Transfer film, laminate manufacturing method, circuit wiring manufacturing method, and electronic device manufacturing method

Abstract

The present invention provides a transfer film in which exterior defects in patterns are unlikely to occur, a laminate manufacturing method, a circuit wiring manufacturing method, and an electronic device manufacturing method. The transfer film according to the present invention includes a temporary support body and a resin composition layer disposed on the temporary support body. The resin composition layer contains: a resin; a block copolymer including a block formed of a structural unit X having a group represented by formula (A) or a group represented by formula (B) and a block formed of a structural unit Y having a poly(oxyalkylene) group; and at least one compound selected from the group consisting of compounds represented by formula (1).

Description

[Technical field]

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

[0002] Because the number of steps required to obtain a pattern of a desired shape is small, a method in which a resin composition layer is provided on any substrate using a transfer film, exposed through a mask containing the desired pattern, and then developed is widely used. For example, Patent Document 1 discloses a transfer film containing a copolymer having a specific fluoroalkyl group. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] International Publication No. 2017 / 057348 Summary of the Invention [Problem to be solved by the invention]

[0004] The present inventors have studied transfer films such as those disclosed in Patent Document 1 and found that the patterns obtained after exposure and development are prone to have poor appearance. Specifically, the patterns tend to peel off or leave residues during pattern formation, making it difficult to obtain high-resolution patterns, and when a pigment is contained in the pattern, there are large density unevennesses, and the pattern has many defects on its surface. Hereinafter, in this specification, the term "less likely to cause defects in the appearance of a pattern" refers to being able to suppress at least one of the following: a pattern is likely to peel off or leave residue during pattern formation, making it difficult to obtain a high-resolution pattern; when a pigment is contained in the pattern, there is significant unevenness in density; and there are many defects on the surface of the pattern.

[0005] In view of the above, an object of the present invention is to provide a transfer film that is less likely to cause defects in the appearance of a pattern. Another object of the present invention is to provide a method for manufacturing a laminate, a method for manufacturing a circuit wiring, and a method for manufacturing an electronic device, which are related to the transfer film. [Means for solving the problem]

[0006] As a result of intensive research by the present inventors to solve the above problems, they have found that the above problems can be achieved by the following configuration.

[0007] [1] A temporary support and a resin composition layer disposed on the temporary support, The resin composition layer comprises a resin, A block copolymer comprising a block of a structural unit X having a group represented by formula (A) described below or a group represented by formula (B) described below, and a block of a structural unit Y having a poly(oxyalkylene) group; and and at least one compound selected from the group consisting of compounds represented by formula (1) described below. [2] The transfer film according to [1], wherein the structural unit X and the compound represented by formula (1) have a group represented by formula (A). [3] The transfer film according to [1], wherein the structural unit X and the compound represented by formula (1) have a group represented by formula (B). [4] The transfer film according to any one of [1] to [3], wherein the compound represented by formula (1) has a molecular weight of 2000 or less. [5] The transfer film according to any one of [1] to [4], wherein the block copolymer has a weight average molecular weight of 5,000 or more. [6] The resin is an alkali-soluble resin; The transfer film according to any one of [1] to [5], wherein the resin composition layer further contains a polymerizable compound. [7] The resin has a structural unit having an acid group protected by an acid-decomposable group, The transfer film according to any one of [1] to [5], wherein the resin composition layer further contains a photoacid generator. [8] The transfer film according to any one of [1] to [7], wherein the resin composition layer is a water-soluble resin composition layer. [9] The transfer film according to [8], wherein the water-soluble resin composition layer contains metal oxide particles.

[10] The transfer film according to any one of [1] to [9], wherein the resin composition layer is a thermoplastic resin composition layer.

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

[10] , wherein the resin composition layer further contains a pigment.

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

[11] , which has two or more resin composition layers.

[13] A bonding step of contacting a substrate with a surface of the transfer film according to any one of [1] to

[12] on the side opposite to the temporary support, thereby bonding the transfer film and the substrate together to obtain a substrate with a transfer film; an exposure step of pattern-exposing the resin composition layer; a developing step of developing the exposed resin composition layer to form a resin pattern; The method for producing a laminate further comprises a peeling step of peeling the temporary support from the substrate with the transfer film between the laminating step and the exposure step, or between the exposure step and the development step.

[14] A bonding step of contacting a surface of the transfer film according to any one of [1] to

[12] opposite to the temporary support with a substrate having a conductive layer, and bonding the transfer film and the substrate having a conductive layer to obtain a substrate with a transfer film; an exposure step of pattern-exposing 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 an area where the resin pattern is not disposed; The method for producing circuit wiring further comprises a peeling step of peeling the temporary support from the substrate with the transfer film between the laminating step and the exposure step, or between the exposure step and the development step.

[15] A method for producing an electronic device, comprising the method for producing the laminate according to

[13] , A method for producing an electronic device, wherein the electronic device comprises a resin pattern as a cured film. Effect of the Invention

[0008] According to the present invention, it is possible to provide a transfer film that is less likely to cause defects in the appearance of a pattern. It is also possible to provide a method for producing a laminate, a method for producing a circuit wiring, and a method for producing an electronic device, which are related to the transfer film. [Brief description of the drawings]

[0009] [Figure 1] FIG. 2 is a schematic diagram showing an example of a configuration of a transfer film. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0010] The present invention will be described in detail below. The following description of the components may be based on representative embodiments of the present invention, but the present invention is not limited to such embodiments. In this specification, a numerical range expressed using "to" means a range that includes the numerical values ​​before and after "to" as the lower and upper limits. In this specification, the bonding direction of a divalent group (for example, --CO--O--) is not particularly limited.

[0011] In this specification, (meth)acrylate refers to acrylate and methacrylate, (meth)acrylic acid refers to acrylic acid and methacrylic acid, and (meth)acryloyl group refers to methacryloyl group or acryloyl group.

[0012] In the present specification, when a group (atomic group) is described without indicating whether it is substituted or unsubstituted, it includes both a group having no substituent and a group having a substituent. For example, an "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group). In addition, in the present specification, an "organic group" refers to a group containing at least one carbon atom.

[0013] In this specification, when it is described as "optionally having a substituent", the type, position, and number of the substituent are not particularly limited. The number of substituents may be, for example, one, two, three, or more. Further, it may be unsubstituted. Examples of the substituent include monovalent non-metal atomic groups excluding a hydrogen atom, and can be selected from, for example, the following substituent group T. (Substituent T) Examples of the substituent T include halogen atoms such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom; alkoxy groups such as a methoxy group, an ethoxy group, and a tert-butoxy group; aryloxy groups such as a phenoxy group and a p-tolyloxy group; alkoxycarbonyl groups such as a methoxycarbonyl group, a butoxycarbonyl group, and a phenoxycarbonyl group; acyloxy groups such as an acetoxy group, a propionyloxy group, and a benzoyloxy group; acyl groups such as an acetyl group, a benzoyl group, an isobutyryl group, an acryloyl group, a methacryloyl group, and a methoxysilyl group; alkylsulfanyl groups such as a methylsulfanyl group and a tert-butylsulfanyl group; arylsulfanyl groups such as a phenylsulfanyl group and a p-tolylsulfanyl group; an alkyl group; a cycloalkyl group; an aryl group; a heteroaryl group; a hydroxyl group; a carboxy group; a formyl group; a sulfo group; a cyano group; an alkylaminocarbonyl group; an arylaminocarbonyl group; a sulfonamide group; a silyl group; an amino group; a monoalkylamino group; a dialkylamino group; an arylamino group; and combinations thereof.

[0014] In this specification, unless otherwise specified, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are values calculated in terms of polystyrene by gel permeation chromatography (GPC). GPC is measured under the following conditions. [Eluent] Tetrahydrofuran (THF) [Apparatus name] EcoSEC HLC-8320GPC (manufactured by Tosoh Corporation) [Column] TSKgel SuperHZM-H, TSKgel SuperHZ4000, and TSKgel SuperHZ200 (manufactured by Tosoh Corporation) [Column temperature] 40℃ [Flow rate] 0.35mL / min

[0015] In this specification, unless otherwise specified, the molecular weight of a compound having a molecular weight distribution is the weight average molecular weight (Mw).

[0016] In this specification, room temperature is 25° C. unless otherwise specified.

[0017] In this specification, "alkali-soluble" means that the solubility in 100 g of a 1% by mass aqueous solution of sodium carbonate at 22°C is 0.1 g or more. In this specification, the term "water-soluble" means that the solubility in 100 g of water having a liquid temperature of 22°C and a pH of 7.0 is 0.1 g or more. In this specification, the layer thickness (film thickness) of each layer in a transfer film or the like is measured by observing a cross section of the layer (film) in a direction perpendicular to the main surface thereof with a scanning electron microscope (SEM), measuring the thickness of each layer at 10 or more points based on the obtained observation image, and calculating the average value.

[0018] [Transfer film] The transfer film has a temporary support and a resin composition layer disposed on the temporary support, the resin composition layer being composed of a resin, a block copolymer (hereinafter also simply referred to as a "block copolymer") including a block composed of a structural unit X having a group represented by formula (A) or a group represented by formula (B), and a block composed of a structural unit Y having a poly(oxyalkylene) group, and at least one compound selected from the group consisting of compounds represented by formula (1) (hereinafter also referred to as "compound (1)").

[0019] The mechanism by which the problem of the present invention is solved by such a configuration is not necessarily clear, but the present inventors speculate as follows. In the transfer film of the prior art, the above-mentioned defective appearance of the pattern may occur in some cases. In particular, depending on the conditions for forming the resin composition layer, the above-mentioned defective appearance of the pattern may occur more significantly in some cases. The present inventors have investigated the cause and found that the above problem is caused by bubbles (voids) in the resin composition layer. On the other hand, it is presumed that in a resin composition layer containing at least one compound selected from the group consisting of a specific 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 occurrence of the above bubbles (voids) is suppressed by having each of the above groups, thereby suppressing the appearance defects of the pattern. Hereinafter, in this specification, the fact that defects in the appearance of the pattern are less likely to occur is also referred to as the effect of the present invention being more excellent.

[0020] The transfer film may be formed by directly laminating the temporary support and one or more resin composition layers described later without any other layer therebetween, or may be formed by laminating the layers via another layer. In addition, another layer may be laminated on the surface of the one or more resin composition layers opposite to the surface facing the temporary support. Another layer may be present between the one or more resin composition layers. That is, the transfer film preferably has one or more resin composition layers, and more preferably has two or more resin composition layers. In the transfer film, of one or more (e.g., 1 to 5) resin composition layers, at least one layer may be a resin composition layer of the present invention, half or more of the layers may be resin composition layers of the present invention, or all of the layers may be resin composition layers of the present invention. It is also preferable that the transfer film includes at least one photosensitive resin composition layer, which will be described later. The photosensitive resin composition layer may be a colored resin composition layer.

[0021] [Temporary Support] The transfer film has a temporary support. The temporary support is a support that supports a resin composition layer described below or a laminate including a resin composition layer, and is peelable.

[0022] The temporary support preferably has light transmittance from the viewpoint of enabling exposure through the temporary support when the resin composition layer is subjected to patternwise exposure. In this specification, "having light transmittance" means that the transmittance of light of the wavelength used for patternwise exposure is 50% or more. From the viewpoint of improving exposure sensitivity, the temporary support preferably has a transmittance of light having a wavelength used for patternwise exposure (more preferably a wavelength of 365 nm) of 60% or more, more preferably 70% or more. The transmittance of the layer of the transfer film is the ratio of the intensity of the emitted light that passes through the layer to the intensity of the incident light when light is incident in a direction perpendicular to the main surface of the layer (thickness direction), and is measured using the MCPD Series manufactured by Otsuka Electronics Co., Ltd.

[0023] Examples of materials constituting the temporary support include a glass substrate, a resin film, and paper. From the viewpoints of strength, flexibility, and light transmittance, a resin film is preferred. Examples of the resin film include a polyethylene terephthalate (PET) film, a cellulose triacetate film, a polystyrene film, and a polycarbonate film. Of these, a PET film is preferred, and a biaxially stretched PET film is more preferred.

[0024] The thickness (layer thickness) of the temporary support is not particularly limited, and may be selected according to the material from the standpoints of strength as a support, flexibility required for bonding to a substrate for forming circuit wiring, and light transmittance required in the initial exposure step. The thickness of the temporary support is preferably from 5 to 100 μm, and from the viewpoints of ease of handling and versatility, it is more preferably from 10 to 50 μm, further preferably from 10 to 20 μm, and particularly preferably from 10 to 16 μm.

[0025] In addition, the film used as the temporary support is preferably free from deformations such as wrinkles, scratches, defects, and the like. From the viewpoint of pattern formability during pattern exposure through the temporary support and the transparency of the temporary support, it is preferable that the number of fine particles, foreign matter, defects, precipitates, etc. contained in the temporary support is small. The number of fine particles, foreign matter, and / or defects having a diameter of 1 μm or more is 50 / 10 mm. 2 Less than 10 pieces / 10mm is preferable. 2 Less than 3 pieces / 10mm is more preferable. 2 Less than 0 / 10mm is more preferable. 2 is particularly preferred.

[0026] Preferred embodiments of the temporary support are described, for example, in paragraphs

[0017] to

[0018] of JP 2014-085643 A, paragraphs

[0019] to

[0026] of JP 2016-027363 A, paragraphs

[0041] to

[0057] of WO 2012 / 081680 A1, paragraphs

[0029] to

[0040] of WO 2018 / 179370 A1, and paragraphs

[0012] to

[0032] of JP 2019-101405 A, the contents of which are incorporated herein by reference.

[0027] [Resin composition layer] The resin composition layer of the present invention contains a resin and at least one compound selected from the group consisting of a block copolymer and the compound (1). The resin composition layer may be, for example, a photosensitive resin composition layer, a thermoplastic resin composition layer, a colored resin composition layer, and / or a water-soluble resin composition layer, which will be described later. Components that may be contained in each resin composition layer in each embodiment will be described below. In addition, a component described as a component of a resin composition layer of a certain embodiment does not mean that it is permitted to be contained only when the resin composition layer is of that embodiment, and may also be used as a component of a resin composition layer of another embodiment. For example, a component described as a component of a photosensitive resin composition layer may be used as a component other than the photosensitive resin composition layer.

[0028] <Resin> The resin composition layer contains a resin. The above resin is a component different from the block copolymer described later. There are no restrictions on the properties and / or characteristics of the resin, and it can be appropriately selected according to the use of the resin composition layer. Details of the resin will be described later according to each form of the resin composition layer.

[0029] <Block copolymer> The block copolymer includes a block (block segment) composed of a structural unit X having a group represented by formula (A) or a group represented by formula (B), and a block (block segment) composed of a structural unit Y having a poly(oxyalkylene) group.

[0030] The block copolymer is a polymer having a molecular structure in which a plurality of types of blocks are linked, and each block is a chain formed by linking structural units. The block structure of the block copolymer is not particularly limited, and examples thereof include block structures a to e represented by formulas (a) to (e).

[0031] Formula (a) (A)-(B) In formula (a), A represents a block composed of structural unit X, and B represents a block composed of structural unit Y. The block structure a represented by formula (a) is a block structure (A-B type) in which a block composed of structural unit X and a block composed of structural unit Y are linked.

[0032] Formula (b) (B)-(A)-(B) In formula (b), A represents a block composed of structural unit X, and B represents a block composed of structural unit Y. The block structure b represented by formula (b) is a block structure (B-A-B type) in which blocks composed of structural unit Y are linked to both ends of a block composed of structural unit X.

[0033] Formula (c) (B)-(A)-(C) In formula (c), A represents a block consisting of the structural unit X, B represents a block consisting of the structural unit Y, and C represents a block consisting of structural units different from the structural units X and Y. The block structure c represented by formula (c) is a block structure (BAC type) in which a block consisting of a structural unit Y, a block consisting of a structural unit X, and a block consisting of a structural unit different from the structural units X and Y are linked in this order.

[0034] Formula (d) (B)-(A)-(C)-(D) In formula (d), A represents a block consisting of the structural unit X, B represents a block consisting of the structural unit Y, C represents a block consisting of the structural unit X and a first structural unit different from the structural unit Y, and D represents a block consisting of the structural unit X, the structural unit Y, and a second structural unit different from the first structural unit. The block structure d represented by formula (d) is a block structure (BACD type) in which a block consisting of a structural unit Y, a block consisting of a structural unit X, a block consisting of a first structural unit different from the structural unit X and the structural unit Y, and a block consisting of the structural unit X, the structural unit Y, and a second structural unit different from the first structural unit are linked in this order.

[0035] Equation (e) (A)-(B)-(A)-(B) In formula (e), A represents a block composed of structural units X, and B represents a block composed of structural units Y. The block structure e represented by formula (e) is a block structure in which blocks made of structural units X and blocks made of structural units Y are alternately linked multiple times. Among these, as the block structure, block structures a to c are preferable, block structure a or c is more preferable, and block structure a is further preferable.

[0036] The number of types of blocks contained in the block structure is 2 or more, preferably 2 to 10, more preferably 2 to 5, still more preferably 2 or 3, and particularly preferably 2, from the viewpoint of solubility.

[0037] (Constituent unit X) The structural unit X has a group represented by formula (A) or a group represented by formula (B). Among these, in terms of obtaining superior effects of the present invention, it is preferable that the structural unit X has a group represented by formula (A).

[0038] Formula (A) *-(CH 2 ) m -(CF 2 ) n -CF 3 In formula (A), m and n each independently represent an integer of 1 to 3. As m, an integer of 2 to 3 is preferable, and 2 is more preferable. As n, an integer of 2 to 3 is preferable, and 3 is more preferable. * indicates the bond position. The number of groups represented by formula (A) contained in the structural unit X is preferably 1 to 3, and more preferably 1.

[0039] Formula (B) *-L 1 -CH(CF 3 )-CF 3 In formula (B), L 1 represents an oxygen atom or an alkylene group. L 1 The alkylene group represented by the formula (I) may be linear or branched. L 1 The alkylene group represented by the following formula (I) preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, further preferably 1 to 3 carbon atoms, and particularly preferably 1 or 2 carbon atoms. L 1 The alkylene group represented by the following formula (1) may have a substituent. The substituent is not particularly limited, and examples thereof include the substituents exemplified in the group T of substituents. L 1 is preferably an oxygen atom or an alkylene group having 1 to 2 carbon atoms, and more preferably an oxygen atom. * indicates the bond position. The number of groups represented by formula (B) contained in the structural unit X is preferably 1 to 3, and more preferably 1.

[0040] The structural unit X is preferably a structural unit represented by formula (C).

[0041] [ka]

[0042] In formula (C), R represents a hydrogen atom or a substituent. The substituent represented by R is not particularly limited, and examples thereof include the substituents exemplified in the substituent group T, and is preferably an alkyl group having 1 to 6 carbon atoms. L represents a single bond or a divalent linking group. Examples of the divalent linking group include -O-, -CO-, -S-, and -SO 2 -, -NR X -(R X represents a hydrogen atom or a substituent.) alkylene groups, alkenylene groups, alkynylene groups, aromatic ring groups, alicyclic groups, and groups combining these groups (e.g., -CO-O-, -CO-O-alkylene groups, etc.). X Examples of the substituent represented by the formula: include the substituents exemplified in the group T of substituents, and an alkyl group having 1 to 2 carbon atoms is preferred. The alkylene group, alkenylene group, alkynylene group, aromatic ring group, and alicyclic group may further have a substituent. Examples of the substituent include the substituents exemplified in the substituent group T. Among them, the substituent is preferably a halogen atom, and more preferably a fluorine atom. The alkylene group, alkenylene group, and alkynylene group may be linear or branched. The alkylene group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and even more preferably 1 to 5 carbon atoms. The alkenylene group and alkynylene group preferably have 2 to 20 carbon atoms, more preferably 2 to 10 carbon atoms, and even more preferably 2 to 5 carbon atoms.

[0043] Z represents a group represented by formula (A) or a group represented by formula (B). The group represented by the formula (A) and the group represented by the formula (B) have the same meanings as the group represented by the formula (A) and the group represented by the formula (B) in the above-mentioned block copolymer, respectively, and the preferred ranges are also the same.

[0044] The structural unit X may be used alone or in combination of two or more kinds. The lower limit of the content of the structural unit X is more than 0 mol%, preferably 1 mol% or more, more preferably 10 mol% or more, even more preferably 30 mol% or more, and particularly preferably 40 mol% or more, based on the number of moles of all structural units in the block copolymer. The upper limit is less than 100 mol%, preferably 90 mol% or less, more preferably 80 mol% or less, and even more preferably 60 mol% or less.

[0045] (Structural unit Y) The structural unit Y has a poly(oxyalkylene) group. The structural unit Y is not particularly limited, but preferably has a group represented by the formula (PAL1).

[0046] [ka]

[0047] In formula (PAL1), AL represents an alkylene group. The alkylene group may be linear or branched. The alkylene group represented by AL preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, further preferably 2 to 4 carbon atoms, and particularly preferably 2 to 3 carbon atoms. nAL represents a number of 2 or more, preferably 2 to 100, more preferably 4 to 20, further preferably 4 to 15, and particularly preferably 4 to 12. The nAL number of ALs may be the same or different, and preferably represent the same structure. The alkylene group represented by AL may have a substituent. The substituent is not particularly limited, but examples thereof include the substituents exemplified in the group T of substituents. Among them, AL is -CH2 CH 2 -, -CH 2 CH 2 CH 2 -, -CH(CH 3 )CH 2 - or -CH(CH 2 CH 3 )CH 2 - is preferred, -CH(CH 3 )CH 2 - or -CH 2 CH 2 -- is more preferred. * indicates the bond position.

[0048] The structural unit Y preferably has a poly(oxyalkylene) group in the side chain, more preferably has a group represented by formula (PAL1) in the side chain, and further preferably is a structural unit derived from a monomer represented by formula (PAL2).

[0049] [ka]

[0050] In formula (PAL2), R 1 represents a hydrogen atom or a methyl group. R 1 is preferably a hydrogen atom.

[0051] Y is an oxygen atom, a sulfur atom, or -N(R 2 )-represents. R 2 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R 2 The alkyl group having 1 to 4 carbon atoms represented by the following formula may be any of linear, branched, and cyclic. R 2 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. Y is preferably an oxygen atom or a sulfur atom, and more preferably an oxygen atom.

[0052] R 3 represents a hydrogen atom or a substituent. R 3 The substituent represented by the formula (I) is not particularly limited, and examples thereof include the substituents exemplified in the group T of substituents, and is preferably an alkyl group having 1 to 6 carbon atoms. R 3 is preferably a hydrogen atom.

[0053] AL and nAL in formula (PAL2) have the same meanings as AL and nAL in formula (PAL1) above, respectively, and the preferred embodiments are also the same.

[0054] The structural unit Y may be used alone or in combination of two or more kinds. The lower limit of the content of the structural unit Y is more than 0 mol%, preferably 1 mol% or more, more preferably 10 mol% or more, even more preferably 30 mol% or more, and particularly preferably 40 mol% or more, based on the number of moles of all structural units in the block copolymer. The upper limit is less than 100 mol%, preferably 90 mol% or less, and more preferably 60 mol% or less.

[0055] (Other structural units) The block copolymer may have other structural units in addition to the structural unit X and the structural unit Y.

[0056] The other structural units are preferably structural units selected from the group consisting of structural units derived from (meth)acrylic acid esters and structural units derived from (meth)acrylic acid. Examples of the (meth)acrylic acid ester include (meth)acrylic acid alkyl esters having an alkyl group with a carbon number of 1 to 18. Specific 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 these, lauryl (meth)acrylate is preferred.

[0057] The other structural units may be used alone or in combination of two or more kinds. The lower limit of the content of the other structural units is preferably 1 mol% or more, more preferably 10 mol% or more, and even more preferably 20 mol% or more, based on the number of moles of all structural units of the block copolymer, and the upper limit is preferably 90 mol% or less, more preferably 60 mol% or less, and even more preferably 40 mol% or less.

[0058] Specific examples of the block copolymer are given below, but the block copolymer in the present invention is not limited to these.

[0059] [ka]

[0060] The lower limit of the weight average molecular weight of the block copolymer is preferably 1,000 or more, more preferably 1,500 or more, even more preferably 2,000 or more, and particularly preferably 5,000 or more, and the upper limit is preferably 100,000 or less, more preferably 50,000 or less, and even more preferably 20,000 or less. The number average molecular weight (Mn) of the block copolymer is preferably from 1,000 to 40,000, more preferably from 2,000 to 20,000, further preferably from 5,000 to 15,000, and particularly preferably from 7,000 to 12,000. The polydispersity (Mw / Mn) of the block copolymer is preferably from 1.00 to 12.00, more preferably from 1.00 to 11.00, further preferably from 1.00 to 10.00, particularly preferably from 1.00 to 5.00, and most preferably from 1.00 to 2.00.

[0061] The block copolymer may be used alone or in combination of two or more kinds. The content of the block copolymer is preferably from 0.001 to 10.00 mass %, more preferably from 0.01 to 3.00 mass %, further preferably from 0.02 to 1.00 mass %, particularly preferably from 0.10 to 1.00 mass %, based on the total mass of the resin composition layer.

[0062] The polymerization method for the block copolymer is not particularly limited, and known polymerization methods can be used. Examples of the polymerization method for the block copolymer include living radical polymerization, living cationic polymerization, and living anionic polymerization. Examples of living radical polymerization, living cationic polymerization, and living anionic polymerization include "Precise Radical Polymerization Guidebook (Aldrich)" (URL: http: / / www.sigmaaldrich.com / japan / materialscience / polymer-science / crp-guide.html), "Polymer Synthesis (Part 1) - Radical Polymerization, Cationic Polymerization, Anionic Polymerization" edited by Endo Tsuyoshi and written by Sawamoto Mitsuo et al., Kodansha, 2010, pp. 60, 105-108, 249-259, 381-386, and paragraphs

[0067] to

[0074] of WO2017 / 014145, the contents of which are incorporated herein by reference.

[0063] <Compound (1)> Compound (1) is a compound represented by formula (1). Formula (1) ZL 2 -W In formula (1), Z represents a group represented by formula (A) or a group represented by formula (B). The group represented by the above formula (A) and the group represented by the above formula (B) have the same meanings as the group represented by the formula (A) and the group represented by the formula (B) in the above-mentioned block copolymer, respectively, and the preferred ranges are also the same.

[0064] L 2 represents a single bond or a divalent linking group. L 2 Examples of the divalent linking group represented by the formula: 2 -, -NR X -(R X represents a hydrogen atom or a substituent.) alkylene groups, alkenylene groups, alkynylene groups, aromatic ring groups, alicyclic groups, and groups combining these groups. XExamples of the substituent represented by the formula: include the substituents exemplified in the group T of substituents, and an alkyl group having 1 to 2 carbon atoms is preferred. The alkylene group, the alkenylene group, the alkynylene group, the aromatic ring group, and the alicyclic group may further have a substituent. Examples of the substituent include the substituents exemplified in the substituent group T. Among them, the substituent is preferably a halogen atom, and more preferably a fluorine atom. The alkylene group, the alkenylene group, and the alkynylene group may be linear or branched. The alkylene group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and even more preferably 1 to 5 carbon atoms. The alkenylene group and the alkynylene group preferably have 2 to 20 carbon atoms, more preferably 2 to 10 carbon atoms, and even more preferably 2 to 5 carbon atoms. Among them, L 2 When Z is a group represented by formula (A), -O- is preferable, and when Z is a group represented by formula (B), a single bond is preferable.

[0065] W represents a group containing a poly(oxyalkylene) group. There are no particular limitations on W, so long as it is a group containing a poly(oxyalkylene) group. Among these, W is preferably a monovalent organic group containing a poly(oxyalkylene) group, more preferably a group containing a group represented by the above formula (PAL1), and even more preferably a group represented by formula (2). Formula (2) *-(AL-O-) nAL -R 3 AL and R in formula (2) 3 The definitions of nAL are the same as those of each group in formula (PAL2) above. * represents a bonding position.

[0066] Specific examples of compound (1) are given below, but compound (1) in the present invention is not limited to these.

[0067] [ka]

[0068] As the lower limit of the molecular weight of compound (1), 100 or more is preferable, and 500 or more is more preferable. As the upper limit of the molecular weight of compound (1), 3,000 or less is preferable, and 2,000 or less is more preferable.

[0069] Compound (1) may be used alone or in combination of two or more. The content of compound (1) is preferably 0.001 to 10.00% by mass, more preferably 0.01 to 3.00% by mass, and still more preferably 0.02 to 1.00% by mass based on the total mass of the resin composition layer.

[0070] <Other components> The resin composition layer may contain other components in addition to the resin, block copolymer, and compound (1). Examples of other components include polymerizable compounds, polymerization initiators, dyes, thermally crosslinkable compounds, additives, plasticizers, sensitizers, pigments, and compounds that generate acids, bases, or radicals upon irradiation with light. Details of other components will be described later for each form of the resin composition layer.

[0071] 〔Photosensitive resin composition layer〕 The resin composition layer may be a photosensitive resin composition layer. After transferring the photosensitive resin composition layer onto the object to be transferred, exposure and development are performed to form a pattern on the object to be transferred. The photosensitive resin composition layer may be positive or negative. A positive photosensitive composition layer is a photosensitive composition layer in which the solubility of the exposed portion in the developer increases upon exposure. A negative photosensitive composition layer is a photosensitive composition layer in which the solubility of the exposed portion in the developer decreases upon exposure. Among them, it is preferable to use a negative photosensitive resin composition layer. When the photosensitive resin composition layer is a negative photosensitive resin composition layer, the formed pattern corresponds to a protective film. The photosensitive resin composition layer preferably further contains an alkali-soluble resin and a polymerizable compound in addition to the above-mentioned block copolymer and compound (1). In addition, the photosensitive resin composition layer preferably contains, in addition to the above-mentioned block copolymer and compound (1), a resin having a structural unit having an acid group protected by an acid-decomposable group, which will be described later, and a photoacid generator, which will be described later.

[0072] The transfer film having a photosensitive resin composition layer may be used to obtain a pattern such as wiring of a touch panel. In display devices (such as organic electroluminescence (EL) display devices and liquid crystal display devices) equipped with a touch panel such as a capacitance-type input device, conductive layer patterns such as an electrode pattern corresponding to a sensor in the visible area, a peripheral wiring portion, and wiring of an extraction wiring portion are provided inside the touch panel. In general, for forming 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, the photosensitive resin composition layer is exposed to light through a mask having a desired pattern, and then developed. Components that may be contained in the photosensitive resin composition layer will be described below.

[0073] <Alkali-soluble resin> 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. The acid value of the polymer P is preferably 220 mgKOH / g or less, more preferably less than 200 mgKOH / g, and even more preferably less than 190 mgKOH / g, from the viewpoint of suppressing swelling of the photosensitive resin composition layer by the developer and thereby achieving better resolution. The lower limit of the acid value of the polymer P is not particularly limited, but from the viewpoint of better developability, it is preferably 60 mgKOH / g or more, more preferably 80 mgKOH / g or more, and even more preferably 90 mgKOH / g or more.

[0074] The acid value is the mass [mg] of potassium hydroxide required to neutralize 1 g of a sample, and is expressed in units of mgKOH / g in this specification. The acid value can be calculated, for example, from the average content of acid groups in a compound. The acid value of the polymer P may be adjusted by changing the type of structural unit constituting the polymer P and the content of the structural unit containing an acid group.

[0075] The weight average molecular weight of the polymer P is preferably 5,000 to 500,000. When the weight average molecular weight is 500,000 or less, it is preferable from the viewpoint of improving resolution and developability. The weight average molecular weight is more preferably 100,000 or less, and even more preferably 60,000 or less. On the other hand, when the weight average molecular weight is 5,000 or more, it is preferable from the viewpoint of controlling the properties of the development aggregate and the properties of the unexposed film such as edge fuse property and cut chip property when the laminate having the photosensitive resin composition layer is made into a laminate having the photosensitive resin composition layer. The weight average molecular weight is more preferably 10,000 or more, more preferably 20,000 or more, and particularly preferably 30,000 or more. The edge fuse property refers to the degree of the tendency of the photosensitive resin composition layer to protrude from the end face of the roll when the laminate having the photosensitive resin composition layer is wound into a roll shape. The cut chip property refers to the degree of the tendency of the chip to fly when the unexposed film is cut with a cutter. If the chips adhere to the upper surface of a laminate having a photosensitive resin composition layer, they will be transferred to a mask in a subsequent exposure step, etc., causing defective products. 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.

[0076] In order to prevent line width increase and resolution deterioration caused by deviation of the focal position during exposure, the photosensitive resin composition layer preferably contains a structural unit based on a monomer having an aromatic hydrocarbon group. Examples of such aromatic hydrocarbon groups include substituted or unsubstituted phenyl groups and substituted or unsubstituted aralkyl groups. The content of the structural units derived from the monomer having an aromatic hydrocarbon group in the polymer P is preferably 20.0% by mass or more, and more preferably 30.0% by mass or more, based on the total mass of the polymer P. There is no particular upper limit, but it is preferably 95.0% by mass or less, and more preferably 85.0% by mass or less. When multiple types of polymer P are included, it is preferable that the average content of the structural units derived from the monomer having an aromatic hydrocarbon group falls within the above range.

[0077] Examples of the monomer having an aromatic hydrocarbon group include a monomer having an aralkyl group, styrene, and a polymerizable styrene derivative (e.g., methylstyrene, vinyltoluene, tert-butoxystyrene, acetoxystyrene, 4-vinylbenzoic acid, styrene dimer, and styrene trimer). Among them, a monomer having an aralkyl group or styrene is preferred. In one embodiment, when the monomer component having an aromatic hydrocarbon group in the polymer P is styrene, the content of the structural unit derived from styrene is preferably 20.0 to 70.0 mass%, more preferably 25.0 to 65.0 mass%, further preferably 30.0 to 60.0 mass%, and particularly preferably 30.0 to 55.0 mass%, based on the total mass of the polymer P.

[0078] Examples of the aralkyl group include a substituted or unsubstituted phenylalkyl group (excluding a benzyl group) and a substituted or unsubstituted benzyl group, with a substituted or unsubstituted benzyl group being preferred.

[0079] An example of a monomer having a phenylalkyl group is phenylethyl (meth)acrylate.

[0080] Examples of the monomer having a benzyl group include (meth)acrylates having a benzyl group, such as benzyl (meth)acrylate and chlorobenzyl (meth)acrylate; and vinyl monomers having a benzyl group, such as vinylbenzyl chloride and vinylbenzyl alcohol. Of these, benzyl (meth)acrylate is preferred. In one embodiment, when the monomer having an aromatic hydrocarbon group 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, based on the total mass of the polymer P.

[0081] The polymer P containing a structural unit derived from a monomer having an aromatic hydrocarbon group is preferably obtained by polymerizing a monomer having an aromatic hydrocarbon group with at least one type of a first monomer described below and / or at least one type of a second monomer described below.

[0082] The polymer P that does not contain a structural unit derived from a monomer having an aromatic hydrocarbon group is preferably obtained by polymerizing at least one type of first monomer described below, and more preferably obtained by copolymerizing at least one type of first monomer with at least one type of second monomer described below.

[0083] The first monomer is a monomer having a carboxy group in the molecule. Examples of the first monomer include (meth)acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, 4-vinylbenzoic acid, maleic anhydride, and maleic acid half ester. Among these, (meth)acrylic acid is preferable. The content of the constitutional unit derived from the first monomer in the polymer P is preferably from 5 to 50 mass %, more preferably from 10 to 40 mass %, and further preferably from 15 to 30 mass %, based on the total mass of the polymer P. A content of 5% by mass or more is preferable from the viewpoints of exhibiting good developability, controlling edge fusing property, etc. A content of 50% by mass or less is preferable from the viewpoints of high resolution and foot shape of the resist pattern, and further from the viewpoint of chemical resistance of the resist pattern.

[0084] The second monomer is a monomer which is non-acidic and has at least one polymerizable unsaturated group in the molecule. Examples of the second monomer include (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, cyclohexyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate; esters of vinyl alcohol such as vinyl acetate; and (meth)acrylonitrile. Among them, methyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, or n-butyl (meth)acrylate is preferred, and methyl (meth)acrylate is more preferred. The content of the constitutional unit derived from the second monomer in the polymer P is preferably from 5 to 60 mass %, more preferably from 15 to 50 mass %, and further preferably from 17 to 45 mass %, based on the total mass of the polymer P.

[0085] When the polymer P contains a structural unit derived from a monomer having an aralkyl group and / or a structural unit derived from styrene, it is preferable from the viewpoint of suppressing line width thickening and deterioration of resolution when the focal position is shifted during exposure. For example, a copolymer containing a structural unit derived from methacrylic acid, a structural unit derived from benzyl methacrylate, and a structural unit derived from styrene, a copolymer containing a structural unit derived from methacrylic acid, a structural unit derived from methyl methacrylate, a structural unit derived from benzyl methacrylate, and a structural unit derived from styrene, etc. are preferable. In one embodiment, the polymer P is preferably a polymer containing 25 to 55 mass% of structural units derived from a monomer having an aromatic hydrocarbon group, 20 to 35 mass% of structural units derived from a first monomer, and 15 to 45 mass% of structural units derived from a second monomer. In another embodiment, the polymer P is preferably a polymer containing 70 to 90 mass% of structural units derived from a monomer having an aromatic hydrocarbon group, and 10 to 25 mass% of structural units derived from a first monomer.

[0086] The polymer P may have a branched structure and / or an alicyclic structure in the side chain. The polymer P may also have a linear 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. Specific examples of monomers containing a group having a branched structure in the side chain include i-propyl (meth)acrylate, i-butyl (meth)acrylate, s-butyl (meth)acrylate, t-butyl (meth)acrylate, i-amyl (meth)acrylate, t-amyl (meth)acrylate, sec-iso-amyl (meth)acrylate, 2-octyl (meth)acrylate, 3-octyl (meth)acrylate, and t-octyl (meth)acrylate, etc. Among these, i-propyl (meth)acrylate, i-butyl (meth)acrylate, or t-butyl methacrylate is preferred, and i-propyl methacrylate or t-butyl methacrylate is more preferred.

[0087] Examples of the alicyclic structure include a monocyclic alicyclic structure and a polycyclic alicyclic structure, and a polycyclic alicyclic structure is preferred. Specific examples of monomers containing a group having an alicyclic structure in the side chain include (meth)acrylates having an alicyclic hydrocarbon group having 5 to 20 carbon atoms. More specific examples include (bicyclo[2.2.1]heptyl-2)(meth)acrylate, 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-2-(meth)acrylate, 2-methyl-2-(meth)acrylate, 2-ethyl-2-(meth)acrylate, 2-hydroxy ... Examples of the acrylate include 1-adamantyl (meth)acrylate, octahydro-4,7-menthanoinden-5-yl (meth)acrylate, octahydro-4,7-menthanoinden-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, (nor)bornyl (meth)acrylate, isobornyl (meth)acrylate, fenchyl (meth)acrylate, 2,2,5-trimethylcyclohexyl (meth)acrylate, and cyclohexyl (meth)acrylate. Among these, cyclohexyl (meth)acrylate, (nor)bornyl (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 preferred, and cyclohexyl (meth)acrylate, (nor)bornyl (meth)acrylate, isobornyl (meth)acrylate, 2-adamantyl (meth)acrylate, or tricyclodecane (meth)acrylate is more preferred.

[0088] The polymer P may be used alone or in combination of two or more. When two or more kinds are used, it is preferable to mix two kinds of polymers P containing structural units derived from monomers having aromatic hydrocarbon groups, or to mix a polymer P containing structural units derived from monomers having aromatic hydrocarbon groups with a polymer P not containing structural units derived from monomers having aromatic hydrocarbon groups. In the latter case, the content of the polymer P containing structural units derived from monomers having aromatic hydrocarbon groups is preferably 50% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, and particularly preferably 90% by mass or more, based on the total mass of the polymer P. There is no particular upper limit, and 100% by mass or less is preferable.

[0089] The synthesis of the polymer P is preferably carried out by adding an appropriate amount of a radical polymerization initiator such as benzoyl peroxide and azoisobutyronitrile to a solution obtained by diluting one or more of the above-mentioned monomers with a solvent such as acetone, methyl ethyl ketone, or isopropanol, and heating and stirring the solution. In some cases, the synthesis is carried out while dropping a part of the mixture into the reaction solution. After the reaction is completed, further solvent may be added to adjust the concentration to the desired level. As a synthesis method, bulk polymerization, suspension polymerization, or emulsion polymerization may be used in addition to solution polymerization.

[0090] 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 less, it is possible to suppress line width thickening and deterioration of resolution when the focal position is shifted during exposure. From this viewpoint, the Tg of the polymer P is more preferably 130°C or less, further preferably 120°C or less, and particularly preferably 110°C or less. In addition, it is preferable to use a polymer P having a Tg of 30°C or more from the viewpoint of improving edge fuse resistance. From this viewpoint, the Tg of the polymer P is more preferably 40°C or more, further preferably 50°C or more, particularly preferably 60°C or more, and most preferably 70°C or more.

[0091] The photosensitive resin composition layer may contain resins other than those mentioned above. 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, polysiloxane resins, polyethyleneimine, polyallylamine, and polyalkylene glycols.

[0092] As the polymer P, an alkali-soluble resin described in the description of the thermoplastic resin composition layer described below may be used.

[0093] The content of the 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 with respect to the total mass of the photosensitive resin composition layer. Setting the content of the polymer P to 90.00% by mass or less is preferable from the viewpoint of controlling the development time. On the other hand, setting the content of the polymer P to 10.00% by mass or more is preferable from the viewpoint of improving the edge fuse resistance.

[0094] <Resin having a structural unit having an acid group protected by an acid-decomposable group> When the photosensitive resin composition layer is a positive photosensitive resin composition layer, the photosensitive resin composition layer preferably 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 resin composition layer described above. The resin having an acid group protected by the above acid-decomposable group is preferably a polymer having a structural unit having an acid group protected by an acid-decomposable group (hereinafter also referred to as "structural unit A") (hereinafter also referred to as "polymer A"). In addition, the positive photosensitive resin composition layer may contain other polymers in addition to the polymer having the structural unit A. In this specification, the polymer having the structural unit A and other polymers are collectively referred to as "polymer components". In the above polymer A, due to the action of a catalytic amount of an acidic substance generated by exposure, the structural unit A having an acid group protected by an acid-decomposable group in the polymer A undergoes a deprotection reaction to become an acid group, making it possible to develop the polymer A with a developer. Preferred embodiments of the structural unit A will be described below.

[0095] The photosensitive resin composition layer may further contain a polymer other than the polymer having a structural unit having an acid group protected by an acid-decomposable group. It is also preferable that all of the polymers contained in the polymer component are polymers having at least a structural unit having an acid group, which will be described later. The photosensitive resin composition layer may further contain a polymer other than the above. The polymer component in this specification is not particularly limited and means one including other polymers that are added as necessary.

[0096] The polymer A is preferably an addition polymerization type resin, and more preferably a polymer having a structural unit derived from (meth)acrylic acid or an ester thereof. The structural unit other than the structural unit derived from (meth)acrylic acid or an ester thereof may have, for example, a structural unit derived from styrene and a structural unit derived from a vinyl compound.

[0097] From the viewpoint of solubility in a developer and transferability, the photosensitive resin composition layer preferably contains, as a polymer component, a polymer having, as the structural unit A, a structural unit A1 represented by formula (A1) described below. The polymer component preferably contains, as the structural unit A, a structural unit A1 represented by formula (A1) described below and a polymer A having a glass transition temperature of 90°C or lower. The polymer component more preferably contains, as the structural unit A, a structural unit A1 represented by formula (A1) described below and a structural unit B having an acid group described below and a polymer A having a glass transition temperature of 90°C or lower.

[0098] (Structural unit A) The structural unit A is a structural unit having an acid group protected by an acid-decomposable group. The acid group protected with an acid-decomposable group includes known acid groups and acid-decomposable groups. Examples of the acid group include a carboxy group and a phenolic hydroxyl group. Examples of the acid group protected by an acid-decomposable group include a group that is relatively easily decomposed by an acid (e.g., an ester group protected by a group represented by formula (A1), a tetrahydropyranyl ester group, a tetrahydrofuranyl ester group, and other acetal-based functional groups), and a group that is relatively difficult to decompose by an acid (e.g., a tertiary alkyl group such as a tert-butyl ester group, and a tertiary alkyl carbonate group such as a tert-butyl carbonate group). Among these, the acid-decomposable group is preferably a group having a structure protected by an acetal functional group. As the structural unit A, the structural units A1 to A4 described below are preferred, the structural units A2 or A4 are more preferred, and the structural unit A2 is even more preferred.

[0099] -Structural unit A1- As the structural unit A having an acid group protected by an acid-decomposable group, a structural unit A1 represented by the following formula (A1) is also preferred from the viewpoints of sensitivity and resolution.

[0100] [ka]

[0101] In formula (A1), R 31 and R 32 each independently represents a hydrogen atom, an alkyl group, or an aryl group; R 31 and R 32 At least one of these represents an alkyl group or an aryl group. R 31 or R 32 When is an alkyl group, R 31 and R 32 R is preferably an alkyl group having 1 to 10 carbon atoms. 31 or R 32 When is an aryl group, R 31 and R 32 R is preferably a phenyl group.31 and R 32 Each of them is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

[0102] R 33 represents an alkyl group or an aryl group, R 31 or R 32 And, R 33 may be linked to form a cyclic ether. The number of ring members of the cyclic ether is not particularly limited, but is preferably 5 to 6, and more preferably 5. R 33 As the alkyl group, an alkyl group having 1 to 10 carbon atoms is preferable, and an alkyl group having 1 to 6 carbon atoms is more preferable. R 31 ~R 33 The alkyl group and aryl group represented by the following formula may have a substituent. The substituent is not particularly limited, and examples thereof include the substituents exemplified in the group T of substituents.

[0103] R 34 represents a hydrogen atom or a methyl group. R 34 From the viewpoint that the Tg of the polymer A can be made lower, a hydrogen atom is preferable. R 34 The content of structural units in which is a hydrogen atom is preferably 20% by mass or more relative to the total amount of structural units A1 contained in polymer A. There is no particular upper limit, and it is preferably 100% by mass or less. In addition, R 34 The content (content ratio: mass ratio) of the structural unit in which the atom is a hydrogen atom is 13 This can be confirmed by the intensity ratio of peak intensities calculated by a conventional method from C-nuclear magnetic resonance spectrum (NMR) measurement.

[0104] X 0 represents a single bond or an arylene group. X 0 As the group, a single bond is preferable. The arylene group may have a substituent. The substituent is not particularly limited, and examples thereof include the substituents exemplified in the substituent group T.

[0105] - Building block A2 -

[0106] [ka]

[0107] In formula (A2), R 34 represents a hydrogen atom or a methyl group. In formula (A2), R 34 In the above formula (A1), R 34 The same definition and preferred range are also the same.

[0108] R 35 ~R 41 each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R 35 ~R 41 is preferably a hydrogen atom.

[0109] Specific examples of the structural units A1 and A2 are shown below. In addition, in the following, R 34 represents a hydrogen atom or a methyl group.

[0110] [ka]

[0111] -Structural unit A3-

[0112] [ka]

[0113] In formula (A3), R B1 ~R B4 are the same as R in the above formula (A1), 31 ~R 34 The same definition and preferred range are also the same.

[0114] X B represents a single bond or a divalent linking group. X B Examples of the divalent linking group represented by the formula (I) include an alkylene group, -C(=O)O-, -C(=O)NR N -, -O-, and combinations thereof. The alkylene group may be linear, branched, or cyclic. The alkylene group may have a substituent. The substituent is not particularly limited, but examples thereof include the substituents exemplified in the substituent group T. The alkylene group preferably has 1 to 10 carbon atoms, and more preferably has 1 to 4 carbon atoms. X B contains -C(=O)O-, the carbon atom contained in -C(=O)O- and R B4 It is preferable that the carbon atom to which X is bonded is directly bonded. B -C(=O)NR N When - is contained, -C(=O)NR N - and the carbon atoms in R B4 It is preferable that the carbon atom to which is bonded is directly bonded to the carbon atom to which is bonded. R N represents an alkyl group or a hydrogen atom, preferably an alkyl group having 1 to 4 carbon atoms or a hydrogen atom, and more preferably a hydrogen atom. Among them, X B As the group, a single bond is preferable.

[0115] R B1 ~R B3 and a group containing X B are preferably bonded to each other at the para position.

[0116] R B12 represents a substituent. R B12 is preferably an alkyl group or a halogen atom. The alkyl group preferably has 1 to 10 carbon atoms, and more preferably has 1 to 4 carbon atoms.

[0117] n represents an integer of 0 to 4. As n, 0 to 1 is preferable, and 0 is more preferable.

[0118] -Structural unit A4-

[0119] [ka]

[0120] In formula (A4), R B4 ~R B11 In formula (A2), R 34 ~R 41 The same definition and preferred range are also the same. In addition, in formula (A4), R B12 and n are each R B12 and n have the same meaning and preferred range.

[0121] Specific examples of the structural unit A4 include the following structural units. In addition, R B4 represents a hydrogen atom or a methyl group.

[0122] [ka]

[0123] The structural unit A may use one type alone, or two or more types. The content of the structural unit A relative to the total mass of the polymer A is preferably 20.0% by mass or more, more preferably from 20.0 to 90.0% by mass, and even more preferably from 30.0 to 70.0% by mass. The content of the monomer derived from the structural unit A relative to the total mass of the polymer A is preferably from 5.0 to 80.0 mass %, more preferably from 10 to 80 mass %, and even more preferably from 30 to 70 mass %.

[0124] (Structural unit B) The polymer A may contain a structural unit B having an acid group. The structural unit B is, for example, a structural unit containing an acid group that is not protected by an acid-decomposable group, i.e., an acid group that does not have a protecting group. When the polymer A contains the structural unit B, the sensitivity during pattern formation is improved, and the polymer A is easily dissolved in an alkaline developer in the development step after pattern exposure, thereby shortening the development time. Examples of the structural unit B include the structural units contained in the alkali-soluble resin described above.

[0125] The structural unit B may be used alone or in combination of two or more kinds. The content of the structural unit B relative to the total mass of the polymer A is preferably from 0.1 to 20.0 mass %, more preferably from 0.5 to 15.0 mass %, and even more preferably from 1 to 10.0 mass %.

[0126] (Other building blocks) In addition to the above-mentioned structural units A and B, the polymer A may also contain another structural unit (hereinafter also referred to as "structural unit C"). Examples of monomers that form the structural unit C include styrenes, (meth)acrylic acid alkyl esters, (meth)acrylic acid cyclic alkyl esters, (meth)acrylic acid aryl esters, unsaturated dicarboxylic acid diesters, bicyclo unsaturated compounds, maleimide compounds, unsaturated aromatic compounds, conjugated diene compounds, unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, unsaturated dicarboxylic acid anhydrides, groups having an aliphatic cyclic skeleton, and other unsaturated compounds. By adjusting at least one of the type and content of the structural unit C, it is possible to adjust various properties of the polymer A. In particular, by appropriately using the structural unit C, it is possible to easily adjust the Tg of the polymer A to 90° C. or less.

[0127] 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, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, benzyl (meth)acrylate, isobornyl (meth)acrylate, acrylonitrile, and ethylene glycol monoacetoacetate mono(meth)acrylate. Further, the compounds described in paragraphs

[0021] to

[0024] of JP-A-2004-264623 are also included.

[0128] As the structural unit C, a structural unit having an aromatic ring or a structural unit having an aliphatic cyclic skeleton is preferable. Examples of monomers that form the above structural units include styrene, tert-butoxystyrene, methylstyrene, α-methylstyrene, dicyclopentanyl (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, and benzyl (meth)acrylate. Of these, as the structural unit C, a structural unit derived from cyclohexyl (meth)acrylate is preferable.

[0129] Furthermore, as the monomer that forms the structural unit C, for example, an alkyl (meth)acrylate is also preferred, and an alkyl (meth)acrylate having an alkyl group having 4 to 12 carbon atoms is more preferred. Specific examples include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate.

[0130] The structural unit C may be used alone or in combination of two or more kinds. The content of the structural unit C is preferably 70.0% by mass or less, more preferably 60.0% by mass or less, and even more preferably 50.0% by mass or less, based on the total mass of the polymer A. The lower limit is preferably 0% by mass or more, more preferably 1.0% by mass or more, and even more preferably 5.0% by mass or more. When it is within the above range, the resolution and adhesion are further improved.

[0131] It is also preferable that polymer A contains, as structural unit C, a structural unit having an ester of an acid group in structural unit B, from the viewpoint of optimizing solubility in a developer and the physical properties of the photosensitive resin composition layer. In particular, it is preferable that the polymer A contains, as the structural unit B, a structural unit having a carboxylic acid group, and further contains, as a copolymerization component, a structural unit C containing a carboxylic acid ester group, and 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 is more preferable.

[0132] Specific examples of the polymer A are given below, but the polymer A in the present invention is not limited thereto.

[0133] [ka]

[0134] The glass transition temperature (Tg) of the polymer A is preferably 90° C. or lower. When the Tg is 90° C. or lower, the photosensitive resin composition layer has high adhesion and is more excellent in transferability. The Tg is more preferably 60° C. or lower, and even more preferably 40° C. or lower. There is no particular restriction on the lower limit of the Tg, but it is preferably −20° C. or higher, and more preferably −10° C. or higher. When the Tg of the polymer A is −20° C. or higher, good pattern formability is maintained, and, for example, when a cover film is used, the deterioration of releasability when the cover film is peeled off is suppressed. The glass transition temperature of the polymer A can be measured by differential scanning calorimetry (DSC). The specific measurement method was performed according to the method described in JIS K7121 (1987) or JIS K6240 (2011). The glass transition temperature in this specification is the extrapolated glass transition onset temperature (hereinafter also referred to as "Tig").

[0135] The molecular weight of polymer A is preferably 60,000 or less, more preferably from 2,000 to 60,000, and even more preferably from 3,000 to 50,000. The weight average molecular weight of polymer A can be measured by the above-mentioned GPC (gel permeation chromatography). The dispersity (Mw / Mn) of polymer A is preferably from 1.0 to 5.0, more preferably from 1.05 to 3.5.

[0136] The method for producing the polymer A is not particularly limited, and a known method may be used. For example, the compound can be synthesized by polymerizing a monomer for forming the structural unit A1, a monomer for forming the structural unit B having an acid group, and a monomer for forming the structural unit C in an organic solvent using a polymerization initiator.

[0137] The photosensitive resin composition layer may contain, in addition to the polymer A, other polymers. When the photosensitive resin composition layer contains another polymer, the content of the other polymer is preferably 50% by mass or less, more preferably 30% by mass or less, and even more preferably 20% by mass or less, based on the total mass of the photosensitive resin composition layer. The lower limit is not particularly limited, but is often 0% by mass or more.

[0138] Examples of other polymers include polyhydroxystyrene. Specific examples include SMA1000P, SMA2000P, SMA3000P, SMA1440F, SMA17352P, SMA2625P, and SMA3840F (all manufactured by Sartomer Corporation), ARUFONUC-3000, ARUFONUC-3510, ARUFONUC-3900, ARUFONUC-3910, ARUFONUC-3920, and ARUFONUC-3080 (all manufactured by Toagosei Co., Ltd.), and Joncryl690, Joncryl678, Joncryl67, and Joncryl586 (all manufactured by BASF).

[0139] The polymer A may be used alone or in combination of two or more. The content of polymer A is preferably from 50.00 to 99.99% by mass, and more preferably from 70.00 to 98.00% by mass, based on the total mass of the photosensitive resin composition layer.

[0140] <Photoacid generator> The photosensitive resin composition layer may contain a photoacid generator. As the photoacid generator, the photoacid generator which may be contained in the thermoplastic resin composition layer described later can be mentioned, and the preferred embodiments are also the same. The photoacid generator may be used alone or in combination of two or more kinds. The content of the photoacid generator is preferably from 0.1 to 30.0% by mass, more preferably from 1.0 to 20.0% by mass, and further preferably from 5.0 to 15.0% by mass, based on the total mass of the photosensitive resin composition layer.

[0141] <Polymerizable compound> The photosensitive resin composition layer may contain a polymerizable compound having a polymerizable group. In this specification, the term "polymerizable compound" means a compound different from the block copolymer, compound (1), and polymer P described above.

[0142] The polymerizable group of the polymerizable compound is not particularly limited as long as it is a group that participates in a polymerization reaction, and examples thereof include groups having an ethylenically unsaturated group, such as a vinyl group, an acryloyl group, a methacryloyl group, a styryl group, and a maleimide group; and groups having a cationic polymerizable group, such as an epoxy group and an oxetane group. The polymerizable group is preferably a group having an ethylenically unsaturated group, and more preferably an acryloyl group or a methacryloyl group.

[0143] As the polymerizable compound, 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, in that the photosensitivity of the photosensitive resin composition layer is superior. From the viewpoint of obtaining superior 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 even more preferably 2 or less.

[0144] In order to obtain a better balance between the photosensitivity, resolution, and peelability of the photosensitive resin composition layer, it is preferable to contain a bifunctional or trifunctional ethylenically unsaturated compound having two or three ethylenically unsaturated groups in one molecule, and it is more preferable to contain a bifunctional ethylenically unsaturated compound having two ethylenically unsaturated groups in one molecule. 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 even more preferably 55% by mass or more, relative to the total mass of the photosensitive resin composition layer, from the viewpoint of excellent peelability. The upper limit is not particularly limited, and may be 100% by mass or less. That is, all of the polymerizable compounds may be bifunctional ethylenically unsaturated compounds. Moreover, the ethylenically unsaturated compound is preferably a (meth)acrylate compound having a (meth)acryloyl group as a polymerizable group.

[0145] (Polymerizable compound B1) The photosensitive resin composition layer also preferably contains a polymerizable compound B1 having an aromatic ring and two ethylenically unsaturated groups. The polymerizable compound B1 is a bifunctional ethylenically unsaturated compound among the above-mentioned polymerizable compounds B, which has one or more aromatic rings in one molecule.

[0146] 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, even more preferably 55% by mass or more, and particularly preferably 60% by mass or more, from the viewpoint of better resolution. The upper limit is not particularly limited, 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, even more preferably 90% by mass or less, and particularly preferably 85% by mass or less.

[0147] The aromatic ring of the polymerizable compound B1 includes, for example, 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, and is preferably aromatic hydrocarbon ring, more preferably benzene ring.The aromatic ring may have a substituent. The polymerizable compound B1 may have only one aromatic ring, or may have two or more aromatic rings.

[0148] The polymerizable compound B1 preferably has a bisphenol structure from the viewpoint of improving the resolution by suppressing swelling of the photosensitive resin composition layer due to a developer. 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), with the bisphenol A structure being preferred.

[0149] An example of the polymerizable compound B1 having a bisphenol structure is a compound having a bisphenol structure and two polymerizable groups (preferably (meth)acryloyl groups) bonded to both ends of the bisphenol structure. Both ends of the bisphenol structure may be directly bonded to the two polymerizable groups, or may be bonded via one or more oxyalkylene groups. The oxyalkylene groups added to both ends of the bisphenol structure are preferably oxyethylene or oxypropylene groups, more preferably oxyethylene groups. The number of oxyalkylene groups added to the bisphenol structure is not particularly limited, but is preferably 4 to 16, more preferably 6 to 14 per molecule. The polymerizable compound B1 having a bisphenol structure is described in paragraphs

[0072] to

[0080] of JP2016-224162A, the contents of which are incorporated herein by reference.

[0150] As the polymerizable compound B1, a bifunctional ethylenically unsaturated compound having a bisphenol A structure is preferable, and 2,2-bis(4-((meth)acryloxypolyalkoxy)phenyl)propane is more preferable. Examples of 2,2-bis(4-((meth)acryloxypolyalkoxy)phenyl)propane include 2,2-bis(4-(methacryloxydiethoxy)phenyl)propane (FA-324M, Hitachi Chemical Co., Ltd.), 2,2-bis(4-(methacryloxyethoxypropoxy)phenyl)propane, 2,2-bis(4-(methacryloxypentaethoxy)phenyl)propane (BPE-500, Shin-Nakamura Chemical Co., Ltd.), and 2,2-bis(4-(methacryloxydodecaethoxy)phenyl)propane. Examples of suitable ethoxylated bisphenol A diacrylates include 2,2-bis(4-(methacryloxytetrapropoxy)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.).

[0151] As the polymerizable compound B1, a compound represented by the following general formula (B1) is also preferred.

[0152] [ka]

[0153] In general formula B1, R 1 and R 2 Each independently represents a hydrogen atom or a methyl group. 2 H 4 B stands for C 3 H 6 Each of n1 and n3 is independently an integer of 1 to 39, and n1+n3 is an integer of 2 to 40. Each of n2 and n4 is independently an integer of 0 to 29, and n2+n4 is an integer of 0 to 30. The arrangement of the structural units -(AO)- and -(BO)- may be random or in a block. In the case of a block, either -(AO)- or -(BO)- may be on the bisphenyl group side. In one embodiment, n1+n2+n3+n4 is preferably an integer of 2 to 20, more preferably an integer of 2 to 16, and even more preferably an integer of 4 to 12. Furthermore, n2+n4 is preferably an integer of 0 to 10, more preferably an integer of 0 to 4, and even more preferably an integer of 0 to 2, and particularly preferably 0.

[0154] The polymerizable compound B1 may be used alone or in combination of two or more kinds. The content of the polymerizable compound B1 is preferably 10% by mass or more, more preferably 20% by mass or more, based on the total mass of the photosensitive resin composition layer from the viewpoint of better resolution. The upper limit is not particularly limited, but is preferably 70% by mass or less, more preferably 60% by mass or less, from the viewpoint of transferability and edge fusion (phenomenon in which the photosensitive resin seeps out from the edge of the transfer member).

[0155] The photosensitive resin composition layer may contain a polymerizable compound other than the above-mentioned polymerizable compound B1. The polymerizable compound other than the polymerizable compound B1 is not particularly limited and 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 without an aromatic ring, and a trifunctional or higher ethylenically unsaturated compound can be mentioned.

[0156] Examples of monofunctional ethylenically unsaturated compounds 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.

[0157] Examples of difunctional ethylenically unsaturated compounds having no aromatic ring include alkylene glycol di(meth)acrylate, polyalkylene glycol di(meth)acrylate, urethane di(meth)acrylate, and trimethylolpropane diacrylate. Examples of alkylene glycol di(meth)acrylates 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 neopentyl glycol di(meth)acrylate. Examples of polyalkylene glycol di(meth)acrylates include polyethylene glycol di(meth)acrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, and polypropylene glycol di(meth)acrylate. Examples of urethane di(meth)acrylate include propylene oxide modified urethane di(meth)acrylate, and ethylene oxide and propylene oxide modified urethane di(meth)acrylate. 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.).

[0158] Examples of tri- or higher functional ethylenically unsaturated compounds include dipentaerythritol (tri / tetra / penta / hexa)(meth)acrylate, pentaerythritol (tri / tetra)(meth)acrylate, trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, trimethylolethane tri(meth)acrylate, isocyanuric acid tri(meth)acrylate, glycerin tri(meth)acrylate, and alkylene oxide modified versions of these. Here, "(tri / tetra / penta / hexa)(meth)acrylate" is a concept that encompasses tri(meth)acrylate, tetra(meth)acrylate, penta(meth)acrylate, and hexa(meth)acrylate, and "(tri / tetra)(meth)acrylate" is a concept that encompasses tri(meth)acrylate and tetra(meth)acrylate. In one embodiment, the photosensitive resin composition layer preferably contains the above-mentioned polymerizable compound B1 and a trifunctional or higher ethylenically unsaturated compound, and more preferably contains the above-mentioned polymerizable compound B1 and two or more trifunctional or higher ethylenically unsaturated compounds. In this case, the mass ratio of the polymerizable compound B1 to the trifunctional or higher ethylenically unsaturated compounds is preferably (total mass of the polymerizable compound B1):(total mass of the trifunctional or higher ethylenically unsaturated compounds)=1:1 to 5:1, more preferably 1.2:1 to 4:1, and even more preferably 1.5:1 to 3:1. In one embodiment, the photosensitive resin composition preferably contains the above-mentioned polymerizable compound B1 and two or more kinds of trifunctional ethylenically unsaturated compounds.

[0159] Examples of alkylene oxide modified trifunctional or higher ethylenically unsaturated compounds 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 Daicel-Allnex Corporation, etc.), ethoxylated glycerin 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.).

[0160] In addition, a polymerizable compound having an acid group (such as a carboxy group) may be used as the polymerizable compound. The acid group may 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.). As the polymerizable compound having an acid group, for example, the polymerizable compounds having an acid group described in paragraphs

[0025] to

[0030] of JP-A-2004-239942 may be used.

[0161] The molecular weight (weight average molecular weight when the polymerizable compound has a molecular weight distribution) of the polymerizable compound (including the polymerizable compound B1) is preferably from 200 to 3,000, more preferably from 280 to 2,200, and even more preferably from 300 to 2,200.

[0162] The polymerizable compounds may be used alone or in combination of two or more. The content of the polymerizable compound is preferably from 1 to 70% by mass, more preferably from 5 to 70% by mass, further preferably from 20 to 70% by mass, and particularly preferably from 40 to 60% by mass, based on the total mass of the photosensitive resin composition layer.

[0163] <Polymerization initiator> The photosensitive resin composition layer may contain a polymerization initiator. The polymerization initiator is selected depending on the type of polymerization reaction, and examples thereof include a thermal polymerization initiator and a photopolymerization initiator. The polymerization initiator may be a radical polymerization initiator or a cationic polymerization initiator.

[0164] The photosensitive resin composition layer preferably contains a photopolymerization initiator. A photopolymerization initiator is a compound that initiates polymerization of a polymerizable compound when exposed to active light such as ultraviolet light, visible light, and X-rays. The photopolymerization initiator is not particularly limited, and any known photopolymerization initiator can be used. Examples of the photopolymerization initiator include a photoradical polymerization initiator and a photocationic polymerization initiator, and a photoradical polymerization initiator is preferred.

[0165] Examples of the photoradical polymerization initiator include a photopolymerization initiator having an oxime ester structure, a photopolymerization initiator having an α-aminoalkylphenone structure, a photopolymerization initiator having an α-hydroxyalkylphenone structure, a photopolymerization initiator having an acylphosphine oxide structure, and a photopolymerization initiator having an N-phenylglycine structure.

[0166] From the viewpoints of photosensitivity, visibility of exposed and non-exposed areas, and resolution, the photosensitive resin composition layer preferably contains, as a photoradical polymerization initiator, at least one selected from the group consisting of 2,4,5-triarylimidazole dimers and derivatives thereof. Note that the two 2,4,5-triarylimidazole structures in the 2,4,5-triarylimidazole dimer and derivatives thereof may be the same or different. Examples of derivatives of 2,4,5-triarylimidazole dimers include 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(o-chlorophenyl)-4,5-di(methoxyphenyl)imidazole dimer, 2-(o-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(o-methoxyphenyl)-4,5-diphenylimidazole dimer, and 2-(p-methoxyphenyl)-4,5-diphenylimidazole dimer.

[0167] As the photoradical polymerization initiator, for example, the polymerization initiators described in paragraphs

[0031] to

[0042] of JP2011-095716A and paragraphs

[0064] to

[0081] of JP2015-014783A may be used.

[0168] Examples of the photoradical polymerization initiator include ethyl dimethylaminobenzoate (DBE, CAS No. 10287-53-3), benzoin methyl ether, anisyl (p,p'-dimethoxybenzyl), TAZ-110 (trade name: manufactured by Midori Chemical Industry Co., Ltd.), benzophenone, 4,4'-bis(diethylamino)benzophenone, TAZ-111 (trade name: manufactured by Midori Chemical Industry Co., Ltd.), IrgacureOXE01, OXE02, OXE03, OXE04 (manufactured by BASF), Omnirad651 and 369 (trade name: manufactured by IGM Resins BV), and 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.).

[0169] Commercially available photoradical polymerization initiators include, for example, 1-[4-(phenylthio)]-1,2-octanedione-2-(O-benzoyloxime) (trade name: IRGACURE (registered trademark) OXE-01, manufactured by BASF), 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone-1-(O-acetyloxime) (trade 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 (trade name: Omnirad 379EG, manufactured by IGM Resins), BV), 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one (trade name: Omnirad 907, IGM Resins BV), 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)benzyl]phenyl}-2-methylpropan-1-one (trade name: Omnirad 127, IGM Resins BV), 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone-1 (trade name: Omnirad 369, IGM Resins BV), 2-hydroxy-2-methyl-1-phenylpropan-1-one (trade name: Omnirad 1173, IGM Resins BV), 1-hydroxycyclohexyl phenyl ketone (trade name: Omnirad 184, IGM Resins BV), BV), 2,2-dimethoxy-1,2-diphenylethan-1-one (trade name: Omnirad 651, IGM Resins BV), 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (trade name: Omnirad TPO H, IGM Resins BV), bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (trade name: Omnirad 819, IGM Resins BV(trade name: Lunar 6, manufactured by DKSH Japan Co., Ltd.), 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbisimidazole (2-(2-chlorophenyl)-4,5-diphenylimidazole dimer) (trade name: B-CIM, manufactured by Hampford Chemical Industry Co., Ltd.), and 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer (trade name: BCTB, manufactured by Tokyo Chemical Industry Co., Ltd.), 1-[4-(phenylthio)phenyl]-3-cyclopentylpropane-1,2-dione-2-(O-benzoyloxime) (trade name: TR-PBG-305, manufactured by Changzhou Chemical Industry Co., Ltd.), Examples of such oxime include 1,2-propanedione, 3-cyclohexyl-1-[9-ethyl-6-(2-furanylcarbonyl)-9H-carbazol-3-yl]-, 2-(O-acetyloxime) (trade name: TR-PBG-326, Changzhou Strong Electronic New Materials Co., Ltd.), and 3-cyclohexyl-1-(6-(2-(benzoyloxyimino)hexanoyl)-9-ethyl-9H-carbazol-3-yl)-propane-1,2-dione-2-(O-benzoyloxime) (trade name: TR-PBG-391, Changzhou Strong Electronic New Materials Co., Ltd.).

[0170] A photocationic polymerization initiator (photoacid generator) is a compound that generates an acid when exposed to actinic rays. As the photocationic polymerization initiator, a compound that responds to actinic rays having a wavelength of 300 nm or more, preferably 300 to 450 nm, and generates an acid is preferred, but the chemical structure is not limited. In addition, even if a photocationic polymerization initiator is not directly sensitive to actinic rays having a wavelength of 300 nm or more, it can be preferably used in combination with a sensitizer as long as it responds to actinic rays having a wavelength of 300 nm or more and generates an acid when used in combination with a sensitizer. As the photocationic polymerization initiator, a photocationic polymerization initiator that generates an acid having a pKa of 4 or less is preferable, a photocationic polymerization initiator that generates an acid having a pKa of 3 or less is more preferable, and a photocationic polymerization initiator that generates an acid having a pKa of 2 or less is particularly preferable. The lower limit of the pKa is not particularly set, but is preferably, for example, -10.0 or more.

[0171] The photocationic polymerization initiator includes an ionic photocationic polymerization initiator and a nonionic photocationic polymerization initiator. Examples of the ionic photocationic polymerization initiator include onium salt compounds such as diaryliodonium salts and triarylsulfonium salts, as well as quaternary ammonium salts. As the ionic photocationic polymerization initiator, the ionic photocationic polymerization initiators described in paragraphs

[0114] to

[0133] of JP2014-085643A may be used.

[0172] Examples of nonionic photocationic polymerization initiators include trichloromethyl-s-triazines, diazomethane compounds, imide sulfonate compounds, and oxime sulfonate compounds. As trichloromethyl-s-triazines, diazomethane compounds, and imide sulfonate compounds, compounds described in paragraphs

[0083] to

[0088] of JP 2011-221494 A may be used. As oxime sulfonate compounds, compounds described in paragraphs

[0084] to

[0088] of WO 2018 / 179640 may be used. Examples of the photocationic polymerization initiator (photoacid generator) include photoacid generators described in the description of the thermoplastic resin composition layer described below and the colored resin composition layer described below.

[0173] The photosensitive resin composition layer preferably contains a photoradical polymerization initiator, and more preferably contains at least one selected from the group consisting of 2,4,5-triarylimidazole dimers and derivatives thereof.

[0174] The polymerization initiator may be used alone or in combination of two or more kinds. The content of the polymerization initiator (preferably a photopolymerization initiator) is not particularly limited, but is preferably 0.1 mass% or more, more preferably 0.5 mass% or more, and even more preferably 1.0 mass% or more, based on the total mass of the photosensitive resin composition layer. The upper limit is not particularly limited, but is preferably 20 mass% or less, more preferably 15 mass% or less, more preferably 10 mass% or less, and particularly preferably 5 mass% or less, based on the total mass of the photosensitive resin composition layer.

[0175] <Dye> From the viewpoints of visibility of exposed and unexposed parts, pattern visibility after development, and resolution, the photosensitive resin composition layer preferably contains a dye (also referred to as "dye N") whose maximum absorption wavelength in the wavelength range of 400 to 780 nm during color development is 450 nm or more and whose maximum absorption wavelength changes with an acid, a base, or a radical. When dye N is contained, the adhesion with adjacent layers (for example, temporary support and intermediate layer) is improved, and the resolution is more excellent, although the detailed mechanism is unknown.

[0176] In this specification, the dye "whose maximum absorption wavelength changes due to an acid, a base, or a radical" may mean any of an embodiment in which a dye in a colored state is decolorized by an acid, a base, or a radical, a dye in a decolorized state is colored by an acid, a base, or a radical, and a dye in a colored state is changed to a colored state of another hue. Specifically, the dye N may be a compound that changes from a decolorized state to a colored state by exposure, or may be a compound that changes from a colored state to a decolored state by exposure. In this case, the dye may be a dye whose colored or decolored state changes when an acid, base, or radical is generated in the photosensitive resin composition layer by exposure and acts on the dye, or a dye whose colored or decolored state changes when the state (e.g., pH) in the photosensitive resin composition layer changes due to an acid, base, or radical. The dye may also be a dye whose colored or decolored state changes when it is directly stimulated by an acid, base, or radical without exposure.

[0177] Among these, from the viewpoints of visibility and resolution of exposed and unexposed areas, dye N is preferably a dye whose maximum absorption wavelength changes in response to an acid or a radical, and more preferably a dye whose maximum absorption wavelength changes in response to a radical. From the viewpoints of visibility and resolution of exposed and unexposed areas, the photosensitive resin composition layer preferably contains, as dye N, both a dye whose maximum absorption wavelength changes due to radicals, and a photoradical polymerization initiator. From the viewpoint of visibility of exposed and unexposed areas, dye N is preferably a dye that develops color in response to an acid, a base, or a radical.

[0178] An example of the color-developing mechanism of dye N is a mode in which a photoradical polymerization initiator, a cationic photopolymerization initiator (photoacid generator), or a photobase generator is added to a photosensitive resin composition layer, and after exposure, a radical-reactive dye, an acid-reactive dye, or a base-reactive dye (e.g., a leuco dye) develops color due to a radical, acid, or base generated from the photoradical polymerization initiator, the photocationic photopolymerization initiator, or the photobase generator.

[0179] From the viewpoint of visibility of exposed and unexposed areas, dye N preferably has a maximum absorption wavelength in the wavelength range of 400 to 780 nm upon color development of 550 nm or more, more preferably 550 to 700 nm, and even more preferably 550 to 650 nm. Furthermore, dye N may have only one maximum absorption wavelength in the wavelength range of 400 to 780 nm when it develops color, or may have two or more maximum absorption wavelengths. When dye N has two or more maximum absorption wavelengths in the wavelength range of 400 to 780 nm when it develops color, it is sufficient that the maximum absorption wavelength having the highest absorbance among the two or more maximum absorption wavelengths is 450 nm or more.

[0180] The maximum absorption wavelength of dye N is obtained by measuring the transmission spectrum of a solution containing dye N (liquid temperature 25°C) in the range of 400 to 780 nm using a spectrophotometer UV3100 (manufactured by Shimadzu Corporation) in an atmospheric environment and detecting the wavelength at which the light intensity is minimal (maximum absorption wavelength).

[0181] Examples of the dye that develops or loses color upon exposure to light include leuco compounds. Examples of dyes that are decolorized by exposure to light include leuco compounds, diarylmethane dyes, oxazine dyes, xanthene dyes, iminonaphthoquinone dyes, azomethine dyes, and anthraquinone dyes. As the dye N, a leuco compound is preferable from the viewpoint of visibility of exposed and non-exposed areas.

[0182] Examples of the leuco compound include leuco compounds having a triarylmethane skeleton (triarylmethane-based dyes), leuco compounds having a spiropyran skeleton (spiropyran-based dyes), leuco compounds having a fluoran skeleton (fluoran-based dyes), leuco compounds having a diarylmethane skeleton (diarylmethane-based dyes), leuco compounds having a rhodamine lactam skeleton (rhodamine lactam-based dyes), leuco compounds having an indolylphthalide skeleton (indolylphthalide-based dyes), and leuco compounds having a leucoauramine skeleton (leucoauramine-based dyes). Among these, triarylmethane dyes or fluoran dyes are preferred, and leuco compounds having a triphenylmethane skeleton (triphenylmethane dyes) or fluoran dyes are more preferred.

[0183] From the viewpoint of visibility of the exposed and non-exposed parts, the leuco compound preferably has a lactone ring, a sultine ring, or a sultone ring. This allows the lactone ring, the sultine ring, or the sultone ring of the leuco compound to react with a radical generated from a photoradical polymerization initiator or an acid generated from a photocationic polymerization initiator, thereby changing the leuco compound to a ring-closed state to cause discoloration, or changing the leuco compound to a ring-open state to cause color development. The leuco compound is preferably a compound having a lactone ring, a sultine ring, or a sultone ring, which is colored by being opened by a radical or an acid, and more preferably a compound having a lactone ring, which is colored by being opened by a radical or an acid.

[0184] Examples of the dye N include the following dyes and leuco compounds. Specific examples of dyes among the pigments N include brilliant green, ethyl violet, methyl green, crystal violet, basic fuchsin, methyl violet 2B, quinaldine red, rose bengal, metanil yellow, thymolsulfophthalein, xylenol blue, methyl orange, paramethyl red, Congo red, benzopurpurin 4B, α-naphthyl red, Nile blue 2B, Nile blue A, methyl violet, malachite green, parafuchsin, Victoria Pure Blue-naphthalenesulfonate, Victoria Pure Blue BOH (manufactured by Hodogaya Chemical Industry Co., Ltd.), Oil Blue #603 (manufactured by Orient Chemical Industry Co., Ltd.), Oil Pink #312 (manufactured by Orient Chemical Industry Co., Ltd.), Oil Red 5B (manufactured by Orient Chemical Industry Co., Ltd.), Oil Scarlet #308 (manufactured by Orient Chemical Industry Co., Ltd.), and Examples of the oil-soluble pigments include Orient Chemical Industry Co., Ltd.), Oil Red OG (Orient Chemical Industry Co., Ltd.), Oil Red RR (Orient Chemical Industry Co., Ltd.), Oil Green #502 (Orient Chemical Industry Co., Ltd.), Spiron Red BEH Special (Hodogaya Chemical Industry Co., Ltd.), m-cresol purple, cresol red, rhodamine B, rhodamine 6G, sulforhodamine B, auramine, 4-p-diethylaminophenyliminonaphthoquinone, 2-carboxyanilino-4-p-diethylaminophenyliminonaphthoquinone, 2-carboxystearylamino-4-pN,N-bis(hydroxyethyl)amino-phenyliminonaphthoquinone, 1-phenyl-3-methyl-4-p-diethylaminophenylimino-5-pyrazolone, and 1-β-naphthyl-4-p-diethylaminophenylimino-5-pyrazolone.

[0185] Specific examples of the leuco compound among the dyes N include p,p',p''-hexamethyltriaminotriphenylmethane (leuco crystal violet), Pergascript Blue SRB (manufactured by Ciba-Geigy), crystal violet lactone, malachite green lactone, benzoyl leucomethylene blue, 2-(N-phenyl-N-methylamino)-6-(Np-tolyl-N-ethyl)aminofluoran, 2-anilino-3-methyl-6-(N-ethyl-p-toluidino)fluoran, 3,6-dimethoxyfluoran, 3-(N,N-diethylamino)-5-methyl-7-(N,N-dibenzylamino)fluoran, 3-(N-cyclohexyl-N-methylamino)-6-(N-cyclohexyl-N-methylamino)fluoran, and the like. -methyl-7-anilinofluoran, 3-(N,N-diethylamino)-6-methyl-7-anilinofluoran, 3-(N,N-diethylamino)-6-methyl-7-xylidinofluoran, 3-(N,N-diethylamino)-6-methyl-7-chlorofluoran, 3-(N,N-diethylamino)-6-methoxy-7-aminofluoran, 3-(N,N-diethylamino)-7-(4-chloroanilino)fluoran, 3-(N,N-diethylamino)-7-chlorofluoran, 3-(N,N-diethylamino)- 3-(N,N-diethylamino)-7-benzylaminofluoran, 3-(N,N-diethylamino)-7,8-benzofluoran, 3-(N,N-dibutylamino)-6-methyl-7-anilinofluoran, 3-(N,N-dibutylamino)-6-methyl-7-xylidinofluoran, 3-piperidino-6-methyl-7-anilinofluoran, 3-pyrrolidino-6-methyl-7-anilinofluoran, 3,3-bis(1-ethyl-2-methylindol-3-yl)phthalide, 3,3-bis(1-n-butyl-2-methylindol-3-yl)phthalide 3-(4-diethylamino-2-ethoxyphenyl)-3-(1-ethyl-2-methylindol-3-yl)phthalide, 3,3-bis(p-dimethylaminophenyl)-6-dimethylaminophthalide, 3-(4-diethylamino-2-ethoxyphenyl)-3-(1-ethyl-2-methylindol-3-yl)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.

[0186] From the viewpoints of visibility of exposed and unexposed areas, pattern visibility after development, and resolution, dye N is preferably a dye whose maximum absorption wavelength changes in response to radicals, and more preferably a dye that develops color in response to radicals. As dye N, leuco crystal violet, crystal violet lactone, brilliant green, or Victoria Pure Blue-naphthalenesulfonate is preferred.

[0187] The dye N may be used alone or in combination of two or more kinds. From the viewpoints of visibility of exposed and unexposed areas, pattern visibility after development, and resolution, the content of dye N is preferably 0.1 mass % or more, more preferably 0.1 to 10 mass %, even more preferably 0.1 to 5 mass %, and particularly preferably 0.1 to 1 mass %, relative to the total mass of the photosensitive resin composition layer.

[0188] The content of dye N means the content of dye when all of dye N contained in the total mass of the photosensitive resin composition layer is in a color-developing state. A method for quantifying the content of dye N will be described below using a dye that develops color by radicals as an example. A solution in which 0.001 g of dye is dissolved and a solution in which 0.01 g of dye is dissolved are prepared in 100 mL of methyl ethyl ketone. A photoradical polymerization initiator Irgacure OXE01 (trade name, manufactured by BASF Japan) is added to each of the obtained solutions, and radicals are generated by irradiating light of 365 nm, causing all of the dyes to develop color. Then, in an air atmosphere, the absorbance of each solution at a liquid temperature of 25°C is measured using a spectrophotometer (UV3100, manufactured by Shimadzu Corporation), and a calibration curve is created. Next, the absorbance of the solution in which all the dye has been colored is measured in the same manner as above, except that 3 g of the photosensitive resin composition layer is dissolved in methyl ethyl ketone instead of the dye. The content of the dye relative to the total mass of the photosensitive resin composition layer is calculated based on the calibration curve from the absorbance of the solution containing the obtained photosensitive resin composition layer.

[0189] <Thermal crosslinkable compound> From the viewpoints of the strength of the resulting cured film and the adhesion of the resulting uncured film, the photosensitive resin composition layer preferably contains a thermally crosslinkable compound. In this specification, a thermally crosslinkable compound having an ethylenically unsaturated group, which will be described later, is not regarded as a polymerizable compound but as a thermally crosslinkable compound. Examples of the thermally crosslinkable compound include methylol compounds and blocked isocyanate compounds. Among these, blocked isocyanate compounds are preferred from the viewpoints of the strength of the resulting cured film and the adhesion of the resulting uncured film. Since the blocked isocyanate compound reacts with a hydroxy group and a carboxy group, for example, when a resin and / or a polymerizable compound has at least one of a hydroxy group and a carboxy group, the hydrophilicity of the formed film tends to decrease, and the functionality tends to be enhanced when the film obtained by curing the photosensitive resin composition layer is used as a protective film. The blocked isocyanate compound refers to a compound having a structure in which the isocyanate group of an isocyanate is protected (so-called masked) with a blocking agent.

[0190] The dissociation temperature of the blocked isocyanate compound is not particularly limited, but is preferably from 100 to 160°C, and more preferably from 130 to 150°C. The dissociation temperature of a blocked isocyanate means "the temperature of an endothermic peak accompanying the deprotection reaction of a blocked isocyanate when measured by DSC (Differential Scanning Calorimetry) analysis using a differential scanning calorimeter." As the differential scanning calorimeter, for example, a differential scanning calorimeter (model: DSC6200) manufactured by Seiko Instruments Inc. can be suitably used. However, the differential scanning calorimeter is not limited to this.

[0191] Examples of blocking agents having a dissociation temperature of 100 to 160°C include active methylene compounds [malonic acid diesters (dimethyl malonate, diethyl malonate, di-n-butyl malonate, di-2-ethylhexyl malonate, etc.)], and oxime compounds (formaldoxime, acetaldoxime, acetoxime, methyl ethyl ketoxime, cyclohexanone oxime, and other compounds having a structure represented by -C(=N-OH)- in the molecule). Among them, as the blocking agent having a dissociation temperature of 100 to 160° C., for example, at least one selected from oxime compounds is preferable from the viewpoint of storage stability.

[0192] The blocked isocyanate compound preferably has an isocyanurate structure from the viewpoints of, for example, improving the brittleness of the film and improving the adhesive strength to the transfer target. A blocked isocyanate compound having an isocyanurate structure can be obtained, for example, by protecting hexamethylene diisocyanate by converting it into an isocyanurate. Among blocked isocyanate compounds having an isocyanurate structure, a compound having an oxime structure in which an oxime compound is used as a blocking agent is preferred from the viewpoints that the dissociation temperature can be set in a preferred range more easily than a compound not having an oxime structure, and that development residues can be reduced.

[0193] The blocked isocyanate compound may have a polymerizable group. The polymerizable group is not particularly limited, and any known polymerizable group can be used, with a radically polymerizable group being preferred. Examples of the polymerizable group include ethylenically unsaturated groups such as a (meth)acryloxy group, a (meth)acrylamide group, and a styryl group, as well as groups having an epoxy group such as a glycidyl group. Of these, the polymerizable group is preferably an ethylenically unsaturated group, more preferably a (meth)acryloxy group, and even more preferably an acryloxy group.

[0194] As the blocked isocyanate compound, commercially available products can be used. Examples of commercially available blocked isocyanate compounds include Karenz (registered trademark) AOI-BM, Karenz (registered trademark) MOI-BM, Karenz (registered trademark) MOI-BP, and the like (all manufactured by Showa Denko K.K.), and the blocked Duranate series (e.g., Duranate (registered trademark) TPA-B80E, Duranate (registered trademark) WT32-B75P, and the like, manufactured by Asahi Kasei Chemicals Corporation). In addition, as the blocked isocyanate compound, a compound having the following structure can also be used.

[0195] [ka]

[0196] The thermally crosslinkable compounds may be used alone or in combination of two or more. The content of the thermally crosslinkable compound is preferably from 1 to 50% by mass, and more preferably from 5 to 30% by mass, based on the total mass of the photosensitive resin composition layer.

[0197] <Additives> The photosensitive resin composition layer may contain known additives, if necessary, in addition to the above components. Examples of additives include radical polymerization inhibitors, sensitizers, plasticizers, heterocyclic compounds (such as triazoles), benzotriazoles, carboxybenzotriazoles, pyridines (such as isonicotinamide), purine bases (such as adenine), and surfactants. Each of the additives may be used alone or in combination of two or more.

[0198] Examples of the radical polymerization inhibitor include the thermal polymerization inhibitors described in paragraph

[0018] of Japanese Patent No. 4502784. Among them, phenothiazine, phenoxazine, or 4-methoxyphenol is preferable. Other radical polymerization inhibitors include naphthylamine, cuprous chloride, nitrosophenylhydroxyamine aluminum salt, and diphenylnitrosamine. In order not to impair the sensitivity of the photosensitive resin composition layer, it is preferable to use nitrosophenylhydroxyamine aluminum salt as the radical polymerization inhibitor.

[0199] Examples of benzotriazoles include 1,2,3-benzotriazole, 1-chloro-1,2,3-benzotriazole, bis(N-2-ethylhexyl)aminomethylene-1,2,3-benzotriazole, bis(N-2-ethylhexyl)aminomethylene-1,2,3-tolyltriazole, and bis(N-2-hydroxyethyl)aminomethylene-1,2,3-benzotriazole.

[0200] Examples of carboxybenzotriazoles include 4-carboxy-1,2,3-benzotriazole, 5-carboxy-1,2,3-benzotriazole, N-(N,N-di-2-ethylhexyl)aminomethylenecarboxybenzotriazole, N-(N,N-di-2-hydroxyethyl)aminomethylenecarboxybenzotriazole, and N-(N,N-di-2-ethylhexyl)aminoethylenecarboxybenzotriazole. Examples of carboxybenzotriazoles that can be used include commercially available products such as CBT-1 (Johoku Chemical Industry Co., Ltd., trade name).

[0201] The total content of the radical polymerization inhibitor, benzotriazoles, and carboxybenzotriazoles is preferably 0.01 to 3 mass%, and more preferably 0.05 to 1 mass%, when the total mass of the photosensitive resin composition layer is taken as 100 mass%. A content of 0.01 mass% or more is preferable from the viewpoint of imparting storage stability to the composition. On the other hand, a content of 3 mass% or less is preferable from the viewpoint of maintaining sensitivity and suppressing decolorization of the dye.

[0202] The sensitizer is not particularly limited, and known sensitizers, dyes and pigments can be used. Examples of the sensitizer include dialkylaminobenzophenone compounds, pyrazoline compounds, anthracene compounds, coumarin compounds, xanthone compounds, thioxanthone compounds, acridone compounds, oxazole compounds, benzoxazole compounds, thiazole compounds, benzothiazole compounds, triazole compounds (e.g., 1,2,4-triazole), stilbene compounds, triazine compounds, thiophene compounds, naphthalimide compounds, triarylamine compounds and aminoacridine compounds.

[0203] The content of the sensitizer can be appropriately selected depending on the purpose. The content of the sensitizer is preferably 0.01 to 5 mass %, and more preferably 0.05 to 1 mass %, based on the total mass of the photosensitive resin composition layer, from the viewpoints of improving the sensitivity to the light source and improving the curing speed by balancing the polymerization rate and chain transfer.

[0204] Examples of the plasticizer and heterocyclic compound include the compounds described in paragraphs

[0097] to

[0103] and

[0111] to

[0118] of WO 2018 / 179640.

[0205] The photosensitive resin composition may further contain known additives such as metal oxide particles, antioxidants, dispersants, acid amplifiers, development accelerators, conductive fibers, ultraviolet absorbers, thickeners, crosslinking agents, and organic or inorganic suspending agents. Additives contained in the photosensitive resin composition include compounds described in paragraphs

[0165] to

[0184] of JP2014-085643A, the contents of which are incorporated herein by reference.

[0206] <Physical Properties of Photosensitive Resin Composition Layer> (Film thickness) The thickness (film thickness) of the photosensitive resin composition layer is not particularly limited, and is, for example, often 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, which can improve the developability of the photosensitive resin composition layer and improve the resolution. In one embodiment, the thickness is preferably from 0.5 to 5 μm, more preferably from 0.5 to 4 μm, and even more preferably from 0.5 to 3 μm.

[0207] From the viewpoint of superior adhesion, the transmittance of light having a wavelength of 365 nm through the photosensitive resin composition layer is preferably 10% or more, more preferably 30% or more, and even more preferably 50% or more. There is no particular upper limit, but it is preferably 99.9% or less.

[0208] (Impurities, etc.) The photosensitive resin composition layer may contain a predetermined amount of impurities. Specific examples of impurities include sodium, potassium, magnesium, calcium, iron, manganese, copper, aluminum, titanium, chromium, cobalt, nickel, zinc, tin, halogens, and ions thereof. Among them, halide ions, sodium ions, and potassium ions are easily mixed in as impurities, so it is preferable to set the content to the following.

[0209] The upper limit of the content of impurities is preferably 80 ppm by mass or less, more preferably 10 ppm by mass or less, and even more preferably 2 ppm by mass or less, based on the total mass of the photosensitive resin composition layer. The lower limit of the content is preferably 1 ppb by mass or more, and more preferably 0.1 ppm by mass or more.

[0210] Methods for keeping the amount of impurities within the above range include selecting a raw material for the photosensitive resin composition layer that has a low content of impurities, preventing the inclusion of impurities during the preparation of the photosensitive resin composition layer, and removing the impurities by washing. By such methods, the amount of impurities can be kept within the above range.

[0211] The amount of impurities can be quantified by known methods such as ICP (Inductively Coupled Plasma) emission spectrometry, atomic absorption spectrometry, and ion chromatography.

[0212] The content 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 is preferably small. The upper limit of the content of these compounds is preferably 100 ppm by mass or less, more preferably 20 ppm by mass or less, and even more preferably 4 ppm by mass or less, based on the total mass of the photosensitive resin composition layer. The lower limit of the content is preferably 10 ppb by mass or more, more preferably 100 ppb by mass or more, based on the total mass of the photosensitive resin composition layer. The content of these compounds can be suppressed in the same manner as the above-mentioned metal impurities. In addition, they can be quantified by a known measurement method.

[0213] (Residual monomer) The photosensitive resin composition layer may contain residual monomers of the structural units of the polymer P and the polymer A described above. From the viewpoints of patterning property and reliability, the content of the residual monomer is preferably 5,000 ppm by mass or less, more preferably 2,000 ppm by mass or less, and even more preferably 500 ppm by mass or less, based on the total mass of the polymer P or the polymer A. Although there is no particular lower limit, the content is preferably 1 ppm by mass or more, and more preferably 10 ppm by mass or more, based on the total mass of the polymer P or the polymer A. From the viewpoints of patterning property and reliability, the residual monomer of each structural unit of polymer P or polymer A is preferably 3,000 ppm by mass or less, more preferably 600 ppm by mass or less, and even more preferably 100 ppm by mass or less, based on the total mass of the photosensitive resin composition layer. Although there is no particular lower limit, it is preferably 0.1 ppm by mass or more, and more preferably 1 ppm by mass or more, based on the total mass of the photosensitive resin composition layer. The amount of the residual monomer can be measured by a known method such as liquid chromatography or gas chromatography.

[0214] [Thermoplastic resin composition layer] The resin composition layer may be a thermoplastic resin composition layer. For example, in a transfer film having a temporary support and a resin composition layer, the thermoplastic resin composition layer is preferably formed between the temporary support and the resin composition layer. By having a thermoplastic resin composition layer between the temporary support and the resin composition layer, the transfer film has improved conformability to the substrate during the bonding process between the transfer film and the substrate, preventing air bubbles from being trapped between the substrate and the transfer film, and improving adhesion to an adjacent layer (e.g., the temporary support).

[0215] The thermoplastic resin composition layer refers to an embodiment in which the alkali-soluble resin in the photosensitive resin composition layer is a thermoplastic resin. The thermoplastic resin may be alkali-soluble, that is, it may be a resin that exhibits thermoplasticity and also exhibits alkali-solubility (hereinafter also referred to as "alkali-soluble thermoplastic resin"). The thermoplastic resin composition layer may contain other thermoplastic resins in addition to the alkali-soluble thermoplastic resin.

[0216] <Alkali-soluble thermoplastic resin> Examples of alkali-soluble thermoplastic resins include acrylic resins, polystyrene 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, polysiloxane resins, polyethyleneimines, polyallylamine, and polyalkylene glycols.

[0217] As the alkali-soluble thermoplastic resin, from the viewpoints of developability and adhesion to adjacent layers, an acrylic resin is preferred. Here, the acrylic resin refers to a resin having at least one type of structural unit selected from the group consisting of structural units derived from (meth)acrylic acid, structural units derived from (meth)acrylic acid esters, and structural units derived from (meth)acrylic acid amides. The acrylic resin preferably has a total content of constituent units derived from (meth)acrylic acid, constituent units derived from (meth)acrylic acid ester, and constituent units derived from (meth)acrylic acid amide of 30 mass% or more, more preferably 50 mass% or more, based on the total mass of the acrylic resin. In particular, the total content of the structural units derived from (meth)acrylic acid and the structural units derived from (meth)acrylic acid esters is preferably 30 to 100 mass %, and more preferably 50 to 100 mass %, based on the total mass of the acrylic resin.

[0218] The alkali-soluble thermoplastic resin is preferably a polymer having an acid group. Examples of the acid group include a carboxy group, a sulfo group, a phosphoric acid group, and a phosphonic acid group, with the carboxy group being preferred. The acid value of the alkali-soluble thermoplastic resin is preferably 60 mgKOH / g or more from the viewpoint of developability. The upper limit of the acid value of the alkali-soluble thermoplastic resin is not particularly limited, but is preferably 300 mgKOH / g or less, more preferably 250 mgKOH / g or less, even more preferably 200 mgKOH / g or less, and particularly preferably 150 mgKOH / g or less.

[0219] The alkali-soluble thermoplastic resin having an acid value of 60 mgKOH / g or more (preferably, a carboxyl group-containing acrylic resin) is not particularly limited, and can be appropriately selected from known resins. Examples of such an alkali-soluble resin include an acrylic resin having a carboxy group with an acid value of 60 mgKOH / g or more among the polymers described in paragraph

[0025] of JP 2011-095716 A, an acrylic resin having a carboxy group with an acid value of 60 mgKOH / g or more among the polymers described in paragraphs

[0033] to

[0052] of JP 2010-237589 A, and an acrylic resin having a carboxy group with an acid value of 60 mgKOH / g or more among the binder polymers described in paragraphs

[0053] to

[0068] of JP 2016-224162 A. The copolymerization ratio of the structural unit having a carboxy group in the acrylic resin having a carboxy group is preferably from 5 to 50 mass %, more preferably from 10 to 40 mass %, and even more preferably from 12 to 30 mass %, based on the total mass of the acrylic resin. As the alkali-soluble thermoplastic resin, from the viewpoints of developability and adhesion to adjacent layers, an acrylic resin having a structural unit derived from (meth)acrylic acid is particularly preferred.

[0220] The alkali-soluble thermoplastic resin may have a reactive group. The reactive group may be any group capable of addition polymerization, and examples of the reactive group include ethylenically unsaturated groups; polycondensable groups such as hydroxyl groups and carboxyl groups; and polyaddition reactive groups such as epoxy groups and (blocked) isocyanate groups.

[0221] 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 even more preferably 20,000 to 50,000.

[0222] The alkali-soluble thermoplastic resin may be used alone or in combination of two or more kinds. From the viewpoints of developability and adhesion to adjacent layers, the content of the alkali-soluble thermoplastic resin is preferably 10.00 to 99.00 mass%, more preferably 20.00 to 90.00 mass%, even more preferably 40.00 to 80.00 mass%, and particularly preferably 50.00 to 75.00 mass%, relative to the total mass of the thermoplastic resin composition layer.

[0223] <Dye> The thermoplastic resin composition layer preferably contains a dye (also simply referred to as "dye B") that has a maximum absorption wavelength of 450 nm or more in the wavelength range of 400 to 780 nm when colored and whose maximum absorption wavelength changes due to an acid, a base, or a radical. A preferred embodiment of dye B is the same as the preferred embodiment of dye N described above, except for the points described below.

[0224] From the viewpoints of visibility of exposed and unexposed areas and resolution, dye B is preferably a dye whose maximum absorption wavelength changes in response to an acid or a radical, and more preferably a dye whose maximum absorption wavelength changes in response to an acid. From the viewpoints of visibility and resolution of exposed and unexposed areas, it is preferable that the thermoplastic resin composition layer contains both a dye, as dye B, whose maximum absorption wavelength changes in response to acid, and a compound that generates an acid when exposed to light, as described below.

[0225] The dye B may be used alone or in combination of two or more kinds. From the viewpoint of visibility of exposed and non-exposed areas, the content of dye B is preferably 0.2 mass% or more, more preferably 0.2 to 6.0 mass%, even more preferably 0.2 to 5.0 mass%, and particularly preferably 0.25 to 3.0 mass%, relative to the total mass of the thermoplastic resin composition layer.

[0226] Here, the content of dye B means the content of dye when all of dye B contained in the thermoplastic resin composition layer is in a colored state. A method for quantifying the content of dye B will be described below using a dye that develops color by radicals as an example. A solution in which 0.001 g of dye is dissolved and a solution in which 0.01 g of dye is dissolved are prepared in 100 mL of methyl ethyl ketone. A photoradical polymerization initiator Irgacure OXE01 (trade name, manufactured by BASF Japan) is added to each of the obtained solutions, and radicals are generated by irradiating light of 365 nm, causing all of the dyes to develop color. Then, in an air atmosphere, the absorbance of each solution at a liquid temperature of 25°C is measured using a spectrophotometer (UV3100, manufactured by Shimadzu Corporation), and a calibration curve is created. Next, the absorbance of the solution in which all the dyes have been colored is measured in the same manner as above, except that 0.1 g of the thermoplastic resin composition layer is dissolved in methyl ethyl ketone instead of the dye. From the absorbance of the solution containing the obtained thermoplastic resin composition layer, the amount of the dye relative to the total mass of the thermoplastic resin composition layer is calculated based on the calibration curve.

[0227] <Compounds that generate acids, bases, or radicals when exposed to light> The thermoplastic resin composition may contain a compound that generates an acid, a base, or a radical when exposed to light (hereinafter, also simply referred to as "compound C"). Compound C is preferably a compound that generates an acid, a base, or a radical upon exposure to actinic rays such as ultraviolet light and visible light. Known photoacid generators, photobase generators, and photoradical polymerization initiators (photoradical generators) can be used as the compound C. Among them, photoacid generators are preferred.

[0228] (Photoacid generator) As the photoacid generator, the above-mentioned cationic photopolymerization initiator that may be contained in the photosensitive resin composition layer can be mentioned, and the preferred embodiments are also the same except for the points described below.

[0229] From the viewpoints of sensitivity and resolution, the photoacid generator preferably contains at least one compound selected from the group consisting of an onium salt compound and an oxime sulfonate compound, and from the viewpoints of sensitivity, resolution and adhesion, it is more preferable that the photoacid generator contains an oxime sulfonate compound. As the photoacid generator, a photoacid generator having the following structure is also preferred.

[0230] [ka]

[0231] (Photoradical polymerization initiator) As the photoradical polymerization initiator, the above-mentioned photoradical polymerization initiators which may be contained in the photosensitive resin composition layer can be mentioned, and the preferred embodiments are also the same.

[0232] (Photobase Generator) The photobase generator is not particularly limited as long as it is a known photobase generator, and examples thereof include 2-nitrobenzylcyclohexylcarbamate, triphenylmethanol, O-carbamoylhydroxylamide, O-carbamoyloxime, [[(2,6-dinitrobenzyl)oxy]carbonyl]cyclohexylamine, bis[[(2-nitrobenzyl)oxy]carbonyl]hexane 1,6-diamine, 4-(methylthiobenzoyl)-1-methyl-1-morpholinoethane, (4-morpholinobenzoyl)- Examples of suitable dimethylamino compounds include 1-benzyl-1-dimethylaminopropane, N-(2-nitrobenzyloxycarbonyl)pyrrolidine, hexaamminecobalt(III) tris(triphenylmethylborate), 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-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.

[0233] The compound C may be used alone or in combination of two or more. The content of compound C is preferably from 0.1 to 10 mass %, more preferably from 0.5 to 5 mass %, based on the total mass of the thermoplastic resin composition layer, from the viewpoints of visibility and resolution of exposed and non-exposed areas.

[0234] <Plasticizer> The thermoplastic resin composition layer preferably contains a plasticizer from the viewpoints of adhesion to adjacent layers, resolution, and developability. The plasticizer preferably has a smaller molecular weight (weight average molecular weight when it is an oligomer or polymer and has a molecular weight distribution) than the alkali-soluble resin. The molecular weight (weight average molecular weight) of the plasticizer is preferably 200 to 2,000. The plasticizer is not particularly limited as long as it is a compound that is compatible with the alkali-soluble thermoplastic resin and exhibits plasticity, but from the viewpoint of imparting plasticity, the plasticizer preferably has an oxyalkylene group in the molecule, more preferably a polyalkylene glycol compound. The oxyalkylene group contained in the plasticizer more preferably has a polyethyleneoxy structure or a polypropyleneoxy structure.

[0235] From the viewpoints of resolution and storage stability, the plasticizer preferably 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. Examples of the (meth)acrylate compound used as the plasticizer include the (meth)acrylate compounds described above as the polymerizable compound contained in the photosensitive resin composition layer. In the transfer film, when the thermoplastic resin composition layer and the photosensitive resin composition layer are laminated in direct contact with each other, 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 thermoplastic resin composition layer and the photosensitive resin composition layer contain the same (meth)acrylate compound, which suppresses component diffusion between the layers and improves storage stability.

[0236] When the thermoplastic resin composition layer contains a (meth)acrylate compound as a plasticizer, it is preferable that the (meth)acrylate compound does not polymerize even in the exposed areas after exposure, from the viewpoint of adhesion between the thermoplastic resin composition layer and an adjacent layer. In addition, as the (meth)acrylate compound used as a plasticizer, from the viewpoints of the 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 preferred. Furthermore, as the (meth)acrylate compound used as the plasticizer, a (meth)acrylate compound having an acid group or a urethane (meth)acrylate compound is also preferred.

[0237] The plasticizers may be used alone or in combination of two or more. From the viewpoints of the resolution of the thermoplastic resin composition layer, adhesion to adjacent layers, and developability, the content of the plasticizer is preferably 1 to 70 mass %, more preferably 10 to 60 mass %, and even more preferably 15 to 50 mass %, relative to the total mass of the thermoplastic resin composition layer.

[0238] <Sensitizer> The thermoplastic resin composition layer may contain a sensitizer. The sensitizer is not particularly limited, and examples thereof include the sensitizers that may be contained in the photosensitive resin composition layer described above.

[0239] The sensitizers may be used alone or in combination of two or more. The content of the sensitizer can be appropriately selected depending on the purpose, but from the viewpoints of improving the sensitivity to the light source and the visibility of the exposed and non-exposed areas, it is preferably 0.01 to 5 mass %, and more preferably 0.05 to 1 mass %, relative to the total mass of the thermoplastic resin composition layer.

[0240] <Additives> The thermoplastic resin composition layer may contain known additives, if necessary, in addition to the above. In addition, the thermoplastic resin composition layer is described in paragraphs

[0189] to

[0193] of JP2014-085643A, and the contents of this publication are incorporated herein by reference.

[0241] <Physical Properties of Thermoplastic Resin Composition Layer> (Film thickness) The thickness of the thermoplastic resin composition layer is not particularly limited, but is preferably 1 μm or more, more preferably 2 μm or more, from the viewpoint of adhesion with adjacent layers. The upper limit is not particularly limited, but is preferably 20 μm or less, more preferably 10 μm or less, and even more preferably 8 μm or less, from the viewpoint of developability and resolution.

[0242] (impurities) The thermoplastic resin composition layer may contain a certain amount of impurities. The impurities are not particularly limited, and include the impurities that may be contained in the photosensitive resin composition layer described above, and the preferred ranges are also the same.

[0243] (Residual monomer) The thermoplastic resin composition layer may contain residual monomers of each structural unit of the above-mentioned alkali-soluble thermoplastic resin. The preferred range of the content of the residual monomer is the same as the content of the residual monomer that may be contained in the photosensitive resin composition layer described above.

[0244] [Colored resin composition layer] The resin composition layer may be a colored resin composition layer. In some cases, in order to protect the liquid crystal display window of recent electronic devices, a cover glass having a black frame-shaped light-shielding layer formed on the periphery of the back surface of a transparent glass substrate, etc. is attached to the liquid crystal display window. A colored resin composition layer can be used to form such a light-shielding layer.

[0245] The colored resin composition layer contains a pigment. The colored resin composition layer may be a colored resin composition layer containing a pigment in addition to a resin (e.g., polymer P, polymer A, etc.), a polymerizable compound, and a block copolymer and / or compound (1). The colored resin composition layer preferably contains a polymerization initiator in addition to a resin (e.g., polymer P, polymer A, etc.), a polymerizable compound, a pigment, and a block copolymer and / or compound (1).

[0246] A pigment may be further added to each of the above-mentioned resin composition layers to form a colored resin composition layer. For example, the above-mentioned photosensitive resin composition layer can be used as a colored resin composition layer by adding a pigment (or a pigment dispersion liquid) as described above. In other words, the above-mentioned photosensitive resin composition layer may be used as a photosensitive resin composition layer that is a colored resin composition layer. Similarly, each of the above-mentioned resin composition layers may be a colored resin composition layer to which a pigment is added. For example, the above-mentioned photosensitive resin composition layer may be a colored resin composition layer containing a pigment as described above. In other words, the above-mentioned photosensitive resin composition layer may be a photosensitive resin composition layer that is a colored resin composition layer.

[0247] <Pigments> The pigment contained in the colored resin composition layer may be appropriately selected according to the desired hue, and may be selected from black pigments, white pigments, and pigments of chromatic colors other than black and white. Among them, when a black pattern is to be formed, a black pigment is preferably selected as the pigment.

[0248] As the black pigment, known black pigments (organic pigments, inorganic pigments, etc.) can be appropriately selected within a range that does not impair the effects of the present invention. Among them, from the viewpoint of optical density, suitable black pigments include, for example, carbon black, titanium oxide, titanium carbide, iron oxide, titanium oxide, and graphite, and carbon black is particularly preferred. As the carbon black, from the viewpoint of surface resistance, carbon black at least a part of the surface of which is coated with a resin is preferred.

[0249] The black pigment, preferably carbon black, is preferably used in the form of a pigment dispersion. The dispersion may be prepared by adding a mixture of a black pigment and a pigment dispersant to an organic solvent (or vehicle) and dispersing the mixture with a dispersing machine. The pigment dispersant may be selected according to the pigment and the solvent, and for example, a commercially available dispersant may be used. The vehicle refers to the medium portion in which the pigment is dispersed when the pigment dispersion is prepared, and is liquid, and includes 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.

[0250] The dispersing machine is not particularly limited, and examples thereof include known dispersing machines such as kneaders, roll mills, attritors, super mills, dissolvers, homomixers, and sand mills. Furthermore, fine pulverization may be performed by utilizing frictional force through mechanical grinding. For details of dispersing machines and fine pulverization, see the description in "Encyclopedia of Pigments" (Kunizo Asakura, First Edition, Asakura Shoten, 2000, pages 438 and 310).

[0251] From the viewpoint of dispersion stability, the particle size of the black pigment is preferably from 0.001 to 0.1 μm, more preferably from 0.01 to 0.08 μm, in terms of number average particle size. Here, the particle size refers to the diameter of a circle whose area is equal to the area of ​​a pigment particle, calculated from a photograph of the pigment particle taken with an electron microscope, and the number average particle size is the average value obtained by calculating the above particle size for any 100 particles and averaging the particle sizes of the 100 particles thus calculated.

[0252] As a pigment other than the black pigment, the white pigment described in paragraphs

[0015] and

[0114] of JP-A-2005-007765 can be used. Specifically, among the white pigments, the inorganic pigment is preferably titanium oxide, zinc oxide, lithopone, precipitated calcium carbonate, white carbon, aluminum oxide, aluminum hydroxide, or barium sulfate, more preferably titanium oxide or zinc oxide, and even more preferably titanium oxide. As the inorganic pigment, rutile or anatase titanium oxide is more preferable, and rutile titanium oxide is particularly preferable. The surface of titanium oxide may be subjected to a silica treatment, an alumina treatment, a titania treatment, a zirconia treatment, or an organic treatment, or may be subjected to two or more of these treatments, which suppresses the catalytic activity of titanium oxide and improves heat resistance, fading resistance, etc. From the viewpoint of reducing the thickness of the photosensitive resin composition layer after heating, the surface treatment of the titanium oxide is preferably at least one of an alumina treatment and a zirconia treatment, and particularly preferably both an alumina treatment and a zirconia treatment.

[0253] From the viewpoint of transferability, it is also preferable that the colored resin composition layer further contains a chromatic pigment other than the black pigment and the white pigment. When the chromatic pigment is contained, it is preferable that the chromatic pigment is well dispersed in the colored resin layer, and from this viewpoint, the particle size is preferably 0.1 μm or less, more preferably 0.08 μm or less. Examples of chromatic pigments include Victoria Pure Blue BO (Color Index (CI) 42595), Auramine (CI 41000), Fat Black HB (CI 26150), Monolight Yellow GT (CI Pigment Yellow 12), Permanent Yellow GR (CI Pigment Yellow 17), Permanent Yellow HR (CI Pigment Yellow 83), Permanent Carmine FBB (CI Pigment Red 146), Hoster Balm Red ESB (CI Pigment Violet 19), Permanent Ruby FBH (CI Pigment Red 11), Fastel Pink B Supra (CI Pigment Red 81), Monastral Fast Blue (CI Pigment Red 146 ... Permanent Yellow GR (CI Pigment Yellow 17), Permanent Yellow HR (CI Pigment Yellow 83), Permanent Carmine FBB (CI Pigment Red 146), Permanent Yellow GR (CI Pigment Yellow 17), Permanent Yellow HR (CI Pigment Yellow 83), Permanent Carmine FBB (CI Pigment Red 146), Permanent Yellow GR (CI Pigment Yellow 17), Permanent Yellow HR (CI Pigment Yellow 83), Permanent Carmine FBB (CI Pigment Red 146), Permanent Yellow CI Pigment Blue 15), Monolight Fast Black B (CI Pigment Black 1) and Carbon, CI Pigment Red 97, CI Pigment Red 122, CI Pigment Red 149, CI Pigment Red 168, CI Pigment Red 177, CI Pigment Red 180, CI Pigment Red 192, CI Pigment Red 215, CI Pigment Green 7, CI Pigment Blue 15:1, CI Pigment Blue 15:4, CI Pigment Blue 22, CI Pigment Blue 60, CI Pigment Blue 64, and CI Pigment Violet 23. Of these, CI Pigment Red 177 is preferred.

[0254] The pigment content is preferably more than 3 mass% and not more than 40 mass%, more preferably more than 3 mass% and not more than 35 mass%, even more preferably more than 5 mass% and not more than 35 mass%, and particularly preferably 10 to 35 mass%, based on the total mass of the colored resin composition layer.

[0255] When pigments other than the black pigment (white pigment and chromatic pigments) are contained, the amount thereof is preferably 30% by mass or less, more preferably 1 to 20% by mass, and even more preferably 3 to 15% by mass, relative to the black pigment.

[0256] <Physical properties of the layer formed>

[0257] (Film thickness) The layer thickness (film thickness) of the colored resin composition layer is often 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.

[0258] (impurities) The colored resin composition layer may contain a predetermined amount of impurities. The impurities are not particularly limited, and include the impurities that may be contained in the photosensitive resin composition layer described above, and the preferred ranges are also the same.

[0259] (Residual monomer) The colored resin composition layer may contain residual monomers of each structural unit of the above-mentioned resins (for example, polymer P, polymer A, alkali-soluble resin, etc.). The preferred range of the content of the residual monomer is the same as the content of the residual monomer that may be contained in the photosensitive resin composition layer described above.

[0260] [Water-soluble resin composition layer] The resin composition layer may be a water-soluble resin composition layer. The water-soluble resin composition layer is a resin composition layer containing a block copolymer and / or compound (1), and a water-soluble resin. Examples of resins 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. When a water-soluble resin composition layer containing a water-soluble resin is used as an intermediate layer, the water-soluble resin is preferably a resin different from the resins contained in the adjacent layers (e.g., polymer P, polymer A, and alkali-soluble thermoplastic resin) in order to suppress mixing of components between multiple layers.

[0261] From the viewpoints of oxygen barrier properties and suppressing mixing of components when applying multiple layers and during storage after application, the water-soluble resin composition layer preferably contains polyvinyl alcohol, and more preferably contains both polyvinyl alcohol and polyvinylpyrrolidone.

[0262] The water-soluble resin composition layer may be used alone or in combination of two or more. The content of the water-soluble resin is not particularly limited, but from the viewpoint of oxygen barrier properties and suppressing mixing of components when applying multiple layers and during storage after application, the content is preferably 50.0 mass% or more and less than 100.0 mass%, more preferably 70.0 mass% or more and less than 100.0 mass%, even more preferably 80.0 mass% or more and less than 100.0 mass%, and particularly preferably 90.0 mass% or more and less than 100.0 mass%, relative to the total mass of the water-soluble resin composition layer.

[0263] The method for forming the water-soluble resin composition layer is not particularly limited, and can be, for example, the same as the method using the photosensitive resin composition. The method for forming the intermediate layer (water-soluble resin layer containing a water-soluble resin) is not particularly limited, and examples thereof include a method in which a water-soluble resin composition is applied to the surface of a thermoplastic resin composition layer or a photosensitive resin composition layer, and the coating film of the water-soluble resin composition is dried to form a water-soluble resin composition layer.

[0264] The thickness of the water-soluble resin composition layer is not particularly limited, but is preferably 0.1 to 5.0 μm, and more preferably 0.5 to 3.0 μm. When the thickness of the water-soluble resin composition layer is within the above range, the oxygen barrier property is not decreased, mixing of components during coating of multiple layers and during storage after coating can be suppressed, and an increase in the time required for removing the water-soluble resin layer during development can be suppressed.

[0265] (impurities) The water-soluble resin composition layer may contain a certain amount of impurities. The impurities are not particularly limited, and include the impurities that may be contained in the photosensitive resin composition layer described above, and the preferred ranges are also the same.

[0266] (Residual monomer) The water-soluble resin composition layer may contain residual monomers of each structural unit of the above-mentioned resins (for example, the water-soluble resin, polymer P, polymer A, and alkali-soluble resin). The preferred range of the content of the residual monomer is the same as the content of the residual monomer that may be contained in the photosensitive resin composition layer described above.

[0267] The resin composition layer is preferably, for example, a layer consisting only of the components contained in the resin composition layer described above. Specifically, the resin composition layer of the present invention is, for example, a layer consisting only of components contained in the above-mentioned photosensitive resin composition layer, thermoplastic resin composition layer, colored resin composition layer, and / or water-soluble resin composition layer. Examples of resin composition layers other than those of the present invention include resin composition layers that are made of components other than the components contained in each of the above-mentioned resin composition layers, in the above-mentioned photosensitive resin composition layer, thermoplastic resin composition layer, colored resin composition layer, and / or water-soluble resin composition layer.

[0268] [Cover film] The transfer film preferably has a cover film in contact with the surface of each resin composition layer that does not face the temporary support. 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 opposite to the first surface is also referred to as the "second surface".

[0269] Materials constituting the cover film include resin films and paper, with resin films being preferred from the standpoints of strength and flexibility. Examples of the resin film include a polyethylene film, a polypropylene film, a polyethylene terephthalate film, a cellulose triacetate film, a polystyrene film, and a polycarbonate film. Among these, a polyethylene film, a polypropylene film, or a polyethylene terephthalate film is preferable.

[0270] The thickness of the cover film is not particularly limited, but is preferably from 5 to 100 μm, and more preferably from 10 to 50 μm. The arithmetic mean roughness Ra value of the surface of the cover film in contact with each resin composition layer (hereinafter also simply referred to as the "surface of the cover film") is preferably 0.3 μm or less, more preferably 0.1 μm or less, and even more preferably 0.05 μm or less, because this provides better resolution. It is believed that the uniformity of the layer thickness of the formed resin pattern is improved by having the Ra value of the surface of the cover film in the above range. There is no particular lower limit for the Ra value of the surface of the cover film, but it is preferably 0.001 μm or more.

[0271] The Ra value of the surface of the cover film is measured by the following method. Using a three-dimensional optical profiler (New View7300, manufactured by Zygo), the surface of the cover film is measured under the following conditions to obtain a surface profile of the optical film. The measurement and analysis software used is Microscope Application of MetroPro ver8.3.2. Next, the Surface Map screen is displayed in the analysis software, and histogram data is obtained in the Surface Map screen. From the obtained histogram data, the arithmetic mean roughness is calculated, and the Ra value of the cover film surface is obtained. When a cover film is attached to the transfer film, the cover film is peeled off from the transfer film, and the Ra value of the surface on the peeled side may be measured.

[0272] [Transfer film manufacturing method] The method for producing the transfer film is not particularly limited, and any known production method, for example, any known method for forming each resin composition layer, can be used. Hereinafter, a method for producing a transfer film will be described with reference to Fig. 1. However, the transfer film is not limited to the structure shown in Fig. 1. Fig. 1 is a schematic diagram showing an example of the configuration of a transfer film. The transfer film 100 shown in Fig. 1 has a configuration in which a temporary support 10, a thermoplastic resin composition layer 12, an intermediate layer 14, a photosensitive resin composition layer 16, and a cover film 18 are laminated in this order. Furthermore, by providing the transfer film with the intermediate layer 14, it is possible to prevent mixing of components when applying multiple layers and during storage after application. The intermediate layer may be an oxygen-blocking layer having an oxygen-blocking function, which is described as a "separation layer" in JP-A-5-072724. When the intermediate layer is an oxygen-blocking layer, the sensitivity during exposure is improved, the time load of the exposure machine is reduced, and productivity is improved, which is preferable. The oxygen barrier layer used as the intermediate layer may be appropriately selected from known layers described in the above publications, etc. Among them, an oxygen barrier layer that exhibits low oxygen permeability and disperses or dissolves in water or an alkaline aqueous solution (a 1% by mass aqueous solution of sodium carbonate at 22° C.) is preferred. The intermediate layer and the resin composition capable of forming the intermediate layer will be described in detail later.

[0273] Examples of a manufacturing method for the transfer film 100 include a method including the steps of applying a thermoplastic resin composition to the surface of the temporary support 10 and then drying the coating of the thermoplastic resin composition to form a thermoplastic resin composition layer 12, applying an intermediate layer-forming resin composition to the surface of the thermoplastic resin composition layer 12 and then drying the coating of the intermediate layer-forming resin composition to form an intermediate layer 14, and applying a photosensitive resin composition to the surface of the intermediate layer 14 and then drying the coating of the photosensitive resin composition to form a photosensitive resin composition layer 16. The thermoplastic resin composition is a composition for forming the above-mentioned thermoplastic resin composition layer, and may contain the above-mentioned various components. The thermoplastic resin composition may contain a solvent to improve the coating property. The photosensitive resin composition is a composition for forming the above-mentioned photosensitive resin composition, and may contain the above-mentioned various components. The photosensitive resin composition may contain a solvent to improve the coating property.

[0274] A cover film 18 is pressure-bonded to the photosensitive resin composition layer 16 of the laminate produced by the above-mentioned production method, thereby producing a transfer film 100. As a manufacturing method for the transfer film of the present invention, it is preferable to include a step of providing a cover film 18 so as to be in contact with the second surface of the photosensitive resin composition layer 16, thereby manufacturing a transfer film 100 having 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. After the transfer film 100 is manufactured by the above manufacturing method, a transfer film in a roll form may be produced and stored by winding up the transfer film 100. The transfer film in a roll form can be provided as it is to a bonding step with a substrate in a roll-to-roll system described later.

[0275] In the above-described manufacturing method, both the thermoplastic resin composition layer and the photosensitive resin composition layer are resin composition layers of the present invention, but at least one of them may be a resin composition layer of the present invention, and the other may be a resin composition layer other than the present invention (for example, a thermoplastic resin composition layer other than the present invention and / or a photosensitive resin composition layer other than the present invention). Similarly, in the transfer film 100, at least one of the thermoplastic resin composition layer 12 and the photosensitive resin composition layer 16 may be a resin composition layer of the present invention, and the other may be a resin composition layer other than that of the present invention.

[0276] [Middle class] The intermediate layer is preferably a water-soluble resin composition layer. The embodiment of the water-soluble resin composition layer is as described above.

[0277] [Refractive index adjusting layer] The transfer film may have a refractive index adjusting layer. The position of the refractive index adjusting layer is not particularly limited, but it is preferably disposed in contact with each resin composition layer. In particular, the transfer film preferably has a temporary support, a photosensitive resin composition layer or a thermoplastic resin composition layer, and a refractive index adjusting layer in this order. In addition, when the transfer film further has the above-mentioned cover film, it preferably has a temporary support, a photosensitive resin composition layer or a thermoplastic resin composition layer, a refractive index adjusting layer, and a cover film in this order.

[0278] The refractive index adjustment layer may be a known refractive index adjustment layer. Examples of materials contained in the refractive index adjustment layer include resin and particles.

[0279] Examples of the resin include the resins that may be contained in the resin composition layer described above, and the polymer P and / or a water-soluble resin are preferred. In addition, in this specification, when the refractive index adjusting layer contains, for example, a water-soluble resin, it also corresponds to a water-soluble resin composition layer.

[0280] The particles include, for example, zirconium oxide particles (ZrO 2 particles), niobium oxide particles (Nb 2 O 5 particles), titanium oxide particles (TiO 2 particles), and silicon dioxide particles (SiO 2 particles).

[0281] The refractive index matching layer preferably contains a metal oxidation inhibitor, which can suppress oxidation of the metal in contact with the refractive index matching layer. The metal oxidation inhibitor is preferably, for example, a compound having an aromatic ring containing a nitrogen atom in the molecule, and examples of the metal oxidation inhibitor include imidazole, benzimidazole, tetrazole, mercaptothiadiazole, and benzotriazole.

[0282] The refractive index of the refractive index adjusting layer is preferably 1.60 or more, and more preferably 1.63 or more. The upper limit of the refractive index of the refractive index adjusting layer is preferably 2.10 or less, and more preferably 1.85 or less.

[0283] The thickness of the refractive index adjusting layer is preferably 500 nm or less, more preferably 110 nm or less, and even more preferably 100 nm or less. There is no particular lower limit, but the thickness is preferably 20 nm or more, and more preferably 50 nm or more. The thickness of the refractive index adjusting layer is calculated as the average value of any five points measured by cross-sectional observation using a scanning electron microscope (SEM).

[0284] The refractive index adjusting layer may be a known refractive index adjusting layer, for example, the second resin layer disclosed in paragraphs

[0200] to

[0214] of JP2020-091322A.

[0285] An example of the embodiment of the transfer film is shown below. In each of the following configurations, one or more layers (such as a cover film) may be removed and / or additional layers may be added between any of the layers as desired. (1) "Temporary support / thermoplastic resin composition layer / intermediate layer (water-soluble resin composition layer) / photosensitive resin composition layer / cover film" (2) "Temporary support / thermoplastic resin composition layer / intermediate layer (water-soluble resin composition layer) / colored resin composition layer / cover film" (3) "Temporary support / thermoplastic resin composition layer / refractive index adjusting layer (water-soluble resin composition layer) / cover film" (4) "Temporary support / photosensitive resin composition layer / cover film" In the resin composition layers (layers other than the temporary support and the cover film) constituting the transfer film having each of the above configurations, at least one of the thermoplastic resin layer and the photosensitive resin composition layer is the resin composition layer of the present invention. In each of the above configurations, it is also preferable that the photosensitive resin composition layer is a colored resin composition layer.

[0286] [Laminate manufacturing method and circuit wiring manufacturing method] The present invention also relates to a method for producing a laminate. The method for producing the laminate is not particularly limited as long as it is a method for producing a laminate using the above-mentioned transfer film. As a method for producing a laminate, a method including a lamination step (hereinafter also referred to as a "lamination step") of contacting a substrate (preferably a substrate having electrical conductivity) with the surface of the transfer film opposite the temporary support (the surface of the composition layer) and laminating the transfer film and the substrate (preferably a substrate having electrical conductivity) to obtain a substrate with a transfer film, an exposure step (hereinafter also referred to as an "exposure step") of exposing the resin composition layer to a pattern, a development step (hereinafter also referred to as a "development step") of developing the exposed resin composition layer to form a resin pattern, and further a peeling step (hereinafter also referred to as a "peeling step") of peeling the temporary support from the substrate with the transfer film between the lamination step and the exposure step or between the exposure step and the development step. The resin composition layer to be pattern-exposed may consist of one layer alone or two or more layers, and at least one of the layers constituting the resin composition layer is the resin composition layer of the present invention. The resin composition layer to be pattern-exposed 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 photosensitive resin composition layer may be a colored resin composition layer.

[0287] The method for producing the circuit wiring is not particularly limited as long as it is a method for producing the circuit wiring using the above-mentioned transfer film. As a method for manufacturing circuit wiring, a method including a step of etching the conductive layer in an area where a resin pattern is not arranged in a laminate in which a substrate, a conductive layer (a conductive layer possessed by the substrate), and a resin pattern manufactured using the above-mentioned transfer film are laminated in this order (hereinafter also referred to as an "etching step"). In other words, the method for manufacturing circuit wiring preferably includes a lamination step (hereinafter also referred to as the "lamination step") of contacting a substrate having a conductive layer with the surface (composition layer) of the transfer film opposite the temporary support and laminating the transfer film and the substrate having a conductive layer to obtain a substrate with a transfer film, an exposure step (hereinafter also referred to as the "exposure step") of exposing the resin composition layer to a pattern, a development step (hereinafter also referred to as the "development step") of developing the exposed resin composition layer to form a resin pattern, a step (hereinafter also referred to as the "etching step") of etching the conductive layer in an area where the resin pattern is not arranged, and further a peeling step (hereinafter also referred to as the "peeling step") of peeling the temporary support from the substrate with the transfer film between the lamination step and the exposure step, or between the exposure step and the development step. The preferred form of the resin composition layer to be pattern-exposed is the same as that described above.

[0288] Below, we will explain each step included in the method for manufacturing a laminate and the method for manufacturing circuit wiring. Unless otherwise specified, the contents explained for each step included in the method for manufacturing a laminate also apply to each step included in the method for manufacturing circuit wiring.

[0289] [Lamination process] The method for producing the laminate preferably includes a lamination step. In the lamination step, it is preferable to bring the substrate (if a conductive layer is provided on the substrate surface) into contact with the surface of the transfer film opposite to the temporary support, and to press the transfer film and the substrate together. In the above embodiment, the adhesion between the resin composition layer and the substrate is improved, and the resin pattern formed after exposure and development can be used as an etching resist when etching a conductive layer.

[0290] When the transfer film has a cover film, the cover film may be removed from the surface of the transfer film before bonding.

[0291] The method for bonding the substrate and the transfer film by pressure is not particularly limited, and known transfer methods and lamination methods can be used. The transfer film is preferably bonded to the substrate by placing the substrate on the surface of the transfer film opposite to the temporary support, and applying pressure and heat using a roll or other means. For the bonding, a known laminator such as a laminator, a vacuum laminator, or an autocut laminator that can further increase productivity can be used.

[0292] The method for producing a laminate and the method for producing a circuit wiring, which include the lamination step, are preferably carried out by a roll-to-roll system. The roll-to-roll method refers to a method in which a substrate that can be wound up and unwound is used as the substrate, and includes a step of unwinding the substrate or a structure including the substrate (hereinafter also referred to as the "unwinding step") before any step included in the manufacturing method of a laminate or a manufacturing method of circuit wiring, and a step of winding up the substrate or the structure including the substrate (hereinafter also referred to as the "winding step") after any step, in which at least any step (preferably all steps, or all steps other than the heating step) is performed while transporting the structure including the substrate or the substrate. The unwinding method in the unwinding step and the winding method in the winding step are not particularly limited, and any known method may be used in a production method that employs a roll-to-roll system.

[0293] <Substrate> As the substrate used in forming a resin pattern using the transfer film according to the present invention, a known substrate may be used, but a substrate having a conductive layer is preferred, and a substrate having a conductive layer on the surface thereof is more preferred. The substrate may have any layer other than the conductive layer, if necessary.

[0294] Examples of the base material that constitutes the substrate include glass, silicon, and films. The base material constituting the substrate is preferably transparent. In this specification, the term "transparent" means that the transmittance of light with a wavelength of 400 to 700 nm is 80% or more. The refractive index of the base material constituting the substrate is preferably 1.50 to 1.52.

[0295] The transparent glass substrate may be a tempered glass such as Gorilla Glass manufactured by Corning Inc. In addition, the transparent glass substrate may be a material described in JP-A-2010-086684, JP-A-2010-152809, and JP-A-2010-257492.

[0296] When a film substrate is used as the substrate, it is preferable to use a film substrate having small optical distortion and / or high transparency. Examples of such a film substrate include polyethylene terephthalate (PET), polyethylene naphthalate, polycarbonate, triacetyl cellulose, and cycloolefin polymer.

[0297] When the substrate is manufactured by a roll-to-roll process, the substrate is preferably a film substrate. When the substrate is manufactured by a roll-to-roll process, the substrate is preferably a sheet-shaped resin composition.

[0298] The conductive layer of the substrate may be a conductive layer used for general circuit wiring or touch panel wiring. From the viewpoints of electrical conductivity and fine line formability, the conductive layer is preferably at least one layer selected from the group consisting of a metal layer, a conductive metal oxide layer, a graphene layer, a carbon nanotube layer, and a conductive polymer layer, more preferably a metal layer, and even more preferably a copper layer or a silver layer. The substrate may have one conductive layer or two or more conductive layers. When the substrate has two or more conductive layers, the conductive layers are preferably made of different materials.

[0299] Materials for the conductive layer include metals and conductive metal oxides. Metals include Al, Zn, Cu, Fe, Ni, Cr, Mo, Ag and Au. Conductive metal oxides include ITO (Indium Tin Oxide), IZO (Indium Zinc Oxide) and SiO 2 Examples include: In this specification, "conductive" means a material having a volume resistivity of 1×10 6 The volume resistivity of conductive metal oxides is less than 1×10 4 Less than Ωcm is preferred.

[0300] When a resin pattern is produced using a substrate having a plurality of conductive layers, at least one of the plurality of conductive layers preferably contains a conductive metal oxide. The conductive layer is preferably an electrode pattern corresponding to a sensor of a visual recognition portion used in a capacitive touch panel or wiring of a peripheral extraction portion.

[0301] [Exposure process] The method for producing the laminate preferably includes, after the lamination step, a step of pattern-exposing the resin composition layer (exposure step).

[0302] The detailed arrangement and specific size of the pattern in the pattern exposure are not particularly limited. In order to improve the display quality of a display device (e.g., a touch panel) equipped with an input device having a circuit wiring manufactured by the manufacturing method for circuit wiring and to reduce the area occupied by the lead wiring, at least a part of the pattern (preferably the electrode pattern of the touch panel and / or the lead wiring part) preferably includes a thin line having a width of 20 μm or less, more preferably includes a thin line having a width of 10 μm or less.

[0303] The light source used for exposure can be appropriately selected and used as long as it irradiates light with a wavelength (e.g., 365 nm or 405 nm) that can expose the photosensitive resin composition layer. Specific examples of the light source include an ultra-high pressure mercury lamp, a high pressure mercury lamp, a metal halide lamp, and an LED (Light Emitting Diode).

[0304] The exposure dose is 5 to 200 mJ / cm 2 is preferable, and 10 to 100 mJ / cm 2 is more preferred.

[0305] [Peeling process] The peeling step is a step of peeling off the temporary support from the substrate with the resin composition layer between the laminating step and the exposure step, or between the exposure step and the development step described below. The peeling method is not particularly limited, and a mechanism similar to the cover film peeling mechanism described in paragraphs

[0161] to

[0162] of JP-A-2010-072589 can be used. Therefore, in the exposure step, the resin composition layer may be exposed to pattern light after the temporary support is peeled off from the resin composition layer, or the temporary support may be exposed to pattern light through the temporary support before peeling off the temporary support. When the temporary support is peeled off before exposure, the mask may be exposed in contact with the resin composition layer, or may be exposed in close proximity without contact. When the temporary support is not peeled off and the mask is exposed, the mask may be exposed in contact with the temporary support, or may be exposed in close proximity without contact. In order to prevent mask contamination due to contact between the composition layer and the mask, and to avoid the influence of foreign matter attached to the mask on the exposure, it is preferable to perform pattern light exposure without peeling off the temporary support. In the case of contact exposure, the exposure method can be appropriately selected from the contact exposure method, and in the case of non-contact exposure method, the proximity exposure method, the projection exposure method of the lens system and the mirror system, and the direct exposure method using the exposure laser or the like. In the case of projection exposure of the lens system and the mirror system, an exposure machine having an appropriate lens numerical aperture (NA) can be used according to the required resolution and focal depth. In the case of the direct exposure method, drawing may be performed directly on the photosensitive resin composition layer, or reduction projection exposure may be performed on the photosensitive resin composition layer through a lens. The exposure may be performed not only under atmospheric conditions but also under reduced pressure or vacuum, and exposure may be performed by interposing a liquid such as water between a light source and the resin composition layer.

[0306] [Development process] The method for producing a laminate preferably includes, after the above-mentioned exposure step, a step of developing the exposed resin composition layer to form a resin pattern (development step). When the resin composition layer includes a photosensitive resin composition layer (a photosensitive resin composition layer of the present invention or a photosensitive resin composition layer other than that of the present invention), the resin composition layer undergoes a curing reaction according to the exposed pattern to become a cured film (a patterned cured film), and it becomes possible to remove only the unexposed parts of the resin composition layer with a developer (such as an alkaline developer).

[0307] When the transfer film has a photosensitive resin composition layer and a different resin composition layer, the different resin composition layer may be removed only in a portion similar to the portion to be removed in the photosensitive resin composition layer, or may be removed entirely including the portion other than the portion to be removed in the photosensitive resin composition layer. For example, when the transfer film has a thermoplastic resin composition layer and / or a water-soluble resin composition layer together with a photosensitive resin composition layer, in the development step, only the thermoplastic resin composition layer and / or the water-soluble resin composition layer in the non-exposed area may be removed together with the photosensitive resin composition layer in the non-exposed area. In addition, in the development step, the thermoplastic resin composition layer and / or the water-soluble resin composition layer in both the exposed and non-exposed areas may be removed in a form dissolved or dispersed in the developer. In the resin pattern obtained after development, a part or all of it may be a layer formed by a change such as a curing reaction of the resin composition layer of the present invention. For example, when the resin composition layer of the transfer film contains the photosensitive resin composition layer of the present invention, a part or all of the resin pattern is a material formed by a curing reaction of the photosensitive resin composition layer of the present invention. Furthermore, the resin pattern obtained after development may not include a layer formed by a change such as a curing reaction of the resin composition layer of the present invention. In other words, the resin pattern obtained after development may consist only of a layer of a resin composition other than the present invention and / or a layer formed by a change such as a curing reaction of the resin composition other than the present invention.

[0308] In the development process, the development of the exposed resin composition layer can be carried out using an alkaline developer. As the alkaline developer, for example, known developers such as the developer described in JP-A-5-072724 can be used. As the alkaline developer, an alkaline aqueous solution-based developer containing a compound with pKa = 7 to 13 at a concentration of 0.05 to 5 mol / L (liter) is preferred. The alkaline developer may contain a water-soluble organic solvent and / or a surfactant. As the alkaline developer, the developer described in paragraph

[0194] of WO 2015 / 093271 is also preferred. The content of the organic solvent in the alkaline developer is preferably 0% by mass or more and less than 90% by mass based on the total mass of the developer.

[0309] The development method is not particularly limited, and any of paddle development, shower development, shower and spin development, and dip development may be used. Shower development is a development process in which a developer is sprayed onto the resin composition layer after exposure by a shower to remove the unexposed portion. After the development process, it is preferable to spray a cleaning agent by a shower and remove the development residue while rubbing with a brush. The liquid temperature of the developer is not particularly limited, but 20 to 40 °C is preferred.

[0310] 〔Etching process〕 The method for manufacturing a circuit wiring preferably includes an etching process (etching process) of etching a conductive layer in a region where the resin pattern is not disposed 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 a manufacturing method including the above lamination process, the above exposure process, and the above development process) are laminated in this order.

[0311] In the etching process, the resin pattern formed from the resin composition layer is used as an etching resist to perform the etching process of the conductive layer. As the etching method, a known method can be applied, and examples thereof include the method described in paragraphs

[0209] to

[0210] of JP2017-120435A, the method described in paragraphs

[0048] to

[0054] of JP2010-152155A, a wet etching method in which the substrate is immersed in an etching solution, and a dry etching method such as plasma etching.

[0312] The etching solution used in the wet etching may be an acidic or alkaline etching solution that is appropriately selected depending on the target to be etched. Examples of the acidic etching solution include an aqueous solution of an acidic component selected from hydrochloric acid, sulfuric acid, nitric acid, acetic acid, hydrofluoric acid, oxalic acid, and phosphoric acid, and an aqueous solution of a mixture of an acidic component and a salt selected from ferric chloride, ammonium fluoride, and potassium permanganate. The acidic component may be a combination of a plurality of acidic components. Examples of the alkaline etching solution include an aqueous solution of an alkaline component selected from sodium hydroxide, potassium hydroxide, ammonia, organic amines, and salts of organic amines (e.g., tetramethylammonium hydroxide), and an aqueous solution of a mixture of an alkaline component and a salt (e.g., potassium permanganate). The alkaline component may be a combination of a plurality of alkaline components.

[0313] [Removal process] In the method for producing circuit wiring, it is preferable to carry out a step of removing the remaining resin pattern (removal step). The removal step is not particularly limited and may be carried out as necessary, but is preferably carried out after the etching step. The method for removing the remaining resin pattern is not particularly limited, but includes a method of removing it by chemical treatment, and a method of removing it by using a removing liquid is preferable. The resin composition layer can be removed by immersing the substrate having the remaining resin pattern in a stirring removal liquid having a liquid temperature of preferably 30 to 80°C, more preferably 50 to 80°C, for 1 to 30 minutes.

[0314] Examples of the removal liquid include removal liquids in which an inorganic or organic alkaline component is dissolved in water, dimethyl sulfoxide, N-methylpyrrolidone, or a mixture thereof. Examples of the inorganic alkaline component include sodium hydroxide and potassium hydroxide. Examples of the organic alkaline component include primary amine compounds, secondary amine compounds, tertiary amine compounds, and quaternary ammonium salt compounds. Alternatively, the removal may be performed by a known method such as a spray method, a shower method, or a paddle method using a removal liquid.

[0315] [Other steps] The method for producing a circuit wiring may include any steps (other steps) other than the steps described above, such as, but not limited to, the following steps. Moreover, examples of the exposure step, development step, and other steps that can be applied to the method for producing circuit wiring include the steps described in paragraphs

[0035] to

[0051] of JP-A-2006-023696.

[0316] <Cover film peeling process> When the transfer film includes a cover film, the laminate manufacturing method and the circuit wiring manufacturing method preferably include a step of peeling the cover film from the transfer film. The method of peeling the cover film is not limited, and a known method can be applied.

[0317] <Step of reducing visible light reflectance> The method for producing circuit wiring may include a step of performing a treatment to reduce the visible light reflectance of some or all of the multiple conductive layers of the substrate. Examples of treatments for reducing the visible light reflectance include oxidation treatments. When the substrate has a conductive layer containing copper, the visible light reflectance of the conductive layer can be reduced by oxidizing the copper to copper oxide and blackening the conductive layer. Treatments for reducing visible light reflectance are described in paragraphs

[0017] to

[0025] of JP 2014-150118 A, and paragraphs

[0041] to

[0042] ,

[0048] , and

[0058] of JP 2013-206315 A, and the contents of these publications are incorporated herein by reference.

[0318] <Step of forming an insulating film, step of forming a new conductive layer on the surface of the insulating film> The method for producing the circuit wiring preferably includes the steps of forming an insulating film on the surface of the circuit wiring, and forming a new conductive layer on the surface of the insulating film. By the above steps, a second electrode pattern insulated from the first electrode pattern can be formed. The step of forming the insulating film is not particularly limited, and may be a known method for forming a permanent film. Alternatively, an insulating film having a desired pattern may be formed by photolithography using a photosensitive material having insulating properties. The step of forming a new conductive layer on the insulating film is not particularly limited, and for example, a new conductive layer having a desired pattern may be formed by photolithography using a photosensitive material having conductivity.

[0319] In the method for producing the circuit wiring, a substrate having a plurality of conductive layers on both surfaces of the substrate is used, and circuits are formed on the conductive layers formed on both surfaces of the substrate, either sequentially or simultaneously. With this configuration, a circuit wiring for a touch panel can be formed in which a first conductive pattern is formed on one surface of the substrate and a second conductive pattern is formed on the other surface. It is also preferable to form the circuit wiring for a touch panel having such a configuration from both sides of the substrate by roll-to-roll.

[0320] [Circuit wiring applications] The circuit wiring manufactured by the manufacturing method of the circuit wiring can be applied to various devices. An example of a device having the circuit wiring manufactured by the manufacturing method is an input device, preferably a touch panel, more preferably a capacitive touch panel. The input device can also be applied to a display device such as an organic EL display device and a liquid crystal display device.

[0321] [Electronic device manufacturing method] The present invention also relates to a method for manufacturing an electronic device. As the method for producing the electronic device, a method for producing an electronic device using the above-mentioned transfer film is preferable. In particular, the method for producing an electronic device preferably includes the method for producing the laminate described above. The electronic device may be, for example, an input device, preferably a touch panel, and may be applied to a display device such as an organic electroluminescence display device or a liquid crystal display device.

[0322] As a method for manufacturing a touch panel, a method including a step of forming wiring for a touch panel by etching the conductive layer in an area where the resin pattern is not arranged in a laminate in which a substrate, a conductive layer (a conductive layer possessed by the substrate), and a resin pattern manufactured using the above-mentioned transfer film are laminated in this order is also preferred, and a method using a resin pattern manufactured by a manufacturing method including the above-mentioned lamination step, the above-mentioned exposure step, and the above-mentioned development step is more preferred.

[0323] In the method for manufacturing a touch panel including a step of forming wiring for a touch panel, specific aspects of each step and the order in which each step is performed are as described above in the section "Method for manufacturing circuit wiring," and the same applies to preferred aspects. Furthermore, the method for manufacturing a touch panel including the step of forming wiring for a touch panel may include any step (other step) other than those described above. As a method for forming wiring for a touch panel, the method shown in FIG. 1 of WO 2016 / 190405 can also be referred to.

[0324] The above-mentioned method for producing a touch panel produces a touch panel having at least a wiring for a touch panel. The touch panel preferably has a transparent substrate, an electrode, and an insulating layer or a protective layer. Examples of detection methods for touch panels include known methods such as a resistive film method, a capacitive method, an ultrasonic method, an electromagnetic induction method, and an optical method, etc. Among these, the capacitive method is preferable.

[0325] Examples of touch panels include so-called in-cell types (e.g., those shown in Figures 5, 6, 7, and 8 of JP-T 2012-517051), so-called on-cell types (e.g., those shown in Figure 19 of JP-A 2013-168125 and those shown in Figures 1 and 5 of JP-A 2012-89102), OGS (One Glass Solution) types, TOL (Touch-on-Lens) types (e.g., those shown in Figure 2 of JP-A 2013-54727), various out-cell types (so-called GG, G1 / G2, GFF, GF2, GF1, G1F, etc.), and other configurations (e.g., those shown in Figure 6 of JP-A 2013-164871). An example of the touch panel is described in paragraph

[0229] of JP2017-120345A. EXAMPLES

[0326] The present invention will be described in more detail below based on examples. The materials, amounts, ratios, processing contents, processing procedures, etc. shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be interpreted as being limited by the following examples. In the following examples, unless otherwise specified, "parts" and "%" mean "parts by mass" and "% by mass", respectively.

[0327] [Synthesis] [Compound (1)] <Compound A-1> Compound A-1 was synthesized according to Synthesis Example 5 in paragraph

[0139] of WO 2011 / 152126. The average number of moles of propylene oxide added in the obtained compound A-1 was 5.

[0328] <Compound A-2> Compound A-2 was synthesized according to Example 3 in paragraph

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

[0329] The structures of the compounds A-1 and A-2 obtained above are shown below.

[0330] [ka]

[0331] [Block Copolymer] <Block copolymer B-1> Block copolymer B-1 was synthesized according to the Journal of Polymer Research, 2018, 25(7), 1-7. As synthesis raw materials, 1H,1H,2H,2H-nonafluorohexyl acrylate (Tokyo Chemical Industry Co., Ltd.), polyethylene glycol monoacrylate (Blenmer AE-400 (average molar number of polyethylene glycol added is 10, NOF Corporation)), methyl-2-bromo-2-methylpropanoate (Tokyo Chemical Industry Co., Ltd.), 2,2'-bipyridine (Fujifilm Wako Pure Chemical Industries, Ltd.), copper bromide (Fujifilm Wako Pure Chemical Industries, Ltd.), and PGMEA (propylene glycol monomethyl ether acetate, Fujifilm Wako Pure Chemical Industries, Ltd.) were used and synthesized. The obtained solid was diluted with PGMEA to obtain a PGMEA solution of block copolymer B-1 (solid content concentration 20% by mass). In this specification, the term "solid content" refers to all components excluding the solvent. In addition, liquid components excluding the solvent are also considered to be solid content.

[0332] <Block copolymer B-2> A PGMEA solution of block copolymer B-2 (solid concentration 20 mass%) was obtained in the same manner as in the above-mentioned <Block copolymer B-1>, except that the synthesis raw materials were changed from 1H,1H,2H,2H-nonafluorohexyl acrylate to 1H,1H,2H,2H-nonafluorohexyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) and from polyethylene glycol monoacrylate (Blemmer AE-400 (average molar number of polyethylene glycol added: 10, manufactured by NOF Corporation)) to polyethylene glycol monoacrylate (Blemmer AE-200 (average molar number of polyethylene glycol added: 4.5, manufactured by NOF Corporation)).

[0333] <Block copolymer B-3> A PGMEA solution of block copolymer B-3 (solid content concentration 20% by mass) was obtained in the same manner as in the above-mentioned <Block Copolymer B-1>, except that the synthesis raw material was changed from 1H,1H,2H,2H-nonafluorohexyl acrylate to 1,1,1,3,3,3-hexafluoroisopropyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.).

[0334] [Comparative compound R-1] Cyclohexanone (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) (25.0 g) was charged into a 300 mL three-neck flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen gas inlet tube, and the temperature was raised to 80° C. Next, a mixed solution consisting of 1H,1H,2H,2H-nonafluorohexyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) (35.5 g, 111.8 mmol), Blenmar AE-400 (n≒10, manufactured by NOF Corporation) (60.5 g, 111.8 mmol), cyclohexanone (25.0 g), and a polymerization initiator V-601 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) (0.342 g) was added dropwise at a constant rate so that the dropwise addition was completed in 180 minutes. After completion of the dropwise addition, stirring was continued for another hour, and immediately after the addition of a solution consisting of V-601 (0.342 g) and cyclohexanone (1.00 g), the temperature was raised to 93° C. and stirring was continued for another 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 mass%) of the comparative compound R-1 (random copolymer).

[0335] The structures of the block copolymers obtained above and the comparative compounds are shown below. The numerical values ​​attached to the structural units in the copolymers indicate the content (mass%) of each structural unit relative to the total mass of each copolymer.

[0336] [ka]

[0337] [ka]

[0338] It should be noted that Megafac F444, F551, F552, and F555 (all manufactured by DIC Corporation) are comparative compounds which do not fall under the category of block copolymers and do not fall under the category of compound (1).

[0339] The weight average molecular weight (Mw), number average molecular weight (Mn), and dispersity (Mw / Mn) of each block copolymer were as follows. The weight average molecular weight (Mw) of the copolymer was calculated in terms of polystyrene by GPC (gel permeation chromatography (EcoSEC HLC-8320GPC (manufactured by Tosoh Corporation)) under the measurement conditions of THF eluent, flow rate of 0.35 ml / min, and temperature of 40°C. The columns used were TSKgel SuperHZM-H, TSKgel SuperHZ4000, and TSKgel SuperHZ200 (manufactured by Tosoh Corporation) connected in series.

[0340] [Table 1]

[0341] 〔resin〕 In the following synthesis examples, each description indicates the following. St: Styrene (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) ·MAA: Methacrylic acid (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) MMA: Methyl methacrylate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) BzMA: Benzyl methacrylate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) AA: Acrylic acid (Tokyo Chemical Industry Co., Ltd.) · MAA-GMA: Glycidyl methacrylate adduct of methacrylic acid CHMA: Cyclohexyl methacrylate (manufactured by Mitsubishi Gas Chemical Co., Ltd.) AMA: Allyl methacrylate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) PGMEA: Propylene glycol monomethyl ether acetate (Showa Denko) MEK: Methyl ethyl ketone (manufactured by Sankyo Chemical Co., Ltd.) V-601: Dimethyl-2,2'-azobis(2-methylpropionate) (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) ATHF: Tetrahydrofuran-2-yl acrylate (synthetic product) EA: Ethyl acrylate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) CHA: Cyclohexyl acrylate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) PMPMA: 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)

[0342] <Resin P-1> PGMEA (116.5 parts) was placed in a three-neck 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 over 2 hours to the flask solution maintained at 90° C.±2° C. After the dropwise addition, the solution in the flask was stirred at 90° C.±2° C. for 2 hours to obtain a solution containing resin P-1 (solid concentration 30.0% by mass).

[0343] <Resin P-2~P-4> Except for changing the types of monomers used as shown in Table 2, a solution containing any one of Resins P-2 to P-4 (all solutions had a solids concentration of 30.0% by mass) was obtained using the same procedure as described above in <Synthesis of Resin P-1>.

[0344] <Resin P-5~P-6> Propylene glycol monomethyl ether acetate (60 g, manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) and propylene glycol monomethyl ether (240 g, manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) were added to a 2000 mL flask. The resulting liquid was heated to 90° C. while being stirred at a stirring speed of 250 rpm (rpm: round per minute). To prepare the dropping liquid (1), methacrylic acid (107.1 g, manufactured by Mitsubishi Rayon Co., Ltd., product name ACRYSTER M), methyl methacrylate (5.46 g, manufactured by Mitsubishi Gas Chemical Co., Ltd., product name MMA), and cyclohexyl methacrylate (231.42 g, manufactured by Mitsubishi Gas Chemical Co., Ltd., product name CHMA) were mixed and diluted with propylene glycol monomethyl ether acetate (60.0 g) to obtain the dropping liquid (1). To prepare the dropping liquid (2), dimethyl 2,2'-azobis(2-methylpropionate) (9.637 g, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., product name V-601) was dissolved in propylene glycol monomethyl ether acetate (136.56 g) to obtain the dropping liquid (2). Droplet (1) and Droplet (2) were simultaneously dropped into the above-mentioned 2000 mL flask (specifically, a 2000 mL flask containing a liquid heated to 90°C) over a period of 3 hours. After the dropwise addition was completed, V-601 (2.401 g) was added to the flask three times every hour. The mixture was then stirred at 90°C for another 3 hours. The solution (reaction solution) obtained in the flask was then diluted with propylene glycol monomethyl ether acetate (178.66 g). Next, tetraethylammonium bromide (1.8 g, Fujifilm Wako Pure Chemical Industries, Ltd.) and hydroquinone monomethyl ether (0.8 g, Fujifilm Wako Pure Chemical Industries, Ltd.) were added to the reaction solution. The temperature of the reaction solution was then raised to 100°C. Next, glycidyl methacrylate (76.03 g, NOF Corp., product name Blenmer G) was added dropwise to the reaction solution over 1 hour. The 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% by mass). The weight average molecular weight of the obtained resin P-5 was 27000, the number average molecular weight was 15000, and the acid value was 95 mgKOH / g. Resin P-6 was synthesized with reference to the synthesis method of Resin P-5.

[0345] <Resin P-7> Propylene glycol monomethyl ether (270.0 g) was added to a three-neck flask, and the temperature was raised to 70° C. under a nitrogen stream with stirring. On the other hand, allyl methacrylate (45.6 g, Fujifilm Wako Pure Chemical Industries, Ltd.) and methacrylic acid (14.4 g) were dissolved in propylene glycol monomethyl ether (270.0 g), and V-65 (3.94 g, Fujifilm Wako Pure Chemical Industries, Ltd.) was further dissolved to prepare a dropping solution, which was dropped into the flask over 2.5 hours. The mixture was stirred for 2.0 hours and reacted. Thereafter, the temperature of the contents of the flask was returned to room temperature, and the contents of the flask were dropped into 2.7 L of stirred ion-exchanged water to perform reprecipitation and obtain a suspension. The suspension was filtered using a Nutsche (Buchner funnel) with filter paper, and the filtrate was further washed with ion-exchanged water to obtain a wet powder. The mixture was subjected to air drying at 45°C, and it was confirmed that the weight had reached a constant level, and resin P-7 was obtained as a powder with a yield of 70%. The amount of residual monomer in the powder, as measured by gas chromatography, was less than 0.1% by mass based on the polymer solid content.

[0346] <Resin P-8> Acrylic acid (72.1 parts by mass, 1.0 molar equivalent) and hexane (72.1 parts by mass) were added to a three-neck flask and cooled to 20°C. Camphorsulfonic acid (0.007 parts by mass, 0.03 mmol equivalent) and 2-dihydrofuran (77.9 parts by mass, 1.0 mol equivalent) were added dropwise to the flask, and the contents of the flask (reaction liquid) were stirred at 20°C ± 2°C for 1.5 hours, then heated to 35°C and stirred for 2 hours. Kyoward 200 (filter material, aluminum hydroxide powder, manufactured by Kyowa Chemical Industry Co., Ltd.) and Kyoward 1000 (filter material, hydrotalcite powder, manufactured by Kyowa Chemical Industry Co., Ltd.) were laid in a Nutsche (Buchner funnel) in this order, and the reaction liquid was filtered to obtain a filtrate. Hydroquinone monomethyl ether (MEHQ, 0.0012 parts) was added to the obtained filtrate, and then the mixture was concentrated under reduced pressure at 40°C to obtain tetrahydrofuran-2-yl acrylate (ATHF) (140.8 parts) as a colorless oil (yield 99.0%). PGMEA (75.0 parts) was placed in a three-neck flask and heated to 90 ° C. under a nitrogen atmosphere. The solution obtained above with 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 to the three-neck flask solution maintained at 90 ° C. ± 2 ° C. After the dropwise addition, the mixture was stirred at 90 ° C. ± 2 ° C. for 2 hours to obtain a solution containing resin P-8 (solid concentration 40.0 mass%).

[0347] Table 2 shows the type and mass ratio of each monomer used to synthesize 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 having an acid group protected by an acid-decomposable group. Resins P-1 to P-6 and P-8 were all added to the resin composition in the form of a solution, and resin P-7 was added to the resin composition in the form of a powder. The amount of monomer in Table 1 is expressed in mass %.

[0348] [Table 2]

[0349] [Thermal crosslinkable compound] <Blocked isocyanate compounds Q-1 to Q-2> Butanone oxime (Idemitsu Kosan Co., Ltd.) (453 g) was dissolved in methyl ethyl ketone (700 g) under a nitrogen gas flow. 1,3-bis(isocyanatomethyl)cyclohexane (cis, trans isomer mixture, Mitsui Chemicals Co., Ltd., Takenate 600) (500 g) was added dropwise to the resulting solution over 1 hour under ice cooling, and the mixture was allowed to react for another 1 hour after the dropwise addition. The solution was then heated to 40°C and allowed to react for 1 hour. 1Completion of the reaction was confirmed by H-NMR (Nuclear Magnetic Resonance) and HPLC (High Performance Liquid Chromatography), and a methyl ethyl ketone solution of a blocked isocyanate compound Q-1 (solid content concentration: 57.7% by mass) was obtained. Further, with reference to the synthesis method of the blocked isocyanate compound Q-1, a methyl ethyl ketone solution of the blocked isocyanate compound Q-2 (solid content concentration: 75.0% by mass) was obtained. The blocked isocyanate compounds Q-1 and Q-2 were all added to the resin composition in the form of a solution.

[0350] [ka]

[0351] [Examples 1 to 3 and Comparative Examples 1 to 2] [Preparation of resin composition] Each component was mixed with stirring according to Tables 3 to 5 to prepare each resin composition. In the table, the numerical value for each component in each resin composition indicates the amount (parts by mass) of each component added. The resin was added to each resin composition in the form of a solution containing the resin. The numerical values ​​in the table indicating the amount of resin added are the mass of the "solution containing the resin" added. Hereinafter, the same applies to components added to the composition in the form of a mixed solution, unless otherwise specified.

[0352] [Table 3]

[0353] In Table 3, each component is as follows. P-4 to P-5: The above-mentioned alkali-soluble resins Acrylic Base FF187: Alkali-soluble thermoplastic resin (solid content 40% by mass, solvent: PGMEA, manufactured by Fujikura Chemical Industries, Ltd.) BB-1: Dye, a compound with the structure shown below

[0354] [ka]

[0355] C-1: Photoacid generator, a compound having the structure shown below (a compound described in paragraph

[0227] of JP2013-047765A, and synthesized according to the method described in paragraph

[0227] ).

[0356] [ka]

[0357] B-1 to B-3: The above-mentioned block copolymers PGMEA: Propylene glycol monomethyl ether acetate (Showa Denko) MEK: Methyl ethyl ketone (manufactured by Sankyo Chemical Co., Ltd.) In the table, the column "Average thickness of thermoplastic resin composition layer (μm)" indicates the average thickness of the thermoplastic resin composition layer formed when a test was conducted using the thermoplastic resin composition.

[0358] [Table 4]

[0359] In Table 4, each component is as follows. PVA 4-88LA: Kuraray Poval 4-88LA (water-soluble resin), manufactured by Kuraray Co., Ltd. PVA 205: Kuraray Poval 205 (water-soluble resin), manufactured by Kuraray Polyvinylpyrrolidone: Water-soluble resin, manufactured by Nippon Shokubai Co., Ltd. A-1 to A-2: Compound (1) described above Megafac F444: Comparative compound, manufactured by DIC Ion-exchanged water Methanol: Solvent, manufactured by Mitsubishi Gas Chemical Company In the table, the column "Average film thickness (μm) of water-soluble resin composition layer" indicates the average film thickness of the water-soluble resin composition layer formed when a test was carried out using the water-soluble resin composition.

[0360] [Table 5]

[0361] In Table 5, each component is as follows. P-1 to P-3: The above-mentioned alkali-soluble resins BPE-500: 2,2-bis(4-((meth)acryloxypentaethoxy)phenyl)propane, manufactured by Shin-Nakamura Chemical Co., Ltd. BPE-200: 2,2-bis(4-((meth)acryloxydiethoxy)phenyl)propane, manufactured by Shin-Nakamura Chemical Co., Ltd. M-270: Polypropylene glycol diacrylate (n≒12), manufactured by Toagosei Co., Ltd. A-TMPT: Trimethylolpropane triacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd. SR-454: Ethoxylated (3) trimethylolpropane triacrylate, manufactured by Arkema SR-502: Ethoxylated (9) trimethylolpropane triacrylate, manufactured by Arkema A-9300-CL1: Caprolactone-modified (meth)acrylate compound, manufactured by Shin-Nakamura Chemical Co., Ltd. B-CIM: 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, Hampford SB-PI 701: 4,4'-bis(diethylamino)benzophenone, Sanyo Trading Co., Ltd. Leuco Crystal Violet: Tokyo Chemical Industry Co., Ltd. Brilliant Green: Tokyo Chemical Industry Co., Ltd. N-Phenylglycine: Tokyo Chemical Industry Co., Ltd. CBT-1: Carboxybenzotriazole, manufactured by Johoku Chemical Co., Ltd. TDP-G: Phenothiazine, manufactured by Kawaguchi Chemicals Irganox 245: Hindered phenolic antioxidant, manufactured by BASF N-nitrosophenylhydroxylamine aluminum salt: Fujifilm Wako Pure Chemical Industries, Ltd. Phenidone: manufactured by Tokyo Chemical Industry Co., Ltd. B-1 to B-3: The above-mentioned block copolymers Megafac F552: Comparative compound, manufactured by DIC R-1: The above-mentioned comparative compound PGMEA: Propylene glycol monomethyl ether acetate (Showa Denko) MEK: Methyl ethyl ketone (manufactured by Sankyo Chemical Co., Ltd.) In the table, the column "Average film thickness (μm) of photosensitive resin composition layer" indicates the average film thickness of the photosensitive resin composition layer formed when a test was carried out using the photosensitive resin composition.

[0362] [Preparation of transfer film] The prepared thermoplastic resin composition 1 was applied to a 16 μm thick polyethylene terephthalate film (temporary support, Lumirror 16KS40 (manufactured by Toray Industries, Inc.)) using a slit nozzle so that the width was 1.0 m and the average film thickness of the composition layer after drying was the specified film thickness, and the film was passed through a 3 m drying zone set at 80° C. and the intake and exhaust volumes were adjusted so that the film surface wind speed was 3 m / sec over 60 seconds, to obtain a laminate A having a temporary support and a thermoplastic resin composition layer. Next, water-soluble resin composition 1 was applied onto the thermoplastic resin composition layer of the obtained laminate A using a slit-shaped nozzle with a width of 1.0 m, and the amount of application was adjusted so that the average film thickness of the water-soluble resin composition layer after drying would be the specified film thickness.Then, the laminate was passed through a 3 m drying zone set at a temperature of 100°C and with the intake and exhaust volumes adjusted to give a film surface wind speed of 3 m / sec for 60 seconds, thereby obtaining a laminate B in which a water-soluble resin composition layer was formed on the above-mentioned thermoplastic resin composition layer. Furthermore, photosensitive resin composition 1 was applied onto the water-soluble resin layer of the obtained laminate B using a slit-shaped nozzle with a width of 1.0 m, and the amount of application was adjusted so that the average film thickness of the photosensitive resin composition layer after drying would be the specified film thickness.Then, the film was passed through a 3 m drying zone over 60 seconds, the temperature of which was 80°C and the intake and exhaust volumes were adjusted so that the film surface wind speed was 3 m / sec, thereby obtaining a transfer film of Example 1 in which a photosensitive resin composition layer was formed on the water-soluble resin composition layer. The obtained transfer film of Example 1 has each resin composition layer in the following order: temporary support / thermoplastic resin composition layer (1st layer) / water-soluble resin composition layer (2nd layer) / photosensitive resin composition layer (3rd layer). 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.

[0363] [Resolution evaluation] A copper layer having a thickness of 200 nm was formed by sputtering on a polyethylene terephthalate (PET) film having a thickness of 100 μm, to prepare a PET substrate with a copper layer. After unwinding each of the prepared transfer films (Examples 1 to 3 and Comparative Examples 1 to 2), the surface of the outermost photosensitive resin composition layer arranged on the temporary support was laminated to the above-mentioned PET substrate with a copper layer under lamination conditions of a roll temperature of 100° C., a linear pressure of 1.0 MPa, and a linear speed of 4.0 m / min, thereby laminating the transfer film with the PET substrate with a copper layer. Next, without peeling off the temporary support, the film was exposed to light using an ultra-high pressure mercury lamp through a line and space pattern mask (duty ratio 1:1, line width 20 μm), and then the temporary support was peeled off and developed. Development was performed by shower development for 30 seconds using a 1.0% aqueous sodium carbonate solution at 25° C. 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 determined as the optimal exposure amount. Any 1 cm of a line and space pattern formed with the optimum exposure dose 2 The area was observed with a scanning electron microscope (SEM) and the minimum line width resolved without peeling of the resist pattern and without leaving any residue was evaluated according to the following evaluation criteria. A rating of A or B is within the practically acceptable range. (Evaluation Criteria) A: The minimum line width is less than 5 μm B: The minimum line width is 5 μm or more and less than 7 μm C: Minimum line width is 7 μm or more and less than 9 μm D: The minimum line width is 9 μm or more and less than 11 μm. E: Minimum line width is 11μm or more

[0364] [Table 6]

[0365] From the results of Examples 1 to 3, it was confirmed that the desired effects were obtained when the transfer film of the present invention was used. From a comparison between Examples 1 and 2 and Example 3, it was confirmed that the effects of the present invention are more excellent when the structural unit X and the compound represented by formula (1) have a group represented by formula (A).

[0366] [Examples 4 to 6 and Comparative Examples 3 to 4] [Preparation of resin composition] Each resin composition was prepared by mixing the components according to Tables 3, 4, and 7 with stirring. In the table, the numerical value for each component in each resin composition indicates the amount (parts by mass) of each component added.

[0367] [Table 7]

[0368] In Table 7, each component is as follows. Black pigment dispersion FDK-T-11: Tokyo Ink Co., Ltd. Acrylic 8KB-001: Alkali-soluble resin, solid content concentration 38% by mass, solvent: PGMEA, manufactured by Taisei Fine Chemical Co., Ltd., Acrylic (registered trademark) 8KB-001) A-NOD-N: 1,9-nonanediol diacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd. A-DCP: Tricyclodecane dimethanol diacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd. 8UX-015A: Urethane acrylate, Taisei Fine Chemical Co., Ltd. · 75 mass % PGMEA solution of KAYARAD DPHA: 75 mass % propylene glycol monomethyl ether acetate solution of KAYARAD DPHA (product name: manufactured by Nippon Kayaku Co., Ltd.). The composition of KAYARAD DPHA is shown below. In the table, the column "Average film thickness of photosensitive resin composition layer (μm)" indicates the average film thickness of the photosensitive resin composition layer formed when a test was carried out using the photosensitive resin composition. Moreover, photosensitive resin compositions 6 to 10 correspond to photosensitive resin compositions that are colored resin compositions.

[0369] [ka]

[0370] Irgacure OXE-02: BASF, ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(o-acetyloxime) 1,2,4-Triazole: Tokyo Chemical Industry Co., Ltd. B-1 to B-3: The above-mentioned block copolymers Megafac F555A: DIC R-1: The above-mentioned comparative compound PGMEA: Propylene glycol monomethyl ether acetate (Showa Denko) MEK: Methyl ethyl ketone (manufactured by Sankyo Chemical Co., Ltd.)

[0371] [Preparation of transfer film] Each transfer film was produced in the same manner as in [Production of transfer film] in Examples 1 to 3 and Comparative Examples 1 and 2 described above, except that each resin composition in accordance with Table 8 was used.

[0372] [Evaluation of density unevenness] A polyethylene terephthalate film (PET substrate) having a thickness of 100 μm was prepared. After unwinding the prepared transfer film, the surface of the outermost photosensitive resin composition layer (colored resin composition layer) arranged on the temporary support was laminated to the above-mentioned PET substrate under lamination conditions of roll temperature 100°C, linear pressure 1.0MPa, and linear speed 4.0m / min, thereby laminating the transfer film to the PET substrate. Next, the film was exposed to light with an ultra-high pressure mercury lamp without peeling off the temporary support, and then the temporary support was peeled off and developed. Development was performed by shower development for 30 seconds using a 1.0% aqueous sodium carbonate solution at 25°C. When a pattern was formed through a line and space pattern mask (duty ratio 1:1, line width 20μm) by the above method, the exposure amount at which the resist line width became 20μm was determined as the optimal exposure amount. The cured film formed with the optimum exposure dose was placed on a high-brightness viewer and visually observed for uneven density. Evaluation was performed according to the following evaluation criteria. Evaluation A or B is within the practically acceptable range. (Evaluation Criteria) A: No unevenness (very good) B: Slight unevenness is visible, but not noticeable (good) C: Unevenness is visible, but still usable (average) D: Uneven (slightly bad) E: Strong unevenness (very bad)

[0373] [Table 8]

[0374] From the results of Examples 4 to 6, it was confirmed that the desired effects were obtained when the transfer film of the present invention was used. From a comparison between Examples 4 and 5 and Example 6, it was confirmed that the effects of the present invention are more excellent when the structural unit X and the compound represented by formula (1) have a group represented by formula (A).

[0375] [Examples 7 to 9 and Comparative Examples 5 to 6] [Preparation of resin composition] Each component was mixed with stirring according to Tables 9 to 10 to prepare each resin composition. In the table, the numerical value for each component in each resin composition indicates the amount (parts by mass) of each component added.

[0376] [Table 9]

[0377] In Table 9, each component is as follows. P-5 to P-6: The above-mentioned alkali-soluble resins A-DCP: Tricyclodecane dimethanol diacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd. A-NOD-N: 1,9-nonanediol diacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd. A-DPH: Dipentaerythritol hexaacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd. Monomer with carboxy group ARONIX TO-2349, manufactured by Toagosei Co., Ltd. Urethane acrylate 8UX-015A, manufactured by Taisei Fine Chemical Co., Ltd. IRGACURE OXE-02: 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone-1-(O-acetyloxime), manufactured by BASF Omnirad 907: 2-Methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, manufactured by BASF Duranate TPA-B80E: Blocked isocyanate compound mentioned above Q-1 to Q-2: The above-mentioned blocked isocyanate compounds N-Phenylglycine: Tokyo Chemical Industry Co., Ltd. Benzimidazole: Tokyo Chemical Industry Co., Ltd. Isonicotinamine: manufactured by Tokyo Chemical Industry Co., Ltd. SMA EF-40: Styrene / maleic anhydride copolymer (4:1 molar ratio), anhydride value 1.94mmol / g, Mw 10,500 (Cray Valley) B-1 to B-3: Block copolymers Megafac F551A: Comparative compound (DIC) MEK: Methyl ethyl ketone In the table, the column "Average film thickness of photosensitive resin composition layer (μm)" indicates the average film thickness of the photosensitive resin composition layer formed when a test was carried out using the photosensitive resin composition.

[0378] [Table 10]

[0379] In Table 10, each component is as follows. Nano Use OZS-30M: ZrO 2 Particles (containing tin oxide) in methanol dispersion (non-volatile content 30.5% by mass), manufactured by Nissan Chemical Industries, Ltd. Ammonia water (25% by weight) P-7: The above-mentioned alkali-soluble resin Alphon UC-3920: Water-soluble resin, manufactured by Toagosei Co., Ltd. Monomers with carboxy groups: Aronix TO-2349, manufactured by Toagosei Co., Ltd. Benzotriazole BT-LX, manufactured by Johoku Chemical Industry Co., Ltd. Adenine, manufactured by Tokyo Industrial Chemical Co., Ltd. N-Methyldiethanolamine, manufactured by Tokyo Industrial Chemical Co., Ltd. Monoisopropanolamine A-1 to A-2: Compound (1) described above Megafac F444: Comparative compound, manufactured by DIC Ion-exchanged water ·methanol In the table, the column "Average film thickness (μm) of water-soluble resin composition layer" indicates the average film thickness of the water-soluble resin composition layer formed when a test was carried out using the water-soluble resin composition. The water-soluble resin compositions 4 to 6 also correspond to compositions for forming a refractive index adjusting layer.

[0380] [Preparation of transfer film] Each transfer film was prepared in the same manner as in [Preparation of transfer film] in Examples 1 to 3 and Comparative Examples 1 and 2 described above, except that each resin composition in accordance with Table 11 was used.

[0381] [Surface defect evaluation] A polyethylene terephthalate film (PET substrate) having a thickness of 100 μm was prepared. After unwinding the prepared transfer film, the outermost layer of the composition layer disposed on the temporary support was laminated under lamination conditions of a roll temperature of 100° C., a linear pressure of 1.0 MPa, and a linear speed of 4.0 m / min. Layer The surface was laminated with the PET substrate, and the transfer film was laminated with the PET substrate. Next, the film was exposed to an ultra-high pressure mercury lamp without peeling off the temporary support, and then the temporary support was peeled off and developed. Development was performed using a 1.0% aqueous sodium carbonate solution at 25°C for 30 seconds by shower development. When a pattern was formed using the above method through a line and space pattern mask (duty ratio 1:1, line width 20 μm), the optimal exposure amount was the exposure amount at which the resist line width became 20 μm. The surface of the cured film formed with the optimum exposure dose was visually observed over an area of ​​10 m in length and 1.5 m in width, and surface defects were evaluated according to the following evaluation criteria, with a rating of A or B being within the practically acceptable range. (Evaluation Criteria) A: Surface defects are 1 / m 2 less than B: Surface defects: 1 / m 2 More than 3 pieces / m 2 less than C: Surface defects are 3 / m 2 More than 5 pieces / m 2 less than D: Surface defects: 5 / m 2 More than 10 pieces / m 2 less than E: Surface defects are 10 / m 2 End

[0382] [Table 11]

[0383] From the results of Examples 7 to 9, it was confirmed that the desired effects were obtained when the transfer film of the present invention was used. From a comparison between Examples 7 and 8 and Example 9, it was confirmed that the effects of the present invention are more excellent when the structural unit X and the compound represented by formula (1) have a group represented by formula (A).

[0384] [Examples 10 to 12 and Comparative Examples 7 to 8] [Preparation of resin composition] Each resin composition was prepared by mixing the components according to Table 12. In the table, the numerical value for each component in each resin composition indicates the amount (parts by mass) of each component added.

[0385] [Table 12]

[0386] In Table 12, each component is as follows. P-8: A resin having a structural unit having an acid group protected by the above-mentioned acid-decomposable group

[0387] C-1: Photoacid generator, a compound having the structure shown below (a compound described in paragraph

[0227] of JP2013-047765A, and synthesized according to the method described in paragraph

[0227] ).

[0388] [ka]

[0389] BB-1: Dye, a compound with the structure shown below

[0390] [ka]

[0391] 1,2,3-Benzotriazole B-1 to B-3: The above-mentioned block copolymers Megafac F552: Comparative compound, manufactured by DIC R-1: The above-mentioned comparative compound n-Propyl acetate In the table, the column "Average film thickness of photosensitive resin composition layer (μm)" indicates the average film thickness of the photosensitive resin composition layer formed when a test was carried out using the photosensitive resin composition.

[0392] [Preparation of transfer film] The prepared photosensitive resin composition 16 was applied to a 16 μm-thick polyethylene terephthalate film (Lumirror 16KS40 (manufactured by Toray Industries, Inc.)) using a slit nozzle so that the width was 1.0 m and the average film thickness of the composition layer after drying was the specified film thickness, and the film was passed through a 3 m drying zone set at 100° C. and the intake and exhaust volumes were adjusted so that the film surface wind speed was 3 m / sec over 60 seconds, thereby obtaining a transfer film of Example 10. In Examples 11 to 12 and Comparative Examples 7 to 8, the transfer films were obtained in the same manner as in Example 10, except that the thermoplastic resin compositions were changed as shown in Table 13.

[0393] [Evaluation of Resolution] The resolution was evaluated according to the same procedures and evaluation criteria as in the [Evaluation of Resolution] in Examples 1 to 3 and Comparative Examples 1 and 2 described above.

[0394] [Table 13]

[0395] From the results of Examples 10 to 12, it was confirmed that the desired effects were obtained when the transfer film of the present invention was used. From a comparison between Examples 10 and 11 and Example 12, it was confirmed that the effects of the present invention are more excellent when the structural unit X and the compound represented by formula (1) have a group represented by formula (A). [Explanation of symbols]

[0396] 10 Temporary support 12 Thermoplastic resin layer 14 Middle Class 16 Photosensitive resin composition layer 18 Cover film 100 Transfer Film

Claims

1. A temporary support and one photosensitive resin composition layer disposed on the temporary support, The photosensitive resin composition layer comprises a resin, A transfer film comprising a block copolymer including a block composed of a structural unit X having a group represented by formula (A) or a group represented by formula (B) and a block composed of a structural unit Y having a poly(oxyalkylene) group. Formula (A) *-(CH ２ )( ｍ -(CF ２ )( ｎ -CF ３ In formula (A), m and n each independently represent an integer of 1 to 3. * 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. * represents a bonding position.

2. A temporary support and one photosensitive resin composition layer disposed on the temporary support, The photosensitive resin composition layer comprises a resin, A transfer film comprising a block copolymer including a block composed of a structural unit X having a group represented by formula (A) or a group represented by formula (B) and a block composed of a structural unit Y having a poly(oxyalkylene) group. However, the photosensitive resin composition layer does not contain a thermal crosslinking agent. Formula (A) *-(CH ２ ) ｍ -(CF ２ ) ｎ -CF ３ In formula (A), m and n each independently represent an integer of 1 to 3. * 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. * represents a bonding position.

3. The transfer film according to claim 1 or 2, wherein the structural unit X has a group represented by formula (A).

4. The transfer film according to claim 1 , wherein the structural unit X has a group represented by formula (B).

5. The transfer film according to any one of claims 1 to 4, comprising the block copolymer, the block copolymer having a weight average molecular weight of 5,000 or more.

6. The resin is an alkali-soluble resin, The transfer film according to any one of claims 1 to 5, wherein the photosensitive resin composition layer further contains a polymerizable compound.

7. the resin has a structural unit having an acid group protected by an acid-decomposable group, The transfer film according to any one of claims 1 to 5, wherein the photosensitive resin composition layer further contains a photoacid generator.

8. The transfer film according to any one of claims 1 to 7, wherein the photosensitive resin composition layer further contains a pigment.

9. The block copolymer has a weight average molecular weight of 5,000 or more, and the structural unit X is a structural unit represented by formula (C), the content of the block copolymer is 0.01 to 3.00% by mass based on the total mass of the photosensitive resin composition layer, the resin is an alkali-soluble resin, and the content of the resin is 20.00 to 80.00% by mass with respect to the total mass of the photosensitive resin composition layer; The transfer film according to claim 1 or 2, wherein the photosensitive resin composition layer further comprises a polymerizable compound, and the polymerizable compound has an ethylenically unsaturated group as a polymerizable group. 【Chemistry 1】 In formula (C), R represents a hydrogen atom or a substituent, L represents a single bond or a divalent linking group, and Z represents a group represented by formula (A) or a group represented by formula (B).

10. A bonding step of contacting a substrate with a surface of the transfer film according to any one of claims 1 to 9 opposite to the temporary support, and bonding the transfer film and the substrate to obtain a substrate with a transfer film; an exposure step of pattern-exposing the photosensitive resin composition layer; a developing step of developing the exposed photosensitive resin composition layer to form a resin pattern; The method for producing a laminate further comprises a peeling step of peeling the temporary support from the substrate with the transfer film between the laminating step and the exposure step, or between the exposure step and the development step.

11. A bonding step of contacting a surface of the transfer film according to any one of claims 1 to 9 opposite to the temporary support with a substrate having a conductive layer, and bonding the transfer film and the substrate having the conductive layer to obtain a substrate with a transfer film; an exposure step of pattern-exposing the photosensitive resin composition layer; a developing step of developing the exposed photosensitive resin composition layer to form a resin pattern; an etching step of etching the conductive layer in an area where the resin pattern is not disposed; The method for producing circuit wiring further comprises a peeling step of peeling the temporary support from the substrate with the transfer film between the laminating step and the exposure step, or between the exposure step and the development step.

12. A method for producing an electronic device, comprising the method for producing a laminate according to claim 10, The electronic device includes the resin pattern as a cured film.

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