polymer A preferably contains a structural unit having a carboxylic acid group, and further contains a structural unit C having a carboxylic acid ester group as the structural unit B as a copolymerization component, and more preferably a polymer A containing a structural unit B derived from methyl (meth)acrylate and a structural unit C derived from cyclohexyl (meth)acrylate and / or ethyl (meth)acrylate.

[0377] Hereinafter, specific examples of the polymer A are shown, but the polymer A in the present invention is not limited to these.

[0378] [Chemical formula 12]

[0379]

[0380] As the glass transition temperature (Tg) of Polymer A, it is preferably 90°C or lower. When the Tg is 90°C or lower, the above photosensitive resin composition layer has high adhesion and more excellent transferability. As the above Tg, it is more preferably 60°C or lower, and further preferably 40°C or lower. As the lower limit value of the above Tg, there is no particular limitation, and it is preferably -20°C or higher, and more preferably -10°C or higher. By having the Tg of Polymer A be -20°C or higher, good pattern formability is maintained, and, for example, when using a cover film, a decrease in peelability during peeling of the cover film is suppressed.

[0381] The glass transition temperature of Polymer A can be measured using differential scanning calorimetry (DSC). The specific measurement method is carried out according to the methods described in JIS K7121 (1987) or JIS K6240 (2011). The glass transition temperature in this specification uses the extrapolated glass transition start temperature (hereinafter, also referred to as "Tig").

[0382] As the molecular weight of Polymer A, it is preferably 60,000 or lower, more preferably 2,000 to 60,000, and further preferably 3,000 to 50,000.

[0383] The weight average molecular weight of Polymer A can be measured by the above GPC method (gel permeation chromatography).

[0384] The dispersity (Mw / Mn) of Polymer A is preferably 1.0 to 5.0, and more preferably 1.05 to 3.5.

[0385] The production method of Polymer A is not particularly limited, and known methods can be used.

[0386] For example, in an organic solvent containing a monomer for forming structural unit A1, a monomer for forming a structural unit B having an acid group, and a monomer for forming structural unit C, it can be synthesized by polymerization using a polymerization initiator.

[0387] In addition to Polymer A, the above photosensitive resin composition layer may contain other polymers.

[0388] When the above photosensitive resin composition layer contains other polymers, the content of the other polymers is preferably 50% by mass or less, more preferably 30% by mass or less, and further preferably 20% by mass or less with respect to the total mass of the photosensitive resin composition layer. The lower limit is not particularly limited, and in most cases, it is 0% by mass or more.

[0389] As other polymers, for example, polyhydroxystyrene can be mentioned. Specifically, SMA1000P, SMA2000P, SMA3000P, SMA1440F, SMA17352P, SMA2625P, and SMA3840F (manufactured by SARTOMER Company), ARUFONUC-3000, ARUFONUC-3510, ARUFONUC-3900, ARUFONUC-3910, ARUFONUC-3920, and ARUFONUC-3080 (manufactured by TOAGOSEI CO., LTD.), and Joncryl690, Joncryl678, Joncryl67, and Joncryl586 (manufactured by BASF Company) can be mentioned.

[0390] Polymer A can be used alone as one kind or two or more kinds can be used.

[0391] The content of Polymer A is preferably 50.00 to 99.99% by mass, more preferably 70.00 to 98.00% by mass, relative to the total mass of the photosensitive resin composition layer.

[0392] <Photoacid generator>

[0393] The photosensitive resin composition layer can contain a photoacid generator.

[0394] As the photoacid generator, the photoacid generators that can be contained in the thermoplastic resin composition layer described later can be mentioned, and the preferred embodiments are the same.

[0395] The photoacid generator can be used alone as one kind or two or more kinds can be used.

[0396] 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 further preferably 5.0 to 15.0% by mass, relative to the total mass of the photosensitive resin composition layer.

[0397] <Polymerizable compound>

[0398] The photosensitive resin composition layer can contain a polymerizable compound having a polymerizable group.

[0399] In this specification, "polymerizable compound" means a compound different from the above-mentioned block copolymer, compound (1), and polymer P.

[0400] The polymerizable group of the polymerizable compound is not particularly limited as long as it is a group related to the polymerization reaction. For example, groups having an ethylenically unsaturated group such as vinyl, acryloyl, methacryloyl, styryl, and maleimido can be cited; and groups having a cationic polymerizable group such as epoxy group and oxetanyl can be cited.

[0401] As the polymerizable group, a group having an ethylenically unsaturated group is preferred, and an acryloyl group or a methacryloyl group is more preferred.

[0402] As the polymerizable compound, from the viewpoint of more excellent photosensitivity of the photosensitive resin composition layer, a compound having one or more ethylenically unsaturated groups (ethylenically unsaturated compound) is preferred, and a compound having two or more ethylenically unsaturated groups in one molecule (polyfunctional ethylenically unsaturated compound) is more preferred.

[0403] Moreover, from the viewpoint of more excellent resolution and peelability, the number of ethylenically unsaturated groups that the ethylenically unsaturated compound has in one molecule is preferably 6 or less, more preferably 3 or less, and further preferably 2 or less.

[0404] From the viewpoint of more excellent balance between the photosensitivity of the photosensitive resin composition layer and the resolution and peelability, a bifunctional or trifunctional ethylenically unsaturated compound having two or three ethylenically unsaturated groups in one molecule is preferably contained, and a bifunctional ethylenically unsaturated compound having two ethylenically unsaturated groups in one molecule is more preferably contained.

[0405] From the viewpoint of excellent peelability, the content of the bifunctional ethylenically unsaturated compound relative to the total mass of the polymerizable compound is preferably 20% by mass or more, more preferably more than 40% by mass, and further preferably 55% by mass or more, relative to the total mass of the photosensitive resin composition layer. The upper limit is not particularly limited and can be 100% by mass or less. That is, the polymerizable compound can all be a bifunctional ethylenically unsaturated compound.

[0406] Moreover, as the ethylenically unsaturated compound, a (meth)acrylate compound having a (meth)acryloyl group as the polymerizable group is preferred.

[0407] (Polymerizable Compound B1)

[0408] It is also preferred that the photosensitive resin composition layer contains a polymerizable compound B1 having an aromatic ring and two ethylenically unsaturated groups.

[0409] 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.

[0410] From the viewpoint of better resolution, in the photosensitive resin composition layer, the mass ratio of the content of the polymerizable compound B1 to the total mass of the polymerizable compounds is preferably 40% by mass or more, more preferably 50% by mass or more, still more preferably 55% by mass or more, and particularly preferably 60% by mass or more. There is no particular limitation on the upper limit, but from the viewpoint of peelability, it is, for example, 100% by mass or less, preferably 99% by mass or less, more preferably 95% by mass or less, still more preferably 90% by mass or less, and particularly preferably 85% by mass or less.

[0411] Examples of the aromatic ring possessed by the polymerizable compound B1 include aromatic hydrocarbon rings such as benzene ring, naphthalene ring and anthracene ring, aromatic heterocycles such as thiophene ring, furan ring, pyrrole ring, imidazole ring, triazole ring and pyridine ring, and condensed rings thereof. An aromatic hydrocarbon ring is preferred, and a benzene ring is more preferred. In addition, the above aromatic ring may have a substituent.

[0412] The polymerizable compound B1 may have only 1 aromatic ring or may have 2 or more aromatic rings.

[0413] From the viewpoint of improving the resolution by suppressing the swelling of the photosensitive resin composition layer caused by the developer, it is preferred that the polymerizable compound B1 has a bisphenol structure.

[0414] Examples of the bisphenol structure include a bisphenol A structure derived from bisphenol A (2,2-bis(4-hydroxyphenyl)propane), a bisphenol F structure derived from bisphenol F (2,2-bis(4-hydroxyphenyl)methane), and a bisphenol B structure derived from bisphenol B (2,2-bis(4-hydroxyphenyl)butane). A bisphenol A structure is preferred.

[0415] Examples of the polymerizable compound B1 having a bisphenol structure include a compound having a bisphenol structure and 2 polymerizable groups (preferably (meth)acryloyl group) bonded to both ends of the bisphenol structure.

[0416] Both ends of the bisphenol structure may be directly bonded to the 2 polymerizable groups or may be bonded via 1 or more oxyalkylene groups. As the oxyalkylene group added to both ends of the bisphenol structure, oxyethylene or oxypropylene is preferred, and oxyethylene is more preferred. There is no particular limitation on the addition number of the oxyalkylene group added to the bisphenol structure, but it is preferably 4 to 16 per molecule, and more preferably 6 to 14.

[0417] Regarding the polymerizable compound B1 having a bisphenol structure, it is described in paragraphs

[0072] to

[0080] of Japanese Patent Application Laid-Open No. 2016-224162, and the content described in this publication is incorporated into this specification.

[0418] As the polymeric compound B1, a 2-functional olefinically unsaturated compound having a bisphenol A structure is preferred, and 2,2-bis(4-((meth)acryloxypolyalkoxy)phenyl)propane is more preferred.

[0419] Examples of 2,2-bis(4-((meth)acryloxypolyalkoxy)phenyl)propane include 2,2-bis(4-(methacryloxydiethoxy)phenyl)propane (FA-324M, manufactured by Hitachi Chemical Co., Ltd.), 2,2-bis(4-(methacryloxyethoxypropoxy)phenyl)propane, 2,2-bis(4-(methacryloxypentaethoxy)phenyl)propane (BPE-500, manufactured by Shin-Nakamura Chemical Co., Ltd.), 2,2-bis(4-(methacryloxydodecaethoxytetrapropoxy)phenyl)propane (FA-3200MY, manufactured by Hitachi Chemical Co., Ltd.), 2,2-bis(4-(methacryloxypentadecaethoxy)phenyl)propane (BPE-1300, manufactured by Shin-Nakamura Chemical Co., Ltd.), 2,2-bis(4-(methacryloxydiethoxy)phenyl)propane (BPE-200, manufactured by Shin-Nakamura Chemical Co., Ltd.), and ethoxylated (10) bisphenol A diacrylate (NK Ester A-BPE-10, manufactured by Shin-Nakamura Chemical Co., Ltd.).

[0420] As the polymeric compound B1, a compound represented by the following general formula (B1) is also preferred.

[0421] [Chemical formula 13]

[0422]

[0423] In the general formula B1, R 1 and R 2 each independently represents a hydrogen atom or a methyl group. A represents C 2 H 4 . B represents C 3 H 6 . n1 and n3 are each independently an integer of 1 to 39, and n1 + n3 is an integer of 2 to 40. n2 and n4 are each independently an integer of 0 to 29, and n2 + n4 is an integer of 0 to 30. The arrangement of the structural units of -(A-O)- and -(B-O)- may be random or block. And in the case of block, both -(A-O)- and -(B-O)- may be on the biphenyl side.

[0424] In one embodiment, n1 + n2 + n3 + n4 is preferably an integer of 2 to 20, more preferably an integer of 2 to 16, and still 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, still more preferably an integer of 0 to 2, and particularly preferably 0.

[0425] The polymerizable compound B1 may be used alone or in combination of two or more.

[0426] From the viewpoint of more excellent resolution, 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. The upper limit is not particularly limited, but from the viewpoints of transferability and edge melting (the phenomenon in which the photosensitive resin oozes out from the end of the transfer member), it is preferably 70% by mass or less, more preferably 60% by mass or less.

[0427] The photosensitive resin composition layer may contain a polymerizable compound other than the above-mentioned polymerizable compound B1.

[0428] The polymerizable compound other than the polymerizable compound B1 is not particularly limited and can be appropriately selected from known compounds. For example, a compound having one ethylenically unsaturated group in one molecule (monofunctional ethylenically unsaturated compound), a bifunctional ethylenically unsaturated compound having no aromatic ring, and a trifunctional or higher-functional ethylenically unsaturated compound can be mentioned.

[0429] Examples of the monofunctional ethylenically unsaturated compound include ethyl (meth)acrylate, ethylhexyl (meth)acrylate, 2-(meth)acryloyloxyethyl succinate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, and phenoxyethyl (meth)acrylate.

[0430] 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.

[0431] Examples of the alkylene glycol di(meth)acrylate include tricyclodecane dimethanol diacrylate (A-DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.), tricyclodecane dimethanol dimethacrylate (DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.), 1,9-nonanediol diacrylate (A-NOD-N, manufactured by Shin-Nakamura Chemical Co., Ltd.), 1,6-hexanediol diacrylate (A-HD-N, manufactured by Shin-Nakamura Chemical Co., Ltd.), ethylene glycol dimethacrylate, 1,10-decanediol diacrylate, and pentaerythritol di(meth)acrylate.

[0432] Examples of the polyalkylene glycol di(meth)acrylate include polyethylene glycol di(meth)acrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, and polypropylene glycol di(meth)acrylate.

[0433] 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 the commercially available products include 8UX-015A (manufactured by TAISEI FINE CHEMICAL CO,., LTD.), UA-32P (manufactured by Shin-Nakamura Chemical Co., Ltd.), and UA-1100H (manufactured by Shin-Nakamura Chemical Co., Ltd.).

[0434] Examples of the ethylenically unsaturated compounds having 3 or more functional groups include dipentaerythritol (tri / tetra / penta / hexa)(meth)acrylate, pentaerythritol (tri / tetra)(meth)acrylate, trimethylolpropane tri(meth)acrylate, di-trimethylolpropane tetra(meth)acrylate, trimethylolethane tri(meth)acrylate, isocyanuric acid tri(meth)acrylate, glycerol tri(meth)acrylate, and their alkylene oxide-modified products.

[0435] Here, the “(tri / tetra / penta / hexa)(meth)acrylate” is a concept including tri(meth)acrylate, tetra(meth)acrylate, penta(meth)acrylate, and hexa(meth)acrylate, and the “(tri / tetra)(meth)acrylate” is a concept including tri(meth)acrylate and tetra(meth)acrylate.

[0436] In one embodiment, the photosensitive resin composition layer preferably contains the above-described polymerizable compound B1 and a polyfunctional ethylenically unsaturated compound having a functionality of 3 or more, and more preferably contains the above-described polymerizable compound B1 and two or more polyfunctional ethylenically unsaturated compounds having a functionality of 3 or more. At this time, the mass ratio of the polymerizable compound B1 to the polyfunctional ethylenically unsaturated compound having a functionality of 3 or more is preferably (total mass of the polymerizable compound B1) : (total mass of the polyfunctional ethylenically unsaturated compound having a functionality of 3 or more) = 1:1 to 5:1, more preferably 1.2:1 to 4:1, and further preferably 1.5:1 to 3:1.

[0437] Moreover, in one embodiment, the photosensitive resin composition preferably contains the above-described polymerizable compound B1 and two or more trifunctional ethylenically unsaturated compounds.

[0438] Examples of the alkylene oxide-modified product of the polyfunctional ethylenically unsaturated compound having a functionality of 3 or more include caprolactone-modified (meth)acrylate compounds (KAYARAD (registered trademark) DPCA-20 manufactured by Nippon Kayaku Co., Ltd., A-9300-1CL manufactured by Shin-Nakamura Chemical Co., Ltd., etc.), alkylene oxide-modified (meth)acrylate compounds (KAYARAD RP-1040 manufactured by Nippon Kayaku Co., Ltd., ATM-35E and A-9300 manufactured by Shin-Nakamura Chemical Co., Ltd., EBECRYL (registered trademark) 135 manufactured by DAI-CELL-ALLNEX LTD., etc.), ethoxylated glycerol triacrylate (A-GLY-9E manufactured by Shin-Nakamura Chemical Co., Ltd., etc.), ARONIX (registered trademark) TO-2349 (manufactured by TOAGOSEI CO., LTD.), ARONIX M-520 (manufactured by TOAGOSEI CO., LTD.), and ARONIX M-510 (manufactured by TOAGOSEI CO., LTD.).

[0439] Moreover, as the polymerizable compound, a polymerizable compound having an acid group (such as a carboxyl group) can be used. The above acid group can form an acid anhydride group. Examples of the polymerizable compound having an acid group include ARONIX (registered trademark) TO-2349 (manufactured by TOAGOSEI CO., LTD.), ARONIX (registered trademark) M-520 (manufactured by TOAGOSEI CO., LTD.), and ARONIX (registered trademark) M-510 (manufactured by TOAGOSEI CO., LTD.).

[0440] As 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 can be used.

[0441] The molecular weight of the polymerizable compound (including the polymerizable compound B1) (in the case of having a molecular weight distribution, the weight average molecular weight) is preferably 200 to 3,000, more preferably 280 to 2,200, and still more preferably 300 to 2,200.

[0442] The polymerizable compound can be used alone or in combination of two or more.

[0443] The content of the polymerizable compound is preferably 1 to 70% by mass, more preferably 5 to 70% by mass, still more preferably 20 to 70% by mass, and particularly preferably 40 to 60% by mass based on the total mass of the photosensitive resin composition layer.

[0444] <Polymerization initiator>

[0445] The photosensitive resin composition layer may contain a polymerization initiator.

[0446] The polymerization initiator can be selected according to the form of the polymerization reaction. For example, a thermal polymerization initiator and a photopolymerization initiator can be mentioned.

[0447] The polymerization initiator can be a radical polymerization initiator or a cationic polymerization initiator.

[0448] The photosensitive resin composition layer preferably contains a photopolymerization initiator.

[0449] The photopolymerization initiator is a compound that receives actinic rays such as ultraviolet rays, visible rays, and X-rays and starts the polymerization of the polymerizable compound. There is no particular limitation on the photopolymerization initiator, and known photopolymerization initiators can be used.

[0450] As the photopolymerization initiator, for example, a photo radical polymerization initiator and a photo cationic polymerization initiator can be mentioned, and a photo radical polymerization initiator is preferred.

[0451] As the photo radical polymerization initiator, for example, a photopolymerization initiator having an oxime ester structure, a photopolymerization initiator having an α-aminoalkyl phenyl ketone structure, a photopolymerization initiator having an α-hydroxyalkyl phenyl ketone structure, a photopolymerization initiator having an acylphosphine oxide structure, and a photopolymerization initiator having an N-phenylglycine structure can be mentioned.

[0452] Further, from the viewpoints of photosensitivity, visibility, and resolution of the exposed portion and the unexposed portion, it is preferable that the photosensitive resin composition layer contains at least one selected from 2,4,5-triaryl imidazole dimers and their derivatives as a photo radical polymerization initiator. In addition, the two 2,4,5-triaryl imidazole structures in the 2,4,5-triaryl imidazole dimers and their derivatives may be the same or different.

[0453] Examples of the derivatives of the 2,4,5-triaryl imidazole dimer include 2-(o-chlorophenyl)-4,5-diphenyl imidazole dimer, 2-(o-chlorophenyl)-4,5-bis(methoxyphenyl) imidazole dimer, 2-(o-fluorophenyl)-4,5-diphenyl imidazole dimer, 2-(o-methoxyphenyl)-4,5-diphenyl imidazole dimer, and 2-(p-methoxyphenyl)-4,5-diphenyl imidazole dimer.

[0454] As the photo radical polymerization initiator, for example, the polymerization initiators described in paragraphs

[0031] to

[0042] of Japanese Patent Application Laid-Open No. 2011-095716 and paragraphs

[0064] to

[0081] of Japanese Patent Application Laid-Open No. 2015-014783 can also be used.

[0455] Examples of the photo radical polymerization initiator include ethyl dimethylaminobenzoate (DBE, CAS No. 10287-53-3), benzoin methyl ether, methoxyphenyl (p,p'-dimethoxybenzyl ester), TAZ-110 (product name: manufactured by Midori Kagaku Co., Ltd.), benzophenone, 4,4'-bis(diethylamino) benzophenone, TAZ-111 (product name: manufactured by Midori Kagaku Co., Ltd.), Irgacure OXE01, OXE02, OXE03, OXE04 (manufactured by BASF), Omnirad 651 and 369 (product name: manufactured by IGM Resins B.V.), and 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.).

[0456] Examples of commercially available photo radical polymerization initiators include 1-[4-(phenylthio)]-1,2-octanedione-2-(o-benzoyl oxime) (product name: IRGACURE (registered trademark) OXE-01, manufactured by BASF), 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone-1-(o-acetoxime) (product name: IRGACURE OXE-02, manufactured by BASF), IRGACURE OXE-03 (manufactured by BASF), IRGACURE OXE-04 (manufactured by BASF), 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone (product name: Omnirad379EG, manufactured by IGM Resins B.V.), 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one (product name: Omnirad 907, manufactured by IGM Resins B.V.), 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropanoyl)benzyl]phenyl}-2-methylpropan-1-one (product name: Omnirad 127, manufactured by IGM Resins B.V.), 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one (product name: Omnirad 369, manufactured by IGM Resins B.V.), 2-hydroxy-2-methyl-1-phenylpropan-1-one (product name: Omnirad1173, manufactured by IGM Resins B.V.), 1-hydroxycyclohexyl phenyl ketone (product name: Omnirad184, manufactured by IGM Resins B.V.), 2,2-dimethoxy-1,2-diphenylethan-1-one (product name: Omnirad 651, manufactured by IGM Resins B.V.), 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (product name: Omnirad TPO H, manufactured by IGM Resins B.V.), bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (product name: Omnirad819, manufactured by IGM Resins B.V.), an oxime ester-based photoinitiator (product name: Lunar 6, manufactured by DKSH Management Ltd.), 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole (2-(2-chlorophenyl)-4,5-diphenylimidazole dimer) (product name: B-CIM, manufactured by Hampford Research Inc.), and 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer (product name: BCTB, manufactured by Tokyo Chemical Industry Co., Ltd.Manufacture), 1-[4-(phenylthio)phenyl]-3-cyclopentylpropane-1,2-dione-2-(o-benzoyl oxime) (Product name: TR-PBG-305, manufactured by Changzhou Tronly New Electronic Materials CO., LTD.), 1,2-propanedione, 3-cyclohexyl-1-[9-ethyl-6-(2-furylcarbonyl)-9H-carbazol-3-yl]-, 2-(o-acetyl oxime) (Product name: TR-PBG-326, manufactured by Changzhou Tronly New Electronic Materials CO., LTD.) and 3-cyclohexyl-1-(6-(2-(benzoyloxyimino)hexanoyl)-9-ethyl-9H-carbazol-3-yl)-propane-1,2-dione-2-(o-benzoyl oxime) (Product name: TR-PBG-391, manufactured by Changzhou Tronly New Electronic Materials CO., LTD.).

[0457] A photo cationic polymerization initiator (photo acid generator) is a compound that generates an acid upon receiving activated light. As the photo cationic polymerization initiator, a compound that preferably generates an acid upon receiving activated light with a wavelength of 300 nm or more, preferably a wavelength of 300 to 450 nm, is used, but its chemical structure is not particularly limited. Moreover, regarding a photo cationic polymerization initiator that does not directly sense activated light with a wavelength of 300 nm or more, if it is a compound that generates an acid by using a sensitizer in combination to sense activated light with a wavelength of 300 nm or more, it can also be appropriately used in combination with the sensitizer.

[0458] As the photo cationic polymerization initiator, a photo cationic polymerization initiator that generates an acid with a pKa of 4 or less is preferred, a photo cationic polymerization initiator that generates an acid with a pKa of 3 or less is more preferred, and a photo cationic polymerization initiator that generates an acid with a pKa of 2 or less is particularly preferred. The lower limit value of pKa is not particularly limited, but for example, it is preferably -10.0 or more.

[0459] As the photo cationic polymerization initiator, ionic photo cationic polymerization initiators and non-ionic photo cationic polymerization initiators can be mentioned.

[0460] As the ionic photo cationic polymerization initiator, for example, diaryl onium salt compounds such as salts and triarylsulfonium salts, and quaternary ammonium salts.

[0461] As the ionic photo cationic polymerization initiator, the ionic photo cationic polymerization initiator described in paragraphs

[0114] to

[0133] of Japanese Patent Application Laid-Open No. 2014-085643 can be used.

[0462] Examples of the nonionic photo cationic polymerization initiator include trichloromethyl-sym-triazine compounds, diazomethane compounds, imide sulfonate compounds, and oxime sulfonate compounds. As the trichloromethyl-sym-triazine compounds, diazomethane compounds, and imide sulfonate compounds, the compounds described in paragraphs

[0083] to

[0088] of JP-A-2011-221494 can be used. Further, as the oxime sulfonate compounds, the compounds described in paragraphs

[0084] to

[0088] of WO2018 / 179640 can be used.

[0463] As the photo cationic polymerization initiator (photo acid generator), the photo acid generators described in the description of the thermoplastic resin composition layer and the colored resin composition layer described later can also be mentioned.

[0464] The photosensitive resin composition layer preferably contains a photo radical polymerization initiator, and more preferably contains at least one selected from 2,4,5-triaryl imidazole dimers and their derivatives.

[0465] The polymerization initiator may be used alone or in combination of two or more.

[0466] The content of the polymerization initiator (preferably a photo polymerization initiator) is not particularly limited, and is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and still more preferably 1.0% by mass or more, relative to the total mass of the photosensitive resin composition layer. The upper limit is not particularly limited, and 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, relative to the total mass of the photosensitive resin composition layer.

[0467] <Dye>

[0468] From the viewpoints of visibility between the exposed portion and the unexposed portion, pattern visibility after development, and resolution, the photosensitive resin composition layer also preferably contains a dye (also referred to as "dye N") having a maximum absorption wavelength in the wavelength range of 400 to 780 nm during color development of 450 nm or more and whose maximum absorption wavelength changes due to an acid, a base, or a radical. When the dye N is contained, although the detailed mechanism is not clear, the adhesion to an adjacent layer (for example, a temporary support and an intermediate layer) is improved, and the resolution is more excellent.

[0469] In the present specification, the phrase "the maximum absorption wavelength of the dye changes due to an acid, a base, or a radical" may refer to any of the following embodiments: an embodiment in which the dye in the colored state is decolorized by an acid, a base, or a radical; an embodiment in which the dye in the decolorized state is colored by an acid, a base, or a radical; and an embodiment in which the dye in the colored state is changed to a colored state of another hue.

[0470] Specifically, the coloring agent N can be a compound that changes from a colorless state to a colored state by exposure, or a compound that changes from a colored state to a colorless state by exposure. At this time, it can be a coloring agent that generates an acid, a base, or a radical in the photosensitive resin composition layer by exposure and functions to change the colored or colorless state, or a coloring agent that changes the colored or colorless state due to a change in the state (e.g., pH) in the photosensitive resin composition layer by an acid, a base, or a radical. Moreover, it can also be a coloring agent that directly receives an acid, a base, or a radical as a stimulus without going through exposure and changes the colored or colorless state.

[0471] Among them, from the viewpoints of the visibility and resolution of the exposed part and the unexposed part, the coloring agent N is preferably a coloring agent whose maximum absorption wavelength changes by an acid or a radical, and more preferably a coloring agent whose maximum absorption wavelength changes by a radical.

[0472] From the viewpoints of the visibility and resolution of the exposed part and the unexposed part, the photosensitive resin composition layer preferably contains both a coloring agent whose maximum absorption wavelength changes by a radical as the coloring agent N and a photo radical polymerization initiator.

[0473] Moreover, from the viewpoint of the visibility of the exposed part and the unexposed part, the coloring agent N is preferably a coloring agent that colors by an acid, a base, or a radical.

[0474] As an example of the coloring mechanism of the coloring agent N, the following embodiments can be cited: A photo radical polymerization initiator, a photo cationic polymerization initiator (photo acid generator), or a photo base generator is added to the photosensitive resin composition layer, and after exposure, a radical-reactive coloring agent, an acid-reactive coloring agent, or a base-reactive coloring agent (e.g., a colorless coloring agent) colors due to the radicals, acids, or bases generated by the photo radical polymerization initiator, the photo cationic polymerization initiator, or the photo base generator.

[0475] Regarding the coloring agent N, from the viewpoint of the visibility of the exposed part and the unexposed part, the maximum absorption wavelength in the wavelength range of 400 to 780 nm during coloring is preferably 550 nm or more, more preferably 550 to 700 nm, and further preferably 550 to 650 nm.

[0476] Moreover, the coloring agent N can have only one maximum absorption wavelength in the wavelength range of 400 to 780 nm during coloring, or can have two or more. When the coloring agent N has two or more maximum absorption wavelengths in the wavelength range of 400 to 780 nm during coloring, it is sufficient that the maximum absorption wavelength with the highest absorbance among the two or more maximum absorption wavelengths is 450 nm or more.

[0477] Regarding the maximum absorption wavelength of the pigment N, it was obtained by measuring the transmission spectrum of a solution containing the pigment N (solution temperature: 25°C) in the range of 400 to 780 nm using a spectrophotometer: UV3100 (manufactured by SHIMADZU CORPORATION) under an atmospheric atmosphere, and detecting the wavelength at which the light intensity reaches a minimum (maximum absorption wavelength).

[0478] As the pigment that develops color or fades by exposure, for example, a colorless compound can be cited.

[0479] As the pigment that fades by exposure, for example, a colorless compound, a diarylmethane-based pigment, an oxazine-based pigment, a xanthene-based pigment, an iminonaphthoquinone-based pigment, an azomethine-based pigment, and an anthraquinone-based pigment can be cited.

[0480] As the pigment N, from the viewpoint of the visibility of the exposed portion and the non-exposed portion, a colorless compound is preferred.

[0481] As the colorless compound, for example, a colorless compound having a triarylmethane skeleton (triarylmethane-based pigment), a colorless compound having a spiropyran skeleton (spiropyran-based pigment), a colorless compound having a fluorane parent skeleton (fluorane parent-based pigment), a colorless compound having a diarylmethane skeleton (diarylmethane-based pigment), a colorless compound having a rhodamine lactam skeleton (rhodamine lactam-based pigment), a colorless compound having an indolylphthalide skeleton (indolylphthalide-based pigment), and a colorless compound having a white auramine skeleton (white auramine-based pigment) can be cited.

[0482] Among them, a triarylmethane-based pigment or a fluorane parent-based pigment is preferred, and a colorless compound having a triphenylmethane skeleton (triphenylmethane-based pigment) or a fluorane parent-based pigment is more preferred.

[0483] As the colorless compound, from the viewpoint of the visibility of the exposed portion and the non-exposed portion, it is preferred to have a lactone ring, a sultine ring, or a sulfone lactone ring. Thereby, it is possible to react the lactone ring, sultine ring, or sulfone lactone ring possessed by the colorless compound with the radical generated by the photoinitiator for free radical polymerization or the acid generated by the photoinitiator for cationic polymerization, and change the colorless compound to a closed-ring state to fade or change the colorless compound to an open-ring state to develop color. As the colorless compound, a compound having a lactone ring, a sultine ring, or a sulfone lactone ring and developing color due to the opening of the lactone ring, sultine ring, or sulfone lactone ring by a radical or an acid is preferred, and a compound having a lactone ring and developing color due to the opening of the lactone ring by a radical or an acid is more preferred.

[0484] As the pigment N, for example, the following dyes and colorless compounds can be cited.

[0485] Specific examples of the dyes in Pigment N include brilliant green, ethyl violet, methyl green, crystal violet, basic fuchsin, methyl violet 2B, methyl quinoline red, eosin B, metanil yellow, bromothymol blue, xylenol blue, methyl orange, p-methyl red, congo red, benzopurpurin 4B, α-naphthyl red, nile blue 2B, nile blue A, methyl violet, malachite green, fuchsin, victoria pure blue-naphthalene sulfonate, victoria pure blue BOH (manufactured by Hodogaya Chemical Co., Ltd.), oil blue #603 (manufactured by Orient Chemical Co., Ltd.), oil pink #312 (manufactured by Orient Chemical Co., Ltd.), oil red 5B (manufactured by Orient Chemical Co., Ltd.), oil scarlet #308 (manufactured by Orient Chemical Co., Ltd.), oil red OG (manufactured by Orient Chemical Co., Ltd.), oil red RR (manufactured by Orient Chemical Co., Ltd.), oil green #502 (manufactured by Orient Chemical Co., Ltd.), SPIRON Red BEH SPECIAL (manufactured by Hodogaya Chemical Co., Ltd.), m-cresol purple, cresol red, rhodamine B, rhodamine 6G, sulforhodamine B, auramine, 4-p-diethylaminophenylimino-1-naphthoquinone, 2-carboxyphenylamino-4-p-diethylaminophenylimino-1-naphthoquinone, 2-carboxystearylamino-4-p-N,N-bis(hydroxyethyl)amino-phenylimino-1-naphthoquinone, 1-phenyl-3-methyl-4-p-diethylaminophenylimino-5-pyrazolone, and 1-β-naphthyl-4-p-diethylaminophenylimino-5-pyrazolone.

[0486] Specific examples of the colorless compound in the coloring agent N include p, p', p''-hexamethyltriaminotriphenylmethane (colorless crystal violet), Pergascript Blue SRB (manufactured by Ciba Geigy), crystal violet lactone, malachite green lactone, benzoyl leucomethylene blue, 2-(N-phenyl-N-methylamino)-6-(N-p-tolyl-N-ethyl) amino fluorane parent, 2-phenylamino-3-methyl-6-(N-ethyl-p-toluidine) fluorane parent, 3,6-dimethoxy fluorane parent, 3-(N,N-diethylamino)-5-methyl-7-(N,N-dibenzylamino) fluorane parent, 3-(N-cyclohexyl-N-methylamino)-6-methyl-7-phenylamino fluorane parent, 3-(N,N-diethylamino)-6-methyl-7-phenylamino fluorane parent, 3-(N,N-diethylamino)-6-methyl-7-xylidino fluorane parent, 3-(N,N-diethylamino)-6-methyl-7-chloro fluorane parent, 3-(N,N-diethylamino)-6-methoxy-7-amino fluorane parent, 3-(N,N-diethylamino)-7-(4-chlorophenylamino) fluorane parent, 3-(N,N-diethylamino)-7-chloro fluorane parent, 3-(N,N-diethylamino)-7-benzylamino fluorane parent, 3-(N,N-diethylamino)-7,8-benzofluoran parent, 3-(N,N-dibutylamino)-6-methyl-7-phenylamino fluorane parent, 3-(N,N-dibutylamino)-6-methyl-7-xylidino fluorane parent, 3-piperidino-6-methyl-7-phenylamino fluorane parent, 3-pyrrolidino-6-methyl-7-phenylamino fluorane parent, 3,3-bis(1-ethyl-2-methylindol-3-yl) phthalide, 3,3-bis(1-n-butyl-2-methylindol-3-yl) phthalide, 3,3-bis(p-dimethylaminophenyl)-6-dimethylamino phthalide, 3-(4-diethylamino-2-ethoxyphenyl)-3-(1-ethyl-2-methylindol-3-yl)-4-aza phthalide, 3-(4-diethylaminophenyl)-3-(1-ethyl-2-methylindol-3-yl) phthalide, and 3',6'-bis(diphenylamino)spiroisobenzofuran-1(3H),9'-[9H]xanthen-3-one.

[0487] From the viewpoints of visibility of the exposed portion and the unexposed portion, visibility of the pattern after development, and resolution, the coloring agent N is preferably a coloring agent whose maximum absorption wavelength is changed by free radicals, and more preferably a coloring agent that develops color by free radicals.

[0488] As the coloring agent N, colorless crystal violet, crystal violet lactone, brilliant green, or Victoria pure blue-naphthalene sulfonate is preferred.

[0489] The coloring agent N may be used alone as one kind, or two or more kinds may be used.

[0490] From the viewpoints of the visibility of the exposed and unexposed portions, the visibility of the pattern after development, and the resolution, the content of the pigment N is preferably 0.1% by mass or more, more preferably 0.1 to 10% by mass, still more preferably 0.1 to 5% by mass, and particularly preferably 0.1 to 1% by mass, based on the total mass of the photosensitive resin composition layer.

[0491] The content of the pigment N is the content of the pigment when all the pigment N contained in the total mass of the photosensitive resin composition layer is in a colored state. Hereinafter, taking the pigment that is colored by radicals as an example, the method for quantifying the content of the pigment N will be described.

[0492] Solutions obtained by dissolving 0.001 g of the pigment and 0.01 g of the pigment in 100 mL of methyl ethyl ketone are prepared. To each of the obtained solutions, a photo radical polymerization initiator, Irgacure OXE01 (product name, manufactured by BASF Japan Ltd.), is added, and light of 365 nm is irradiated thereto to generate radicals, thereby bringing all the pigments into a colored state. Then, in an atmospheric atmosphere, using a spectrophotometer (UV3100, manufactured by SHIMADZU CORPORATION), the absorbance of each solution at a liquid temperature of 25°C is measured, and a calibration curve is prepared.

[0493] Next, instead of the pigment, 3 g of the photosensitive resin composition layer is dissolved in methyl ethyl ketone, and otherwise, the absorbance of the solution in which all the pigments are colored is measured by the same method as described above. From the absorbance of the solution containing the photosensitive resin composition layer obtained, the content of the pigment relative to the total mass of the photosensitive resin composition layer is calculated based on the calibration curve.

[0494] <Thermally crosslinkable compound>

[0495] From the viewpoints of the strength of the obtained cured film and the adhesiveness of the obtained uncured film, the photosensitive resin composition layer preferably contains a thermally crosslinkable compound.

[0496] In addition, in the present specification, a thermally crosslinkable compound having an ethylenically unsaturated group described later is not regarded as a polymerizable compound, but is regarded as a thermally crosslinkable compound.

[0497] Examples of the thermally crosslinkable compound include hydroxymethyl compounds and blocked isocyanate compounds. Among them, from the viewpoints of the strength of the obtained cured film and the adhesiveness of the obtained uncured film, a blocked isocyanate compound is preferred.

[0498] The blocked isocyanate compound reacts with hydroxyl groups and carboxyl groups. Therefore, for example, when there is at least one of hydroxyl groups and carboxyl groups in a resin and / or a polymerizable compound, etc., the hydrophilicity of the formed film decreases, and there is a tendency to enhance the function when using the film obtained by curing the photosensitive resin composition layer as a protective film.

[0499] In addition, 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".

[0500] 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.

[0501] The dissociation temperature of the blocked isocyanate refers to "the temperature of the endothermic peak accompanying the deprotection reaction of the blocked isocyanate when measured by DSC (Differential Scanning Calorimetry) analysis using a differential scanning calorimeter".

[0502] As the differential scanning calorimeter, for example, a differential scanning calorimeter (model: DSC6200) manufactured by Seiko Instruments Inc. can be appropriately used. However, the differential scanning calorimeter is not limited thereto.

[0503] As the blocking agent having a dissociation temperature of 100 to 160 °C, active methylene compounds [malonic acid diesters (dimethyl malonate, diethyl malonate, dibutyl malonate, di-2-ethylhexyl malonate, etc.)], oxime compounds (formaldehyde oxime, acetaldehyde oxime, acetyl oxime, methyl ethyl ketone oxime, cyclohexanone oxime, etc., compounds having a structure represented by -C(=N-OH)- in the molecule) can be mentioned.

[0504] Among them, as the blocking agent having a dissociation temperature of 100 to 160 °C, for example, from the viewpoint of storage stability, at least one selected from oxime compounds is preferred.

[0505] For example, from the viewpoints of improving the brittleness of the film and increasing the adhesion force to the transfer body, etc., it is preferred that the blocked isocyanate compound has an isocyanurate structure.

[0506] The blocked isocyanate compound having an isocyanurate structure is obtained, for example, by protecting hexamethylene diisocyanate by isocyanuration.

[0507] Among the blocked isocyanate compounds having an isocyanurate structure, a compound having an oxime structure using an oxime compound as a blocking agent is preferred from the viewpoints that it is easier to set the dissociation temperature within a preferred range compared to a compound not having an oxime structure and it is easier to reduce development residues.

[0508] The blocked isocyanate compound may have a polymerizable group.

[0509] As the polymerizable group, there is no particular limitation, and known polymerizable groups can be used, preferably a radical polymerizable group.

[0510] Examples of the polymerizable group include ethylenically unsaturated groups such as (meth)acryloyloxy, (meth)acrylamino, and styryl, and groups having an epoxy group such as glycidyl.

[0511] Among them, as the polymerizable group, an ethylenically unsaturated group is preferred, (meth)acryloyloxy is more preferred, and acryloyloxy is further preferred.

[0512] As the blocked isocyanate compound, commercially available products can be used.

[0513] Examples of commercially available products of the blocked isocyanate compound include Karenz (registered trademark) AOI - BM, Karenz (registered trademark) MOI - BM, Karenz (registered trademark) MOI - BP, etc. (manufactured by SHOWA DENKO K.K.), block - type DURANATE series (for example, DURANATE (registered trademark) TPA - B80E, DURANATE (registered trademark) WT32 - B75P, etc., manufactured by Asahi Kasei Chemicals Corporation).

[0514] Moreover, as the blocked isocyanate compound, compounds having the following structure can also be used.

[0515] [Chemical formula 14]

[0516]

[0517] The thermally cross - linkable compound can be used alone or in combination of two or more.

[0518] The content of the thermally cross - linkable 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.

[0519] <Additive>

[0520] In addition to the above components, the photosensitive resin composition layer may contain known additives as needed.

[0521] Examples of the additive include radical inhibitors, sensitizers, plasticizers, heterocyclic compounds (such as triazoles), benzotriazoles, carboxybenzotriazoles, pyridines (such as isoniazide), purine bases (such as adenine), and surfactants.

[0522] Each additive can be used alone, one kind, or two or more kinds can be used.

[0523] As the radical inhibitor, for example, the thermal inhibitors described in paragraph

[0018] of Japanese Patent No. 4502784 can be cited. Among them, phenothiazine, phenoxazine or 4-methoxyphenol is preferred. As other radical inhibitors, naphthylamine, cuprous chloride, aluminum salt of nitrosophenylhydroxylamine and diphenylnitrosamine can be cited. In order not to impair the sensitivity of the photosensitive resin composition layer, the aluminum salt of nitrosophenylhydroxylamine is preferably used as the radical inhibitor.

[0524] As the benzotriazoles, for example, 1,2,3-benzotriazole, 1-chloro-1,2,3-benzotriazole, bis(N-2-ethylhexyl)aminomethyl-1,2,3-benzotriazole, bis(N-2-ethylhexyl)aminomethyl-1,2,3-tolyltriazole and bis(N-2-hydroxyethyl)aminomethyl-1,2,3-benzotriazole can be cited.

[0525] As the carboxybenzotriazoles, for example, 4-carboxy-1,2,3-benzotriazole, 5-carboxy-1,2,3-benzotriazole, N-(N,N-di-2-ethylhexyl)aminomethylcarboxybenzotriazole, N-(N,N-di-2-hydroxyethyl)aminomethylcarboxybenzotriazole and N-(N,N-di-2-ethylhexyl)aminoethylcarboxybenzotriazole can be cited. As the carboxybenzotriazoles, for example, commercially available products such as CBT-1 (JOHOKU CHEMICAL CO., LTD, product name) can be used.

[0526] When the total mass of the photosensitive resin composition layer is set to 100% by mass, the total content of the radical inhibitor, benzotriazoles and carboxybenzotriazoles is preferably 0.01 to 3% by mass, more preferably 0.05 to 1% by mass. From the viewpoint of imparting storage stability to the composition, it is preferable to set the above content to 0.01% by mass or more. On the other hand, from the viewpoints of maintaining sensitivity and suppressing the decolorization of the dye, it is preferable to set the above content to 3% by mass or less.

[0527] Regarding the sensitizer, there is no particular limitation, and known sensitizers, dyes and pigments can be used. As the sensitizer, for example, dialkylaminobenzophenone compounds, pyrazoline compounds, anthracene compounds, coumarin compounds, xanthenone compounds, thioxanthone compounds, acridone compounds, oxazole compounds, benzoxazole compounds, thiazole compounds, benzothiazole compounds, triazole compounds (for example, 1,2,4-triazole), stilbene compounds, triazine compounds, thiophene compounds, naphthalenedicarboximide compounds, triarylamine compounds and aminoacridine compounds can be cited.

[0528] The content of the sensitizer can be appropriately selected according to the purpose.

[0529] From the viewpoints of improving the sensitivity to light sources and the curing rate based on the balance between the polymerization rate and chain transfer, the content of the sensitizer is preferably 0.01 to 5% by mass, more preferably 0.05 to 1% by mass, relative to the total mass of the photosensitive resin composition layer.

[0530] Examples of the plasticizer and heterocyclic compound include the compounds described in paragraphs

[0097] to

[0103] and

[0111] to

[0118] of International Publication No. 2018 / 179640.

[0531] The photosensitive resin composition may further contain known additives such as metal oxide particles, antioxidants, dispersants, acid generators, development accelerators, conductive fibers, ultraviolet absorbers, thickeners, crosslinking agents, and organic or inorganic anti-precipitants.

[0532] Examples of the additives contained in the photosensitive resin composition include the compounds described in paragraphs

[0165] to

[0184] of Japanese Patent Application Laid-Open No. 2014-085643, and the content of this publication is incorporated into this specification.

[0533] <Physical properties of the photosensitive resin composition layer>

[0534] (Film thickness)

[0535] The layer thickness (film thickness) of the photosensitive resin composition layer is not particularly limited. For example, in most cases, it is 0.1 to 300 μm, preferably 0.2 to 100 μm, more preferably 0.5 to 50 μm, further preferably 0.5 to 15 μm, particularly preferably 0.5 to 10 μm, and most preferably 0.5 to 8 μm. Thereby, the developability of the photosensitive resin composition layer is improved, and the resolution can be enhanced.

[0536] Moreover, in one embodiment, it is preferably 0.5 to 5 μm, more preferably 0.5 to 4 μm, and further preferably 0.5 to 3 μm.

[0537] Furthermore, from the viewpoint of more excellent adhesion, the transmittance of light with a wavelength of 365 nm of the photosensitive resin composition layer is preferably 10% or more, more preferably 30% or more, and further preferably 50% or more. The upper limit is not particularly limited, but it is preferably 99.9% or less.

[0538] (Impurities, etc.)

[0539] The photosensitive resin composition layer may contain a predetermined amount of impurities.

[0540] As specific examples of the impurities, sodium, potassium, magnesium, calcium, iron, manganese, copper, aluminum, titanium, chromium, cobalt, nickel, zinc, tin, halogens, and ions thereof can be cited. Among them, halide ions, sodium ions, and potassium ions are likely to be mixed as impurities, and thus preferably have the following contents.

[0541] The upper limit of the content of the impurities is preferably 80 mass ppm or less, more preferably 10 mass ppm or less, and still more preferably 2 mass ppm or less, relative to the total mass of the photosensitive resin composition layer. The lower limit of the above content is preferably 1 mass ppb or more, more preferably 0.1 mass ppm or more.

[0542] As a method for setting the impurities within the above range, the following can be cited: selecting raw materials with a low content of impurities as raw materials for the photosensitive resin composition layer; preventing impurities from being mixed in during the production of the photosensitive resin composition layer; and performing cleaning to remove them. By this method, the amount of impurities can be set within the above range.

[0543] Regarding the impurities, for example, they can be quantified by known methods such as ICP (Inductively Coupled Plasma) emission spectrometry, atomic absorption spectrometry, and ion chromatography.

[0544] The contents of compounds such as benzene, formaldehyde, trichloroethylene, 1,3-butadiene, carbon tetrachloride, chloroform, N,N-dimethylformamide, N,N-dimethylacetamide, and hexane in the photosensitive resin composition layer are preferably low. As the upper limit of the content of these compounds, it is preferably 100 mass ppm or less, more preferably 20 mass ppm or less, and still more preferably 4 mass ppm or less, relative to the total mass of the photosensitive resin composition layer.

[0545] As the lower limit of the above content, it is preferably 10 mass ppb or more, more preferably 100 mass ppb or more, relative to the total mass of the photosensitive resin composition layer. Regarding these compounds, the content can be suppressed by the same method as the impurities of the above metals. And they can be quantified by known measurement methods.

[0546] (Residual monomers)

[0547] The photosensitive resin composition layer may contain residual monomers of the respective structural units of the above polymers P and A.

[0548] From the viewpoints of patterning properties and reliability, the content of the residual monomers is preferably 5,000 mass ppm or less, more preferably 2,000 mass ppm or less, and still more preferably 500 mass ppm or less, relative to the total mass of polymer P or polymer A. The lower limit is not particularly limited, and is preferably 1 mass ppm or more, more preferably 10 mass ppm or more, relative to the total mass of polymer P or polymer A.

[0549] From the viewpoints of patternability and reliability, the residual monomer of each structural unit of polymer P or polymer A is preferably 3,000 mass ppm or less, more preferably 600 mass ppm or less, and still more preferably 100 mass ppm or less, based on the total mass of the photosensitive resin composition layer. The lower limit is not particularly limited, and is preferably 0.1 mass ppm or more, more preferably 1 mass ppm or more, based on the total mass of the photosensitive resin composition layer.

[0550] The amount of the residual monomer can be measured by known methods such as liquid chromatography and gas chromatography analysis.

[0551] 〔Thermoplastic resin composition〕

[0552] The resin composition layer may be a thermoplastic resin composition layer.

[0553] For example, in a transfer film having a temporary support and a resin composition layer, it is preferred that the thermoplastic resin composition layer is formed between the temporary support and the resin composition layer.

[0554] By having a thermoplastic resin composition layer between the temporary support and the resin composition layer, the followability to the substrate in the process of bonding the transfer film to the substrate is improved, the incorporation of air bubbles between the substrate and the transfer film is suppressed, and the adhesion to an adjacent layer (for example, the temporary support) can be improved.

[0555] The thermoplastic resin composition layer represents an embodiment in which the alkali-soluble resin in the photosensitive resin composition layer is a thermoplastic resin.

[0556] The thermoplastic resin may be an alkali-soluble resin. That is, it may be a resin that exhibits thermoplasticity and alkali-solubility (hereinafter, also referred to as "alkali-soluble thermoplastic resin").

[0557] The thermoplastic resin composition layer may contain other thermoplastic resins in addition to the alkali-soluble thermoplastic resin.

[0558] <Alkali-soluble thermoplastic resin>

[0559] Examples of the alkali-soluble thermoplastic resin include acrylic resin, polystyrene resin, styrene-acrylic copolymer, polyurethane resin, polyvinyl alcohol, polyvinyl formal, polyamide resin, polyester resin, polyamide resin, epoxy resin, polyacetal resin, polyhydroxystyrene resin, polyimide resin, polybenzoxazole resin, siloxane resin, polyethyleneimine, polyallylamine, and polyalkylene glycol.

[0560] As the alkali-soluble thermoplastic resin, from the viewpoints of developability and adhesion to an adjacent layer, acrylic resin is preferred.

[0561] Herein, the acrylic resin refers to a resin having at least one structural unit selected from a structural unit derived from (meth)acrylic acid, a structural unit derived from (meth)acrylate, and a structural unit derived from (meth)acrylamide.

[0562] As the acrylic resin, relative to the total mass of the acrylic resin, the total content of the structural unit derived from (meth)acrylic acid, the structural unit derived from (meth)acrylate, and the structural unit derived from (meth)acrylamide is preferably 30% by mass or more, more preferably 50% by mass or more.

[0563] Among them, relative to the total mass of the acrylic resin, the total content of the structural unit derived from (meth)acrylic acid and the structural unit derived from (meth)acrylate is preferably 30 to 100% by mass, more preferably 50 to 100% by mass.

[0564] Moreover, the alkali-soluble thermoplastic resin is preferably a polymer having an acid group.

[0565] Examples of the acid group include a carboxyl group, a sulfo group, a phosphoric acid group, and a phosphonic acid group, and a carboxyl group is preferred.

[0566] From the viewpoint of developability, as the acid value of the alkali-soluble thermoplastic resin, the acid value is preferably 60 mgKOH / g or more.

[0567] There is no particular limitation on the upper limit of the acid value of the alkali-soluble thermoplastic resin, but it 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.

[0568] As the alkali-soluble thermoplastic resin having an acid value of 60 mgKOH / g or more (preferably an acrylic resin containing a carboxyl group), there is no particular limitation, and it can be appropriately selected and used from known resins.

[0569] For example, an acrylic resin having a carboxyl group with an acid value of 60 mgKOH / g or more in the polymer described in paragraph

[0025] of Japanese Patent Laid-Open No. 2011-095716, an acrylic resin having a carboxyl group with an acid value of 60 mgKOH / g or more in the polymer described in paragraphs

[0033] to

[0052] of Japanese Patent Laid-Open No. 2010-237589, and an acrylic resin having a carboxyl group with an acid value of 60 mgKOH / g or more in the adhesive polymer described in paragraphs

[0053] to

[0068] of Japanese Patent Laid-Open No. 2016-224162 can be mentioned.

[0570] The copolymerization ratio of the structural unit having a carboxyl group in the above-mentioned acrylic resin having a carboxyl group is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, and still more preferably 12 to 30% by mass, relative to the total mass of the acrylic resin.

[0571] As the alkali-soluble thermoplastic resin, an acrylic resin having a structural unit derived from (meth)acrylic acid is particularly preferred from the viewpoints of developability and adhesion to an adjacent layer.

[0572] The alkali-soluble thermoplastic resin may have a reactive group.

[0573] As the reactive group, any group capable of addition polymerization may be used, and examples thereof include an ethylenically unsaturated group; a polycondensable group such as a hydroxyl group and a carboxyl group; and a polyaddition reactive group such as an epoxy group and a (block) isocyanate group.

[0574] 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, and still more preferably 20,000 to 50,000.

[0575] The alkali-soluble thermoplastic resin may be used alone or in combination of two or more.

[0576] From the viewpoints of developability and adhesion to an adjacent layer, the content of the alkali-soluble thermoplastic resin is preferably 10.00 to 99.00% by mass, more preferably 20.00 to 90.00% by mass, still more preferably 40.00 to 80.00% by mass, and particularly preferably 50.00 to 75.00% by mass, relative to the total mass of the thermoplastic resin composition layer.

[0577] <Dye>

[0578] The thermoplastic resin composition layer preferably contains a dye (also simply referred to as "dye B") having a maximum absorption wavelength of 450 nm or more in the wavelength range of 400 to 780 nm during color development and whose maximum absorption wavelength is changed by an acid, a base, or a radical.

[0579] The preferred embodiment of dye B is the same as the preferred embodiment of the above-mentioned dye N except for the points described later.

[0580] From the viewpoints of visibility and resolution of the exposed portion and the unexposed portion, 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.

[0581] From the viewpoints of the visibility and resolution of the exposed and unexposed portions, the thermoplastic resin composition layer preferably contains both a pigment B whose maximum absorption wavelength is changed by an acid and a compound that generates an acid upon exposure to light, which will be described later.

[0582] The pigment B may be used alone in one kind or two or more kinds may be used.

[0583] From the viewpoint of the visibility of the exposed and unexposed portions, the content of the pigment B is preferably 0.2% by mass or more, more preferably 0.2 to 6.0% by mass, still more preferably 0.2 to 5.0% by mass, and particularly preferably 0.25 to 3.0% by mass with respect to the total mass of the thermoplastic resin composition.

[0584] Here, the content of the pigment B refers to the content of the pigment when all the pigment B contained in the thermoplastic resin composition layer is in a colored state. Hereinafter, a method for quantifying the content of the pigment B will be described by taking a pigment that is colored by a free radical as an example.

[0585] Solutions obtained by dissolving 0.001 g of a pigment and 0.01 g of a pigment in 100 mL of methyl ethyl ketone were prepared. A photo radical polymerization initiator, Irgacure OXEO1 (product name, manufactured by BASF Japan Ltd.), was added to each of the obtained solutions, and light at 365 nm was irradiated thereto to generate free radicals, thereby bringing all the pigments into a colored state. Then, in an air atmosphere, the absorbance of each solution at a liquid temperature of 25 °C was measured using a spectrophotometer (UV3100, manufactured by SHIMADZU CORPORATION), and a calibration curve was prepared.

[0586] Next, 0.1 g of the thermoplastic resin composition was dissolved in methyl ethyl ketone instead of the pigment, and the absorbance of the solution in which all the pigments were colored was measured in the same manner as above. Based on the absorbance of the solution containing the thermoplastic resin composition layer thus obtained, the amount of the pigment relative to the total mass of the thermoplastic resin composition layer was calculated based on the calibration curve.

[0587] <Compound that generates an acid, base, or free radical upon exposure to light>

[0588] The thermoplastic resin composition may contain a compound that generates an acid, base, or free radical upon exposure to light (hereinafter, also simply referred to as "compound C").

[0589] As the compound C, a compound that generates an acid, base, or free radical upon receiving actinic rays such as ultraviolet rays and visible light is preferred.

[0590] As the compound C, known photoacid generators, photobase generators, and photo radical polymerization initiators (photo radical generators) can be used. Among them, a photoacid generator is preferred.

[0591] (Photoacid generator)

[0592] As the photoacid generator, the photo cationic polymerization initiator that can be contained in the above-described photosensitive resin composition layer can be cited. Except for the points described later, the preferred embodiments are the same.

[0593] As the photoacid generator, from the viewpoints of sensitivity and resolution, it is preferably at least one compound selected from the group consisting of onium salt compounds and oxime sulfonate compounds. From the viewpoints of sensitivity, resolution, and adhesion, it is more preferably an oxime sulfonate compound.

[0594] In addition, as the photoacid generator, a photoacid generator having the following structure is also preferred.

[0595] [Chemical formula 15]

[0596]

[0597] (Photo radical polymerization initiator)

[0598] As the photo radical polymerization initiator, the photo radical polymerization initiator that can be contained in the above-described photosensitive resin composition layer can be cited. The preferred embodiments are the same.

[0599] (Photo base generator)

[0600] As the photo base generator, as long as it is a known photo base generator, there is no particular limitation. For example, 2-nitrobenzyl cyclohexylcarbamate, triphenylmethanol, o-carbamoyl hydroxamic acid, o-carbamoyl oxime, [[(2,6-dinitrobenzyl)oxy]carbonyl]cyclohexylamine, bis[[(2-nitrobenzyl)oxy]carbonyl]hexane-1,6-diamine, 4-(methylthiobenzoyl)-1-methyl-1-phenanthroline ethane, (4-phenanthroline benzoyl)-1-benzyl-1-dimethylaminopropane, N-(2-nitrobenzyloxycarbonyl)pyrrolidine, hexaamine cobalt(III) tris(triphenylmethyl borate), 2-benzyl-2-dimethylamino-1-(4-phenanthrolinyl)phenyl-1-butanone, 2,6-dimethyl-3,5-diacetyl-4-(2-nitrophenyl)-1,4-dihydropyridine, and 2,6-dimethyl-3,5-diacetyl-4-(2,4-dinitrophenyl)-1,4-dihydropyridine can be cited.

[0601] Compound C can be used alone or in combination of two or more.

[0602] From the viewpoints of visibility and resolution of the exposed portion and the unexposed portion, the content of Compound C is preferably 0.1 to 10% by mass, more preferably 0.5 to 5% by mass, based on the total mass of the thermoplastic resin composition layer.

[0603] <Plasticizer>

[0604] From the viewpoints of adhesion to adjacent layers, resolution, and developability, the thermoplastic resin composition layer preferably contains a plasticizer.

[0605] Preferably, the molecular weight of the plasticizer (in the case of an oligomer or polymer having a molecular weight distribution, the weight-average molecular weight) is smaller than that of the alkali-soluble resin. The molecular weight (weight-average molecular weight) of the plasticizer is preferably 200 to 2,000.

[0606] Regarding the plasticizer, there is no limitation as long as it is a compound that is compatible with the alkali-soluble thermoplastic resin and exhibits plasticizing properties. From the viewpoint of imparting plasticizing properties, it is preferable that the plasticizer has an oxyalkylene group in the molecule, and a polyalkylene glycol compound is more preferable. The oxyalkylene group contained in the plasticizer more preferably has a polyethyleneoxy structure or a polypropyleneoxy structure.

[0607] Furthermore, from the viewpoints of resolution and storage stability, it is preferable that the plasticizer contains a (meth)acrylate compound. From the viewpoints of compatibility, resolution, and adhesion to adjacent layers, it is more preferable that the alkali-soluble resin is an acrylic resin and the plasticizer contains a (meth)acrylate compound.

[0608] As the (meth)acrylate compound that can be used as a plasticizer, the (meth)acrylate compounds described as the polymerizable compounds contained in the above-described photosensitive resin composition layer can be cited.

[0609] In the transfer film, when the thermoplastic resin composition layer and the photosensitive resin composition layer are directly contacted and laminated, it is preferable that both the thermoplastic resin composition layer and the photosensitive resin composition layer contain the same (meth)acrylate compound. This is because the diffusion of components between layers is suppressed and the storage stability is improved by the thermoplastic resin composition layer and the photosensitive resin composition layer containing the same (meth)acrylate compound.

[0610] When the thermoplastic resin composition layer contains a (meth)acrylate compound as a plasticizer, from the viewpoint of adhesion of the thermoplastic resin composition layer to adjacent layers, it is preferable that the (meth)acrylate compound does not polymerize even in the exposed portion after exposure.

[0611] Furthermore, as the (meth)acrylate compound that can be used as a plasticizer, from the viewpoints of resolution of the thermoplastic resin composition layer, adhesion to adjacent layers, and developability, a polyfunctional (meth)acrylate compound having two or more (meth)acryloyl groups in one molecule is preferable.

[0612] Furthermore, as the (meth)acrylate compound that can be used as a plasticizer, a (meth)acrylate compound having an acid group or a urethane (meth)acrylate compound is also preferred.

[0613] The plasticizer can be used alone or in combination of two or more.

[0614] From the viewpoints of the resolution of the thermoplastic resin composition layer, the adhesion to an adjacent layer, and the developability, the content of the plasticizer is preferably 1 to 70% by mass, more preferably 10 to 60% by mass, and still more preferably 15 to 50% by mass with respect to the total mass of the thermoplastic resin composition layer.

[0615] <Sensitizer>

[0616] The thermoplastic resin composition layer may contain a sensitizer.

[0617] As the sensitizer, there is no particular limitation, and examples thereof include the sensitizers that the above-described photosensitive resin composition layer may contain.

[0618] The sensitizer can be used alone or in combination of two or more.

[0619] The content of the sensitizer can be appropriately selected according to the purpose, but from the viewpoints of improving the sensitivity to a light source and the visibility of the exposed portion and the unexposed portion, it is preferably 0.01 to 5% by mass, more preferably 0.05 to 1% by mass with respect to the total mass of the thermoplastic resin composition layer.

[0620] <Additive>

[0621] In addition to the above, the thermoplastic resin composition layer may contain known additives as needed.

[0622] Moreover, regarding the thermoplastic resin composition layer, paragraphs

[0189] to

[0193] described in Japanese Patent Laid-Open No. 2014-085643 are incorporated herein by reference.

[0623] <Physical properties of thermoplastic resin composition layer>

[0624] (Film thickness)

[0625] The layer thickness of the thermoplastic resin composition layer is not particularly limited, but from the viewpoint of the adhesion to an adjacent layer, it is preferably 1 μm or more, more preferably 2 μm or more. The upper limit is not particularly limited, but from the viewpoints of developability and resolution, it is preferably 20 μm or less, more preferably 10 μm or less, and still more preferably 8 μm or less.

[0626] (Impurities)

[0627] The thermoplastic resin composition layer may contain a predetermined amount of impurities.

[0628] There are no particular limitations on the impurities, and examples thereof include the impurities that the photosensitive resin composition layer may contain, and the preferred ranges are also the same.

[0629] (Residual monomer)

[0630] The thermoplastic resin composition layer sometimes contains the residual monomers of the respective structural units of the above-mentioned alkali-soluble thermoplastic resin.

[0631] The preferred range of the content of the above-mentioned residual monomer is the same as the content of the residual monomer that the photosensitive resin composition layer may contain.

[0632] [Colored resin composition layer]

[0633] The resin composition layer may be a colored resin composition layer.

[0634] In recent years, a cover glass having a black frame-shaped light-shielding layer formed on the peripheral edge portion of the back surface of a transparent glass substrate or the like is sometimes installed on the liquid crystal display window of an electronic device to protect the liquid crystal display window. A colored resin composition layer can be used to form such a light-shielding layer.

[0635] The colored resin composition layer contains a pigment.

[0636] The colored resin composition layer may further contain a pigment in addition to the resin (for example, polymer P and polymer A, etc.), the polymerizable compound, and the block copolymer and / or compound (1). The colored resin composition layer preferably further contains a polymerization initiator in addition to the resin (for example, polymer P and polymer A, etc.), the polymerizable compound, the pigment, and the block copolymer and / or compound (1).

[0637] A pigment can be further added to each of the above resin composition layers to form a colored resin composition layer.

[0638] For example, a pigment (or a pigment dispersion) can be added to the above-mentioned photosensitive resin composition layer as described above to be used as a colored resin composition layer. That is, the above-mentioned photosensitive resin composition layer can be made into a photosensitive resin composition layer as a colored resin composition layer.

[0639] And, similarly, each of the above resin composition layers can be made into a colored resin composition layer added with a pigment. For example, as described above, the above-mentioned photosensitive resin composition layer can become a colored resin composition layer containing a pigment. That is, the above-mentioned photosensitive resin composition layer can be made into a photosensitive resin composition layer as a colored resin composition layer.

[0640] [Pigment]

[0641] As the pigment contained in the colored resin composition layer, it can be appropriately selected according to the desired hue, and can be selected from black pigments, white pigments, and colored pigments other than black and white. Among them, in the case of forming a black pattern, a black pigment can be appropriately selected as the pigment.

[0642] As the black pigment, as long as it is within the range that does not impair the effects of the present invention, known black pigments (organic pigments, inorganic pigments, etc.) can be appropriately selected. Among them, from the viewpoint of optical density, as the black pigment, for example, carbon black, titanium oxide, titanium carbide, iron oxide, titanium oxide, and graphite can be appropriately cited, and carbon black is particularly preferred. As carbon black, from the viewpoint of surface resistance, carbon black in which at least a part of the surface is coated with resin is preferred.

[0643] It is preferred to use the black pigment (preferably carbon black) in the form of a pigment dispersion.

[0644] The dispersion can be a dispersion prepared by adding a mixture obtained by premixing a black pigment and a pigment dispersant in an organic solvent (or vehicle) and dispersing it using a dispersing machine. Regarding the pigment dispersant, it can be selected according to the pigment and the solvent, and for example, commercially available dispersants can be used. In addition, the vehicle refers to the part of the medium in which the pigment is dispersed when it is made into a pigment dispersion, and is liquid, and contains a binder component that holds the black pigment in a dispersed state and a solvent component (organic solvent) that dissolves and dilutes the binder component.

[0645] There is no particular limitation on the dispersing machine. For example, known dispersing machines such as kneaders, roll mills, grinders, super mills, dissolvers, homogenizing mixers, and sand mixers can be cited. Furthermore, mechanical grinding can be used to perform fine pulverization by frictional force. Regarding the dispersing machine and fine pulverization, the descriptions in "Encyclopedia of Pigments" (written by Kunizo Asakura, first edition, Asakura Publishing Co., Ltd., 2000, pages 438 and 310) can be referred to.

[0646] Regarding the particle size of the black pigment, from the viewpoint of dispersion stability, the number average particle size is preferably 0.001 to 0.1 μm, and more preferably 0.01 to 0.08 μm.

[0647] Here, the particle size refers to the diameter of a circle when the area of the pigment particle is obtained from a photograph of the pigment particle taken with an electron microscope and a circle having the same area as the area of the pigment particle is considered. The number average particle size is the average value obtained by calculating the above particle size for any 100 particles and averaging the 100 obtained particle sizes.

[0648] As a pigment other than the black pigment, regarding the white pigment, the white pigments described in paragraphs

[0015] and

[0114] of Japanese Patent Laid-Open No. 2005-007765 can be used. Specifically, as the inorganic pigment in the white pigment, titanium oxide, zinc oxide, lithopone, light calcium carbonate, white carbon, aluminum oxide, aluminum hydroxide, or barium sulfate is preferable, titanium oxide or zinc oxide is more preferable, and titanium oxide is further preferable. As the inorganic pigment, rutile type or anatase type titanium oxide is further preferable, and rutile type titanium oxide is particularly preferable.

[0649] Moreover, the surface of titanium oxide can be subjected to silica treatment, alumina treatment, titanium dioxide treatment, zirconia treatment, or organic substance treatment, or two or more kinds of treatments can be carried out. Thereby, the catalytic activity of titanium oxide is suppressed, and heat resistance, light fading property, etc. are improved.

[0650] From the viewpoint of reducing the thickness of the photosensitive resin composition layer after heating, as the surface treatment of the surface of titanium oxide, at least one of alumina treatment and zirconia treatment is preferable, and both alumina treatment and zirconia treatment are particularly preferable.

[0651] Moreover, from the viewpoint of transferability, it is also preferable that the colored resin composition layer further contains a colored pigment other than the black pigment and the white pigment. In the case of containing a colored pigment, it is desired that the colored pigment is well dispersed in the colored resin layer. From this viewpoint, the particle diameter is preferably 0.1 μm or less, and more preferably 0.08 μm or less.

[0652] As color pigments, for example, Victoria Pure Blue B0 (Color Index: hereinafter referred to as C.I.) 42595, Auramine (C.I. 41000), Fat Black HB (C.I. 26150), Monolite Yellow GT (C.I. Pigment Yellow 12), Permanent Yellow GR (C.I. Pigment Yellow 17), Permanent Yellow HR (C.I. Pigment Yellow 83), Permanent Magenta FBB (C.I. Pigment Red 146), Hostasol Red ESB (C.I. Pigment Violet 19), Permanent Rubine FBH (C.I. Pigment Red 11), Fastogen Pink B Supra (C.I. Pigment Red 81), Monastral Fast Blue (C.I. Pigment Blue 15), Monolite Fast Black B (C.I. Pigment Black 1), and carbon, C.I. Pigment Red 97, C.I. Pigment Red 122, C.I. Pigment Red 149, C.I. Pigment Red 168, C.I. Pigment Red 177, C.I. Pigment Red 180, C.I. Pigment Red 192, C.I. Pigment Red 215, C.I. Pigment Green 7, C.I. Pigment Blue 15:1, C.I. Pigment Blue 15:4, C.I. Pigment Blue 22, C.I. Pigment Blue 60, C.I. Pigment Blue 64, and C.I. Pigment Violet 23 can be mentioned. Among them, C.I. Pigment Red 177 is preferred.

[0653] As the content of the pigment, relative to the total mass of the colored composition layer, it 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, further preferably more than 5% by mass and 35% by mass or less, and particularly preferably 10 to 35% by mass or less.

[0654] In the case of containing pigments other than black pigments (white pigments and color pigments), relative to the black pigment, it is preferably 30% by mass or less, more preferably 1 to 20% by mass, and further preferably 3 to 15% by mass.

[0655] <Physical properties of the formed layer>

[0656] (Film thickness)

[0657] As the layer thickness (film thickness) of the colored resin composition layer, in most cases, it is 0.1 to 300 μm, preferably 0.2 to 100 μm, more preferably 0.5 to 50 μm, further preferably 0.5 to 15 μm, particularly preferably 0.5 to 10 μm, and most preferably 0.5 to 8 μm.

[0658] (Impurities)

[0659] The colored resin composition layer may contain a predetermined amount of impurities.

[0660] There are no particular restrictions on the impurities, and examples thereof include the impurities that the above photosensitive resin composition layer may contain, and the preferred ranges are also the same.

[0661] Residual monomer

[0662] The colored resin composition layer sometimes contains residual monomers of each structural unit of the above resins (for example, polymer P, polymer A, alkali-soluble resin, etc.).

[0663] The preferred range of the content of the above residual monomers is the same as the content of the residual monomers that the photosensitive resin composition layer can contain.

[0664] 〔Water-soluble resin composition layer〕

[0665] The resin composition layer can be a water-soluble resin composition layer.

[0666] The water-soluble resin composition layer is a resin composition layer containing a block copolymer and / or compound (1) and a water-soluble resin.

[0667] Examples of the resin that can be used as the water-soluble resin include polyvinyl alcohol-based resins, polyvinylpyrrolidone-based resins, cellulose-based resins, acrylamide-based resins, polyethylene oxide-based resins, gelatin, vinyl ether-based resins, polyamide resins, and copolymers thereof.

[0668] In addition, when the water-soluble resin composition layer containing a water-soluble resin is used as an intermediate layer, from the viewpoint of suppressing the mixing of components between layers, the water-soluble resin is preferably a resin different from the resins contained in the adjacent layers (for example, polymer P, polymer A, and alkali-soluble thermoplastic resin).

[0669] From the viewpoints of oxygen barrier properties and suppressing the mixing of components during coating of multiple layers and during storage after coating, the water-soluble resin composition layer preferably contains polyvinyl alcohol, and more preferably contains both polyvinyl alcohol and polyvinylpyrrolidone.

[0670] The water-soluble resin composition layer can be used alone or in combination of two or more.

[0671] The content of the water-soluble resin is not particularly limited, but from the viewpoints of oxygen barrier properties and suppressing the mixing of components during coating of multiple layers and during storage after coating, it is preferably 50.0% by mass or more and less than 100.0% by mass, more preferably 70.0% by mass or more and less than 100.0% by mass, still more preferably 80.0% by mass or more and less than 100.0% by mass, and particularly preferably 90.0% by mass or more and less than 100.0% by mass, based on the total mass of the water-soluble resin composition layer.

[0672] The method for forming the water-soluble resin composition layer is not particularly limited. For example, it can be carried out in the same manner as the method using the photosensitive resin composition.

[0673] The method for forming the intermediate layer (water-soluble resin layer containing a water-soluble resin) is not particularly limited. For example, a method of forming a water-soluble resin composition layer by coating a water-soluble resin composition on the surface of a thermoplastic resin composition layer or a photosensitive resin composition layer and drying the coating film of the water-soluble resin composition can be cited.

[0674] The layer thickness of the water-soluble resin composition layer is not particularly limited, but it is preferably 0.1 to 5.0 μm, more preferably 0.5 to 3.0 μm. This is because: if the thickness of the water-soluble resin composition layer is within the above range, the mixing of components during coating of multiple layers and during storage after coating can be suppressed without reducing the oxygen barrier property, and an increase in the removal time of the water-soluble resin layer during development can be suppressed.

[0675] (Impurities)

[0676] The water-soluble resin composition layer may contain a predetermined amount of impurities.

[0677] There is no particular limitation on the impurities, and examples thereof include the impurities that the above photosensitive resin composition layer may contain, and the preferred range is also the same.

[0678] (Residual monomers)

[0679] The water-soluble resin composition layer sometimes contains residual monomers of each structural unit of the above resins (for example, water-soluble resins, polymer P, polymer A, alkali-soluble resins, etc.).

[0680] The preferred range of the content of the above residual monomers is the same as the content of the residual monomers that the above photosensitive resin composition layer may contain.

[0681] The resin composition layer is preferably a layer that contains only the components contained in the above resin composition layer.

[0682] Specifically, the resin composition layer of the present invention is, for example, a layer that contains only the components contained in the above photosensitive resin composition layer, thermoplastic resin composition layer, colored resin composition layer, and / or water-soluble resin composition layer.

[0683] Regarding resin composition layers other than the present invention, for example, a resin composition layer that contains components other than the components contained in each of the above resin composition layers in the above photosensitive resin composition layer, thermoplastic resin composition layer, colored resin composition layer, and / or water-soluble resin composition layer can be cited.

[0684] [Cover film]

[0685] The transfer film preferably has a cover film that contacts the surface of each composition layer that does not face the temporary support.

[0686] Hereinafter, in this specification, the surface of the composition layer facing the temporary support is also referred to as the "first surface", and the surface on the side opposite to the first surface is also referred to as the "second surface".

[0687] Examples of the material constituting the covering film include a resin film and paper. From the viewpoints of strength and flexibility, a resin film is preferred.

[0688] 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. Among them, a polyethylene film, a polypropylene film, or a polyethylene terephthalate film is preferred.

[0689] The thickness of the covering film is not particularly limited, and is preferably 5 to 100 μm, more preferably 10 to 50 μm.

[0690] Furthermore, from the viewpoint of more excellent resolution, the arithmetic mean roughness Ra value of the surface of the covering film in contact with each resin composition layer (hereinafter, also simply referred to as the "covering film surface") is preferably 0.3 μm or less, more preferably 0.1 μm or less, and further preferably 0.05 μm or less. It is considered that this is because the uniformity of the layer thickness of the resin pattern formed by the Ra value of the covering film surface being within the above range is improved.

[0691] The lower limit of the Ra value of the covering film surface is not particularly limited, but is preferably 0.001 μm or more.

[0692] The Ra value of the covering film surface can be measured by the following method.

[0693] Using a three-dimensional optical profiler (New View7300, manufactured by Zygo Corporation), measure the surface of the covering film under the following conditions to obtain the surface profile of the optical film.

[0694] As the measurement and analysis software, use the Microscope Application of MetroPro ver8.3.2. Then, display the Surface Map screen using the above analysis software, and obtain histogram data in the Surface Map screen. Calculate the arithmetic mean roughness based on the obtained histogram data to obtain the Ra value of the covering film surface.

[0695] When the covering film is adhered to the transfer film, it is only necessary to peel off the covering film from the transfer film and measure the Ra value of the surface on the peeled side.

[0696] [Method for manufacturing transfer film]

[0697] The manufacturing method of the transfer film is not particularly limited, and known manufacturing methods can be used, such as known methods for forming each resin composition layer.

[0698] Hereinafter, with reference to Figure 1 , the manufacturing method of the transfer film will be described. However, the transfer film is not limited to the transfer film having the structure shown in Figure 1 .

[0699] Figure 1 is a schematic diagram showing an example of the structure of the transfer film. Figure 1 The transfer film 100 shown in

[0700] 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 sequence.

[0701] As the intermediate layer, an oxygen barrier layer having an oxygen barrier function described as a "separation layer" in Japanese Patent Laid-Open No. 5-072724 can be cited. If the intermediate layer is an oxygen barrier layer, the sensitivity during exposure is improved, the time load on the exposure machine is reduced, and the productivity is improved, so it is preferred.

[0702] Regarding the oxygen barrier layer that can be used as the intermediate layer, it can be appropriately selected from known layers described in the above-mentioned gazettes and the like. Among them, an oxygen barrier layer that exhibits low oxygen permeability and is dispersed or dissolved in water or an aqueous alkali solution (1% by mass aqueous sodium carbonate solution at 22°C) is preferred.

[0703] The intermediate layer and the resin composition capable of forming the intermediate layer will be described in detail in the latter part.

[0704] As a manufacturing method of the above-mentioned transfer film 100, for example, a method including the following steps can be cited: a step of forming a thermoplastic resin composition layer 12 by coating a thermoplastic resin composition on the surface of the temporary support 10 and then drying the coating film of the thermoplastic resin composition; a step of forming an intermediate layer 14 by coating an intermediate layer-forming resin composition on the surface of the thermoplastic resin composition layer 12 and then drying the coating film of the intermediate layer-forming resin composition; and a step of forming a photosensitive resin composition layer 16 by coating a photosensitive resin composition on the surface of the intermediate layer 14 and then drying the coating film of the photosensitive resin composition.

[0705] The thermoplastic resin composition is a composition for forming the above-mentioned thermoplastic resin composition layer and can contain the above various components. A solvent can be contained in the thermoplastic resin composition to improve coatability.

[0706] The photosensitive resin composition is a composition for forming the above photosensitive resin composition and may contain the various components described above. A solvent may be included in the photosensitive resin composition to improve coatability.

[0707] The transfer film 100 is manufactured by pressing the cover film 18 against the photosensitive resin composition layer 16 of the laminate manufactured by the above manufacturing method.

[0708] As a method for manufacturing the transfer film of the present invention, it is preferable to manufacture the transfer film 100 including the temporary support 10, the thermoplastic resin composition layer 12, the intermediate layer 14, the photosensitive resin composition layer 16, and the cover film 18 by including a step of disposing the cover film 18 in contact with the second surface of the photosensitive resin composition layer 16.

[0709] After manufacturing the transfer film 100 by the above manufacturing method, the transfer film 100 is wound, whereby a transfer film in the form of a roll can be produced and stored. Regarding the transfer film in the form of a roll, it can be provided in its original form in the bonding step with the substrate in the roll-to-roll method described later.

[0710] In the above manufacturing method, both the thermoplastic resin composition layer and the photosensitive resin composition layer are resin composition layers of the present invention, but as long as at least one of these is a resin composition layer of the present invention, one can 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).

[0711] Similarly, in the transfer film 1(0(0, as long as at least one of the thermoplastic resin composition layer 12 and the photosensitive resin composition layer 16 is a resin composition layer of the present invention, the other one can be a resin composition layer other than the present invention.

[0712] 〔Intermediate layer〕

[0713] As the intermediate layer, a water-soluble resin composition layer is preferable.

[0714] The embodiments of the water-soluble resin composition layer are as described above.

[0715] 〔Refractive index adjustment layer〕

[0716] The transfer film may have a refractive index adjustment layer.

[0717] The position of the refractive index adjustment layer is not particularly limited, and it is preferably disposed in contact with each resin composition layer. Among them, it is preferable that the transfer film sequentially has a temporary support, a photosensitive resin composition layer or a thermoplastic resin composition layer, and a refractive index adjustment layer.

[0718] In addition, when the transfer film further has the above-mentioned covering film, it preferably has a temporary support, a photosensitive resin composition layer or a thermoplastic resin composition layer, a refractive index adjustment layer, and a covering film in this order.

[0719] As the refractive index adjustment layer, a known refractive index adjustment layer can be applied. Examples of the materials contained in the refractive index adjustment layer include resins and particles.

[0720] Examples of the resin include the resins that the above-mentioned resin composition layer may contain, and preferably polymer P and / or a water-soluble resin.

[0721] In addition, in this specification, when the refractive index adjustment layer contains a water-soluble resin, it also corresponds to a water-soluble resin composition layer.

[0722] Examples of the particles include zirconia particles (ZrO 2 particles), niobium oxide particles (Nh 2 O 5 particles), titanium oxide particles (TiO 2 particles), and silica particles (SiO 2 particles).

[0723] In addition, the refractive index adjustment layer preferably contains a metal oxidation inhibitor. By including a metal oxidation inhibitor in the refractive index adjustment layer, oxidation of the metal in contact with the refractive index adjustment layer can be inhibited.

[0724] Examples of the metal oxidation inhibitor preferably include compounds having an aromatic ring containing a nitrogen atom in the molecule. Examples of the metal oxidation inhibitor include imidazole, benzimidazole, tetrazole, mercaptothiadiazole, and benzotriazole.

[0725] The refractive index of the refractive index adjustment layer is preferably 1.60 or more, more preferably 1.63 or more.

[0726] The upper limit of the refractive index of the refractive index adjustment layer is preferably 2.10 or less, more preferably 1.85 or less.

[0727] The thickness of the refractive index adjustment layer is preferably 500 nm or less, more preferably 110 nm or less, and further preferably 100 nm or less. The lower limit is not particularly limited, and preferably 20 nm or more, more preferably 50 nm or more.

[0728] The thickness of the refractive index adjustment layer is the average value calculated by measuring any five places through cross-sectional observation based on a scanning electron microscope (SEM).

[0729] As the refractive index adjustment layer, a publicly known refractive index adjustment layer can be used. For example, the second resin layer disclosed in paragraphs

[0200] to

[0214] of Japanese Unexamined Patent Application Publication No. 2020-091322 can be cited.

[0730] An example of an embodiment of the transfer film is shown below.

[0731] In the following respective structures, one or more layers (such as a cover film) can be removed as needed, or additional layers can be added between any layers.

[0732] (1) "Temporary support / thermoplastic resin composition layer / intermediate layer (water-soluble resin composition layer) / photosensitive resin composition layer / cover film"

[0733] (2) "Temporary support / thermoplastic resin composition layer / intermediate layer (water-soluble resin composition layer) / colored resin composition layer / cover film"

[0734] (3) "Temporary support / thermoplastic resin composition layer / refractive index adjustment layer (water-soluble resin composition layer) / cover film"

[0735] (4) "Temporary support / photosensitive resin composition layer / cover film"

[0736] In the resin composition layers (layers other than the temporary support and the cover film) of the transfer film constituting the above respective structures, at least one of the thermoplastic resin layer and the photosensitive resin composition layer is the resin composition layer of the present invention.

[0737] In the above respective structures, the photosensitive resin composition layer is also preferably a colored resin composition layer.

[0738] [Method for manufacturing a laminate and method for manufacturing circuit wiring]

[0739] The present invention also relates to a method for manufacturing a laminate.

[0740] Regarding the method for manufacturing a laminate, as long as it is a method for manufacturing a laminate using the above transfer film, there is no particular limitation.

[0741] As a method for manufacturing a laminate, a method including the following steps is preferably used: It includes: a lamination step (hereinafter also referred to as the "lamination step").), bringing a substrate (preferably a conductive substrate) into contact with the surface on the side opposite to the temporary support of the transfer film (the surface of the composition layer), laminating the transfer film and the substrate (preferably a conductive substrate), thereby obtaining a substrate with a transfer film; an exposure step (hereinafter also referred to as the "exposure step").), performing pattern exposure on the resin composition layer; and a development step (hereinafter also referred to as the "development step").), developing the exposed resin composition layer to form a resin pattern; and a peeling step (hereinafter also referred to as the "peeling step").), which is between the lamination step and the exposure step or between the exposure step and the development step, and peeling the temporary support from the substrate with the transfer film.

[0742] In addition, the resin composition layer subjected to the above pattern exposure may include a single layer or two or more layers, and at least one layer constituting the resin composition layer is the resin composition layer of the present invention.

[0743] Moreover, the resin composition layer subjected to the above pattern exposure preferably includes at least one photosensitive resin composition layer (the photosensitive resin composition layer of the present invention or a photosensitive resin composition layer other than the present invention). The above photosensitive resin composition layer may become a colored resin composition layer.

[0744] Regarding the method for manufacturing circuit wiring, there is no particular limitation as long as it is a method for manufacturing circuit wiring using the above transfer film.

[0745] As a method for manufacturing circuit wiring, a method including the following steps is preferably used: In a laminate in which a substrate, a conductive layer (the conductive layer of the substrate), and a resin pattern manufactured using the above transfer film are sequentially laminated, an etching process (hereinafter also referred to as the "etching process").) for etching the conductive layer in the region where the resin pattern is not disposed.

[0746] That is, the method for manufacturing circuit wiring is preferably a method including the following steps: It includes: a lamination step (hereinafter also referred to as the "lamination step").), bringing a substrate with a conductive layer into contact with the surface on the side opposite to the temporary support of the transfer film (the composition layer), laminating the transfer film and the substrate with the conductive layer, thereby obtaining a substrate with a transfer film; an exposure step (hereinafter also referred to as the "exposure step").), performing pattern exposure on the resin composition layer; a development step (hereinafter also referred to as the "development step").), developing the exposed resin composition layer to form a resin pattern; and an etching process (hereinafter also referred to as the "etching process") for etching the conductive layer in the region where the resin pattern is not disposed; and a peeling step (hereinafter also referred to as the "peeling step").), which is between the lamination step and the exposure step or between the exposure step and the development step, and peeling the temporary support from the substrate with the transfer film.

[0747] The preferred form of the resin composition layer for the above-described pattern exposure is also the same as above.

[0748] Hereinafter, each step included in the method for manufacturing a laminate and the method for manufacturing circuit wiring will be described. However, unless otherwise specifically mentioned, the content described for each step included in the method for manufacturing a laminate is also applied to each step included in the method for manufacturing circuit wiring.

[0749] 〔Laminating step〕

[0750] The method for manufacturing a laminate preferably includes a laminating step.

[0751] In the laminating step, it is preferable to bring the substrate (when there is a conductive layer provided on the surface of the substrate, it is the conductive layer) into contact with the surface on the side opposite to the temporary support of the transfer film, and press the transfer film and the substrate. In the above-described embodiment, since 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 a resin pattern formed after exposure and development.

[0752] In addition, when the transfer film has a cover film, it is only necessary to remove the cover film from the surface of the transfer film and then perform lamination.

[0753] As a method for pressing the substrate and the transfer film, there is no particular limitation, and known transfer methods and lamination methods can be used.

[0754] For the lamination of the transfer film and the substrate, it 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 using a method such as a roller. In the lamination, known laminators such as a laminator, a vacuum laminator, and an automatic cutting laminator that can further improve productivity can be used.

[0755] The method for manufacturing a laminate and the method for manufacturing circuit wiring including the laminating step are preferably performed by a roll-to-roll method.

[0756] The roll-to-roll method refers to the following method, which includes: using a substrate that can be wound and unwound as the substrate, and an unwinding step (hereinafter, also referred to as the "unwinding step") of unwinding the substrate or a structure including the substrate before any step included in the method for manufacturing a laminate or the method for manufacturing circuit wiring; and a winding step (hereinafter, also referred to as the "winding step") of winding the substrate or a structure including the substrate after any step, and performing at least any step (preferably all steps or all steps except the heating step) while conveying the substrate or a structure including the substrate.

[0757] As the unwinding method in the unwinding process and the winding method in the winding process, there is no particular limitation, and as long as it is a manufacturing method using the roll-to-roll method, a known method can be used.

[0758] <Substrate>

[0759] As the substrate for forming the resin pattern using the transfer film of the present invention, any known substrate can be used, but a substrate having a conductive layer is preferred, and more preferably a substrate having a conductive layer on the surface of the base material.

[0760] As needed, the substrate may have any layer other than the conductive layer.

[0761] Examples of the base material constituting the substrate include glass, silicon, and thin films.

[0762] The base material constituting the substrate is preferably transparent. In this specification, "transparent" means that the transmittance of light with a wavelength of 400 to 700 nm is 80% or more.

[0763] Moreover, the refractive index of the base material constituting the substrate is preferably 1.50 to 1.52.

[0764] Examples of the transparent glass base material include tempered glass represented by Gorilla Glass of Corning Incorporated. Moreover, as the transparent glass base material, the materials used in JP-A-2010-086684, JP-A-2010-152809, and JP-A-2010-257492 can be used.

[0765] In the case of using a thin film base material as the base material, a thin film base material with low optical distortion and / or high transparency is preferably used. Examples of such a thin film base material include polyethylene terephthalate (PET), polyethylene naphthalate, polycarbonate, triacetyl cellulose, and cycloolefin polymer.

[0766] As the base material of the substrate, in the case of manufacturing by the roll-to-roll method, a thin film base material is preferred. Moreover, in the case of manufacturing circuit wiring for a touch panel by the roll-to-roll method, the base material is preferably a sheet-like resin composition.

[0767] Examples of the conductive layer included in the substrate include the conductive layers used in general circuit wiring and touch panel wiring.

[0768] As the conductive layer, from the viewpoints of conductivity and fine line formability, at least one layer selected from a metal layer, a conductive metal oxide layer, a graphene layer, a carbon nanotube layer, and a conductive polymer layer is preferred, a metal layer is more preferred, and a copper layer or a silver layer is further preferred.

[0769] The substrate may have a single conductive layer or two or more conductive layers. In the case of having two or more conductive layers, it is preferable to have conductive layers of different materials.

[0770] Examples of the material for the conductive layer include metals and conductive metal oxides.

[0771] Examples of the metal include Al, Zn, Cu, Fe, Ni, Cr, Mo, Ag, and Au.

[0772] Examples of the conductive metal oxide include ITO (Indium Tin Oxide), IZO (Indium Zinc Oxide), and SiO 2 。

[0773] In addition, in this specification, "conductive" means that the volume resistivity is less than 1×10 6 Ωcm. The volume resistivity of the conductive metal oxide is preferably less than 1×10 4 Qcm.

[0774] When manufacturing a resin pattern using a substrate having a plurality of conductive layers, at least one of the plurality of conductive layers preferably contains a conductive metal oxide.

[0775] As the conductive layer, it is preferably an electrode pattern corresponding to a sensor of a visual recognition unit or a wiring of a peripheral extraction unit used in a capacitive touch panel.

[0776] 〔Exposure process〕

[0777] The method for manufacturing the laminate preferably includes a step of pattern-exposing the resin composition layer after the above-mentioned lamination step (exposure step).

[0778] There are no particular limitations on the detailed configuration and specific dimensions of the pattern in the pattern exposure. At least a part of the pattern (preferably the electrode pattern of the touch panel and / or the part of the extraction wiring) preferably includes fine lines with a width of 20 μm or less to improve the display quality of a display device (such as a touch panel) having a circuit wiring manufactured by a manufacturing method of a circuit wiring and to reduce the area occupied by the extraction wiring, and more preferably includes fine lines with a width of 10 μm or less.

[0779] Regarding the light source used in the exposure, as long as it is a light source that irradiates light having a wavelength capable of exposing the photosensitive resin composition layer (for example, 365 nm or 405 nm), it can be appropriately selected and used. Specifically, examples include a ultra-high pressure mercury lamp, a high pressure mercury lamp, a metal halide lamp, and an LED (Light Emitting Diode).

[0780] As the exposure amount, it is preferably 5 to 200 mJ / cm 2 , more preferably 10 to 100 mJ / cm 2 .

[0781] [Peeling step]

[0782] The peeling step is a step of peeling the temporary support from the substrate with the resin composition layer between the lamination step and the exposure step or between the exposure step and the development step described later.

[0783] The peeling method is not particularly limited, and a mechanism similar to the cover film peeling mechanism described in paragraphs

[0161] to

[0162] of Japanese Patent Application Laid-Open No. 2010-072589 can be used.

[0784] Therefore, in the exposure step, pattern exposure can be performed after peeling the temporary support from the resin composition layer, or pattern exposure can be performed through the temporary support before peeling the temporary support, and then the temporary support is peeled. Regarding the mask, when the temporary support is peeled before exposure, exposure can be performed in contact with the resin composition layer or in proximity without contact. When exposure is performed without peeling the temporary support, the mask can be exposed in contact with the temporary support or in proximity without contact. To prevent mask contamination caused by contact between the composition layer and the mask and to avoid the influence on exposure caused by foreign matter adhering to the mask, it is preferable to perform pattern exposure without peeling the temporary support. In addition, regarding the exposure method, in the case of contact exposure, the contact exposure method can be appropriately selected and used, and in the case of non-contact exposure, the proximity exposure method, the lens system and mirror system projection exposure method, and the direct exposure method using exposure laser or the like can be appropriately selected and used. In the case of lens system and mirror system projection exposure, an exposure machine with an appropriate lens numerical aperture (NA) can be used according to the required resolution and depth of focus. In the case of the direct exposure method, direct drawing can be performed on the photosensitive resin composition layer, or reduced projection exposure can be performed on the photosensitive resin composition layer through a lens. Moreover, exposure can be performed not only under atmospheric pressure but also under reduced pressure or in a vacuum, and furthermore, exposure can be performed with a liquid such as water interposed between the light source and the resin composition layer.

[0785] [Development step]

[0786] The method for manufacturing the laminate preferably includes a step (development step) of developing the exposed resin composition layer to form a resin pattern after the above exposure step.

[0787] When the resin composition layer includes a photosensitive resin composition layer (the photosensitive resin composition layer of the present invention or a photosensitive resin composition layer other than the present invention), the resin composition layer can be cured according to the exposed pattern to form a cured film (pattern-shaped cured film), and only the unexposed portion of the resin composition layer can be removed using a developer (alkali developer, etc.).

[0788] When the transfer film has a photosensitive resin composition layer and a resin composition layer different from these, the above-mentioned different resin composition layer can remove only the same portion as the portion removed in the photosensitive resin composition layer, or can include the portion other than the portion removed in the photosensitive resin composition layer and be removed entirely.

[0789] For example, when the transfer film has a photosensitive resin composition layer, and a thermoplastic resin composition layer and / or a water-soluble resin composition layer, in the developing step, only the thermoplastic resin composition layer and / or the water-soluble resin composition layer in the unexposed portion can be removed together with the photosensitive resin composition layer in the unexposed portion. And, in the developing step, the thermoplastic resin composition layer and / or the water-soluble resin composition layer in both the exposed portion and the unexposed portion can be removed in a form dissolved or dispersed in the developer.

[0790] In the resin pattern obtained after development, a part or all of it can be a layer formed by changes such as curing reaction of the resin composition layer of the present invention. For example, when the resin composition layer of the transfer film includes the photosensitive resin composition layer of the present invention, a part or all of the resin pattern is a material formed by the curing reaction of the photosensitive resin composition layer of the present invention.

[0791] And, in the resin pattern obtained after development, it may not include a layer formed by changes such as curing reaction of the resin composition layer of the present invention. That is, the resin pattern obtained after development may only include a resin composition layer other than the present invention and / or a layer formed by changes such as curing reaction of a resin composition other than the present invention.

[0792] The development of the exposed resin composition layer in the developing step can be carried out using an alkali developer.

[0793] As the alkali developer, for example, a known developer such as the developer described in Japanese Patent Laid-Open No. 5-072724 can be used.

[0794] As the alkali developer, an alkaline aqueous solution developer containing a compound with a pKa of 7 to 13 at a concentration of 0.05 to 5 mol / L (liter) is preferably used. The alkali developer may contain a water-soluble organic solvent and / or a surfactant. As the alkali developer, the developer described in paragraph

[0194] of International Publication No. 2015 / 093271 is also preferably used. The content of the organic solvent in the alkali developer is preferably 0% by mass or more and less than 90% by mass relative to the total mass of the developer.

[0795] As the developing method, there is no particular limitation, and it may be any one of spin immersion development, spray development, spray and rotation development, and dip development. Spray development refers to a developing process in which a developer is sprayed onto the exposed resin composition layer by spraying to remove the unexposed portion.

[0796] After the developing step, it is preferable to remove the developing residue while spraying a cleaning agent by spraying and wiping with a brush.

[0797] The liquid temperature of the developer is not particularly limited, but is preferably 20 to 40°C.

[0798] 〔Etching step〕

[0799] The method for manufacturing a circuit wiring preferably includes the following step: in a laminate in which a substrate, a conductive layer (the conductive layer of the substrate), and a resin pattern (more preferably a resin pattern manufactured by the manufacturing method including the above-mentioned lamination step, the above-mentioned exposure step, and the above-mentioned developing step) are laminated in sequence, an etching step of etching the conductive layer in the region where the resin pattern is not disposed.

[0800] In the etching step, the resin pattern formed by the resin composition layer is used as an etching resist, and the etching treatment of the conductive layer is performed.

[0801] As the method of the etching treatment, a known method can be applied. For example, the methods described in paragraphs

[0209] to

[0210] of Japanese Patent Application Laid-Open No. 2017-120435, the methods described in paragraphs

[0048] to

[0054] of Japanese Patent Application Laid-Open No. 2010-152155, a wet etching method of immersing in an etching solution, and a dry etching method such as plasma etching can be cited.

[0802] Regarding the etching solution used in the wet etching, an acidic or alkaline etching solution can be appropriately selected according to the etching object.

[0803] As the acidic etching solution, for example, an aqueous solution containing only acidic components selected from hydrochloric acid, sulfuric acid, nitric acid, acetic acid, hydrofluoric acid, oxalic acid, and phosphoric acid, and a mixed aqueous solution of acidic components and a salt selected from ferric chloride, ammonium fluoride, and potassium permanganate can be cited. The acidic component may be a component formed by combining a plurality of acidic components.

[0804] As the alkaline etching solution, an aqueous solution containing only alkaline components selected from sodium hydroxide, potassium hydroxide, ammonia, organic amines, and salts of organic amines (such as tetramethylammonium hydroxide), and a mixed aqueous solution of alkaline components and a salt (such as potassium permanganate) can be cited. The alkaline component may be a component formed by combining a plurality of alkaline components.

[0805] 〔Removal process〕

[0806] In the method for manufacturing a circuit wiring, it is preferable to perform a process of removing the remaining resin pattern (removal process).

[0807] The removal process is not particularly limited and can be performed as needed, but it is preferably performed after the etching process.

[0808] As a method for removing the remaining resin pattern, there is no particular limitation, but a method of removing by chemical treatment can be cited, and a method of removing using a removal liquid is preferably used.

[0809] As a method for removing the resin composition layer, a method of immersing a substrate having a remaining resin pattern in a stirred removal liquid at a liquid temperature preferably of 30 to 80°C, more preferably 50 to 80°C, for 1 to 30 minutes can be cited.

[0810] As the removal liquid, for example, a removal liquid obtained by dissolving an inorganic basic component or an organic basic component in water, dimethyl sulfoxide, N-methylpyrrolidone, or a mixed solution thereof can be cited. As the inorganic basic component, for example, sodium hydroxide and potassium hydroxide can be cited. As the organic basic component, primary amine compounds, secondary amine compounds, tertiary amine compounds, and quaternary ammonium salt compounds can be cited.

[0811] Moreover, a removal liquid can be used, and it can be removed by a known method such as a spraying method, a spraying method, and a spin coating immersion method.

[0812] 〔Other processes〕

[0813] The method for manufacturing a circuit wiring may include any process (other processes) other than the above-described processes. For example, the following processes can be cited, but are not limited to these processes.

[0814] Moreover, as the exposure process, development process, and other processes that can be applied in the method for manufacturing a circuit wiring, the processes described in paragraphs

[0035] to

[0051] of Japanese Patent Application Laid-Open No. 2006-023696 can be cited.

[0815] <Cover film peeling process>

[0816] When the transfer film has a cover film, the method for manufacturing a laminate and the method for manufacturing a circuit wiring preferably include a process of peeling the cover film from the transfer film. The method for peeling the cover film is not limited, and known methods can be applied.

[0817] <Process for reducing visible light reflectance>

[0818] The method for manufacturing a circuit wiring may include a process of performing a treatment for reducing the visible light reflectance of part or all of a plurality of conductive layers provided on a substrate.

[0819] Examples of the treatment for reducing the visible light reflectance include an oxidation treatment. When the substrate has a conductive layer containing copper, the copper is oxidized to form copper oxide, and the conductive layer is blackened, thereby reducing the visible light reflectance of the conductive layer.

[0820] Regarding the treatment for reducing the visible light reflectance, it is described in paragraphs

[0017] to

[0025] of Japanese Patent Laid-Open No. 2014-150118, paragraphs

[0041] to

[0042] ,

[0048] , and

[0058] of Japanese Patent Laid-Open No. 2013-206315, and the contents described in these publications are incorporated into this specification.

[0821] <Process for forming an insulating film, process for forming a new conductive layer on the surface of the insulating film>

[0822] It is also preferable that the method for manufacturing a circuit wiring includes a process of forming an insulating film on the surface of the circuit wiring and a process of forming a new conductive layer on the surface of the insulating film.

[0823] Through the above processes, a second electrode pattern insulated from the first electrode pattern can be formed.

[0824] As the process for forming the insulating film, there is no particular limitation, and examples include a method for forming a known permanent film. Further, a photosensitive material having insulating properties can be used to form an insulating film having a desired pattern by photolithography.

[0825] The process for forming a new conductive layer on the insulating film is not particularly limited. For example, a photosensitive material having conductivity can be used to form a new conductive layer having a desired pattern by photolithography.

[0826] In the method for manufacturing circuit wiring, it is also preferable to use a substrate having a plurality of conductive layers on each of two surfaces of a base material, and to form circuits on the conductive layers formed on the two surfaces of the base material successively or simultaneously. With this structure, it is possible to form circuit wiring for a touch panel in which a first conductive pattern is formed on one surface of the base material and a second conductive pattern is formed on the other surface. Further, it is also preferable to form circuit wiring for a touch panel having such a structure from both sides of the base material by roll-to-roll method.

[0827] [Use of Circuit Wiring]

[0828] The circuit wiring manufactured by the method for manufacturing circuit wiring can be applied to various devices. As a device including the circuit wiring manufactured by the above-described manufacturing method, for example, an input device can be cited, preferably a touch panel, more preferably a capacitive touch panel. Further, the above-described input device can be applied to display devices such as an organic EL display device and a liquid crystal display device.

[0829] [Method for Manufacturing Electronic Device]

[0830] The present invention also relates to a method for manufacturing an electronic device.

[0831] As the method for manufacturing the above-described electronic device, a method for manufacturing an electronic device using the above-described transfer film is preferable.

[0832] Among them, the method for manufacturing an electronic device preferably includes the method for manufacturing the above-described laminate.

[0833] As the above-described electronic device, for example, an input device or the like can be cited, preferably a touch panel. Further, the above-described input device can be applied to display devices such as an organic electroluminescence display device and a liquid crystal display device.

[0834] As a method for manufacturing a touch panel, a method including the following steps is also preferable: in a laminate in which a substrate, a conductive layer (conductive layer provided on the substrate), and a resin pattern manufactured using the above-described transfer film are laminated in this order, an etching process is performed on the conductive layer in a region where the resin pattern is not disposed, thereby forming wiring for a touch panel. More preferably, a method using a resin pattern manufactured by a manufacturing method including the above-described laminating step, the above-described exposure step, and the above-described development step is used.

[0835] Regarding the specific embodiments of each step and the order of performing each step in the method for manufacturing a touch panel including the step of forming wiring for a touch panel, as described in the above item “Method for Manufacturing Circuit Wiring”, the preferred embodiments are also the same.

[0836] Further, the method for manufacturing a touch panel including the step of forming wiring for a touch panel may include any step (other steps) other than the above.

[0837] As a method for forming wirings for a touch panel, the method described in International Publication No. 2016 / 190405 can also be referred to. Figure 1 The method described in

[0838] By the above manufacturing method of the touch panel, a touch panel having at least wirings for a touch panel can be manufactured. Preferably, the touch panel has a transparent substrate, electrodes, and an insulating layer or a protective layer.

[0839] As a detection method in the touch panel, known methods such as a resistive film method, a capacitive method, an ultrasonic method, an electromagnetic induction method, and an optical method can be cited. Among them, the capacitive method is preferred.

[0840] As the touch panel, there can be cited a so-called in-cell type (for example, the touch panels described in FIGS. 5, 6, 7, and 8 of Japanese Patent Application Laid-Open No. 2012-517051), a so-called on-cell type (for example, the touch panel described in FIG. 19 of Japanese Patent Application Laid-Open No. 2013-168125, and Figure 1 the touch panel described in FIGS. 5 of Japanese Patent Application Laid-Open No. 2012-89102), an OGS (One Glass Solution) type, a TOL (Touch-on-Lens) type (for example, the touch panel described in FIG. 2 of Japanese Patent Application Laid-Open No. 2013-54727), various external attachment types (so-called GG, G1·G2, GFF, GF2, GF1, and G1F, etc.), and other structures (for example, the touch panel described in FIG. 6 of Japanese Patent Application Laid-Open No. 2013-164871).

[0841] As the touch panel, for example, the touch panel described in paragraph

[0229] of Japanese Patent Application Laid-Open No. 2017-120345 can be cited.

[0842] Examples

[0843] Hereinafter, the present invention will be described in further detail based on examples. The materials, amounts used, ratios, processing contents, processing steps, etc. shown in the following examples can be appropriately changed as long as they do not depart from the gist of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the examples shown below.

[0844] In the following examples, unless otherwise specified, "parts" and "%" respectively refer to "parts by mass" and "% by mass".

[0845] [Synthesis]

[0846] [Compound (1)]

[0847] <Compound A-1>[[]] ​

[0848] Compound A-1 was synthesized according to Synthesis Example 5 in Paragraph

[0139] of International Publication No. 2011 / 152126. The average number of moles of propylene oxide added to the obtained Compound A-1 was 5.

[0849] <Compound A-2>

[0850] Compound A-2 was synthesized according to Example 3 in Paragraph

[0033] of CN102911353. The average number of moles of propylene oxide added to the obtained Compound A-2 was 3.

[0851] Hereinafter, the structures of the above-obtained Compounds A-1 to A-2 are shown.

[0852] [Chemical Formula 16]

[0853]

[0854] 〔Block copolymer〕

[0855] <Block copolymer B-1>

[0856] Block copolymer B-1 was synthesized according to Journal of Polymer Reseach, 2018, 25(7), 1-7.

[0857] As synthesis raw materials, 1H, 1H, 2H, 2H-nonafluorohexyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.), polyethylene glycol monoacrylate (BLEMMER AE-400 (average number of moles of polyethylene glycol added was 10, manufactured by NOF CORPORATION)), methyl-2-bromo-2-methylpropionate (manufactured by Tokyo Chemical Industry Co., Ltd.), 2,2'-bipyridine (manufactured by FUJTFILM Wako Pure Chemical Corporation), copper bromide (manufactured by FUJIFILM Wako Pure Chemical Corporation) and PGMEA (propylene glycol monomethyl ether acetate, manufactured by FUJIFILM Wako Pure Chemical Corporation) were used for synthesis. The obtained solid was diluted with PGMEA to obtain a PGMEA solution of block copolymer B-1 (solid component concentration: 20% by mass).

[0858] In the present specification, the "solid component" means all components other than the solvent. And, if it is a component other than the solvent, a liquid component is also regarded as a solid component.

[0859] <Block copolymer B-2>

[0860] As a synthetic raw material, except that 1H,1H,2H,2H-nonafluorohexyl acrylate was changed to 1H,1H,2H,2H-nonafluorohexyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.), and polyethylene glycol monoacrylate (BLEMMER AE-400 (average added mole number of polyethylene glycol is 10, manufactured by NOF CORPORATION)) was changed to polyethylene glycol monoacrylate (BLEMMER AF-200 (average added mole number of polyethylene glycol is 4.5, manufactured by NOF CORPORATION)), a PGMEA solution (solid content concentration: 20% by mass) of block copolymer B-2 was obtained in the same manner as the above <block copolymer B-1>.

[0861] <Block copolymer B-3>

[0862] As a synthetic raw material, except that 1H,1H,2H,2H-nonafluorohexyl acrylate was changed to 1,1,1,3,3,3-hexafluoroisopropyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.), a PGMEA solution (solid content concentration: 20% by mass) of block copolymer B-3 was obtained in the same manner as the above <block copolymer B-1>.

[0863] 〔Compound R-1 for comparison〕

[0864] Into a 300 mL three-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen inlet tube, cyclohexanone (manufactured by FUJIFILM Wako Pure Chemical Corporation) (25.0 g) was added, and the temperature was raised to 80 °C. Then, a mixed solution containing 1H,1H,2H,2H-nonafluorohexyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) (35.5 g, 111.8 mmol), BLEMMER AE-400 (n≈10, manufactured by NOF CORPORATION) (60.5 g, 111.8 mmol), cyclohexanone (25.0 g), and polymerization initiator V-601 (manufactured by FUJIFILM Wako Pure Chemical Corporation) (0.342 g) was added dropwise at a constant rate so that the addition was completed within 180 minutes. After completion of the addition, stirring was continued for 1 hour. After adding a solution containing V-601 (0.342 g) and cyclohexanone (1.00 g), the temperature was immediately raised to 93 °C, and stirring was further continued for 2 hours. After obtaining a solid by reprecipitation treatment, the obtained solid was diluted with PGMEA to obtain a PGMEA solution (120 g, solid content concentration: 20% by mass) of comparative compound R-1 (random copolymer).

[0865] The structures of the block copolymer and the comparative compound obtained above are as described below. In addition, the numerical values of the structural units incorporated into the copolymer represent the content (mass %) of each structural unit relative to the total mass of each copolymer.

[0866] [Chemical formula 17]

[0867]

[0868] [Chemical formula 18]

[0869]

[0870] In addition, Megaface F444, F551, F552, and F555 (all manufactured by DIC CORPORATION) are comparative compounds that are neither equivalent to the block copolymer nor equivalent to compound (1).

[0871] The weight-average molecular weight (Mw), number-average molecular weight (Mn), and dispersity (Mw / Mn) of each block copolymer are as shown below. In addition, the weight-average molecular weight (Mw) of the copolymer was calculated in terms of polystyrene by GPC (gel permeation chromatography (EcoSEC HLC-8320GPC (manufactured by TOSOH CORPORATION))) under the measurement conditions of THF eluent, a flow rate of 0.35 ml / min, and a temperature of 40°C. As the columns used, TSKgel SuperHZM-H, TSKgel SuperHZ4000, and TSKgel SuperHZ200 (manufactured by TOSOH CORPORATION) were used in series.

[0872] [Table 1]

[0873]

[0874] [Resin]

[0875] In the following synthesis examples, each description is shown below.

[0876] · St: Styrene (manufactured by FUJIFILM Wako Pure Chemical Corporation)

[0877] · MAA: Methacrylic acid (manufactured by FUJIFILM Wako Pure Chemical Corporation)

[0878] · MMA: Methyl methacrylate (manufactured by FUJIFILM Wako Pure Chemical Corporation)

[0879] · BzMA: Benzyl methacrylate (manufactured by FUjIFILM Wako Pure Chemical Corporation)

[0880] · AA: Acrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0881] · MAA-GMA: Methacrylic acid glycidyl methacrylate adduct

[0882] · CHMA: Cyclohexyl methacrylate (manufactured by MITSUBISHI GAS CHEMICAL COMPANY, INC.)

[0883] · AMA: Allyl methacrylate (manufactured by FUJIFILM Wako Pure Chemical Corporation)

[0884] · PGMEA: Propylene glycol monomethyl ether acetate (manufactured by SHOWA DENKO K.K.)

[0885] · MEK: Methyl ethyl ketone (manufactured by SANKYO CHEMICAL Co., Ltd.)

[0886] · V - 601: Dimethyl - 2,2’ - azobis(2 - methylpropionate) (manufactured by FUJIFILM Wako Pure Chemical Corporation)

[0887] · ATHF: Tetrahydrofuran - 2 - yl acrylate (synthetic product)

[0888] · EA: Ethyl acrylate (manufactured by FUJIFILM Wako Pure Chemical Corporation)

[0889] · CHA: Cyclohexyl acrylate (manufactured by FUJIFILM Wako Pure Chemical Corporation)

[0890] · PMPMA: 1,2,2,6,6 - Pentamethyl - 4 - piperidyl methacrylate (manufactured by FUJIFILM Wako Pure Chemical Corporation)

[0891] <Resin P - 1>

[0892] PGMEA (116.5 parts) was placed in a three - necked flask and heated 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 dropwise to the solution in the above flask maintained at 90 °C ± 2 °C over 2 hours. After the addition was completed, the solution in the above flask was stirred at 90 °C ± 2 °C for 2 hours, thereby obtaining a solution containing Resin P - 1 (solid component concentration: 30.0 mass%).

[0893] <Resins P - 2 to P - 4>

[0894] Except for changing the types of monomers used, etc. as shown in Table 2, solutions containing any one of Resins P - 2 to P - 4 (all solutions had a solid component concentration of 30.0 mass%) were obtained in the same procedure as the above <Synthesis of Resin P - 1>.

[0895] <Resins P - 5 to P - 6>

[0896] Propylene glycol monomethyl ether acetate (60 g, manufactured by FUJIFILM Wako Pure Chemical Corporation) and propylene glycol monomethyl ether (240 g, manufactured by FUJIFILM Wako Pure Chemical Corporation) were added to a 2000 mL flask. The resulting liquid was stirred at a stirring speed of 250 rpm (rpm: round per minute), and at the same time, it was heated to 90 °C.

[0897] For the preparation of the dropping solution (1), methacrylic acid (107.1 g, manufactured by MITSUBISHI RAYON CO., LTD., product name: Acryester M), methyl methacrylate (5.46 g, manufactured by MITSUBISHI GAS CHEMICAL COMPANY, INC., product name: MMA), and cyclohexyl methacrylate (231.42 g, manufactured by MITSUBISHI GAS CHEMICAL COMPANY, INC., product name: CHMA) were mixed and diluted with propylene glycol monomethyl ether acetate (60.0 g), thereby obtaining the dropping solution (1).

[0898] For the preparation of the dropping solution (2), 2,2'-azobis(2-methylpropionate) dimethyl (9.637 g, manufactured by FUJIFILM Wako Pure Chemical Corporation, product name: V-601) was dissolved in propylene glycol monomethyl ether acetate (136.56 g), thereby obtaining the dropping solution (2).

[0899] The dropping solution (1) and the dropping solution (2) were simultaneously dropped into the above-mentioned 2000 mL flask (specifically, a 2000 mL flask containing a liquid heated to 90 °C) over 3 hours. After the dropping was completed, V-601 (2.401 g) was added to the above flask 3 times at 1-hour intervals. Then, it was further stirred at 90 °C for 3 hours.

[0900] Then, the solution (reaction solution) obtained in the above flask was diluted with propylene glycol monomethyl ether acetate (178.66 g). Next, tetraethylammonium bromide (1.8 g, manufactured by FUJIFILM Wako Pure Chemical Corporation) and hydroquinone monomethyl ether (0.8 g, manufactured by FUJIFILM Wako Pure Chemical Corporation) were added to the reaction solution. Then, the temperature of the reaction solution was raised to 100 °C.

[0901] Next, glycidyl methacrylate (76.03 g, manufactured by NOF CORPORATION, product name: BLEMMER G) was added dropwise to the reaction solution over 1 hour. The above reaction solution was reacted at 100 °C for 6 hours to obtain 1158 g of a solution of resin P-5 (solid content concentration: 36.3 mass%). The weight-average molecular weight of the obtained resin P-5 was 27,000, the number-average molecular weight was 15,000, and the acid value was 95 mgKOH / g.

[0902] Resin P-6 was synthesized with reference to the synthesis method of resin P-5.

[0903] <Resin P-7>

[0904] Propylene glycol monomethyl ether (270.0 g) was added to a three-necked flask, and the temperature was raised to 70 °C under a nitrogen stream while stirring.

[0905] On the other hand, an allyl methacrylate (45.6 g, manufactured by FUJIFILM Wako Pure Chemical Corporation) and methacrylic acid (14.4 g) were dissolved in propylene glycol monomethyl ether (270.0 g), and V-65 (3.94 g, manufactured by FUJIFILM Wako Pure Chemical Corporation) was further dissolved to prepare a dropping solution, which was added dropwise to the above flask over 2.5 hours. The mixture was stirred as it was for 2.0 hours for reaction. Then, the temperature of the content in the above flask was returned to room temperature, and the content in the above flask was added dropwise to 2.7 L of ion-exchanged water under stirring to perform reprecipitation, thereby obtaining a suspension. The suspension was filtered with a suction filter (Buchner funnel) with filter paper, and the filtrate was further washed with ion-exchanged water to obtain a wet powder. After drying with blowing air at 45 °C until a constant weight was confirmed, resin P-7 was obtained as a powder with a yield of 70%. The amount of residual monomer in the powder measured by gas chromatography was less than 0.1 mass% relative to the polymer solid content.

[0906] <Resin P-8>

[0907] Acrylic acid (72.1 parts by mass, 1.0 molar equivalent) and hexane (72.1 parts by mass) were added to a three-necked flask and cooled to 20 °C. After dropwise adding camphenesulfonic acid (0.007 parts by mass, 0.03 mmol equivalent) and 2-dihydrofuran (77.9 parts by mass, 1.0 mol equivalent) to the above flask, the contents (reaction solution) of the above flask were stirred at 20 °C ± 2 °C for 1.5 hours, and then the temperature was raised to 35 °C and stirred for 2 hours. After successively packing Kyoward 200 (filter material, aluminum hydroxide powder, manufactured by Kyowa Chemical Industry Co., Ltd.) and Kyoward 1000 (filter material, hydrotalcite-based powder, manufactured by Kyowa Chemical Industry Co., Ltd.) into a suction filter (Buchner funnel), the reaction solution was filtered to obtain a filtrate. After adding hydroquinone monomethyl ether (MEHQ, 0.0012 parts) to the obtained filtrate, concentration under reduced pressure was carried out at 40 °C to obtain acrylic acid tetrahydrofuran-2-yl (ATHF) (140.8 parts) as a colorless oily substance (yield 99.0%).

[0908] PGMEA (75.0 parts) was placed in a three-necked flask and heated to 90 °C under a nitrogen atmosphere. In the solution of the three-necked flask maintained at 90 °C ± 2 °C, a solution obtained by adding the above-obtained ATHF (29.0 parts), MMA (35.0 parts), ethyl acrylate (EA, 30.0 parts), cyclohexyl acrylate (CHA, 5.0 parts), 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate (PMPMA, 1.0 part), V-601 (4.0 parts), and PGMEA (75.0 parts) was added dropwise over 2 hours. After completion of the dropwise addition, stirring was carried out at 90 °C ± 2 °C for 2 hours to obtain a solution containing resin P-8 (solid content concentration: 40.0% by mass).

[0909] Table 2 shows the types and mass ratios of the respective monomers 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 corresponds to a resin (polymer A) having a structural unit with an acid group protected by an acid-decomposable group. In addition, resins P-1 to P-6 and P-8 are all added to the resin composition in the form of a solution, and resin P-7 is added to the resin composition in the form of a powder.

[0910] In addition, the unit of the amount of the monomer in Table 1 represents mass%.

[0911] [Table 2]

[0912] P-1 P-2 P-3 P-4 P-5 P-6 P-7 P-8 St 52.0 32.0 47.7 BzMA 81.0 75.0 MAA 29.0 19.0 28.0 10.0 26.5 19.0 24.0 35.0 MMA 19.0 40.0 2.0 1.3 AA 15.0 MAA - GMA 20.0 32.0 CHMA 51.5 AMA 76.0 ATHF 29.0 EA 30.0 CHA 5.0 PMPMA 1.0 Mw 60,000 40,000 40,000 30,000 27，000 17，000 25,000 30，000

[0913] [Thermal crosslinking compound]

[0914] <Blocked isocyanate compounds Q-1 to Q-2>

[0915] Under a nitrogen stream, methyl ethyl ketoxime (manufactured by Idemitsu Kosan Co., Ltd.) (453 g) was dissolved in methyl ethyl ketone (700 g). Under ice-cooling, 1,3-bis(isocyanatomethyl)cyclohexane (cis, trans isomer mixture, manufactured by Mitsui Chemicals, Inc., Takenate 600) (500 g) was added dropwise to the obtained solution over 1 hour, and the reaction was further carried out for 1 hour after the addition. Then, the temperature of the above solution was raised to 40 °C and the reaction was carried out for 1 hour. The completion of the reaction was confirmed by 1 1H-NMR (Nuclear Magnetic Resonance) and HPLC (High Performance Liquid Chromatography), and a methyl ethyl ketone solution of blocked isocyanate compound Q-1 (solid component concentration: 57.7 mass%) was obtained.

[0916] Furthermore, referring to the synthesis method of blocked isocyanate compound Q-1, a methyl ethyl ketone solution of blocked isocyanate compound Q-2 (solid component concentration: 75.0 mass%) was obtained.

[0917] In addition, blocked isocyanate compounds Q-1 to Q-2 were all added to the resin composition in the form of a solution.

[0918] [Chemical formula 19]

[0919]

[0920] [Examples 1 to 3 and Comparative Examples 1 to 2]

[0921] [Preparation of resin composition]

[0922] Each resin composition was prepared by stirring and mixing the respective components according to Tables 3 to 5.

[0923] In the table, the numerical values for each component in each resin composition represent the addition amounts (parts by mass) of the respective components.

[0924] Furthermore, the resin was added to each resin composition in the form of a solution containing the resin. The numerical values in the table representing the addition amount of the resin are the mass of the "solution containing the resin" added.

[0925] Hereinafter, regarding the components added to the composition in the form contained in the mixed solution, unless otherwise specified, they are assumed to be the same.

[0926] [Table 3]

[0927]

[0928] In Table 3, each component is as follows.

[0929] ·P-4 to P-5: The above alkali-soluble resin

[0930] ·Acrybase FF187: Alkali-soluble thermoplastic resin (solid content concentration: 40% by mass, solvent: PGMEA, manufactured by FUJIKURA KASEI CO., LTD.)

[0931] ·BB-1: Dye, compound with the structure shown below

[0932] [Chemical formula 20]

[0933]

[0934] ·C-1: Photoacid generator, compound with the structure shown below (compound described in paragraph

[0227] of Japanese Patent Application Laid-Open No. 2013-047765 and synthesized according to the method described in paragraph

[0227] .)

[0935] [Chemical formula 21]

[0936]

[0937] ·B-1 to B-3: The above block copolymer

[0938] ·PGMEA: Propylene glycol monomethyl ether acetate (manufactured by SHOWA DENKO K.K.)

[0939] ·MEK: Methyl ethyl ketone (manufactured by SANKYO CHEMICAL Co., Ltd.)

[0940] In addition, in the table, the column of "average film thickness (μm) of the thermoplastic resin composition layer" represents the average film thickness of the thermoplastic resin composition layer formed when testing with the thermoplastic resin composition.

[0941] [Table 4]

[0942]

[0943] In Table 4, each component is as follows.

[0944] ·PVA 4-88LA: KURARAY POVAL4-88LA (water-soluble resin), manufactured by KURARAY CO., LTD

[0945] · PVA 205: KURARAY POVAL205 (water-soluble resin), manufactured by KURARAY CO., LTD

[0946] · Polyvinylpyrrolidone: water-soluble resin, manufactured by NIPPON SHOKUBAI CO., LTD.

[0947] · A-1 to A-2: the above compound (1)

[0948] · Megaface F444: comparative compound, manufactured by DIC CORPORATION

[0949] · Ion-exchanged water

[0950] · Methanol: solvent, manufactured by MITSUBISHI GAS CHEMICAL COMPANY, INC.

[0951] In addition, in the table, the column of "Average film thickness (μm) of the water-soluble resin composition layer" represents the average film thickness of the water-soluble resin composition layer formed when testing with the water-soluble resin composition.

[0952] [Table 5]

[0953]

[0954] In Table 5, each component is as follows.

[0955] · P-1 to P-3: the above alkali-soluble resin

[0956] · BPE-500: 2,2-bis(4-((methacryloyloxy)pentaethoxy)phenyl)propane, manufactured by Shin-NakamuraChomical Co., Ltd.

[0957] · BPE-200: 2,2-bis(4-((methacryloyloxy)diethoxy)phenyl)propane, manufactured by Shin-NakamuraChemical Co., Ltd.

[0958] · M-270: polypropylene glycol diacrylate (n≈12), manufactured by TOAGOSEI CO., LTD.

[0959] · A-TMPT: trimethylolpropane triacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.

[0960] · SR-454: ethoxylated (3) trimethylolpropane triacrylate, manufactured by Arkema

[0961] · SR-502: Ethoxylated (9) trimethylolpropane triacrylate, manufactured by Arkema

[0962] · A-9300-CL1: Caprolactone-modified (meth)acrylate compound, manufactured by Shin-Nakamura Chemical Co., Ltd.

[0963] · B-CIM: 2,2'-Bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, Hampford

[0964] · SB-PI 701: 4,4'-Bis(diethylamino)benzophenone, manufactured by SANYO TRADING CO., LTD.

[0965] · Colorless crystal violet, manufactured by Tokyo Chemical Industry Co., Ltd.

[0966] · Brilliant green, manufactured by Tokyo Chemical Industry Co., Ltd.

[0967] · N-Phenylglycine, manufactured by Tokyo Chemical Industry Co., Ltd.

[0968] · CBT-1: Carboxybenzotriazole, manufactured by JOHOKU CHEMICAL CO., LTD

[0969] · TDP-G: Phenothiazine, manufactured by Kawaguchi Chemical Industry Co., LTD.

[0970] · Irganox245: Hindered phenol antioxidant, manufactured by BASF

[0971] · Aluminum N-nitrosophenylhydroxylamine, manufactured by FUJIFILM Wako Pure Chemical Corporation

[0972] · Phenidone, manufactured by Tokyo Chemical Industry Co., Ltd.

[0973] · B-1 to B-3: The above block copolymer

[0974] · Megaface F552: Comparative compound, manufactured by DIC CORPORATION

[0975] · R-1: The above comparative compound

[0976] ·PGMEA: Propylene glycol monomethyl ether acetate (manufactured by SHOWA DENKO K.K.)

[0977] ·MEK: Methyl ethyl ketone (manufactured by SANKYO CHEMICAL Co., Ltd.)

[0978] In addition, in the table, the column of "average film thickness (μm) of the photosensitive resin composition layer" represents the average film thickness of the photosensitive resin composition layer formed when testing with the photosensitive resin composition.

[0979] [Production of transfer film]

[0980] Using a slit nozzle, the prepared thermoplastic resin composition 1 was coated on a polyethylene terephthalate film with a thickness of 16 μm (temporary support, Lumirror 16KS40 (manufactured by TORAY INDUSTRIES, INC.)) with a width of 1.0 m so that the average film thickness of the dried composition layer became the specified film thickness, and it was passed through a 3 m drying zone set at 80°C and adjusting the intake and exhaust air volumes to make the film surface wind speed 3 m / sec for 60 seconds, thereby obtaining a laminate A having a temporary support and a thermoplastic resin composition layer.

[0981] Next, using a slit nozzle, on the thermoplastic resin composition layer of the obtained laminate A, the coating amount was adjusted so that the average film thickness of the dried water-soluble resin composition layer became the specified film thickness. After coating the water-soluble resin composition 1, it was passed through a 3 m drying zone set at a temperature of 100°C and adjusting the intake and exhaust air volumes to make the film surface wind speed 3 m / sec for 60 seconds, thereby obtaining a laminate B having a water-soluble resin composition layer formed on the above thermoplastic resin composition layer.

[0982] Furthermore, using a slit nozzle, on the water-soluble resin layer of the obtained laminate B, the coating amount was adjusted so that the average film thickness of the dried photosensitive resin composition layer became the specified film thickness. After coating the photosensitive resin composition 1, it was passed through a 3 m drying zone set at a temperature of 80°C and adjusting the intake and exhaust air volumes to make the film surface wind speed 3 m / sec for 60 seconds, thereby obtaining the transfer film of Example 1 having a photosensitive resin composition layer formed on the above water-soluble resin composition layer.

[0983] The obtained transfer film of Example 1 successively has the following resin composition layers: temporary support / thermoplastic resin composition layer (first layer) / water-soluble resin composition layer (second layer) / photosensitive resin composition layer (third layer).

[0984] In Examples 2 to 3 and Comparative Examples 1 to 2, each transfer film was obtained in the same manner as in Example 1, except that the resin composition layers were changed as shown in Table 6.

[0985] 〔Resolution evaluation〕

[0986] A PET substrate with a copper layer was prepared by depositing a 200-nm-thick copper layer on a 100-μm-thick polyethylene terephthalate (PET) film using sputtering.

[0987] After unwinding each of the produced transfer films (Examples 1 to 3 and Comparative Examples 1 to 2), the surface of the outermost photosensitive resin composition layer disposed on the temporary support and the PET substrate with the above copper layer were laminated under lamination conditions of a roll temperature of 100°C, a line pressure of 1.0 MPa, and a line speed of 4.0 m / min, so that the PET substrate with the copper layer was laminated on the transfer film. Then, without peeling the temporary support and via a line and space pattern (duty ratio 1:1, line width 20 μm), exposure was performed under an ultra-high-pressure mercury lamp, and then the temporary support was peeled off and development was carried out. A 1.0% sodium carbonate aqueous solution at 25°C was used for development, and spray development was performed for 30 seconds. When a line and space pattern was formed by the above method, the exposure amount at which the resist line width became 20 μm was set as the most preferable exposure amount.

[0988] An arbitrary 1-cm 2 region of the line and space pattern formed at the optimum exposure amount was observed by a scanning electron microscope (SEM), and the minimum line width analyzed in a state where the resist pattern was not peeled off and no residue was generated was evaluated according to the following evaluation criteria. Evaluation A or B is a range that can be tolerated in practical applications.

[0989] (Evaluation criteria)

[0990] A: The minimum line width is less than 5 μm

[0991] B: The minimum line width is 5 μm or more and less than 7 μm

[0992] C: The minimum line width is 7 μm or more and less than 9 μm

[0993] D: The minimum line width is 9 μm or more and less than 11 μm

[0994] E: The minimum line width is 11 μm or more

[0995] [Table 6]

[0996]

[0997] From the results of Examples 1 to 3, it was confirmed that the desired effects could be obtained when the transfer film of the present invention was used.

[0998] It was confirmed from the comparison between Examples 1 to 2 and Example 3 that when the structural unit X and the compound represented by the formula (1) have the group represented by the formula (A), the effects of the present invention are more excellent.

[0999] [Examples 4 to 6 and Comparative Examples 3 to 4]

[1000] [Preparation of resin composition]

[1001] Each resin composition was prepared by stirring and mixing each component according to Tables 3, 4 and 7.

[1002] In the table, the numerical values of each component in each resin composition represent the addition amount (parts by mass) of each component.

[1003] [Table 7]

[1004]

[1005] In Table 7, each component is as follows.

[1006] · Black pigment dispersion FDK-T-11: Manufactured by TOKYO PRINTING INK MFG CO., LTD.

[1007] · ACRIT 8KB-001: Alkali-soluble resin, solid content concentration is 38% by mass, solvent: PGMEA, manufactured by TAISEIFINE CHEMICAL CO,., LTD., ACRIT (registered trademark) 8KB-001)

[1008] · A-NOD-N: 1,9-Nonanediol diacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.

[1009] · A-DCP: Tricyclodecane dimethanol diacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.

[1010] · 8UX-015A: Urethane acrylate, manufactured by TAISEI FINE CHEMICAL CO,., LTD.

[1011] · 75% by mass PGMEA solution of KAYARAD DPHA: 75% by mass propylene glycol monomethyl ether acetate solution of KAYARAD DPHA (product name: manufactured by Nippon KayakuCo., Ltd.). The composition of KAYARAD DPHA is shown below.

[1012] In addition, in the table, the column of "average film thickness (μm) of the photosensitive resin composition layer" represents the average film thickness of the photosensitive resin composition layer formed when testing with the photosensitive resin composition.

[1013] Moreover, photosensitive resin compositions 6 to 10 correspond to the colored resin composition, i.e., the photosensitive resin composition.

[1014] [Chemical formula 22]

[1015]

[1016] · Irgacure OXE-02: Manufactured by BASF Corporation, acetophenone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(o-acetoxime)

[1017] · 1,2,4-triazole: Manufactured by Tokyo Chemical Industry Co., Ltd.

[1018] · B-1 to B-3: The above-mentioned block copolymer

[1019] · Megaface F555A: Manufactured by DIC CORPORATION

[1020] · R-1: The above-mentioned comparative compound

[1021] · PGMEA: Propylene glycol monomethyl ether acetate (manufactured by SHOWA DENKO K.K.)

[1022] · MEK: Methyl ethyl ketone (manufactured by SANKYO CHEMICAL C0., Ltd.)

[1023] [Production of transfer film]

[1024] According to Table 8, except for using each resin composition, each transfer film was produced in the same steps as in [Production of transfer film] in Examples 1 to 3 and Comparative Examples 1 to 2 above.

[1025] [Evaluation of concentration non-uniformity]

[1026] A polyethylene terephthalate film (PET substrate) with a thickness of 100 μm was prepared.

[1027] After unwinding the produced transfer film, the surface of the outermost photosensitive resin composition layer (colored resin composition layer) disposed on the temporary support and the above-mentioned PET substrate were laminated under the lamination conditions of a roller temperature of 100 °C, a line pressure of 1.0 MPa, and a line speed of 4.0 m / min, whereby the PET substrate was laminated on the transfer film. Then, after exposure with an ultra-high pressure mercury lamp without peeling the temporary support, the temporary support was peeled off and development was carried out. A 1.0% aqueous sodium carbonate solution at 25 °C was used for development, and spray development was carried out for 30 seconds. When forming a pattern by the above method via a line and space pattern mask (duty ratio 1:1, line width 20 μm), the exposure amount at which the resist line width becomes 20 μm was set as the most preferable exposure amount.

[1028] The cured film formed at the optimum exposure amount was placed on a high-brightness picture observation device (Schaukasten), and density unevenness was visually observed. Evaluation was carried out according to the following evaluation criteria. Evaluation A or B is within the range allowable in practical applications.

[1029] (Evaluation criteria)

[1030] A: No unevenness was observed (very good)

[1031] B: Slight unevenness was observed, but at a negligible level (good)

[1032] C: Unevenness was observed, but at a level that can be practically applied (ordinary)

[1033] D: There is unevenness (slightly poor)

[1034] E: There is strong unevenness (very poor)

[1035] [Table 8]

[1036]

[1037] From the results of Examples 4 to 6, it was confirmed that the desired effects can be obtained when the transfer film of the present invention is used.

[1038] From the comparison between Examples 4 to 5 and Example 6, it was confirmed that when the structural unit X and the compound represented by the formula (1) have the group represented by the formula (A), the effects of the present invention are more excellent.

[1039] [Examples 7 to 9 and Comparative Examples 5 to 6]

[1040] [Preparation of resin composition]

[1041] Each resin composition was prepared by stirring and mixing each component according to Tables 9 to 10.

[1042] In the table, the values for each component in each resin composition represent the addition amount (parts by mass) of each component.

[1043] [Table 9]

[1044]

[1045] In Table 9, each component is as follows.

[1046] · P-5 to P-6: the above-mentioned alkali-soluble resin

[1047] · A-DCP: tricyclodecane dimethanol diacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.

[1048] · A-NOD-N: 1,9-nonanediol diacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.

[1049] · A-DPH: dipentaerythritol hexaacrylate, manufactured by Shin Nakamura Chemical Industry Co., LTD.

[1050] · Monomer with carboxyl group ARONIX TO-2349, manufactured by TOAGOSEI CO., LTD.

[1051] · Urethane acrylate 8UX-015A, manufactured by TAISEI FINE CHEMICAL CO,.LTD.

[1052] · IRGACURE OXE-02: 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone-1-(o-acetoxime), manufactured by BASF

[1053] · Omnirad 907: 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropane, manufactured by BASF

[1054] · Duranate TPA-B80E: the above-mentioned blocked isocyanate compound

[1055] · Q-1 to Q-2: the above-mentioned blocked isocyanate compound

[1056] · N-phenylglycine, manufactured by Tokyo Chemical Industry Co., Ltd.

[1057] · Benzimidazole, manufactured by Tokyo Chemical Industry Co., Ltd.

[1058] · Isonicotinamide: manufactured by Tokyo Chemical Industry Co., Ltd.

[1059] · SMA EF-40: copolymer of styrene / maleic anhydride = 4:1 (molar ratio), anhydride value 1.94 mmol / g, Mw 10,500 (manufactured by Cray Valley)

[1060] · B-1 to B-3: block copolymer

[1061] · Megaface F551A: compound for comparison (manufactured by DIC CORPORATION)

[1062] · MEK: methyl ethyl ketone

[1063] In addition, in the table, the column of "average film thickness (μm) of the photosensitive resin composition layer" indicates the average film thickness of the photosensitive resin composition layer formed when testing with the photosensitive resin composition.

[1064] [Table 10]

[1065]

[1066] In Table 10, each component is as follows.

[1067] · NanoUse OZS-30M: ZrO 2 Particle (containing tin oxide) methanol dispersion (non-volatile component 30.5 mass%), manufactured by Nissan Chemical Industries, Ltd.

[1068] · Ammonia water (25 mass%)

[1069] · P-7: the above alkali-soluble resin

[1070] · ARUFON UC-3920: water-soluble resin, manufactured by TOAGOSEI CO., LTD.

[1071] · Monomer with carboxyl group: ARONIX TO-2349, manufactured by TOAGOSEI C0., LTD.

[1072] · Benzotriazole BT-LX, manufactured by JOHOKU CHEMICAL C0., LTD

[1073] · Adenine, manufactured by Tokyo Chemical Industry Co., Ltd.

[1074] ·N-Methyldiethanolamine, manufactured by Tokyo Chemical Industry Co., Ltd.

[1075] ·Monoisopropanolamine

[1076] ·A-1 to A-2: The above compound (1)

[1077] ·Megaface F444: A comparative compound, manufactured by DIC CORPORATION

[1078] ·Ion-exchanged water

[1079] ·Methanol

[1080] In addition, in the table, the column of "Average film thickness of water-soluble resin composition layer (μm)" represents the average film thickness of the water-soluble resin composition layer formed when testing with the water-soluble resin composition.

[1081] Moreover, water-soluble resin compositions 4 to 6 also correspond to compositions for forming a refractive index adjustment layer.

[1082] [Production of transfer film]

[1083] According to Table 11, except for using each resin composition, each transfer film was produced in the same steps as [Production of transfer film] in Examples 1 to 3 and Comparative Examples 1 to 2 above.

[1084] [Surface defect evaluation]

[1085] A polyethylene terephthalate film (PET substrate) with a thickness of 100 μm was prepared.

[1086] After unrolling the produced transfer film, under the lamination conditions of a roller temperature of 100 °C, a line pressure of 1.0 MPa, and a line speed of 4.0 m / min, the surface of the outermost layer (photosensitive resin composition layer) of the composition layer disposed on the temporary support was laminated with the above PET substrate, so that the PET substrate was laminated on the transfer film. Then, after exposure with an ultra-high pressure mercury lamp without peeling the temporary support, the temporary support was peeled off and development was carried out. A 1.0% sodium carbonate aqueous solution at 25 °C was used for development, and spray development was carried out for 30 seconds. When forming a pattern by the above method via a line and space pattern mask (Duty ratio 1:1, line width 20 μm), the exposure amount at which the resist line width becomes 20 μm was set as the most preferable exposure amount.

[1087] Regarding the surface of the cured film formed at the optimal exposure amount, a region with a length of 10 m and a width of 1.5 m was visually observed, and the surface defects were evaluated according to the following evaluation criteria. Evaluation A or B is within the range that can be tolerated in practical applications.

[1088] (Evaluation Criteria)

[1089] A: Surface defects are less than 1 per m 2

[1090] B: Surface defects are 1 per m 2 or more and less than 3 per m 2

[1091] C: Surface defects are 3 per m 2 or more and less than 5 per m 2

[1092] D: Surface defects are 5 per m 2 or more and less than 10 per m 2

[1093] E: Surface defects are 10 per m 2 or more

[1094] [Table 11]

[1095]

[1096] From the results of Examples 7 to 9, it was confirmed that the desired effects can be obtained when the transfer film of the present invention is used.

[1097] From the comparison between Examples 7 to 8 and Example 9, it was confirmed that when the structural unit X and the compound represented by the formula (1) have the group represented by the formula (A), the effects of the present invention are more excellent.

[1098] [Examples 10 to 12 and Comparative Examples 7 to 8]

[1099] [Preparation of Resin Composition]

[1100] Each resin composition was prepared by stirring and mixing each component according to Table 12.

[1101] In the table, the numerical values of each component in each resin composition represent the addition amount (parts by mass) of each component.

[1102] [Table 12]

[1103]

[1104] In Table 12, each component is as follows.

[1105] ·P-8: Resin having a structural unit with an acid group protected by the above acid-decomposable group

[1106] ·C-1: Photoacid generator, a compound having the following structure (the compound described in paragraph

[0227] of Japanese Patent Application Laid-Open No. 2013-047765 and synthesized according to the method described in paragraph

[0227] ).

[1107] [Chemical formula 23]

[1108]

[1109] ·BB-1: Dye, a compound having the following structure

[1110] [Chemical formula 24]

[1111]

[1112] ·1,2,3-Benzotriazole

[1113] ·B-1 to B-3: The above-mentioned block copolymer

[1114] ·Megaface F552: Comparative compound, manufactured by DIC CORPORATION

[1115] ·R-1: The above-mentioned comparative compound

[1116] ·n-Propyl acetate

[1117] In addition, in the table, the column of "Average film thickness (μm) of the photosensitive resin composition layer" indicates the average film thickness of the photosensitive resin composition layer formed when the photosensitive resin composition is used for the test.

[1118] [Production of transfer film]

[1119] Using a slit nozzle, the prepared photosensitive resin composition 16 was coated on a polyethylene terephthalate film (Lumirror 16KS40 (manufactured by TORAY INDUSTRIES, INC.)) with a thickness of 16 μm in a width of 1.0 m so that the average film thickness of the dried composition layer became the specified film thickness, and it was passed through a 3-m drying zone set at 100 °C with the air intake and exhaust volumes adjusted so that the wind speed on the film surface was 3 m / sec for 60 seconds, thereby obtaining the transfer film of Example 10.

[1120] In Examples 11 to 12 and Comparative Examples 7 to 8, except that the thermoplastic resin composition was changed as shown in Table 13, the respective transfer films were obtained in the same manner as in Example 10.

[1121] [Evaluation of resolution]

[1122] The resolution was evaluated in the same steps and evaluation criteria as in [Evaluation of Resolution] in the above Examples 1 to 3 and Comparative Examples 1 to 2.

[1123] [Table 13]

[1124]

[1125] From the results of Examples 10 to 12, it was confirmed that the desired effects can be obtained when the transfer film of the present invention is used.

[1126] From the comparison between Examples 10 to 11 and Example 12, it was confirmed that when the structural unit X and the compound represented by the formula (1) have the group represented by the formula (A), the effects of the present invention are more excellent.

[1127] Symbol Explanation

[1128] 10 - Temporary support, 12 - Thermoplastic resin layer, 14 - Intermediate layer, 16 - Photosensitive resin composition layer, 18 - Covering film, 100 - Transfer film.

Claims

1. A transfer film having a temporary support and a resin composition layer disposed on the temporary support, The resin composition layer contains: A resin which is any one of a resin containing an alkali-soluble resin or a resin having a structural unit having an acid group protected by an acid-decomposable group; and At least one compound selected from a block copolymer and a compound represented by the formula (1), the block copolymer containing: a block containing a structural unit X having a group represented by the formula (A) or a group represented by the formula (B) and a block containing a structural unit Y having a poly(oxyalkylene) group, Formula (A) *- (CH 2 ) m - (CF 2 ) n -CF 3 In the formula (A), m and n each independently represent an integer of 1 to 3, and * represents a bonding position, Formula (B) *-L 1 -CH(CF 3 )-CF 3 In formula (B), L 1 represents an oxygen atom or an alkylene group, and * represents the bonding position, Formula (1) Z-L 2 -W In the formula (1), Z represents the group represented by the formula (A) or the group represented by the formula (B), L 2 represents a single bond or a divalent linking group W represents a group containing a poly(oxyalkylene) group.

2. The transfer film according to claim 1, wherein, The structural unit X and the compound represented by the formula (1) have the group represented by the formula (A).

3. The transfer film according to claim 1, wherein, The structural unit X and the compound represented by the formula (1) have the group represented by the formula (B).

4. The transfer film according to any one of claims 1 to 3, which contains the compound represented by the formula (1), and the molecular weight of the compound represented by the formula (1) is 2000 or less.

5. The transfer film according to any one of claims 1 to 3, which contains the block copolymer, and the weight-average molecular weight of the block copolymer is 5000 or more.

6. The transfer film according to any one of claims 1 to 3, wherein, The resin is an alkali-soluble resin, The resin composition layer further contains a polymerizable compound.

7. The transfer film according to any one of claims 1 to 3, wherein, The resin is a resin having a structural unit having an acid group protected by an acid-decomposable group, The resin composition layer further contains a photoacid generator.

8. The transfer film according to any one of claims 1 to 3, wherein, The resin composition layer is a water-soluble resin composition layer.

9. The transfer film according to claim 8, wherein, The water-soluble resin composition layer contains metal oxide particles.

10. The transfer film according to any one of claims 1 to 3, wherein, The resin composition layer is a thermoplastic resin composition layer.

11. The transfer film according to any one of claims 1 to 3, wherein, The resin composition layer further contains a pigment.

12. The transfer film according to any one of claims 1 to 3, wherein, The resin composition layer is two or more resin composition layers.

13. The transfer film according to claim 1, which contains the block copolymer, the weight-average molecular weight of the block copolymer is 5000 or more, and the structural unit X is a structural unit represented by the formula (C), The content of the block copolymer is 0.01% by mass to 3.00% by mass relative to the total mass of the resin composition layer, The resin is an alkali-soluble resin, and the content of the resin is 20.00% by mass to 80.00% by mass relative to the total mass of the resin composition layer. The resin composition layer further contains a polymerizable compound having an ethylenically unsaturated group as a polymerizable group. In formula (C), R represents a hydrogen atom or a substituent, L represents a single bond or a divalent linking group, and Z represents the group represented by formula (A) or the group represented by formula (B).

14. A method for manufacturing a laminate, which comprises: a laminating step of bringing a substrate into contact with the surface on the side opposite to the temporary support of the transfer film according to any one of claims 1 to 13, laminating the transfer film and the substrate to obtain a substrate with a transfer film; an exposure step of performing pattern exposure on the resin composition layer; a developing step of developing the exposed resin composition layer to form a resin pattern; and a peeling step of peeling the temporary support from the substrate with a transfer film between the laminating step and the exposure step or between the exposure step and the developing step.

15. A method for manufacturing a circuit wiring, which comprises: a laminating step of bringing a substrate having a conductive layer into contact with the surface on the side opposite to the temporary support of the transfer film according to any one of claims 1 to 13, laminating the transfer film and the substrate having a conductive layer to obtain a substrate with a transfer film; an exposure step of performing pattern exposure on the resin composition layer; a developing step of developing the exposed resin composition layer to form a resin pattern; an etching step of etching the conductive layer in the region where the resin pattern is not disposed; and a peeling step of peeling the temporary support from the substrate with a transfer film between the laminating step and the exposure step or between the exposure step and the developing step.

16. A method for manufacturing an electronic device, which includes the method for manufacturing a laminate according to claim 14, wherein the electronic device includes the resin pattern as a cured film.

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