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

Abstract

The present invention addresses the problem of providing a transfer film that can form a pattern having exceptional development residue suppression properties even when developed after being left for a prescribed period after exposure. The present invention also addresses the problem of providing a method for producing a laminate using the transfer film, and a method for producing a circuit wiring.　This transfer film has a temporary support and a composition layer, the composition layer including a photosensitive composition layer, and the photosensitive composition layer containing a polymer, a polymerizable compound, and a photopolymerization initiator that satisfy both requirements 1 and 2 indicated below.　Requirement 1: The number-average molecular weight in terms of standard polystyrene obtained by gel permeation chromatography is 3,000-50,000.　Requirement 2: The content ratio of components having a molecular weight equivalent to at least ten times the above number-average molecular weight, which is derived from an integrated molecular weight distribution curve in terms of standard polystyrene obtained by gel permeation chromatography, is 3.0% or less.

Description

[Technical Field]

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

[0002] 2. Description of the Related Art Transfer films such as photosensitive transfer materials have been increasingly used in various fields in recent years. Photosensitive transfer materials can contribute to reducing product costs, and so their use as etching resist films, wiring protection films, and the like has been proposed. On the other hand, the functions required of photosensitive transfer materials are becoming increasingly sophisticated, and a structure in which a plurality of functional layers are stacked is also being considered.

[0003] For example, Patent Document 1 discloses a transfer film for etching resist and a transfer film for wiring protection film, each of which is formed by laminating a plurality of functional layers. Specifically, it discloses a transfer film for etching resist, each of which is formed by laminating a temporary support, a thermoplastic resin layer, an intermediate layer, and a photosensitive composition layer (paragraphs

[0203] to

[0207] , etc.), and a transfer film for wiring protection film, each of which is formed by laminating a temporary support, a photosensitive composition layer, and a second transparent resin layer (paragraphs

[0197] and

[0208] , etc.). [Prior art documents] [Patent documents]

[0004] [Patent Document 1] International Publication No. 2017 / 057348 Summary of the Invention [Problem to be solved by the invention]

[0005] The present inventors have studied the transfer film described in Patent Document 1 and have found that when the photosensitive composition layer of the transfer film is left for a predetermined period after exposure and then developed, a large amount of development residue is generated in the formed pattern. In other words, it has been found that there is room for further improvement in the suppression of development residue in the pattern formed by leaving the photosensitive composition layer of the transfer film for a predetermined period after exposure and then developing it.

[0006] Therefore, an object of the present invention is to provide a transfer film that can form a pattern with excellent development residue suppression even when the film is left for a predetermined period of time after exposure and then developed. Another object of the present invention is to provide a method for manufacturing a laminate and a method for manufacturing circuit wiring using the transfer film. [Means for solving the problem]

[0007] As a result of extensive research into the above-mentioned problems, the present inventors have found that the above-mentioned problems can be solved by the following configuration.

[0008] [1] A transfer film having a temporary support and a composition layer, the composition layer includes a photosensitive composition layer, The photosensitive composition layer of the transfer film contains a polymer, a polymerizable compound, and a photopolymerization initiator that satisfy both the following requirements 1 and 2: Requirement 1: The number average molecular weight, calculated as standard polystyrene, obtained by gel permeation chromatography is 3,000 to 50,000. Requirement 2: The content ratio of components with a molecular weight equivalent to 10 times or more of the number average molecular weight, as determined from an integrated molecular weight distribution curve converted into standard polystyrene by gel permeation chromatography, is 3.0% or less. [2] The transfer film according to [1], wherein the polymer further satisfies the following requirement 3. Requirement 3: The content ratio of components with a molecular weight equivalent to at least five times the number average molecular weight, as determined from an integrated molecular weight distribution curve converted into standard polystyrene by gel permeation chromatography, is 15.0% or less. [3] The transfer film according to [1] or [2], wherein the photopolymerization initiator includes a hexaarylbiimidazole derivative. [4] The transfer film according to any one of [1] to [3], wherein the polymerizable compound includes a compound BPA1 having a bisphenol A structure. [5] The compound BPA1 includes a compound BPA2 having a bisphenol A structure and two ethylenically unsaturated groups in the molecule, The transfer film according to [4], wherein the content of the compound BPA2 is 80% by mass or more relative to the total mass of the polymerizable compound. [6] The transfer film according to any one of [1] to [5], wherein the content of the compound having two or more ethylenically unsaturated groups in the molecule of the polymerizable compound is 90 to 100 mass % relative to the total mass of the polymerizable compound. [7] The transfer film according to any one of [1] to [6], wherein the content of the compound having three or more ethylenically unsaturated groups in the molecule of the polymerizable compound is 0 to 20 mass % relative to the total mass of the polymerizable compound. [8] The transfer film according to any one of [1] to [7], wherein the content of the compound having four or more ethylenically unsaturated groups in the molecule of the polymerizable compound is 0 to 10 mass % relative to the total mass of the polymerizable compound. [9] The transfer film according to any one of [1] to [8], wherein the polymer contains at least one of a structural unit having an aromatic group and a structural unit having an aliphatic hydrocarbon ring group.

[10] The transfer film according to any one of [1] to [9], wherein the polymer contains a structural unit having a polymerizable group.

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

[10] , which is used for forming a protective film for a touch panel.

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

[10] , which is used for forming an etching resist film.

[13] a lamination step in which a surface of the transfer film according to any one of [1] to

[10] opposite to the temporary support is brought into contact with a substrate having a conductive layer and laminated to obtain a composition layer-bearing substrate having the substrate, the conductive layer, the composition layer, and the temporary support in this order; an exposure step of pattern-exposing the composition layer; a developing step of developing the exposed composition layer to form a protective film pattern that protects the conductive layer; The method for producing a laminate further comprises a peeling step of peeling the temporary support from the composition layer-carrying substrate between the laminating step and the exposing step, or between the exposing step and the developing step.

[14] The method for producing a laminate according to

[13] , wherein the substrate having the conductive layer is a substrate having at least one of a touch panel electrode and a touch panel wiring.

[15] A lamination step of bringing a surface of the transfer film according to any one of [1] to

[10] opposite to the temporary support into contact with a substrate having a conductive layer to obtain a composition layer-bearing substrate having the substrate, the conductive layer, the composition layer, and the temporary support in this order; an exposure step of pattern-exposing the composition layer; a developing step of developing the exposed 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 composition layer between the laminating step and the exposure step, or between the exposure step and the development step. [Effects of the Invention]

[0009] According to the present invention, it is possible to provide a transfer film that can form a pattern with excellent development residue suppression properties even when the film is developed after being left for a predetermined period of time after exposure. Furthermore, the present invention can provide a method for producing a laminate and a method for producing circuit wiring using the transfer film. [Brief explanation of the drawings]

[0010] [Figure 1] FIG. 2 is a schematic diagram for explaining an integrated molecular weight curve. [Figure 2] FIG. 2 is a schematic diagram showing an example of the configuration of the transfer film of the first embodiment. [Figure 3] FIG. 10 is a schematic diagram showing an example of the configuration of a transfer film according to a second embodiment. DETAILED DESCRIPTION OF THE INVENTION

[0011] The present invention will be described in detail below. 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 the present specification, in the numerical ranges described in stages, the upper or lower limit value described in a certain numerical range may be replaced with the upper or lower limit value of another numerical range described in stages. Furthermore, in the numerical ranges described in the present specification, the upper or lower limit value described in a certain numerical range may be replaced with a value shown in the examples.

[0012] In this specification, the term "process" includes not only an independent process but also a process that cannot be clearly distinguished from other processes, as long as the intended purpose of the process is achieved.

[0013] In this specification, the term "transparent" means that the average transmittance of visible light with a wavelength of 400 to 700 nm is 80% or more, and preferably 90% or more. In this specification, the average transmittance of visible light is a value measured using a spectrophotometer, and can be measured using, for example, a spectrophotometer U-3310 manufactured by Hitachi, Ltd.

[0014] In this specification, unless otherwise specified, the weight average molecular weight (Mw), number average molecular weight (Mn) and content ratio (%) of a component of a predetermined molecular weight of a polymer are values ​​measured by gel permeation chromatography (GPC) under the following conditions.

[0015] (GPC conditions) Apparatus: Tosoh high-speed GPC apparatus HLC-8420GPC (product name), manufactured by Tosoh Corporation Guard column: Tosoh Corporation, HZ-L Separation column: Three columns of TSK gel Super HZM-N (product name) manufactured by Tosoh Corporation connected in series Measurement temperature: 40℃ Eluent: THF (tetrahydrofuran) Flow rate: Sample pump 0.35 mL / min, reference pump 0.175 mL / min Injection volume: 10μL Detector: differential refractometer GPC column calibration standard solution: Tosoh standard polystyrene

[0016] In this specification, unless otherwise specified, the molecular weight of a compound having a molecular weight distribution is the weight average molecular weight (Mw). In this specification, unless otherwise specified, the content of metal elements is a value measured using an inductively coupled plasma (ICP) spectroscopic analyzer. In this specification, unless otherwise specified, the refractive index is a value measured using an ellipsometer at a wavelength of 550 nm. In this specification, unless otherwise specified, the hue is a value measured using a color difference meter (CR-221, manufactured by Minolta Co., Ltd.).

[0017] In this specification, "(meth)acrylic" is a concept that encompasses both acrylic and methacrylic, "(meth)acryloyloxy group" is a concept that encompasses both acryloyloxy group and methacryloyloxy group, "(meth)acrylamide group" is a concept that encompasses both acrylamide group and methacrylamide group, and "(meth)acrylate" is a concept that encompasses both acrylate and methacrylate.

[0018] In this specification, "alkali-soluble" means that the solubility in 100 g of a 1% by mass aqueous sodium carbonate solution at a liquid temperature of 22° C. is 0.1 g or more. Therefore, for example, an alkali-soluble resin refers to a resin that satisfies the above-mentioned solubility conditions.

[0019] As used herein, "water-soluble" means that the solubility in 100 g of water having a pH of 7.0 and a liquid temperature of 22° C. is 0.1 g or more. Therefore, for example, a water-soluble resin refers to a resin that satisfies the above-mentioned solubility conditions.

[0020] In this specification, the "solid content" of a composition refers to components that form a composition layer formed using the composition, and when the composition contains a solvent (organic solvent, water, etc.), it refers to all components excluding the solvent. Furthermore, liquid components that form a composition layer are also considered to be solid content.

[0021] [Transfer film] The transfer film of the present invention is a transfer film having a temporary support and a composition layer, the composition layer includes a photosensitive composition layer, The photosensitive composition layer contains a polymer (hereinafter also referred to as a "specific polymer") that satisfies both the following requirements 1 and 2, a polymerizable compound, and a photopolymerization initiator. Requirement 1: The number average molecular weight, calculated as standard polystyrene, obtained by gel permeation chromatography is 3,000 to 50,000. Requirement 2: The content ratio of components with a molecular weight equivalent to 10 times or more of the number average molecular weight, as determined from an integrated molecular weight distribution curve converted into standard polystyrene by gel permeation chromatography, is 3.0% or less.

[0022] Due to the above-mentioned configuration, the transfer film of the present invention can form a pattern with excellent development residue suppression (in other words, with little development residue) even if the photosensitive composition layer in the transfer film is left for a predetermined period of time after exposure and then developed.

[0009] The present inventors' recent investigations have revealed that the development residues generated after exposure are due to the presence of high-molecular-weight components contained in the polymer contained in the photosensitive composition layer. Further investigations based on the above findings have revealed that when the polymer contained in the photosensitive composition layer satisfies the above requirements 1 and 2, a pattern with significantly reduced development residues can be formed when the photosensitive composition layer in the transfer film is exposed to light and then developed after being left for a predetermined period of time.

[0023] Hereinafter, the ability to form a pattern with excellent suppression of development residues even when the photosensitive composition layer in the transfer film is left for a predetermined period of time after exposure and then developed may also be referred to as "the effects of the present invention being better."

[0024] The transfer film of the present invention will be described below. The transfer film of the present invention has a temporary support and a composition layer, and the composition layer includes a photosensitive composition layer. The composition layer is not particularly limited as long as it includes a photosensitive composition layer. The photosensitive composition layer may be a negative photosensitive composition layer or a chemically amplified photosensitive composition layer, but is preferably a negative photosensitive composition layer. The composition layer may have a single layer structure or a structure of two or more layers. When the composition layer includes a composition layer other than the photosensitive composition layer, examples of the other composition layer include a thermoplastic resin layer, an intermediate layer, and a refractive index adjusting layer. The transfer film may also have a protective film (hereinafter sometimes referred to as a "cover film") on the composition layer.

[0025] The photosensitive composition layer contains a polymer (specific polymer) that satisfies both the following requirements 1 and 2, a polymerizable compound, and a photopolymerization initiator. Requirement 1: The number average molecular weight, calculated as standard polystyrene, obtained by gel permeation chromatography is 3,000 to 50,000. Requirement 2: The content ratio of components with a molecular weight equivalent to 10 times or more of the number average molecular weight, as determined from an integrated molecular weight distribution curve converted into standard polystyrene by gel permeation chromatography, is 3.0% or less.

[0026] In order to obtain better effects of the present invention, it is preferable that the specific polymer further satisfies the following requirement 3. Requirement 3: The content ratio of components with a molecular weight equivalent to at least five times the number average molecular weight, as determined from an integrated molecular weight distribution curve converted into standard polystyrene by gel permeation chromatography, is 15.0% or less.

[0027] (Weight average molecular weight (Mw) and number average molecular weight (Mn)) The weight average molecular weight (Mw) and number average molecular weight (Mn) of the polymer are determined by the GPC measurement described above.

[0028] (Content ratio) The content ratio of components having molecular weights corresponding to 5 or more times or 10 or more times the number average molecular weight (Mn) is calculated by observing the integrated molecular weight distribution curve (X axis: LogM, Y axis: integrated molecular weight distribution (%)) obtained by the above-mentioned GPC measurement. For example, when the integrated molecular weight distribution curve shown in Figure 1 is obtained by GPC measurement of a polymer, the content ratio of components having a molecular weight of less than 100,000 can be calculated to be 88% based on the integrated molecular weight distribution of components whose LogM falls in the range of less than 5, and the content ratio of components having a molecular weight of 100,000 or more can be calculated to be 12% based on the integrated molecular weight distribution of components whose LogM falls in the range of 5 or more.

[0029] An example of the embodiment of the transfer film of the present invention will be shown below, but the present invention is not limited to this. (1) "Temporary support / intermediate layer / photosensitive composition layer / protective film" (2) "Temporary support / thermoplastic resin layer / intermediate layer / photosensitive composition layer / protective film" (3) "Temporary support / photosensitive composition layer / refractive index adjusting layer / protective film" (4) "Temporary support / photosensitive composition layer / protective film" In each of the above-described configurations, the photosensitive composition layer is preferably a negative photosensitive composition layer, and is also preferably a colored resin layer. The transfer film of the present invention may be used as a transfer film for an etching resist, as will be described later, or as a transfer film for a wiring protection film. When used as a transfer film for etching resist, the transfer film preferably has the above-mentioned configuration (1), (2), or (4).When used as a transfer film for wiring protection film, the transfer film preferably has the above-mentioned configuration (3) or (4).

[0030] The transfer film of the present invention will be described below by taking an example of a specific embodiment. The transfer film of the first embodiment below has a configuration suitable for use as a transfer film for etching resist, and the transfer film of the second embodiment below has a configuration suitable for use as a transfer film for wiring protection film.

[0031] [Transfer film of the first embodiment] An example of the transfer film of the first embodiment will be described below. 2 has, in this order, a temporary support 1, a thermoplastic resin layer 3, an intermediate layer 5, a composition layer 2 including a photosensitive composition layer 7, and a protective film 9. The photosensitive composition layer 7 contains a specific polymer (hereinafter, the specific polymer contained in the photosensitive composition layer of the transfer film of the first embodiment will also be referred to as "specific polymer A"), a polymerizable compound, and a photopolymerization initiator. Although the transfer film 10 shown in FIG. 2 has a protective film 9 disposed thereon, the protective film 9 does not necessarily have to be disposed. Furthermore, although the transfer film 10 shown in FIG. 2 has the thermoplastic resin layer 3 and the intermediate layer 5 arranged therein, the thermoplastic resin layer 3 and the intermediate layer 5 do not necessarily have to be arranged. Each element constituting the transfer film will be described below.

[0032] <<Temporary support>> The transfer film has a temporary support. The temporary support is a member that supports the composition layer, and is ultimately removed by a peeling treatment.

[0033] The temporary support may have a single-layer structure or a multi-layer structure. The temporary support is preferably a film, more preferably a resin film, which is flexible and does not significantly deform, shrink, or stretch under pressure or under pressure and heat. Examples of the film include polyethylene terephthalate film (for example, biaxially stretched polyethylene terephthalate film), polymethyl methacrylate film, cellulose triacetate film, polystyrene film, polyimide film, and polycarbonate film. Among these, a polyethylene terephthalate film is preferred as the temporary support. Furthermore, it is preferable that the film used as the temporary support is free from deformations such as wrinkles and scratches.

[0034] The temporary support preferably has high transparency so that pattern exposure can be performed through the temporary support, and the transmittance at one or more wavelengths selected from 313 nm, 365 nm, 313 nm, 405 nm, and 436 nm is preferably 60% or more, more preferably 70% or more, even more preferably 80% or more, and particularly preferably 90% or more. Preferred transmittance values ​​include, for example, 87%, 92%, and 98%. From the viewpoints of pattern formability during pattern exposure through the temporary support and transparency of the temporary support, it is preferable that the haze of the temporary support is small. Specifically, the haze value of the temporary support is preferably 2% or less, more preferably 0.5% or less, and even more preferably 0.1% or less. From the viewpoint of pattern formation 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, and defects contained in the temporary support is small. The number of fine particles, foreign matter, and defects with a diameter of 1 μm or more in the temporary support is 50 / 10 mm. 2 Preferably less than 10 pieces / 10mm 2 Less than 3 pieces / 10mm is more preferable. 2 Less than 0 / 10mm is more preferable. 2 is particularly preferred.

[0035] The thickness of the temporary support is not particularly limited, but is preferably 5 to 200 μm, and from the viewpoint of ease of handling and versatility, is more preferably 10 to 150 μm, and even more preferably 10 to 50 μm. The thickness of the temporary support is calculated as the average value of measurements taken at any five points by cross-sectional observation using an SEM (Scanning Electron Microscope).

[0036] Examples of the temporary support include a biaxially oriented polyethylene terephthalate film having a thickness of 16 μm, a biaxially oriented polyethylene terephthalate film having a thickness of 12 μm, and a biaxially oriented polyethylene terephthalate film having a thickness of 9 μm.

[0037] Preferred forms 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 A, and paragraphs

[0029] to

[0040] of WO 2018 / 179370 A, the contents of which are incorporated herein by reference.

[0038] To improve handling properties, a layer containing fine particles (lubricant layer) may be provided on the surface of the temporary support. The lubricant layer may be provided on one side or both sides of the temporary support. The diameter of the particles contained in the lubricant layer is preferably 0.05 to 0.8 μm. The thickness of the lubricant layer is preferably 0.05 to 1.0 μm. Commercially available temporary supports include Lumirror 16KS40 and Lumirror 16FB40 (both manufactured by Toray Industries, Inc.), Cosmoshine A4100, Cosmoshine A4160, Cosmoshine A4300, and Cosmoshine A8300 (all manufactured by Toyobo Co., Ltd.).

[0039] <<Photosensitive composition layer>> In display devices (organic electroluminescence (EL) display devices, liquid crystal display devices, etc.) equipped with a touch panel such as a capacitance-type input device, a conductive layer pattern such as an electrode pattern corresponding to the sensor of the viewing area, and wiring of the peripheral wiring portion and the lead-out wiring portion is provided inside the touch panel. Generally, a method of forming a patterned layer is widely adopted in which a negative photosensitive composition layer (photosensitive layer) is provided on a substrate using a transfer film or the like, and the photosensitive layer is exposed to light through a mask having a desired pattern, and then developed. Therefore, the photosensitive composition layer is usually a negative photosensitive composition layer, and the formed pattern corresponds to a cured layer.

[0040] The photosensitive composition layer contains a specific polymer A, a polymerizable compound, and a photopolymerization initiator. Each component will be described in turn below.

[0041] <Specific polymer A> The photosensitive composition layer contains a specific polymer A. The specific polymer A is preferably an alkali-soluble resin. The acid value of the specific polymer A is preferably 250 mgKOH / g or less, more preferably 220 mgKOH / g or less, and even more preferably less than 200 mgKOH / g, in order to suppress swelling of the photosensitive composition layer by the developer and thereby achieve better resolution. The lower limit of the acid value of the specific polymer A is not particularly limited, but in terms of better developability, it is preferably 60 mgKOH / g or more, more preferably 90 mgKOH / g or more, even more preferably 110 mgKOH / g or more, and particularly preferably 120 mgKOH / g or more.

[0042] The acid value (mgKOH / g) is the mass [mg] of potassium hydroxide required to neutralize 1 g of sample. The acid value can be determined according to the method described in JIS K0070:1992. The acid value of the specific polymer A may be adjusted by changing the type of structural unit constituting the specific polymer and the content of the structural unit containing an acid group.

[0043] The number average molecular weight of the specific polymer A satisfies the above-mentioned requirement 1. A number-average molecular weight of 50,000 or less is preferred in terms of improving resolution and developability. A number-average molecular weight of 40,000 or less is more preferred, and 30,000 or less is even more preferred. On the other hand, a number-average molecular weight of 3,000 or more is preferred in terms of controlling the properties of development aggregates and the properties of unexposed films, such as edge fusing and cut-chip resistance. A number-average molecular weight of 6,000 or more is more preferred, more preferably 10,000 or more, and particularly preferably 15,000 or more. Edge fusing refers to the degree to which the photosensitive composition layer easily protrudes from the edge of a roll when the transfer film is wound into a roll. Cut-chip resistance refers to the degree to which chips fly off when the unexposed film of the photosensitive composition layer is cut with a cutter. If these chips adhere to the top surface of the photosensitive composition layer, they may be transferred to a mask during a subsequent exposure process, resulting in defective products. The dispersity of the specific polymer A is preferably from 1.0 to 6.0, more preferably from 1.0 to 5.0, still more preferably from 1.0 to 4.0, and particularly preferably from 1.0 to 3.0.

[0044] The content of specific polymer A is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, even more preferably 30 to 70% by mass, and particularly preferably 40 to 60% by mass, relative to the total mass of the photosensitive composition layer. A content of specific polymer A of 90% by mass or less is preferred from the viewpoint of controlling the development time. On the other hand, a content of specific polymer A of 10% by mass or more is preferred from the viewpoint of improving edge fuse resistance. The specific polymer A may be used alone or in combination of two or more.

[0045] The structure of the specific polymer A will be described below.

[0046] (Embodiment 1 of Specific Polymer A) Suitable embodiments of the specific polymer A include acrylic resins, styrene-acrylic copolymers, epoxy resins, amide resins, amide-epoxy resins, alkyd resins, phenolic resins, ester resins, urethane resins, and acid-modified epoxy acrylate resins obtained by reacting epoxy acrylate resins with acid anhydrides. Among these, acrylic resins are preferred as the specific polymer A. In this specification, acrylic resin refers to a resin having structural units derived from (meth)acrylic compounds. In the acrylic resin, the content of structural units derived from (meth)acrylic compounds is preferably 30% by mass or more, more preferably 40% by mass or more, and even more preferably 50% by mass or more, based on the total structural units of the acrylic resin.

[0047] (Embodiment 2 of Specific Polymer A) In another preferred embodiment of the specific polymer A, it is preferable that the specific polymer A contains at least one of a structural unit having an aromatic group and a structural unit having an aliphatic hydrocarbon ring group, from the viewpoint of suppressing line width thickening and deterioration of resolution when the focus position is shifted during exposure (and thus from the viewpoint of achieving better LWR (Line Width Roughness) performance of metal wiring when a cured film formed by pattern-curing the photosensitive composition layer is used as an etching resist). In other words, it is preferable that the specific polymer A contains at least one of a structural unit based on a monomer having an aromatic group and a structural unit based on a monomer having an aliphatic hydrocarbon ring group. Examples of the aromatic group include aromatic hydrocarbon ring groups, specifically substituted or unsubstituted phenyl groups and substituted or unsubstituted aralkyl groups, etc. Examples of the aliphatic hydrocarbon ring groups include substituted or unsubstituted monocyclic or polycyclic cycloalkyl groups having 5 to 20 carbon atoms (e.g., substituted or unsubstituted cyclohexyl groups and substituted or unsubstituted dicyclopentanyl groups).

[0048] The content of structural units based on monomers having an aromatic group in specific polymer A is preferably 20% by mass or more, and more preferably 30% by mass or more, based on all structural units of specific polymer A. There is no particular upper limit, but it is preferably 95% by mass or less, and more preferably 85% by mass or less. When multiple types of specific polymer A are contained, it is preferable that the average content of structural units based on monomers having an aromatic group falls within the above range.

[0049] The content of structural units based on monomers having an aliphatic hydrocarbon ring group in the specific polymer A is preferably 15% by mass or more, and more preferably 20% by mass or more, based on all structural units of the specific polymer A. There is no particular upper limit, but it is preferably 70% by mass or less, and more preferably 60% by mass or less. When multiple types of specific polymer A are contained, it is preferable that the average content of structural units based on monomers having an aliphatic hydrocarbon ring group falls within the above range.

[0050] When the specific polymer A contains both a structural unit based on a monomer having an aromatic group and a structural unit based on a monomer having an aliphatic hydrocarbon ring group, the total content of both is preferably 95% by mass or less, more preferably 85% by mass or less.

[0051] Examples of the monomer having an aromatic group include a monomer having an aralkyl group, styrene, and polymerizable styrene derivatives (e.g., methylstyrene, vinyltoluene, tert-butoxystyrene, acetoxystyrene, 4-vinylbenzoic acid, styrene dimer, and styrene trimer). Among these, a monomer having an aralkyl group or styrene is preferred. In one embodiment, when the aromatic group-containing monomer component in the specific polymer A is styrene, the content of structural units based on styrene is preferably 20 to 70% by mass, more preferably 25 to 65% by mass, even more preferably 30 to 60% by mass, and particularly preferably 30 to 55% by mass, based on the total structural units of the specific polymer A.

[0052] 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.

[0053] Examples of the monomer having a phenyl alkyl group include phenylethyl (meth)acrylate.

[0054] 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 aromatic group-containing monomer component in the specific polymer A is benzyl (meth)acrylate, the content of the structural units based on benzyl (meth)acrylate is preferably 50 to 95% by mass, more preferably 60 to 90% by mass, and even more preferably 70 to 90% by mass, based on the total structural units of the specific polymer A.

[0055] Examples of monomers having an aliphatic hydrocarbon ring group include monomers having a monocyclic or polycyclic cycloalkyl group having 5 to 20 carbon atoms (for example, a substituted or unsubstituted cyclohexyl group, and a substituted or unsubstituted dicyclopentanyl group). Examples of the monomer having a monocyclic or polycyclic cycloalkyl group having 5 to 20 carbon atoms include (meth)acrylates having a monocyclic or polycyclic cycloalkyl 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, and 3-hydroxy-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, cyclohexyl (meth)acrylate, and dicyclopentanyl (meth)acrylate.Among these (meth)acrylic acid esters, cyclohexyl (meth)acrylate, dicyclopentanyl (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, dicyclopentanyl (meth)acrylate, (nor)bornyl (meth)acrylate, isobornyl (meth)acrylate, 2-adamantyl (meth)acrylate, or tricyclodecane (meth)acrylate is more preferred.

[0056] The specific polymer A more preferably contains a structural unit having an aromatic group (in other words, a structural unit based on a monomer having an aromatic group) in that the metal wiring formed when the cured film formed by pattern-curing the photosensitive composition layer is used as an etching resist has better LWR (Line Width Roughness) performance.

[0057] As one embodiment of the specific polymer A containing a structural unit based on a monomer having an aromatic group, it is preferable that the specific polymer A is obtained by polymerizing a monomer having an aromatic group with at least one type of first monomer described below and / or at least one type of second monomer described below.

[0058] One embodiment of the specific polymer A containing a structural unit based on a monomer having an aromatic group is preferably obtained by polymerizing a monomer having an aromatic group, a structural unit based on a monomer having an aliphatic hydrocarbon group, and at least one type of first monomer described below and / or at least one type of second monomer described below.

[0059] In one embodiment of the specific polymer A that does not contain a structural unit based on a monomer having an aromatic group, it 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.

[0060] In one embodiment of the specific polymer A that does not contain a structural unit based on a monomer having an aromatic group, the specific polymer A is preferably obtained by polymerizing a structural unit based on a monomer having an aliphatic hydrocarbon group with at least one type of first monomer described below, and more preferably obtained by copolymerizing a structural unit based on a monomer having an aliphatic hydrocarbon group with at least one type of first monomer and at least one type of second monomer described below.

[0061] The first monomer is a monomer having a carboxyl 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 preferred. The content of the structural units based on the first monomer in specific polymer A is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, and even more preferably 15 to 30% by mass, relative to all structural units of specific polymer A. A content of 5% by mass or more is preferred from the viewpoints of achieving good developability and controlling edge fusing properties. A content of 50% by mass or less is preferred from the viewpoints of high resolution and foot shape of the resist pattern, as well as chemical resistance of the resist pattern.

[0062] The second monomer 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; vinyl alcohol esters such as vinyl acetate; and (meth)acrylonitrile. Among these, 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 structural units based on the second monomer in the specific polymer A is preferably from 5 to 60 mass %, more preferably from 15 to 50 mass %, and even more preferably from 17 to 45 mass %, based on the total structural units of the specific polymer A.

[0063] When the specific polymer A contains a structural unit based on a monomer having an aralkyl group and / or a structural unit based on a monomer of styrene, it is preferable in terms of suppressing line width thickening and deterioration of resolution when the focus position is shifted during exposure (and thus, in terms of better LWR performance of the metal wiring formed when the cured film formed by pattern-curing the photosensitive composition layer is used as an etching resist). For example, a copolymer containing a structural unit based on methacrylic acid and a structural unit based on benzyl methacrylate, a copolymer containing a structural unit based on methacrylic acid, a structural unit based on benzyl methacrylate, and a structural unit based on styrene, a copolymer containing a structural unit based on methacrylic acid, a structural unit based on methyl methacrylate, and a structural unit based on styrene, and a copolymer containing a structural unit based on methacrylic acid, a structural unit based on methyl methacrylate, a structural unit based on benzyl methacrylate, and a structural unit based on styrene. In one embodiment, the specific polymer A is preferably a polymer containing 25 to 55 mass% of structural units based on a monomer having an aromatic group, 20 to 35 mass% of structural units based on a first monomer, and 15 to 45 mass% of structural units based on a second monomer. In another embodiment, the specific polymer A is preferably a polymer containing 70 to 90 mass% of structural units based on a monomer having an aromatic group, and 10 to 25 mass% of structural units based on the first monomer.

[0064] The specific polymer A may have a branched structure in the side chain. A branched structure can be introduced into the side chain of the specific polymer A by using a monomer containing a group having a branched structure in the side chain. 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.

[0065] The synthesis of specific polymer A is preferably carried out by adding a solution containing one or more of the above-mentioned monomers and a solution containing a radical polymerization initiator to a solvent heated to 60 to 110°C under an inert gas (preferably nitrogen) stream over a period of 1 to 5 hours, followed by heating and stirring. The radical polymerization initiator may be added additionally. Preferred radical polymerization initiators are azo-based polymerization initiators (such as azobisisobutronitrile and azobis(methyl isobutyrate)) and peroxides (such as benzoyl peroxide). After the reaction is complete, additional solvent may be added to adjust the concentration to the desired level. In addition to solution polymerization, bulk polymerization, suspension polymerization, or emulsion polymerization may also be used as a synthesis method.

[0066] The glass transition temperature Tg of the specific polymer A is preferably 30 to 135°C. By using a specific polymer A 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 specific polymer A is more preferably 130°C or less, further preferably 120°C or less, and particularly preferably 110°C or less. Furthermore, using a specific polymer A having a Tg of 30°C or more is preferred in terms of improving edge fuse resistance. From this viewpoint, the Tg of the specific polymer A is more preferably 40°C or more, even more preferably 50°C or more, particularly preferably 60°C or more, and most preferably 70°C or more.

[0067] (Embodiment 3 of Specific Polymer A) Other preferred embodiments of the specific polymer A include acrylic resin, styrene-acrylic copolymer, polyurethane resin, polyvinyl alcohol, polyvinyl formal, polyamide resin, polyester resin, polyamide resin, epoxy resin, polyacetal resin, polyhydroxystyrene resin, polyimide resin, polybenzoxazole resin, polysiloxane resin, polyethyleneimine, polyallylamine, and polyalkylene glycol.

[0068] (Embodiment 4 of Specific Polymer A) Another preferred embodiment of the specific polymer A is an alkali-soluble resin, which will be described later in the description of the thermoplastic resin layer.

[0069] The specific polymer A mentioned in the embodiments 1 to 4 of the specific polymer A preferably further has a polymerizable group, and more preferably contains a structural unit having a polymerizable group. The polymerizable group is preferably a radically polymerizable group, more preferably an ethylenically unsaturated group.

[0070] <Polymerizable compound> The photosensitive composition layer contains a polymerizable compound. In this specification, the term "polymerizable compound" refers to a compound that has a polymerizable group and is polymerized by the action of a polymerization initiator described later, and is different from the specific polymer A described above.

[0071] The polymerizable group contained in 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 cationically polymerizable group such as an epoxy group and an oxetane group. The polymerizable group is preferably a group having an ethylenically unsaturated group, more preferably an acryloyl group or a methacryloyl group.

[0072] As the polymerizable compound, a compound having one or more ethylenically unsaturated groups in the molecule (ethylenically unsaturated compound) is preferred, and a compound having two or more ethylenically unsaturated groups in the molecule (polyfunctional ethylenically unsaturated compound) is more preferred, in that the photosensitivity of the photosensitive composition layer is superior. Furthermore, in terms of achieving better effects of the present invention and / or better resolution (and thus better LWR performance of metal wiring formed when a cured film formed by pattern-curing the photosensitive composition layer is used as an etching resist), the number of ethylenically unsaturated groups that the ethylenically unsaturated compound has in its molecule is preferably 6 or less, more preferably 3 or less, and even more preferably 2 or less.

[0073] As the polymerizable compound, a (meth)acrylate compound having a (meth)acryloyl group is preferred.

[0074] In addition, in order to obtain better effects of the present invention and / or better resolution (and thus better LWR performance of metal wiring formed when a cured film formed by pattern-curing the photosensitive composition layer is used as an etching resist), the content of the polymerizable compound having two or more ethylenically unsaturated groups in the molecule in the photosensitive composition layer is preferably 70% by mass or more, more preferably 80% by mass or more, and even more preferably 90% by mass or more, based on the total mass of the polymerizable compounds. The upper limit is preferably 100% by mass or less.

[0075] Furthermore, in terms of achieving better effects of the present invention and / or better resolution (and thus better LWR performance of metal wiring formed when a cured film formed by pattern-curing the photosensitive composition layer is used as an etching resist), the content of the compound having three or more ethylenically unsaturated groups in the molecule in the photosensitive composition layer is preferably 0 to 20 mass % relative to the total mass of the polymerizable compounds.

[0076] Furthermore, in terms of achieving better effects of the present invention and / or better resolution (and thus better LWR performance of metal wiring formed when a cured film formed by pattern-curing the photosensitive composition layer is used as an etching resist), the content of the compound having four or more ethylenically unsaturated groups in the molecule in the photosensitive composition layer is preferably 0 to 10 mass % relative to the total mass of the polymerizable compounds.

[0077] In addition, in order to obtain better effects of the present invention and / or better resolution (and thus better LWR performance of metal wiring formed when a cured film formed by pattern-curing the photosensitive composition layer is used as an etching resist), the content of the compound having six or more ethylenically unsaturated groups in the molecule in the photosensitive composition layer is preferably 10% by mass or less, more preferably less than 10% by mass, and more preferably 5% by mass or less, based on the total mass of the polymerizable compounds. The lower limit is preferably 0% by mass.

[0078] In particular, in terms of achieving better effects of the present invention and / or better resolution (and thus better LWR performance of metal wiring formed when a cured film formed by pattern-curing the photosensitive composition layer is used as an etching resist), the content of the polymerizable compound having two ethylenically unsaturated groups in the molecule in the photosensitive composition layer is preferably 70% by mass or more, more preferably 80% by mass or more, and even more preferably 90% by mass or more, based on the total mass of the polymerizable compounds. The upper limit is preferably 100% by mass or less.

[0079] Preferred embodiments of the polymerizable compound will be described below.

[0080] (Polymerizable compound B1) The photosensitive composition layer preferably contains a polymerizable compound B1 having an aromatic ring and two ethylenically unsaturated groups. The polymerizable compound B1 is a bifunctional ethylenically unsaturated compound having one or more aromatic rings in the molecule, among the above-mentioned polymerizable compounds.

[0081] In the photosensitive composition layer, the mass ratio of the content of the polymerizable compound B1 to the total mass of the polymerizable compounds is preferably 50 mass% or more, more preferably 60 mass% or more, even more preferably 70 mass% or more, and most preferably 80 mass% or more, from the viewpoint of achieving better effects of the present invention and / or better resolution (and thus better LWR performance of metal wiring formed when a cured film formed by pattern-curing the photosensitive composition layer is used as an etching resist). The upper limit is not particularly limited, but from the viewpoint of peelability, it is, for example, 100 mass% or less, preferably 99 mass% or less, more preferably 95 mass% or less, even more preferably 90 mass% or less, and particularly preferably 85 mass% or less.

[0082] Examples of the aromatic ring that the polymerizable compound B1 has include aromatic hydrocarbon rings such as benzene ring, naphthalene ring, and anthracene ring, aromatic heterocycles such as thiophene ring, furan ring, pyrrole ring, imidazole ring, triazole ring, and pyridine ring, and condensed rings thereof, and aromatic hydrocarbon rings are preferred, and benzene ring is more preferred. Note that 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.

[0083] The polymerizable compound B1 is preferably a compound having a bisphenol structure, since it suppresses swelling of the photosensitive composition layer due to a developer, thereby providing superior resolution (and thus superior LWR performance of metal wiring formed when a cured film formed by pattern-curing the photosensitive composition layer is used as an etching resist). 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), and among these, the bisphenol A structure is preferred.

[0084] Examples of the polymerizable compound B1 having a bisphenol structure include a compound having a bisphenol structure and two polymerizable groups (preferably ethylenically unsaturated groups, more preferably (meth)acryloyl groups) bonded to both ends of the bisphenol structure. The two polymerizable groups may be bonded to both ends of the bisphenol structure directly or via one or more alkyleneoxy groups. The alkyleneoxy groups added to both ends of the bisphenol structure are preferably ethyleneoxy groups or propyleneoxy groups, more preferably ethyleneoxy groups. The number of alkyleneoxy 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 JP 2016-224162 A, the contents of which are incorporated herein by reference.

[0085] The polymerizable compound B1 is preferably a compound having a bisphenol A structure (hereinafter sometimes referred to as "compound BPA1"). Among these, compound BPA1 is preferably a bifunctional ethylenically unsaturated compound having a bisphenol A structure (in other words, a compound having a bisphenol A structure and two ethylenically unsaturated groups (hereinafter also referred to as "compound BPA2")), more preferably a (meth)acrylate compound having a bisphenol A structure and two (meth)acryloyl groups, and even more preferably 2,2-bis(4-((meth)acryloyloxypolyalkoxy)phenyl)propane. Examples of 2,2-bis(4-((meth)acryloyloxypolyalkoxy)phenyl)propane include 2,2-bis(4-(methacryloxydiethoxy)phenyl)propane (FA-324M, manufactured by Hitachi Chemical Co., Ltd.), 2,2-bis(4-(methacryloxyethoxypropoxy)phenyl)propane, 2,2-bis(4-(methacryloxypentaethoxy)phenyl)propane (BPE-500, manufactured by Shin-Nakamura Chemical Co., Ltd.), and 2,2-bis(4-(methacryloxydodecaethoxytetrapropoxy)phenyl)propane. Examples of suitable bisphenol A copolymers include bisphenol A ethoxylate (NK Ester A-BPE-10, manufactured by Shin-Nakamura Chemical Co., Ltd.), bisphenol A dimethacrylate (NK Ester A-BPE-10, manufactured by Shin-Nakamura Chemical Co., Ltd.), and bisphenol A dimethacrylate (SR-480, manufactured by Arkema). In one embodiment of the polymerizable compound, when the polymerizable compound contains the compound BPA2, the content of the compound BPA2 is preferably 80% by mass or more relative to the total mass of the polymerizable compound. The upper limit is not particularly limited, but is, for example, 100% by mass or less.

[0086] The polymerizable compound B1 is also preferably a compound represented by the following general formula (B1).

[0087] [ka]

[0088] In general formula B1, R1 and R2 each independently represent a hydrogen atom or a methyl group. A represents C2H4. B represents C3H6. n1 and n3 each independently represent an integer of 1 to 39, and n1 + n3 is an integer of 2 to 40. n2 and n4 each independently represent an integer of 0 to 29, and n2 + n4 is an integer of 0 to 30. The arrangement of the -(AO)- and -(BO)- structural units 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 2 to 20, more preferably 2 to 16, and even more preferably 4 to 12. Furthermore, n2+n4 is preferably 0 to 10, more preferably 0 to 4, even more preferably 0 to 2, and particularly preferably 0.

[0089] The polymerizable compound B1 may be used alone or in combination of two or more. The content of the polymerizable compound B1 is preferably 10% by mass or more, more preferably 20% by mass or more, based on the total mass of the photosensitive composition layer, from the viewpoint of achieving better effects of the present invention and / or better resolution (and thus better LWR performance of metal wiring formed when a cured film formed by pattern-curing the photosensitive composition layer is used as an etching resist). There is no particular upper limit, but from the viewpoints of transferability and edge fusion (a phenomenon in which the photosensitive resin seeps out from the edge of a transfer member), it is preferably 70% by mass or less, more preferably 60% by mass or less.

[0090] The photosensitive 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, such as a compound having one ethylenically unsaturated group in the molecule (monofunctional ethylenically unsaturated compound), a bifunctional ethylenically unsaturated compound having no aromatic ring, and a trifunctional or higher ethylenically unsaturated compound.

[0091] 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, phenoxyethyl (meth)acrylate, and m-phenoxybenzyl acrylate.

[0092] Examples of the difunctional ethylenically unsaturated compound having no aromatic ring include alkylene glycol di(meth)acrylate, polyalkylene glycol di(meth)acrylate, urethane di(meth)acrylate, and trimethylolpropane diacrylate. 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 (M-270, manufactured by Toagosei Co., Ltd.). 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.).

[0093] 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 products thereof. Commercially available trimethylolpropane triacrylate products include A-TMPT (manufactured by Shin-Nakamura Chemical Co., Ltd.), and commercially available dipentaerythritol hexaacrylate products include A-DPH (manufactured by Shin-Nakamura Chemical Co., Ltd.). 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 composition layer preferably contains the above-described polymerizable compound B1 and a trifunctional or higher ethylenically unsaturated compound, and more preferably contains the above-described 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 (total mass of the polymerizable compound B1):(total mass of the trifunctional or higher ethylenically unsaturated compounds) is preferably 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 composition layer preferably contains the above-mentioned polymerizable compound B1 and two or more trifunctional ethylenically unsaturated compounds.

[0094] Examples of alkylene oxide-modified tri- or higher functional 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.).

[0095] Furthermore, 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 polymerizable compounds 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 compound having an acid group described in paragraphs

[0025] to

[0030] of JP-A No. 2004-239942 may be used.

[0096] The polymerizable compounds may be used alone or in combination of two or more. The content of the polymerizable compound is preferably from 10 to 70% by mass, more preferably from 15 to 70% by mass, and even more preferably from 20 to 70% by mass, based on the total mass of the photosensitive composition layer.

[0097] The molecular weight (weight average molecular weight when the polymerizable compound (including polymerizable compound B1) has a molecular weight distribution) is preferably from 200 to 3,000, more preferably from 280 to 2,200, and even more preferably from 300 to 2,200.

[0098] <Polymerization initiator> The photosensitive composition layer contains a photopolymerization initiator. A photopolymerization initiator is a compound that initiates polymerization of a polymerizable compound when exposed to actinic rays such as ultraviolet light, visible light, and X-rays. The photopolymerization initiator is not particularly limited, and known photopolymerization initiators can be used. Examples of the photopolymerization initiator include a photoradical polymerization initiator and a photocationic polymerization initiator.

[0099] Of these, the photopolymerization initiator is preferably a photoradical polymerization initiator. Examples of the photoradical polymerization initiator include a photopolymerization initiator having an oxime ester structure (oxime ester-based photopolymerization initiator), a photopolymerization initiator having an α-aminoalkylphenone structure (α-aminoalkylphenone-based photopolymerization initiator), a photopolymerization initiator having an α-hydroxyalkylphenone structure (α-hydroxyalkylphenone-based photopolymerization initiator), a photopolymerization initiator having an acylphosphine oxide structure (acylphosphine oxide-based photopolymerization initiator), and a photopolymerization initiator having an N-phenylglycine structure (N-phenylglycine-based photopolymerization initiator).

[0100] Further, the photoradical polymerization initiator also includes hexaarylbiimidazole derivatives (HABI). Examples of hexaarylbiimidazole derivatives include 2,4,5-triarylimidazole dimers and derivatives thereof, in which the two 2,4,5-triarylimidazole structures may be the same or different. Specific examples of the 2,4,5-triarylimidazole dimer and its derivatives 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.

[0101] Further, examples of the photoradical polymerization initiator include the polymerization initiators described in paragraphs

[0031] to

[0042] of JP-A No. 2011-095716 and paragraphs

[0064] to

[0081] of JP-A No. 2015-014783.

[0102] 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.). 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), and the like. 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.), oxime ester photoinitiator (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 Strong Electronic New Materials Co., Ltd.), 1,2-propanedione, 3-cyclopentyl Other examples include 3-cyclohexyl-1-[9-ethyl-6-(2-furanylcarbonyl)-9H-carbazol-3-yl]-2-(O-acetyloxime) (trade name: TR-PBG-326, Changzhou Powerful Electronic New Materials Co., Ltd.), 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 Powerful Electronic New Materials Co., Ltd.), and 1-(biphenyl-4-yl)-2-methyl-2-morpholinopropan-1-one (trade name: APi-307, Shenzhen UV-ChemTech Ltd.).

[0103] The photosensitive composition layer preferably contains a photoradical polymerization initiator, and more preferably contains a hexaarylbiimidazole derivative, in terms of better effects of the present invention, better photosensitivity, better visibility of exposed and unexposed areas, and / or better resolution (and thus better LWR performance of metal wiring formed when a cured film formed by pattern-curing the photosensitive composition layer is used as an etching resist).

[0104] The polymerization initiator may be used alone or in combination of two or more. The content of the polymerization initiator (preferably a photopolymerization initiator) is not particularly limited, but is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and even more preferably 1.0% by mass or more, relative to the total mass of the photosensitive composition layer. The upper limit is not particularly limited, but is preferably 20% by mass or less, more preferably 15% by mass or less, and even more preferably 10% by mass or less, relative to the total mass of the photosensitive composition layer.

[0105] <Dye> From the viewpoints of the visibility of exposed and unexposed areas, the pattern visibility after development, and resolution, the photosensitive composition layer preferably contains a dye (also referred to as "dye N") that has a maximum absorption wavelength of 450 nm or more in the wavelength range of 400 to 780 nm during color development and whose maximum absorption wavelength changes in response to an acid, a base, or a radical. When dye N is contained, adhesion to adjacent layers (for example, a water-soluble resin layer) is improved, resulting in better resolution, although the detailed mechanism is unknown.

[0106] In this specification, the expression "the maximum absorption wavelength of a dye changes in response to an acid, a base, or a radical" may mean any of the following: 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, dye N may be a compound that changes from a decolorized state to develop a color upon exposure, or a compound that changes from a colored state to decolorize upon exposure. In this case, the dye may be one whose color-developing or decolorizing state changes when an acid, base, or radical is generated and acts within the photosensitive composition layer upon exposure, or one whose color-developing or decolorizing state changes when the state (e.g., pH) within the photosensitive composition layer changes due to an acid, base, or radical. Alternatively, the dye may be one whose color-developing or decolorizing state changes upon direct stimulation by an acid, base, or radical without exposure.

[0107] In particular, from the viewpoint of the 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 viewpoint of the visibility of exposed and unexposed areas and resolution, the photosensitive composition layer preferably contains both a dye N whose maximum absorption wavelength changes in response 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.

[0108] An example of the color-developing mechanism of dye N is an embodiment in which a photoradical polymerization initiator, a cationic photopolymerization initiator (photoacid generator), or a photobase generator is added to the photosensitive 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 cationic photopolymerization initiator, or the photobase generator.

[0109] From the viewpoint of visibility of exposed and unexposed areas, dye N preferably has a maximum absorption wavelength of 550 nm or more in the wavelength range of 400 to 780 nm upon color development, more preferably 550 to 700 nm, and even more preferably 550 to 650 nm. Furthermore, dye N may have only one or two or more maximum absorption wavelengths in the wavelength range of 400 to 780 nm when it develops color. 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 with the highest absorbance among the two or more maximum absorption wavelengths is 450 nm or longer.

[0110] The maximum absorption wavelength of dye N can be 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 (Shimadzu Corporation) in an atmospheric environment and detecting the wavelength at which the light intensity is minimum (maximum absorption wavelength).

[0111] Examples of dyes that develop or lose color upon exposure include leuco compounds. Examples of dyes that are decolorized by exposure include leuco compounds, diarylmethane dyes, oxazine dyes, xanthene dyes, iminonaphthoquinone dyes, azomethine dyes, and anthraquinone dyes. As the dye N, a leuco compound is preferred from the viewpoint of visibility of exposed and unexposed areas.

[0112] Examples of leuco compounds 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.

[0113] From the viewpoint of visibility of exposed and unexposed areas, the leuco compound preferably has a lactone ring, a sultine ring, or a sultone ring. This allows the lactone ring, sultine ring, or 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 converting the leuco compound into a ring-closed state and thereby discoloring, or converting the leuco compound into a ring-open state and thereby developing a color. The leuco compound is preferably a compound having a lactone ring, a sultine ring, or a sultone ring, which develops a color upon ring-opening of the lactone ring, the sultine ring, or the sultone ring by a radical or an acid, and more preferably a compound having a lactone ring, which develops a color upon ring-opening of the lactone ring by a radical or an acid.

[0114] Examples of the dye N include the following dyes and leuco compounds. Specific examples of dyes among the dyes 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 naphthalene sulfonate, Victoria Pure Blue BOH (manufactured by Hodogaya Chemical Co., Ltd.), Oil Blue #603 (manufactured by Orient Chemical Co., Ltd.), Oil Pink #312 (manufactured by Orient Chemical Co., Ltd.), Oil Red 5B (manufactured by Orient Chemical Co., Ltd.), and Oil Scarlet #308 (manufactured by Orient Chemical Co., Ltd.). Examples of suitable anti-inflammatory agents 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 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.

[0115] Specific examples of the leuco compounds 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-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-di 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- 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.

[0116] 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-naphthalene sulfonate is preferred.

[0117] The dye N may be used alone or in combination of two or more. 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 composition layer.

[0118] The content of dye N means the content of dye when all of dye N contained in the total mass of the photosensitive 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. Solutions were prepared by dissolving 0.001 g and 0.01 g of dye in 100 mL of methyl ethyl ketone. The photoradical polymerization initiator Irgacure OXE01 (BASF Japan Ltd.) was added to each solution, and radicals were generated by irradiating with 365 nm light, causing all dyes to develop color. The absorbance of each solution was then measured at 25°C using a spectrophotometer (UV3100, Shimadzu Corporation) under atmospheric conditions, and a calibration curve was created. Next, the absorbance of the solution in which all the dyes have developed is measured in the same manner as above, except that 3 g of the photosensitive composition layer is dissolved in methyl ethyl ketone instead of the dye. The content of the dye contained in the photosensitive composition layer is calculated based on the absorbance of the solution containing the photosensitive composition layer obtained and a calibration curve. The photosensitive composition layer 3g is the same as the total solid content 3g in the photosensitive composition.

[0119] <Thermal crosslinkable compound> The photosensitive composition layer preferably contains a thermally crosslinkable compound from the viewpoints of the strength of the pattern (cured film) to be formed and the adhesiveness of the uncured film. In this specification, a thermally crosslinkable compound having an ethylenically unsaturated group, which will be described later, is not considered to be a polymerizable compound but is considered to be 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 pattern (cured film) to be formed and the adhesiveness of the uncured 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. The blocked isocyanate compound reacts with a hydroxy group and a carboxy group. Therefore, when, for example, the specific polymer A and / or the polymerizable compound has at least one of a hydroxy group and a carboxy group, the hydrophilicity of the formed pattern (cured film) tends to decrease, and the functionality of the pattern when used as an etching resist film tends to be enhanced.

[0120] The dissociation temperature of the blocked isocyanate compound is not particularly limited, but is preferably 100 to 160°C, more preferably 130 to 150°C. The dissociation temperature of a blocked isocyanate means "the temperature of the endothermic peak accompanying the deprotection reaction of the blocked isocyanate when measured by DSC (Differential Scanning Calorimetry) analysis using a differential scanning calorimeter." As the differential scanning calorimeter, for example, a differential scanning calorimeter (model: DSC6200) manufactured by Seiko Instruments Inc. can be suitably used, but the differential scanning calorimeter is not limited to this.

[0121] 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 (compounds having a structure represented by -C(=N-OH)- in the molecule, such as formaldoxime, acetaldoxime, acetoxime, methylethylketoxime, and cyclohexanoneoxime). Among these, as the blocking agent having a dissociation temperature of 100 to 160° C., at least one selected from oxime compounds is preferred from the viewpoint of storage stability, for example.

[0122] The blocked isocyanate compound preferably has an isocyanurate structure, for example, from the viewpoint of 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 isocyanuration. Among blocked isocyanate compounds having an isocyanurate structure, compounds having an oxime structure in which an oxime compound is used as a blocking agent are preferred from the viewpoints that the dissociation temperature can be more easily adjusted to a preferred range and development residues can be more easily reduced than compounds not having an oxime structure.

[0123] 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 radical polymerizable group being preferred. Examples of the polymerizable group include ethylenically unsaturated groups such as a (meth)acryloyloxy 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)acryloyloxy group, and even more preferably an acryloyloxy group.

[0124] 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). Furthermore, as the blocked isocyanate compound, a compound having the following structure can also be used.

[0125] [ka]

[0126] The thermally crosslinkable compounds may be used alone or in combination of two or more. When the photosensitive composition layer contains a thermally crosslinkable compound, the content of the thermally crosslinkable compound is preferably 1 to 50 mass %, more preferably 5 to 30 mass %, based on the total mass of the photosensitive composition layer.

[0127] <Other additives> The photosensitive composition layer may contain known additives in addition to the above components, if necessary. Examples of additives include radical polymerization inhibitors, sensitizers, rust inhibitors, antioxidants, surfactants, plasticizers, heterocyclic compounds (triazoles, etc.), benzotriazoles, carboxybenzotriazoles, pyridines (isonicotinamide, etc.), and purine bases (adenine, etc.). Each additive may be used alone or in combination of two or more.

[0128] The photosensitive composition layer may contain a radical polymerization inhibitor. Examples of radical polymerization inhibitors include the thermal polymerization inhibitors described in paragraph

[0018] of Japanese Patent No. 4502784. Among these, phenothiazine, phenoxazine, or 4-methoxyphenol is preferred. Other radical polymerization inhibitors include naphthylamine, cuprous chloride, nitrosophenylhydroxyamine aluminum salt, and diphenylnitrosamine. To avoid impairing the sensitivity of the photosensitive composition layer, it is preferable to use nitrosophenylhydroxyamine aluminum salt as the radical polymerization inhibitor.

[0129] 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.

[0130] 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.).

[0131] The total content of the radical polymerization inhibitor, benzotriazoles, and carboxybenzotriazoles is preferably 0.01 to 3% by mass, more preferably 0.05 to 1% by mass, based on the total mass of the photosensitive composition layer. When the content is 0.01% by mass or more, the storage stability of the photosensitive composition layer is improved. On the other hand, when the content is 3% by mass or less, the sensitivity is maintained and the decolorization of the dye is suppressed better.

[0132] The photosensitive composition layer may contain a sensitizer. The sensitizer is not particularly limited, and known sensitizers, dyes, and pigments can be used. Examples of the sensitizer include dialkylaminobenzophenone compounds, pyrazoline compounds, anthracene compounds, coumarin compounds, xanthone compounds, thioxanthone compounds, acridone compounds, oxazole compounds, benzoxazole compounds, thiazole compounds, benzothiazole compounds, triazole compounds (e.g., 1,2,4-triazole), stilbene compounds, triazine compounds, thiophene compounds, naphthalimide compounds, triarylamine compounds, and aminoacridine compounds.

[0133] The sensitizers may be used alone or in combination of two or more. When the photosensitive composition layer contains a sensitizer, the content of the sensitizer can be appropriately selected depending on the purpose. From the viewpoints of improving sensitivity to the light source and improving the curing rate by balancing the polymerization rate and chain transfer, the content is preferably 0.01 to 5 mass %, and more preferably 0.05 to 1 mass %, relative to the total mass of the photosensitive composition layer.

[0134] The photosensitive composition layer may contain at least one selected from the group consisting of plasticizers and heterocyclic compounds. Examples of the plasticizer and heterocyclic compound include the compounds described in paragraphs

[0097] to

[0103] and paragraphs

[0111] to

[0118] of WO 2018 / 179640.

[0135] The photosensitive composition layer may contain a rust inhibitor. An example of a commercially available rust inhibitor is CBT-1 (manufactured by Johoku Chemical Industry Co., Ltd.).

[0136] The photosensitive composition layer may contain a surfactant. The surfactant is not particularly limited, but a fluorine-based surfactant, a nonionic surfactant, or a silicone-based surfactant is preferred.

[0137] Commercially available fluorine-based surfactants include, for example, Megafac F-171, F-172, F-173, F-176, F-177, F-141, F-142, F-143, F-144, F-437, F-475, F-477, F-479, F-482, F-551-A, F-552, F-554, F-555-A, F-556, F-557, F-558, F-559, F-560, F-561, F-565, F-563, F-568, F-575, F-780, and EXP.MFS-33. 0, EXP.MFS-578, EXP.MFS-578-2, EXP.MFS-579, EXP.MFS-586, EXP.MFS-587, EXP.MFS-628, EXP.MFS-631, EXP.MFS-603, R-41, R-41-LM, R-01, R-40, R-40-LM, RS-43, TF-1956, RS-90, R-94, RS-72-K, DS-21 (all manufactured by DIC Corporation); Fluorad FC430, FC431, FC171 (all manufactured by Sumitomo 3M Limited); Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, KH-40 (all manufactured by AGC Inc.); PolyFox PF636, PF656, PF6320, PF6520, PF7002 (all manufactured by OMNOVA); Futergent Examples include 710FM, 710FL, 610FM, 601AD, 601ADH2, 602A, 215M, 245F, 251, 212M, 250, 209F, 222F, 208G, 710LA, 710FS, 730LM, 650AC, and 681 (all manufactured by NEOS Co., Ltd.); and U-120E (Unichem Co., Ltd.). In addition, acrylic compounds that have a molecular structure with a functional group containing a fluorine atom and that volatilize when heated by cleavage of the fluorine atom-containing functional group can also be used as fluorosurfactants. Examples of such fluorosurfactants include the Megafac DS series manufactured by DIC Corporation (The Chemical Daily, February 22, 2016; The Nikkei Business Daily, February 23, 2016), such as Megafac DS-21. It is also preferred to use, as the fluorine-based surfactant, a polymer of a fluorine atom-containing vinyl ether compound having a fluorinated alkyl group or a fluorinated alkylene ether group and a hydrophilic vinyl ether compound. The fluorine-containing surfactant is preferably a block polymer. The fluorine-containing surfactant may also be a fluorine-containing polymer compound containing a repeating unit derived from a (meth)acrylate compound having a fluorine atom and a repeating unit derived from a (meth)acrylate compound having two or more (preferably five or more) alkyleneoxy groups (preferably ethyleneoxy groups or propyleneoxy groups). The fluorine-containing surfactant may be a fluorine-containing polymer having an ethylenically unsaturated bond-containing group in the side chain, such as Megafac RS-101, RS-102, RS-718K, or RS-72-K (all manufactured by DIC Corporation). From the viewpoint of improving environmental friendliness, it is preferable that the fluorosurfactant be a surfactant derived from an alternative material to compounds having a perfluoroalkyl group having seven or more carbon atoms, such as perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic acid (PFOS).

[0138] Examples of silicone surfactants include linear polymers consisting of siloxane bonds and modified siloxane polymers in which organic groups have been introduced into the side chains or terminals. Commercially available silicone surfactants include EXP.S-309-2, EXP.S-315, EXP.S-503-2, and EXP.S-505-2 (all manufactured by DIC Corporation), DOWSIL 8032 ADDITIVE, Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, and Toray Silicone SH8400 (all manufactured by Dow Corning Toray Co., Ltd.); X-22-4952, X-22-4272, and X- 22-6266, KF-351A, K354L, KF-355A, KF-945, KF-640, KF-642, KF-643, X-22-6191, X-22-4515, KF-600 4, KP-341, KF-6001, KF-6002, KP-101KP-103, KP-104, KP-105, KP-106, KP-109, KP-109, KP-112, KP-1 20, KP-121, KP-124, KP-125, KP-301, KP-306, KP-310, KP-322, KP-323, KP-327, KP-341, KP-368, KP-369, KP-611, KP-620, KP-621, KP-626, KP-652 (all manufactured by Shin-Etsu Silicone Co., Ltd.); F-4440, TSF-4300, TSF-4445, TSF- 4460, TSF-4452 (all manufactured by Momentive Performance Materials); BYK307, BYK323, BYK330, BYK313, BYK315N, BYK331, BYK333, BYK345, BYK347, BYK348, BYK349, BYK370, BYK377, BYK378, BYK323 (all manufactured by BYK-Chemie); and the like.

[0139] Examples of nonionic surfactants include glycerol, trimethylolpropane, and trimethylolethane, as well as their ethoxylates and propoxylates (e.g., glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, and sorbitan fatty acid esters.

[0140] Commercially available nonionic surfactants include Pluronic (registered trademark) L10, L31, L61, L62, 10R5, 17R2, and 25R2 (all manufactured by BASF); Tetronic 304, 701, 704, 901, 904, and 150R1 (all manufactured by BASF); Solsperse 20000 (manufactured by Lubrizol Nippon Co., Ltd.); NCW-101, NCW-1001, and NCW-1002 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.); Paionin D-6112, D-6112-W, and D-6315 (manufactured by Takemoto Oil & Fat Co., Ltd.); and Olfine E1010, Surfynol 104, 400, and 440 (manufactured by Nissin Chemical Industry Co., Ltd.).

[0141] Furthermore, as the surfactant, for example, surfactants described in paragraph

[0017] of Japanese Patent No. 4502784 and paragraphs

[0060] to

[0071] of Japanese Patent Laid-Open No. 2009-237362 can also be used.

[0142] The surfactants may be used alone or in combination of two or more. When the photosensitive composition layer contains a surfactant, the content of the surfactant is preferably 0.01 to 3.0 mass %, more preferably 0.05 to 1.0 mass %, and even more preferably 0.10 to 0.80 mass %, relative to the total mass of the photosensitive composition layer.

[0143] The photosensitive composition layer may further contain known additives such as metal oxide particles, antioxidants, dispersants, acid amplifiers, development accelerators, conductive fibers, ultraviolet absorbers, thickeners, crosslinkers, and organic or inorganic suspending agents. Additives contained in the photosensitive composition layer are described in paragraphs

[0165] to

[0184] of JP-A-2014-085643, the contents of which are incorporated herein by reference.

[0144] The thickness (film thickness) of the photosensitive composition layer is generally 0.1 to 300 μm, preferably 0.2 to 100 μm, more preferably 0.5 to 50 μm, still more 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 composition layer and improve the resolution. In one embodiment, the thickness is preferably 0.5 to 5 μm, more preferably 0.5 to 4 μm, and even more preferably 0.5 to 3 μm.

[0145] From the viewpoint of achieving superior adhesion, the transmittance of the photosensitive composition layer at a wavelength of 365 nm 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.

[0146] <Impurities, etc.> The photosensitive composition layer may contain a certain 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 these, halide ions, sodium ions, and potassium ions are likely to be mixed in as impurities, so it is preferable to set the contents to the following ranges.

[0147] The content of impurities in the photosensitive composition layer is preferably 80 ppm or less, more preferably 10 ppm or less, and even more preferably 2 ppm or less, by mass. The content of impurities can be 1 ppb or more, or may be 0.1 ppm or more, by mass.

[0148] Methods for controlling the amount of impurities within the above range include selecting raw materials for the composition that contain a small amount of impurities, preventing impurities from being mixed in during the production of the photosensitive composition layer, and removing impurities by washing. By using such methods, the amount of impurities can be controlled within the above range.

[0149] The amount of impurities can be determined by known methods such as ICP (Inductively Coupled Plasma) emission spectroscopy, atomic absorption spectroscopy, and ion chromatography.

[0150] 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 composition layer is preferably small, and the content of these compounds relative to the total mass of the photosensitive composition layer is preferably 100 ppm or less, more preferably 20 ppm or less, and even more preferably 4 ppm or less, by mass. The lower limit, based on mass, can be 10 ppb or more, and can be 100 ppb or more, based on the total mass of the photosensitive composition layer. The content of these compounds can be reduced in the same manner as for the metal impurities described above. Furthermore, they can be quantified by known measurement methods.

[0151] The content of water in the photosensitive composition layer is preferably from 0.01 to 1.0% by mass, more preferably from 0.05 to 0.5% by mass, from the viewpoint of improving reliability and lamination properties.

[0152] <Pigments> The photosensitive composition layer may be a colored resin layer containing a pigment. 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 or the like is sometimes attached. A colored resin layer can be used to form such a light-shielding layer. The pigment 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. In particular, when a black pattern is to be formed, a black pigment is preferably selected as the pigment.

[0153] As the black pigment, any known black pigment (organic pigment, inorganic pigment, etc.) can be appropriately selected as long as the effects of the present invention are not impaired. 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, with carbon black being particularly preferred. As the carbon black, from the viewpoint of surface resistance, carbon black at least a portion of the surface of which is coated with a resin is preferred.

[0154] From the viewpoint of dispersion stability, the particle size of the black pigment is preferably 0.001 to 0.1 μm, more preferably 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 particle size for 100 random particles and averaging the particle sizes of the 100 particles.

[0155] As for the white pigment other than the black pigment, the white pigments described in paragraphs

[0015] and

[0114] of JP-A No. 2005-007765 can be used. Specifically, among the white pigments, inorganic pigments such as titanium oxide, zinc oxide, lithopone, precipitated calcium carbonate, white carbon, aluminum oxide, aluminum hydroxide, and barium sulfate are preferred, with titanium oxide or zinc oxide being more preferred, and titanium oxide being even more preferred. As the inorganic pigment, rutile or anatase titanium oxide is more preferred, with rutile titanium oxide being particularly preferred. The surface of titanium oxide may be subjected to a silica treatment, alumina treatment, titania treatment, zirconia treatment, or 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 composition layer after heating, the surface treatment of the titanium oxide is preferably at least one of alumina treatment and zirconia treatment, and particularly preferably both alumina treatment and zirconia treatment.

[0156] When the photosensitive composition layer is a colored resin layer, it is also preferable that the photosensitive composition layer further contains a chromatic pigment other than a black pigment and a white pigment from the viewpoint of transferability. When a chromatic pigment is contained, the particle size of the chromatic pigment is preferably 0.1 μm or less, and more preferably 0.08 μm or less, in terms of better dispersibility. 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), and Permanent Yellow GR (CI Pigment Yellow 17). Examples of pigments that can be used include 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.

[0157] When the photosensitive composition layer contains a pigment, the content of the pigment 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 mass% or more and not more than 35 mass%.

[0158] When the photosensitive composition layer contains pigments other than black pigments (white pigments and chromatic pigments), the content of the pigments other than black pigments 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.

[0159] In addition, when the photosensitive composition layer contains a black pigment and is formed from a photosensitive composition, the black pigment (preferably carbon black) is preferably introduced into the photosensitive composition in the form of a pigment dispersion. The dispersion may be prepared by premixing a black pigment and a pigment dispersant, adding the resulting mixture to an organic solvent (or vehicle), and dispersing the mixture using a disperser. The pigment dispersant may be selected depending on the pigment and solvent, and commercially available dispersants may be used, for example. The vehicle refers to the medium in which the pigment is dispersed when a pigment dispersion is prepared. The vehicle is liquid and includes a binder component that maintains the black pigment in a dispersed state and a solvent component (organic solvent) that dissolves and dilutes the binder component.

[0160] The dispersing machine is not particularly limited, and examples thereof include known dispersing machines such as a kneader, a roll mill, an attritor, a super mill, a dissolver, a homomixer, and a sand mill. Furthermore, fine pulverization may be performed by utilizing frictional force through mechanical grinding. For details about dispersing machines and fine pulverization, please refer to the descriptions in "Pigment Dictionary" (Kunizo Asakura, 1st Edition, Asakura Shoten, 2000, pp. 438 and 310).

[0161] <<Thermoplastic resin layer>> The thermoplastic resin layer is usually disposed between the temporary support and the photosensitive composition layer. By providing the transfer film with the thermoplastic resin layer, the conformability to the substrate during the lamination process between the transfer film and the substrate is improved, and the inclusion of air bubbles between the substrate and the transfer film can be suppressed. As a result, the adhesion between the thermoplastic resin layer and an adjacent layer (e.g., temporary support) can be ensured.

[0162] The thermoplastic resin layer contains a resin. The resin contains a thermoplastic resin as a part or the whole. That is, in one embodiment, the thermoplastic resin layer preferably contains a thermoplastic resin.

[0163] <Alkali-soluble resin (thermoplastic resin)> The thermoplastic resin is preferably an alkali-soluble resin. Examples of alkali-soluble 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, polyethyleneimine, polyallylamine, and polyalkylene glycols.

[0164] As the alkali-soluble resin, an acrylic resin is preferred from the viewpoint of developability and adhesion to adjacent layers. Here, the acrylic resin means 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 contains structural units derived from (meth)acrylic acid, structural units derived from (meth)acrylic acid esters, and structural units derived from (meth)acrylic acid amides in a total content of 50% by mass or more relative to 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 ester is preferably 30 to 100 mass %, more preferably 50 to 100 mass %, relative to the total mass of the acrylic resin.

[0165] The alkali-soluble 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 a carboxy group being preferred. From the viewpoint of developability, the alkali-soluble resin is preferably an alkali-soluble resin having an acid value of 60 mgKOH / g or more, and more preferably a carboxyl group-containing acrylic resin having an acid value of 60 mgKOH / g or more. The upper limit of the acid value of the alkali-soluble resin is not particularly limited, but is preferably 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.

[0166] The carboxyl group-containing acrylic resin having an acid value of 60 mgKOH / g or more is not particularly limited, and can be appropriately selected from known resins. Examples include alkali-soluble resins that are carboxyl group-containing acrylic resins having an acid value of 60 mgKOH / g or more among the polymers described in paragraph

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

[0033] to

[0052] of JP 2010-237589 A, and carboxyl group-containing acrylic resins having 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 carboxy group-containing acrylic resin is preferably 5 to 50 mass %, more preferably 10 to 40 mass %, and even more preferably 12 to 30 mass %, relative to the total mass of the acrylic resin. Among the alkali-soluble resins, from the viewpoints of developability and adhesion to adjacent layers, acrylic resins having structural units derived from (meth)acrylic acid are preferred, and acrylic resins having structural units derived from (meth)acrylic acid and structural units derived from (meth)acrylic acid esters are more preferred.

[0167] The alkali-soluble resin may have a polymerizable group. The polymerizable group may be any group capable of addition polymerization, and examples thereof include ethylenically unsaturated groups, polycondensable groups such as hydroxy groups and carboxy groups, and polyaddition-polymerizable groups such as epoxy groups and (blocked) isocyanate groups.

[0168] The weight average molecular weight (Mw) of the alkali-soluble resin is preferably 1,000 or more, more preferably from 10,000 to 100,000, and even more preferably from 20,000 to 50,000.

[0169] The alkali-soluble resins may be used alone or in combination of two or more. From the viewpoints of developability and adhesion to adjacent layers, the content of the alkali-soluble resin is preferably 10 to 99% by mass, more preferably 20 to 90% by mass, even more preferably 40 to 80% by mass, and particularly preferably 50 to 75% by mass, relative to the total mass of the thermoplastic resin layer.

[0170] <Dye> The thermoplastic resin layer preferably contains a dye (also simply referred to as "dye B") 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. Preferred embodiments of dye B are the same as the preferred embodiments of dye N described above, except for the points described below.

[0171] 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 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, the thermoplastic resin layer preferably contains both a dye whose maximum absorption wavelength changes in response to acid as dye B, and a compound that generates acid when exposed to light, as described below.

[0172] The dye B may be used alone or in combination of two or more. From the viewpoint of visibility of exposed and unexposed areas, the content of dye B is preferably 0.2 mass% or more, more preferably 0.2 to 6 mass%, even more preferably 0.2 to 5 mass%, and particularly preferably 0.25 to 3.0 mass%, relative to the total mass of the thermoplastic resin layer.

[0173] Here, the content of dye B means the content of dye when all of the dye B contained in the thermoplastic resin layer is in a color-developing 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. Solutions were prepared by dissolving 0.001 g and 0.01 g of dye in 100 mL of methyl ethyl ketone. The photoradical polymerization initiator Irgacure OXE01 (BASF Japan Ltd.) was added to each solution, and radicals were generated by irradiating with 365 nm light, causing all dyes to develop color. The absorbance of each solution was then measured at 25°C using a spectrophotometer (UV3100, Shimadzu Corporation) under atmospheric conditions, and a calibration curve was created. Next, the absorbance of the solution in which all the dye has developed is measured in the same manner as above, except that 0.1 g of the thermoplastic resin layer is dissolved in methyl ethyl ketone instead of the dye. The amount of the dye contained in the thermoplastic resin layer is calculated based on the absorbance of the obtained solution containing the thermoplastic resin layer and a calibration curve. The thermoplastic resin layer 3g is the same as the 3g of solid content of the composition.

[0174] <Compounds that generate acids, bases, or radicals when exposed to light> The thermoplastic resin layer may contain a compound that generates an acid, a base, or a radical when exposed to light (also simply referred to as "compound C"). Compound C is preferably a compound that generates an acid, a base, or a radical when exposed to actinic rays such as ultraviolet light and visible light. As the compound C, known photoacid generators, photobase generators, and photoradical polymerization initiators (photoradical generators) can be used.

[0175] (Photoacid generator) The thermoplastic resin layer may contain a photoacid generator from the viewpoint of resolution. Examples of the photoacid generator include the cationic photopolymerization initiators that may be contained in the photosensitive composition layer described above, and preferred embodiments are the same except for the points described below.

[0176] 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. Furthermore, as the photoacid generator, a photoacid generator having the following structure is also preferred.

[0177] [ka]

[0178] (Photoradical polymerization initiator) The thermoplastic resin layer may contain a photoradical polymerization initiator. Examples of the photoradical polymerization initiator include the photoradical polymerization initiators that may be contained in the photosensitive composition layer described above, and preferred embodiments are also the same.

[0179] (Photobase Generator) The thermoplastic resin composition may contain a 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 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.

[0180] The compound C may be used alone or in combination of two or more. The content of compound C is preferably 0.1 to 10% by mass, more preferably 0.5 to 5% by mass, based on the total mass of the thermoplastic resin layer, from the viewpoints of visibility and resolution of exposed and unexposed areas.

[0181] <Plasticizer> The thermoplastic resin layer preferably contains a plasticizer from the viewpoints of resolution, adhesion to adjacent layers, 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 resin and exhibits plasticity, but from the viewpoint of imparting plasticity, the plasticizer preferably has an alkyleneoxy group in the molecule, more preferably a polyalkylene glycol compound, and the alkyleneoxy group contained in the plasticizer more preferably has a polyethyleneoxy structure or a polypropyleneoxy structure.

[0182] 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 composition layer. In the transfer film, when the thermoplastic resin layer and the photosensitive composition layer are laminated in direct contact with each other, it is preferable that both the thermoplastic resin layer and the photosensitive composition layer contain the same (meth)acrylate compound, because the thermoplastic resin layer and the photosensitive composition layer each contain the same (meth)acrylate compound, which suppresses component diffusion between the layers and improves storage stability.

[0183] When the thermoplastic resin layer contains a (meth)acrylate compound as a plasticizer, it is preferable that the (meth)acrylate compound does not polymerize even in the exposed area after exposure, from the viewpoint of adhesion between the thermoplastic resin layer and the adjacent layer. Furthermore, as the (meth)acrylate compound used as a plasticizer, from the viewpoints of the resolution of the thermoplastic resin layer, adhesion to adjacent layers, and developability, a polyfunctional (meth)acrylate compound having two or more (meth)acryloyl groups in the molecule is preferred. Furthermore, as the (meth)acrylate compound used as a plasticizer, a (meth)acrylate compound having an acid group or a urethane (meth)acrylate compound is also preferred.

[0184] The plasticizers may be used alone or in combination of two or more. From the viewpoints of the resolution of the thermoplastic resin 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 20 to 50 mass %, relative to the total mass of the thermoplastic resin layer.

[0185] <Sensitizer> The thermoplastic resin layer may contain a sensitizer. The sensitizer is not particularly limited, and examples thereof include the sensitizers that may be contained in the photosensitive composition layer described above.

[0186] 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 viewpoint of improving sensitivity to the light source and visibility of exposed and unexposed 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 layer.

[0187] <Additives, etc.> The thermoplastic resin layer may contain known additives in addition to the above components, if necessary. The thermoplastic resin layer is described in paragraphs

[0189] to

[0193] of JP 2014-085643 A, and the contents of this publication are incorporated herein by reference.

[0188] The thickness of the thermoplastic resin layer is not particularly limited, but is preferably 1 μm or more, more preferably 2 μm or more, from the viewpoint of adhesion to 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.

[0189] <<Middle Class>> In the transfer film 10, the intermediate layer 5 is present between the thermoplastic resin layer 3 and the photosensitive composition layer 7, thereby preventing mixing of components that may occur during the coating and formation of the thermoplastic resin layer 3 and the photosensitive composition layer 7 and during storage after coating and formation. As the intermediate layer, a water-soluble resin layer containing a water-soluble resin can be used. The intermediate layer may also be an oxygen-blocking layer having an oxygen-blocking function, as 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 on the exposure machine is reduced, and productivity is improved, which is preferable. The oxygen-blocking layer used as the intermediate layer may be appropriately selected from known layers described in the above publications, etc. Among them, an oxygen-blocking 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.

[0190] Hereinafter, each component that may be contained in the water-soluble resin layer (intermediate layer) will be described.

[0191] The water-soluble resin layer (intermediate layer) contains a resin. The resin includes a water-soluble resin as a part or the whole thereof. 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. Furthermore, as the water-soluble resin, a copolymer of (meth)acrylic acid / vinyl compound can also be used. As the copolymer of (meth)acrylic acid / vinyl compound, a copolymer of (meth)acrylic acid / allyl (meth)acrylate is preferred, and a copolymer of methacrylic acid / allyl methacrylate is more preferred. When the water-soluble resin is a copolymer of (meth)acrylic acid and a vinyl compound, the composition ratio (mol %) is, for example, preferably from 90 / 10 to 20 / 80, and more preferably from 80 / 20 to 30 / 70.

[0192] The lower limit of the weight-average molecular weight of the water-soluble resin is preferably 5,000 or more, more preferably 7,000 or more, and even more preferably 10,000 or more, and the upper limit is preferably 200,000 or less, more preferably 100,000 or less, and even more preferably 50,000 or less. The dispersity (Mw / Mn) of the water-soluble resin is preferably 1-10, and more preferably 1-5.

[0193] In order to further improve the interlayer mixing suppression ability of the water-soluble resin layer (intermediate layer), it is preferable that the resin in the water-soluble resin layer (intermediate layer) is different from the resin contained in the layer disposed on one side of the water-soluble resin layer (intermediate layer) and the resin contained in the layer disposed on the other side. For example, when the photosensitive composition layer 7 contains a specific polymer A and the thermoplastic resin layer 13 contains a thermoplastic resin (alkali-soluble resin), it is preferable that the resin in the water-soluble resin layer (intermediate layer) 15 is different from the specific polymer A and the thermoplastic resin (alkali-soluble resin).

[0194] The water-soluble resin preferably contains polyvinyl alcohol, more preferably both polyvinyl alcohol and polyvinylpyrrolidone, in order to further improve the oxygen barrier property and the ability to inhibit interlayer mixing.

[0195] The water-soluble resins may be used alone or in combination of two or more. The content of the water-soluble resin is not particularly limited, but is preferably 50% by mass or more, more preferably 70% by mass or more, based on the total mass of the water-soluble resin layer (intermediate layer) in order to further improve the oxygen barrier property and the interlayer mixing suppression ability. The upper limit is not particularly limited, but is, for example, preferably 99.9% by mass or less, more preferably 99.8% by mass or less.

[0196] The thickness of the water-soluble resin layer (intermediate layer) is not particularly limited, but is preferably 0.1 to 5 μm, more preferably 0.5 to 3 μm. When the thickness of the water-soluble resin layer (intermediate layer) is within the above range, the oxygen barrier property is not reduced and the ability to suppress interlayer mixing is excellent. Furthermore, the increase in the time required to remove the water-soluble resin layer (intermediate layer) during development can be suppressed.

[0197] <<Protective film>> The transfer film may have a protective film. As the protective film, a resin film having heat resistance and solvent resistance can be used, and examples thereof include polyolefin films such as polypropylene film and polyethylene film, polyester films such as polyethylene terephthalate film, polycarbonate film, and polystyrene film. Furthermore, a resin film made of the same material as the temporary support may be used as the protective film. Among these, the protective film is preferably a polyolefin film, more preferably a polypropylene film or a polyethylene film, and even more preferably a polyethylene film.

[0198] The thickness of the protective film is preferably from 1 to 100 μm, more preferably from 5 to 50 μm, even more preferably from 5 to 40 μm, and particularly preferably from 15 to 30 μm. The thickness of the protective film is preferably 1 μm or more in terms of excellent mechanical strength, and is preferably 100 μm or less in terms of being relatively inexpensive.

[0199] In addition, the number of fisheyes with a diameter of 80 μm or more contained in the protective film is 5 / m 2 It is preferable that: "Fisheyes" are foreign matter, unmelted material, and oxidized degradation products of the material that are trapped in the film when the material is thermally melted and then kneaded, extruded, biaxially stretched, cast, or other methods are used to produce the film.

[0200] The number of particles with a diameter of 3 μm or more contained in the protective film is 30 / mm 2 Preferably less than 10 pieces / mm 2 Less than 5 pieces / mm is more preferable. 2 The following is even more preferred: This makes it possible to suppress defects caused by the transfer of irregularities due to particles contained in the protective film to the photosensitive composition layer or the conductive layer.

[0201] In order to provide good winding properties, the arithmetic mean roughness Ra of the surface of the protective film opposite to the surface in contact with the composition layer is preferably 0.01 μm or more, more preferably 0.02 μm or more, and even more preferably 0.03 μm or more, and is preferably less than 0.50 μm, more preferably 0.40 μm or less, and even more preferably 0.30 μm or less. In order to prevent defects during transfer, the surface roughness Ra of the protective film on the surface in contact with the composition layer is preferably 0.01 μm or more, more preferably 0.02 μm or more, and even more preferably 0.03 μm or more, and is preferably less than 0.50 μm, more preferably 0.40 μm or less, and even more preferably 0.30 μm or less.

[0202] <<Method for manufacturing transfer film according to the first embodiment>> The method for producing the transfer film of the first embodiment is not particularly limited, and any known method can be used. Examples of methods for manufacturing the transfer film 10 include the steps of applying a thermoplastic resin composition to the surface of the temporary support 1 to form a coating film, and then drying the coating film to form the thermoplastic resin layer 3; applying a water-soluble resin composition to the surface of the thermoplastic resin layer 3 to form a coating film, and then drying the coating film to form the intermediate layer 5; and applying a photosensitive composition to the surface of the intermediate layer 5 to form a coating film, and then drying the coating film to form the photosensitive composition layer 7.

[0203] A protective film 9 is pressed onto the photosensitive composition layer 7 of the laminate produced by the above-mentioned production method, thereby producing a transfer film 10. As a manufacturing method for the transfer film of the first embodiment, it is preferable to include a step of providing a protective film 9 so that it is in contact with the side of the photosensitive composition layer 7 opposite to the side having the temporary support 1, thereby manufacturing a transfer film 10 comprising the temporary support 1, the thermoplastic resin layer 3, the intermediate layer 5, the photosensitive composition layer 7, and the protective film 9. After the transfer film 10 is manufactured by the above manufacturing method, the transfer film 10 may be wound up to produce and store a transfer film in roll form. The transfer film in roll form can be provided in its original form for the lamination step with a substrate in a roll-to-roll system described below.

[0204] In addition, the method for manufacturing the above-mentioned transfer film 10 may be a method in which a photosensitive composition layer 7 and an intermediate layer 5 are formed on a cover film 9, and then a thermoplastic resin layer 3 is formed on the surface of the intermediate layer 5.

[0205] <Composition for forming thermoplastic resin layer and method for forming thermoplastic resin layer> The method for forming the thermoplastic resin layer on the temporary support is not particularly limited, and any known method can be used. For example, the thermoplastic resin layer can be formed by applying a composition for forming a thermoplastic resin layer on the temporary support and drying it as necessary. The thermoplastic resin layer-forming composition preferably contains the various components for forming the thermoplastic resin layer described above and a solvent. Note that, in the thermoplastic resin layer-forming composition, the preferred range of the content of each component relative to the total solid content of the composition is the same as the preferred range of the content of each component relative to the total mass of the thermoplastic resin layer described above. The solvent is not particularly limited as long as it can dissolve or disperse the components other than the solvent, and any known solvent can be used. Examples of the solvent include the same solvents as those contained in the photosensitive composition described below, and preferred embodiments are also the same. The content of the solvent is preferably 50 to 1,900 parts by mass, more preferably 100 to 900 parts by mass, per 100 parts by mass of the total solid content of the composition.

[0206] The method for forming the thermoplastic resin layer is not particularly limited as long as it is a method capable of forming a layer containing the above components, and examples thereof include known coating methods (slit coating, spin coating, curtain coating, inkjet coating, etc.).

[0207] <Water-soluble resin composition and method for forming intermediate layer (water-soluble resin layer)> The method for forming the intermediate layer on the thermoplastic resin layer is not particularly limited, and any known method can be used. For example, the intermediate layer can be formed by applying a water-soluble resin composition onto the thermoplastic resin layer and drying it as necessary. The water-soluble resin composition preferably contains the various components forming the intermediate layer (water-soluble resin layer) described above and a solvent. Note that in the water-soluble resin composition, the preferred range of the content of each component relative to the total solid content of the composition is the same as the preferred range of the content of each component relative to the total mass of the water-soluble resin layer described above. The solvent is not particularly limited as long as it can dissolve or disperse the water-soluble resin, and is preferably at least one selected from the group consisting of water and water-miscible organic solvents, and more preferably water or a mixed solvent of water and a water-miscible organic solvent. Examples of water-miscible organic solvents include alcohols having 1 to 3 carbon atoms, acetone, ethylene glycol, and glycerin, with alcohols having 1 to 3 carbon atoms being preferred, and methanol or ethanol being more preferred. The solvents may be used alone or in combination of two or more. The content of the solvent is preferably 50 to 2,500 parts by mass, more preferably 50 to 1,900 parts by mass, and even more preferably 100 to 900 parts by mass, relative to 100 parts by mass of the total solid content of the composition.

[0208] The method for forming the water-soluble resin layer is not particularly limited as long as it is a method capable of forming a layer containing the above components, and examples thereof include known coating methods (slit coating, spin coating, curtain coating, inkjet coating, etc.).

[0209] <Photosensitive composition and method for forming photosensitive composition layer> The method for forming the photosensitive composition layer on the intermediate layer is not particularly limited, and any known method can be used. For example, the photosensitive composition can be applied to the intermediate layer and then dried as necessary. The photosensitive composition preferably contains the various components forming the photosensitive composition layer described above and a solvent. Note that the preferred range of the content of each component in the photosensitive composition relative to the total solid content of the composition is the same as the preferred range of the content of each component relative to the total mass of the photosensitive composition layer described above. The solvent is not particularly limited as long as it can dissolve or disperse each component other than the solvent, and any known solvent can be used. Specific examples include alkylene glycol ether solvents, alkylene glycol ether acetate solvents, alcohol solvents (methanol, ethanol, etc.), ketone solvents (acetone, methyl ethyl ketone, etc.), aromatic hydrocarbon solvents (toluene, etc.), aprotic polar solvents (N,N-dimethylformamide, etc.), cyclic ether solvents (tetrahydrofuran, etc.), ester solvents (n-propyl acetate, etc.), amide solvents, lactone solvents, and mixed solvents containing two or more of these.

[0210] The solvent preferably contains at least one selected from the group consisting of alkylene glycol ether solvents and alkylene glycol ether acetate solvents. Among these, a mixed solvent containing at least one selected from the group consisting of alkylene glycol ether solvents and alkylene glycol ether acetate solvents and at least one selected from the group consisting of ketone solvents and cyclic ether solvents is more preferred, and a mixed solvent containing at least three of at least one selected from the group consisting of alkylene glycol ether solvents and alkylene glycol ether acetate solvents, a ketone solvent, and a cyclic ether solvent is even more preferred.

[0211] Examples of alkylene glycol ether solvents include ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, propylene glycol monoalkyl ethers (such as propylene glycol monomethyl ether acetate), propylene glycol dialkyl ethers, diethylene glycol dialkyl ethers, dipropylene glycol monoalkyl ethers, and dipropylene glycol dialkyl ethers. Alkylene glycol ether acetate solvents include, for example, ethylene glycol monoalkyl ether acetate, propylene glycol monoalkyl ether acetate, diethylene glycol monoalkyl ether acetate, and dipropylene glycol monoalkyl ether acetate. As the solvent, the solvents described in paragraphs

[0092] to

[0094] of International Publication No. 2018 / 179640 and the solvents described in paragraph

[0014] of Japanese Patent Application Laid-Open No. 2018-177889 may be used, the contents of which are incorporated herein by reference. The solvents may be used alone or in combination of two or more. The content of the solvent is preferably 50 to 1,900 parts by mass, more preferably 100 to 1,200 parts by mass, and even more preferably 100 to 900 parts by mass, relative to 100 parts by mass of the total solid content of the composition.

[0212] Examples of methods for applying the photosensitive composition include printing, spraying, roll coating, bar coating, curtain coating, spin coating, and die coating (that is, slit coating).

[0213] As a method for drying the coating film of the photosensitive composition, heat drying and reduced pressure drying are preferred.

[0214] Furthermore, by laminating a protective film to the photosensitive composition layer, the transfer film of the first embodiment can be produced. The method for laminating the protective film to the photosensitive composition layer is not particularly limited, and known methods can be used. Examples of a device for laminating the protective film to the photosensitive composition layer include known laminators such as a vacuum laminator and an auto-cut laminator. The laminator is preferably equipped with any heatable roller such as a rubber roller and is capable of applying pressure and heat.

[0215] [Transfer film of second embodiment] An example of the transfer film of the second embodiment will be described below. 3 has, in this order, a temporary support 11, a composition layer 12 including a photosensitive composition layer 13 and a refractive index adjusting layer 15, and a protective film 17. The photosensitive composition layer 13 contains a specific polymer (hereinafter, the specific polymer contained in the photosensitive composition layer of the transfer film of the second embodiment will also be referred to as "specific polymer B"), a polymerizable compound, and a photopolymerization initiator. Although the transfer film 20 shown in FIG. 3 has the protective film 17 disposed thereon, the protective film 17 does not necessarily have to be disposed. Furthermore, although the transfer film 20 shown in FIG. 3 has the refractive index adjusting layer 15 arranged thereon, the refractive index adjusting layer 15 does not necessarily have to be arranged. Each element constituting the transfer film will be described below. In the transfer film of the second embodiment, the temporary support 11 and the protective film 17 may be the same as the temporary support 1 and the protective film 9 of the first embodiment described above, and the preferred embodiments are also the same.

[0216] <<Photosensitive composition layer>> The transfer film has a photosensitive composition layer. After the photosensitive composition layer is transferred onto a transfer-receiving material, it is exposed to light and developed, thereby forming a pattern on the transfer-receiving material. The photosensitive composition layer is preferably a negative photosensitive composition layer. The negative photosensitive composition layer is a photosensitive composition layer in which the solubility of the exposed portion in a developer is reduced by exposure. When the photosensitive composition layer is a negative photosensitive composition layer, the formed pattern corresponds to a cured layer.

[0217] The photosensitive composition layer contains a specific polymer B, a polymerizable compound, and a photopolymerization initiator. Components that can be contained in the photosensitive composition layer will be described in detail below.

[0218] <Specific polymer B> The photosensitive composition layer contains a specific polymer B. The number average molecular weight of the specific polymer B satisfies the above-mentioned requirement 1. A number-average molecular weight of 50,000 or less is preferred from the viewpoint of improving resolution and developability. The number-average molecular weight is more preferably 40,000 or less, even more preferably 30,000 or less, particularly preferably 20,000 or less, and most preferably 15,000 or less. On the other hand, a number-average molecular weight of 3,000 or more is preferred from the viewpoint of controlling the properties of development aggregates and the properties of unexposed films, such as edge fuse properties and cut-chip properties. The number-average molecular weight is more preferably 4,000 or more, even more preferably 5,000 or more.

[0219] The weight average molecular weight (Mw) of the specific polymer B is preferably 5,000 or more, more preferably 10,000 or more, further preferably from 10,000 to 50,000, and particularly preferably from 14,000 to 35,000, in terms of achieving better effects of the present invention.

[0220] The acid value of the specific polymer B is preferably from 10 to 200 mgKOH / g, more preferably from 60 to 200 mgKOH / g, still more preferably from 60 to 150 mgKOH / g, and particularly preferably from 70 to 140 mgKOH / g. The acid value can be determined according to the method described in JIS K0070:1992.

[0221] The content of specific polymer B is preferably from 10 to 90% by mass, more preferably from 20 to 80% by mass, and even more preferably from 30 to 70% by mass, based on the total mass of the photosensitive composition layer, in terms of achieving better effects of the present invention. The specific polymer B may be used alone or in combination of two or more.

[0222] The structure of the specific polymer B will be described below. The type of specific polymer B is not particularly limited, and examples thereof include (meth)acrylic resin, styrene resin, epoxy resin, amide resin, amide epoxy resin, alkyd resin, phenol resin, ester resin, urethane resin, epoxy acrylate resin obtained by reacting an epoxy resin with (meth)acrylic acid, and acid-modified epoxy acrylate resin obtained by reacting an epoxy acrylate resin with an acid anhydride.

[0223] (Embodiment 1 of Specific Polymer B) An example of a suitable embodiment of the specific polymer B is a (meth)acrylic resin, which has excellent alkaline developability and film-forming properties. Here, the (meth)acrylic resin refers to a resin having structural units derived from a (meth)acrylic compound. The content of the structural units derived from a (meth)acrylic compound is preferably 50% by mass or more, more preferably 70% by mass or more, and even more preferably 90% by mass or more, based on the total structural units of the (meth)acrylic resin. The (meth)acrylic resin may be composed solely of structural units derived from (meth)acrylic compounds, or may contain structural units derived from polymerizable monomers other than (meth)acrylic compounds. That is, the upper limit of the content of structural units derived from (meth)acrylic compounds is 100% by mass or less of all structural units of the (meth)acrylic resin.

[0224] Examples of the (meth)acrylic compound include (meth)acrylic acid, (meth)acrylic acid esters, (meth)acrylamide, and (meth)acrylonitrile. Examples of (meth)acrylic acid esters include (meth)acrylic acid alkyl esters, (meth)acrylic acid tetrahydrofurfuryl esters, (meth)acrylic acid dimethylaminoethyl esters, (meth)acrylic acid diethylaminoethyl esters, (meth)acrylic acid glycidyl esters, (meth)acrylic acid benzyl esters, 2,2,2-trifluoroethyl (meth)acrylate, and 2,2,3,3-tetrafluoropropyl (meth)acrylate, and (meth)acrylic acid alkyl esters are preferred. Examples of (meth)acrylamides include acrylamides such as diacetone acrylamide.

[0225] Examples of the (meth)acrylic acid alkyl ester include (meth)acrylic acid alkyl esters having an alkyl group having 1 to 12 carbon atoms, such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, and dodecyl (meth)acrylate.

[0226] The (meth)acrylic acid alkyl ester is also preferably a (meth)acrylic acid alkyl ester having a monocyclic or polycyclic aliphatic hydrocarbon ring group. Examples of the aliphatic hydrocarbon ring include a tricyclodecane ring, a cyclohexane ring, a cyclopentane ring, a norbornane ring, an isoborone ring, and a dicyclopentane ring. Among these, in view of the superior effect of the present invention, a ring in which two or more aliphatic hydrocarbon rings are condensed is preferred, and a dicyclopentane ring or a tetrahydrodicyclopentadiene ring (tricyclo[5.2.1.0]) is particularly preferred. 2,6 ]decane ring) is more preferred. Examples of the (meth)acrylic acid alkyl ester having a monocyclic or polycyclic aliphatic hydrocarbon ring group include dicyclopentanyl (meth)acrylate, cyclohexyl (meth)acrylate, and isobornyl (meth)acrylate.

[0227] As the (meth)acrylic acid ester, a (meth)acrylic acid alkyl ester having an alkyl group having 1 to 4 carbon atoms is preferred, and methyl (meth)acrylate or ethyl (meth)acrylate is more preferred.

[0228] The (meth)acrylic resin may have a structural unit other than the structural unit derived from the (meth)acrylic compound. The polymerizable monomer that forms the structural unit is not particularly limited as long as it is a compound other than a (meth)acrylic compound that is copolymerizable with a (meth)acrylic compound, and examples thereof include styrene compounds that may have a substituent at the α-position or on the aromatic ring, such as styrene, vinyltoluene, and α-methylstyrene; vinyl alcohol esters such as acrylonitrile and vinyl-n-butyl ether; maleic acid monoesters such as maleic acid, maleic anhydride, monomethyl maleate, monoethyl maleate, and monoisopropyl maleate; fumaric acid, cinnamic acid, α-cyanocinnamic acid, itaconic acid, and crotonic acid. These polymerizable monomers may be used alone or in combination of two or more.

[0229] In order to improve alkaline developability, the (meth)acrylic resin preferably contains a structural unit having an acid group, such as a carboxy group, a sulfo group, a phosphate group, or a phosphonate group. In particular, the (meth)acrylic resin more preferably has a structural unit having a carboxy group, and even more preferably has a structural unit derived from the above-mentioned (meth)acrylic acid.

[0230] The content of structural units having an acid group in the (meth)acrylic resin (preferably structural units derived from (meth)acrylic acid) is preferably 10% by mass or more relative to all structural units of the (meth)acrylic resin in terms of excellent developability. Although there is no particular upper limit, it is preferably 50% by mass or less, more preferably 40% by mass or less, in terms of excellent alkali resistance.

[0231] Furthermore, the (meth)acrylic resin more preferably has a structural unit derived from the above-mentioned alkyl (meth)acrylate ester. The content of structural units derived from (meth)acrylic acid alkyl ester in the (meth)acrylic resin is preferably 50% by mass or more, more preferably 60% by mass or more, and even more preferably 65% ​​by mass or more, based on the total structural units of the (meth)acrylic resin. The upper limit is preferably, for example, 90% by mass or less.

[0232] As the (meth)acrylic resin, a resin having both a structural unit derived from (meth)acrylic acid and a structural unit derived from a (meth)acrylic acid alkyl ester is preferred, and a resin composed only of a structural unit derived from (meth)acrylic acid and a structural unit derived from a (meth)acrylic acid alkyl ester is more preferred. Furthermore, as the (meth)acrylic resin, an acrylic resin having a structural unit derived from methacrylic acid, a structural unit derived from methyl methacrylate, and a structural unit derived from ethyl acrylate is also preferred.

[0233] Furthermore, in order to achieve better effects of the present invention, the (meth)acrylic resin preferably has at least one selected from the group consisting of structural units derived from methacrylic acid and structural units derived from a methacrylic acid alkyl ester, and more preferably has both structural units derived from methacrylic acid and structural units derived from a methacrylic acid alkyl ester. The total content of the structural units derived from methacrylic acid and the structural units derived from alkyl methacrylate in the (meth)acrylic resin is preferably 40% by mass or more, more preferably 60% by mass or more, based on the total structural units of the (meth)acrylic resin, in order to obtain better effects of the present invention. The upper limit is not particularly limited, and may be 100% by mass or less, preferably 80% by mass or less.

[0234] In addition, in terms of achieving better effects of the present invention, it is also preferable that the (meth)acrylic resin has at least one selected from the group consisting of structural units derived from methacrylic acid and structural units derived from methacrylic acid alkyl esters, and at least one selected from the group consisting of structural units derived from acrylic acid and structural units derived from acrylic acid alkyl esters. In order to obtain better effects of the present invention, the total content of the structural units derived from methacrylic acid and the structural units derived from an alkyl methacrylate ester is preferably in a mass ratio of 60 / 40 to 80 / 20 relative to the total content of the structural units derived from acrylic acid and the structural units derived from an alkyl acrylate ester.

[0235] The (meth)acrylic resin preferably has an ester group at the end, in order to provide excellent developability of the photosensitive composition layer after transfer. The terminals of the (meth)acrylic resin are composed of moieties derived from the polymerization initiator used in the synthesis. A (meth)acrylic resin having an ester group at its terminal can be synthesized by using a polymerization initiator that generates a radical having an ester group.

[0236] (Embodiment 2 of Specific Polymer B) Another preferred embodiment of the specific polymer B is an alkali-soluble resin. From the viewpoint of developability, the specific polymer B preferably has an acid value of 60 mgKOH / g or more. Furthermore, the specific polymer B is more preferably a resin having a carboxy group with an acid value of 60 mgKOH / g or more (a so-called carboxy group-containing resin), and even more preferably a (meth)acrylic resin having a carboxy group with an acid value of 60 mgKOH / g or more (a so-called carboxy group-containing (meth)acrylic resin), from the viewpoint that it is easy to thermally crosslink with the crosslinking component by heating and form a strong film, for example. When the specific polymer B is a resin having a carboxy group, the three-dimensional crosslinking density can be increased by, for example, adding a thermally crosslinkable compound such as a blocked isocyanate compound to cause thermal crosslinking. Furthermore, when the carboxy group of the resin having a carboxy group is dehydrated and made hydrophobic, the wet heat resistance can be improved.

[0237] The carboxyl group-containing (meth)acrylic resin having an acid value of 60 mgKOH / g or more is not particularly limited as long as it satisfies the above-mentioned acid value condition, and can be appropriately selected from known (meth)acrylic resins. For example, among the polymers described in paragraph

[0025] of JP-A No. 2011-095716, carboxyl group-containing acrylic resins having an acid value of 60 mgKOH / g or more, and among the polymers described in paragraphs

[0033] to

[0052] of JP-A No. 2010-237589, carboxyl group-containing acrylic resins having an acid value of 60 mgKOH / g or more can be preferably used.

[0238] (Embodiment 3 of Specific Polymer B) Another preferred embodiment of the specific polymer B is a styrene-acrylic copolymer. In this specification, a styrene-acrylic copolymer refers to a resin having structural units derived from a styrene compound and structural units derived from a (meth)acrylic compound, and the total content of the structural units derived from the styrene compound and the structural units derived from the (meth)acrylic compound is preferably 30% by mass or more, and more preferably 50% by mass or more, of all structural units of the copolymer. The content of the structural units derived from the styrene compound is preferably 1% by mass or more, more preferably 5% by mass or more, and even more preferably 5 to 80% by mass, based on all structural units of the copolymer. The content of the structural units derived from the (meth)acrylic compound is preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 20 to 95% by mass, based on all structural units of the copolymer.

[0239] In order to obtain a more excellent effect of the present invention, the specific polymer B preferably has an aromatic group, and more preferably has a structural unit having an aromatic group. Examples of the aromatic group include an aromatic hydrocarbon ring group. Examples of monomers that form structural units having an aromatic group include styrene compounds such as styrene, tert-butoxystyrene, methylstyrene, and α-methylstyrene, as well as benzyl (meth)acrylate. Of these, styrene compounds are preferred, and styrene is more preferred. Furthermore, in terms of achieving better effects of the present invention, the specific polymer B more preferably has a structural unit represented by the following formula (S) (a structural unit derived from styrene).

[0240] [ka]

[0241] When the specific polymer B has a structural unit having an aromatic group, the content of the structural unit having an aromatic group is preferably 5 to 90 mass%, more preferably 10 to 70 mass%, and even more preferably 20 to 60 mass%, based on the total structural units of the specific polymer B, in terms of better effects of the present invention. Furthermore, the content of the structural units having an aromatic group in the specific polymer B is preferably 5 to 70 mol %, more preferably 10 to 60 mol %, and even more preferably 20 to 60 mol %, based on the total structural units of the specific polymer B, in order to achieve better effects of the present invention. Furthermore, the content of the structural unit represented by the above formula (S) in specific polymer B is preferably 5 to 70 mol %, more preferably 10 to 60 mol %, even more preferably 20 to 60 mol %, and particularly preferably 20 to 50 mol %, relative to all structural units of specific polymer B, in terms of achieving better effects of the present invention. In this specification, when the content of a "structural unit" is specified by a molar ratio, the "structural unit" is considered to have the same meaning as a "monomer unit." In addition, in this specification, the "monomer unit" may be modified after polymerization by a polymer reaction or the like. The same applies hereinafter.

[0242] In order to obtain better effects of the present invention, the specific polymer B preferably has a monocyclic or polycyclic aliphatic hydrocarbon ring group. That is, the specific polymer B preferably has a structural unit having an aliphatic hydrocarbon ring group. In particular, the specific polymer B more preferably has an aliphatic hydrocarbon ring group having a structure in which two or more aliphatic hydrocarbon rings are condensed.

[0243] Examples of the aliphatic hydrocarbon ring in the structural unit having an aliphatic hydrocarbon ring group include a tricyclodecane ring, a cyclohexane ring, a cyclopentane ring, a norbornane ring, an isoborone ring, and a dicyclopentane ring. Among these, in terms of achieving better effects of the present invention, a ring in which two or more aliphatic hydrocarbon rings are condensed is preferred, and a dicyclopentane ring or a tetrahydrodicyclopentadiene ring (tricyclo[5.2.1.0]) is particularly preferred. 2,6 ]decane ring) is more preferred. Examples of monomers that form structural units having an aliphatic hydrocarbon ring group include dicyclopentanyl (meth)acrylate, cyclohexyl (meth)acrylate, and isobornyl (meth)acrylate. Furthermore, in terms of achieving better effects of the present invention, specific polymer B more preferably has a structural unit represented by formula (Cy) below, and more preferably has a structural unit represented by formula (S) above and a structural unit represented by formula (Cy) below.

[0244] [ka]

[0245] In the formula (Cy), R M represents a hydrogen atom or a methyl group, and R Cy represents an aliphatic hydrocarbon ring group.

[0246] R in formula (Cy) M is preferably a methyl group. R in formula (Cy) Cy In terms of achieving better effects of the present invention, is preferably an aliphatic hydrocarbon ring group having 5 to 20 carbon atoms, more preferably an aliphatic hydrocarbon ring group having 6 to 16 carbon atoms, and even more preferably an aliphatic hydrocarbon ring group having 8 to 14 carbon atoms. Also, R in formula (Cy) Cy In terms of achieving better effects of the present invention, the aliphatic hydrocarbon ring group represented by the formula (I) is preferably a cyclopentyl group, a cyclohexyl group, a tetrahydrodicyclopentadienyl group, a norbornyl group, or an isobornyl group, and more preferably a cyclohexyl group, a dicyclopentanyl group, or a tetrahydrodicyclopentadinyl group. Furthermore, R in formula (Cy) Cy The aliphatic hydrocarbon ring contained in the aliphatic hydrocarbon ring group represented by the formula (I) is preferably a ring formed by condensing two or more aliphatic hydrocarbon rings, and more preferably a ring formed by condensing two to four aliphatic hydrocarbon rings, in terms of achieving better effects of the present invention. R in formula (Cy)Cy As the alkyl group, a cyclohexyl group or a dicyclopentanyl group is more preferable, and a dicyclopentanyl group is even more preferable, in terms of achieving better effects of the present invention.

[0247] The specific polymer B may have one type of structural unit having an aliphatic hydrocarbon ring group, or may have two or more types of structural units. When the specific polymer B has a structural unit having an aliphatic hydrocarbon ring group, the content of the structural unit having an aliphatic hydrocarbon ring group is preferably 5 to 90 mass%, more preferably 10 to 80 mass%, and even more preferably 20 to 70 mass%, based on the total structural units of the specific polymer B, in terms of better effects of the present invention. Furthermore, the content of the structural units having an aliphatic hydrocarbon ring group in the specific polymer B is preferably 5 to 70 mol %, more preferably 10 to 60 mol %, and even more preferably 20 to 50 mol %, based on the total structural units of the specific polymer B, in order to achieve better effects of the present invention. Furthermore, the content of the structural unit represented by the above formula (Cy) in the specific polymer B is preferably 5 to 90 mass %, more preferably 10 to 80 mass %, and even more preferably 20 to 70 mass %, based on the total structural units of the specific polymer B, in order to achieve better effects of the present invention. Furthermore, the content of the structural unit represented by the above formula (Cy) in the specific polymer B is preferably 5 to 70 mol %, more preferably 10 to 60 mol %, and even more preferably 20 to 50 mol %, based on the total structural units of the specific polymer B, in order to achieve better effects of the present invention.

[0248] The specific polymer B preferably contains at least one of the above-mentioned structural units having an aromatic group and structural units having an aliphatic hydrocarbon ring group.

[0249] When the specific polymer B has a structural unit having an aromatic group and a structural unit having an aliphatic hydrocarbon ring group, the total content of the structural units having an aromatic group and the structural units having an aliphatic hydrocarbon ring group is preferably 10 to 90 mass%, more preferably 20 to 80 mass%, and even more preferably 40 to 75 mass%, based on the total structural units of the specific polymer B, in terms of achieving better effects of the present invention. Furthermore, the total content of the structural units having an aromatic group and the structural units having an aliphatic hydrocarbon ring group in the specific polymer B is preferably 10 to 80 mol %, more preferably 20 to 70 mol %, and even more preferably 40 to 60 mol %, based on the total structural units of the specific polymer B, in terms of achieving better effects of the present invention. Furthermore, the total content of the structural units represented by the above formula (S) and the structural units represented by the above formula (Cy) in the specific polymer B is preferably 10 to 80% by mass, more preferably 20 to 70% by mass, and even more preferably 40 to 60% by mass, relative to all structural units of the specific polymer B, in terms of achieving better effects of the present invention. Furthermore, the total content of the structural units represented by the above formula (S) and the structural units represented by the above formula (Cy) in the specific polymer B is preferably 10 to 80 mol %, more preferably 20 to 70 mol %, and even more preferably 40 to 60 mol %, relative to all structural units of the specific polymer B, in terms of achieving better effects of the present invention. Furthermore, in terms of achieving better effects of the present invention, the molar amount nS of the structural unit represented by the above formula (S) and the molar amount nCy of the structural unit represented by the above formula (Cy) in specific polymer B preferably satisfy the relationship shown in the following formula (SCy), more preferably satisfy the following formula (SCy-1), and even more preferably satisfy the following formula (SCy-2). 0.2≦nS / (nS+nCy)≦0.8 Formula (SCy) 0.30≦nS / (nS+nCy)≦0.75 Formula (SCy-1) 0.40≦nS / (nS+nCy)≦0.70 Formula (SCy-2)

[0250] The specific polymer B preferably has a structural unit having an acid group, in order to obtain better effects of the present invention. Examples of the acid group include a carboxy group, a sulfo group, a phosphonic acid group, and a phosphoric acid group, with a carboxy group being preferred. As the structural unit having an acid group, a structural unit derived from (meth)acrylic acid shown below is preferred, and a structural unit derived from methacrylic acid is more preferred.

[0251] [ka]

[0252] The specific polymer B may have one type of structural unit having an acid group, or two or more types of structural units having an acid group. When the specific polymer B has a structural unit having an acid group, the content of the structural unit having an acid group is preferably 5 to 50 mass%, more preferably 5 to 40 mass%, and even more preferably 10 to 30 mass%, based on the total structural units of the specific polymer B, in terms of better effects of the present invention. Furthermore, the content of the structural units having an acid group in the specific polymer B is preferably 5 to 70 mol %, more preferably 10 to 50 mol %, and even more preferably 20 to 40 mol %, based on the total structural units of the specific polymer B, in order to achieve better effects of the present invention. Furthermore, the content of the (meth)acrylic acid-derived structural units in the specific polymer B is preferably 5 to 70 mol %, more preferably 10 to 50 mol %, and even more preferably 20 to 40 mol %, based on the total structural units of the specific polymer B, in order to achieve better effects of the present invention.

[0253] In terms of achieving better effects of the present invention, the specific polymer B preferably has a polymerizable group, and more preferably has a structural unit having a polymerizable group. The polymerizable group is preferably a radically polymerizable group, more preferably an ethylenically unsaturated group. When the specific polymer B has an ethylenically unsaturated group, the specific polymer B preferably has a structural unit having an ethylenically unsaturated group in a side chain. In this specification, the term "main chain" refers to the relatively longest bond chain in the molecule of the polymer compound that constitutes the resin, and the term "side chain" refers to an atomic group branching off from the main chain. The ethylenically unsaturated group is more preferably an allyl group or a (meth)acryloyloxy group. Examples of the structural unit having a polymerizable group include, but are not limited to, those shown below.

[0254] [ka]

[0255] The specific polymer B may have one type of structural unit having a polymerizable group, or may have two or more types of structural units. When the specific polymer B has a structural unit having a polymerizable group, the content of the structural unit having a polymerizable group is preferably 5 to 70 mass %, more preferably 10 to 50 mass %, and even more preferably 20 to 40 mass %, based on the total structural units of the specific polymer B, in terms of better effects of the present invention. Furthermore, the content of the structural unit having a polymerizable group in the specific polymer B is preferably 5 to 70 mol %, more preferably 10 to 60 mol %, and even more preferably 20 to 50 mol %, based on the total structural units of the specific polymer B, in order to achieve better effects of the present invention.

[0256] Examples of a method for introducing a polymerizable group into the specific polymer B include a method of reacting a functional group such as a hydroxy group, a carboxy group, a primary amino group, a secondary amino group, an acetoacetyl group, or a sulfo group with a compound such as an epoxy compound, a blocked isocyanate compound, an isocyanate compound, a vinyl sulfone compound, an aldehyde compound, a methylol compound, or a carboxylic acid anhydride. A preferred example of a method for introducing a polymerizable group into the specific polymer B is to synthesize a polymer having a carboxy group by polymerization, and then react some of the carboxy groups of the resulting polymer with glycidyl (meth)acrylate by a polymer reaction to introduce a (meth)acryloyloxy group into the polymer. By this method, a specific polymer B having a (meth)acryloyloxy group in its side chain can be obtained. The polymerization reaction is preferably carried out at a temperature of 70 to 100°C, more preferably at a temperature of 80 to 90°C. The polymerization initiator used in the polymerization reaction is preferably an azo-based initiator, more preferably V-601 (trade name) or V-65 (trade name) manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. The polymerization reaction is preferably carried out at a temperature of 80 to 110°C. In the polymerization reaction, it is preferable to use a catalyst such as an ammonium salt.

[0257] The specific polymer B is preferably the polymers X1 to X4 shown below, as they provide better effects of the present invention. The content ratios (a to d) of the structural units shown below and the weight average molecular weight Mw can be changed as appropriate depending on the purpose, but the following structures are particularly preferred, as they provide better effects of the present invention. (Polymer X1) a: 20-60% by mass, b: 10-50% by mass, c: 5.0-25% by mass, d: 10-50% by mass. (Polymer X2) a: 20-60% by mass, b: 10-50% by mass, c: 5.0-25% by mass, d: 10-50% by mass. (Polymer X3) a: 30-65% by mass, b: 1.0-20% by mass, c: 5.0-25% by mass, d: 10-50% by mass. (Polymer X4) a: 1.0-20% by mass, b: 20-60% by mass, c: 5.0-25% by mass, d: 10-50% by mass.

[0258] [ka] JPEG0007787089000009.jpg47106JPEG0007787089000010.jpg47103JPEG0007787089000011.jpg50108

[0259] <Polymerizable compound> The photosensitive composition layer contains a polymerizable compound. In this specification, the term "polymerizable compound" refers to a compound that has a polymerizable group and is polymerized by the action of a polymerization initiator described later, and is different from the specific polymer B described above. The polymerizable group contained in 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 cationically polymerizable group such as an epoxy group and an oxetane group. The polymerizable group is preferably a group having an ethylenically unsaturated group, more preferably a (meth)acryloyl group. That is, the polymerizable compound preferably contains a polymerizable compound having an ethylenically unsaturated group (hereinafter also simply referred to as "ethylenically unsaturated compound"), more preferably contains a polymerizable compound having a (meth)acryloyl group. The molecular weight of the ethylenically unsaturated compound in this specification is preferably less than 5,000.

[0260] As the polymerizable compound, a compound having one or more ethylenically unsaturated groups in the molecule (ethylenically unsaturated compound) is preferred, and a compound having two or more ethylenically unsaturated groups in the molecule (polyfunctional ethylenically unsaturated compound) is more preferred, in that the photosensitivity of the photosensitive composition layer is superior. In addition, the number of ethylenically unsaturated groups that the ethylenically unsaturated compound has in the molecule is preferably 6 or less, in order to obtain better effects of the present invention.

[0261] As the polymerizable compound, a (meth)acrylate compound having a (meth)acryloyl group is preferred.

[0262] In one embodiment of the photosensitive composition layer, the content of the polymerizable compound having two or more ethylenically unsaturated groups in the molecule in the photosensitive composition layer is preferably 70 to 100 mass% or more, more preferably 80 to 100 mass% or more, and even more preferably 90 to 100 mass% based on the total mass of the polymerizable compound.

[0263] In one embodiment of the photosensitive composition layer, the content of the compound having three or more ethylenically unsaturated groups in the molecule in the photosensitive composition layer is preferably 0 to 20% by mass relative to the total mass of the polymerizable compounds.

[0264] In addition, as one embodiment of the photosensitive composition layer, the content of the compound having four or more ethylenically unsaturated groups in the molecule in the photosensitive composition layer is preferably 0 to 10% by mass relative to the total mass of the polymerizable compound.

[0265] In one embodiment of the photosensitive composition layer, the content of the compound having six or more ethylenically unsaturated groups in the molecule is preferably 10% by mass or less, more preferably less than 10% by mass, and more preferably 5% by mass or less, based on the total mass of the polymerizable compounds. The lower limit is preferably 0% by mass.

[0266] Preferred embodiments of the polymerizable compound will be described below.

[0267] One preferred embodiment of the polymerizable compound is a compound represented by the following formula (M) (also simply referred to as "compound M"). Q 2 -R 1 -Q 1 Formula (M) In formula (M), Q 1 and Q 2 each independently represents a (meth)acryloyloxy group, R 1 represents a divalent linking group having a chain structure.

[0268] Q in formula (M) 1 and Q 2 In terms of ease of synthesis, Q1 and Q 2 are preferably the same group. Also, Q in formula (M) 1 and Q 2 is preferably an acryloyloxy group from the viewpoint of reactivity. R in formula (M) 1 As the alkylene group, an alkyleneoxyalkylene group (-L 1 -OL 1 -), or a polyalkyleneoxyalkylene group (-(L 1 -O) p -L 1 -) is preferred, an alkylene group having 2 to 20 carbon atoms or a polyalkyleneoxyalkylene group is more preferred, an alkylene group having 4 to 20 carbon atoms is further preferred, and a linear alkylene group having 6 to 18 carbon atoms is particularly preferred. The alkylene group may have a chain structure at least in part, and the portion other than the chain structure is not particularly limited and may be, for example, a branched, cyclic, or straight-chain alkylene group having 1 to 5 carbon atoms, an arylene group, an ether bond, or a combination thereof. An alkylene group or a group combining two or more alkylene groups and one or more arylene groups is preferred, an alkylene group is more preferred, and a straight-chain alkylene group is even more preferred. In addition, the above L 1 each independently represents an alkylene group, preferably an ethylene group, a propylene group, or a butylene group, and more preferably an ethylene group or a 1,2-propylene group. p represents an integer of 2 or more, preferably an integer of 2 to 10.

[0269] Also, Q in compound M 1 and Q 2 The number of atoms in the shortest linking chain between is preferably 3 to 50, more preferably 4 to 40, even more preferably 6 to 20, and particularly preferably 8 to 12, in terms of achieving better effects of the present invention. As used herein, "Q 1 and Q 2 The number of atoms in the shortest chain connecting the1 Connect to R 1 Q from atoms in 2 Connect to R 1 is the shortest number of atoms that connects to the atom in

[0270] The compound represented by the above formula (M) includes R 1 represents an alkylene group and has a moiety other than a chain structure, R 1 As -L 2 -X 1 -L 2 -(L 2 : a substituted or unsubstituted methylene group, X 1 It is preferable that the compound is a compound other than a tricyclodecanediyl group.

[0271] Specific examples of compound M include 1,3-butanediol di(meth)acrylate, tetramethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,7-heptanediol di(meth)acrylate, 1,8-octanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, di(meth)acrylate of hydrogenated bisphenol A, di(meth)acrylate of hydrogenated bisphenol F, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, poly(ethylene glycol / propylene glycol) di(meth)acrylate, and polybutylene glycol di(meth)acrylate. The above ester monomers can also be used as a mixture. Among the above compounds, in terms of achieving better effects of the present invention, at least one compound selected from the group consisting of 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, and neopentyl glycol di(meth)acrylate is preferred, at least one compound selected from the group consisting of 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, and 1,10-decanediol di(meth)acrylate is more preferred, and at least one compound selected from the group consisting of 1,9-nonanediol di(meth)acrylate and 1,10-decanediol di(meth)acrylate is even more preferred.

[0272] One preferred embodiment of the polymerizable compound is a di- or higher functional ethylenically unsaturated compound. In this specification, the term "di- or higher functional ethylenically unsaturated compound" means a compound having two or more ethylenically unsaturated groups in the molecule. The ethylenically unsaturated group in the ethylenically unsaturated compound is preferably a (meth)acryloyl group. As the ethylenically unsaturated compound, a (meth)acrylate compound is preferred.

[0273] The difunctional ethylenically unsaturated compound is not particularly limited and can be appropriately selected from known compounds. Examples of the difunctional ethylenically unsaturated compound other than the compound M include tricyclodecane dimethanol di(meth)acrylate and β,β-dimethyl-1,3-dioxane-2-ethanol diacrylate.

[0274] Commercially available bifunctional ethylenically unsaturated compounds include tricyclodecane dimethanol diacrylate (trade name: NK Ester A-DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.), tricyclodecane dimethanol dimethacrylate (trade name: NK Ester DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.), 1,9-nonanediol diacrylate (trade name: NK Ester A-NOD-N, manufactured by Shin-Nakamura Chemical Co., Ltd.), 1,6-hexanediol diacrylate (trade name: NK Ester A-HD-N, manufactured by Shin-Nakamura Chemical Co., Ltd.), and β,β-dimethyl-1,3-dioxane-2-ethanol diacrylate (trade name: KAYARAD R-604, manufactured by Nippon Kayaku Co., Ltd.).

[0275] The tri- or higher functional ethylenically unsaturated compound is not particularly limited and can be appropriately selected from known compounds. 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, trishydroxyethyl isocyanuric acid (di / tri)(meth)acrylate, and glycerin tri(meth)acrylate.

[0276] 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.

[0277] Examples of the polymerizable compound 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 (registered trademark) 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.), and ethoxylated glycerin triacrylate (NK Ester A-GLY-9E manufactured by Shin-Nakamura Chemical Co., Ltd., etc.).

[0278] The polymerizable compound also includes a urethane (meth)acrylate compound. Examples of urethane (meth)acrylates include urethane di(meth)acrylates, such as propylene oxide-modified urethane di(meth)acrylates and ethylene oxide and propylene oxide-modified urethane di(meth)acrylates. Further, the urethane (meth)acrylate may be a trifunctional or higher functional urethane (meth)acrylate. The lower limit of the number of functional groups is preferably 6 or more, and more preferably 8 or more. The upper limit of the number of functional groups is preferably 20 or less. Examples of trifunctional or higher functional urethane (meth)acrylates include 8UX-015A (manufactured by Taisei Fine Chemical Co., Ltd.), UA-32P (manufactured by Shin-Nakamura Chemical Co., Ltd.), U-15HA (manufactured by Shin-Nakamura Chemical Co., Ltd.), UA-1100H (manufactured by Shin-Nakamura Chemical Co., Ltd.), AH-600 (trade name) manufactured by Kyoeisha Chemical Co., Ltd., and UA-306H, UA-306T, UA-306I, UA-510H, and UX-5000 (all manufactured by Nippon Kayaku Co., Ltd.).

[0279] One preferred embodiment of the polymerizable compound is an ethylenically unsaturated compound having an acid group. Acid groups include phosphate groups, sulfo groups, and carboxy groups. Of these, the acid group is preferably a carboxy group. Examples of the ethylenically unsaturated compound having an acid group include a tri- or tetrafunctional ethylenically unsaturated compound having an acid group [a compound having a carboxy group introduced into a pentaerythritol tri- or tetraacrylate (PETA) skeleton (acid value: 80 to 120 mg KOH / g)], a penta- or hexafunctional ethylenically unsaturated compound having an acid group [a compound having a carboxy group introduced into a dipentaerythritol penta- or hexaacrylate (DPHA) skeleton (acid value: 25 to 70 mg KOH / g)], and the like. These tri- or higher functional ethylenically unsaturated compounds having an acid group may be used in combination with a difunctional ethylenically unsaturated compound having an acid group, if necessary.

[0280] The ethylenically unsaturated compound having an acid group is preferably at least one selected from the group consisting of di- or higher functional ethylenically unsaturated compounds having a carboxy group and carboxylic acid anhydrides thereof. When the ethylenically unsaturated compound having an acid group is at least one selected from the group consisting of di- or higher functional ethylenically unsaturated compounds having a carboxy group and carboxylic acid anhydrides thereof, the developability and film strength are further improved. The di- or higher functional ethylenically unsaturated compound having a carboxy group is not particularly limited and can be appropriately selected from known compounds. Examples of difunctional or higher ethylenically unsaturated compounds having a carboxy 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.).

[0281] As the ethylenically unsaturated compound having an acid group, the polymerizable compound having an acid group described in paragraphs

[0025] to

[0030] of JP-A-2004-239942 is preferred, and the contents of this publication are incorporated herein by reference.

[0282] One preferred embodiment of the polymerizable compound is an ethylenically unsaturated compound having an acid group. Examples of the polymerizable compound include compounds obtained by reacting a polyhydric alcohol with an α,β-unsaturated carboxylic acid, compounds obtained by reacting a glycidyl group-containing compound with an α,β-unsaturated carboxylic acid, urethane monomers such as (meth)acrylate compounds having a urethane bond, phthalic acid compounds such as γ-chloro-β-hydroxypropyl-β'-(meth)acryloyloxyethyl-o-phthalate, β-hydroxyethyl-β'-(meth)acryloyloxyethyl-o-phthalate, and β-hydroxypropyl-β'-(meth)acryloyloxyethyl-o-phthalate, and alkyl (meth)acrylates. These may be used alone or in combination of two or more.

[0283] Examples of compounds obtained by reacting a polyhydric alcohol with an α,β-unsaturated carboxylic acid include bisphenol A-based (meth)acrylate compounds such as 2,2-bis(4-((meth)acryloyloxypolyethoxy)phenyl)propane, 2,2-bis(4-((meth)acryloyloxypolypropoxy)phenyl)propane, and 2,2-bis(4-((meth)acryloyloxypolyethoxypolypropoxy)phenyl)propane; polyethylene glycol di(meth)acrylate having 2 to 14 ethylene oxide groups; polypropylene glycol di(meth)acrylate having 2 to 14 propylene oxide groups; and polyethylene polypropylene glycol di(meth)acrylate having 2 to 14 ethylene oxide groups and 2 to 14 propylene oxide groups. acrylate, trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolpropane ethoxy tri(meth)acrylate, trimethylolpropane diethoxy tri(meth)acrylate, trimethylolpropane triethoxy tri(meth)acrylate, trimethylolpropane tetraethoxy tri(meth)acrylate, trimethylolpropane pentaethoxy tri(meth)acrylate, di(trimethylolpropane) tetraacrylate, tetramethylolmethane tri(meth)acrylate, tetramethylolmethane tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, and dipentaerythritol hexa(meth)acrylate. Among these, ethylenically unsaturated compounds having a tetramethylolmethane structure or a trimethylolpropane structure are preferred, and tetramethylolmethane tri(meth)acrylate, tetramethylolmethane tetra(meth)acrylate, trimethylolpropane tri(meth)acrylate, or di(trimethylolpropane)tetraacrylate is more preferred.

[0284] Examples of the polymerizable compound include caprolactone-modified ethylenically unsaturated compounds (e.g., KAYARAD (registered trademark) DPCA-20 manufactured by Nippon Kayaku Co., Ltd., A-9300-1CL manufactured by Shin-Nakamura Chemical Co., Ltd.), alkylene oxide-modified ethylenically unsaturated compounds (e.g., 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), and ethoxylated glycerin triacrylate (A-GLY-9E manufactured by Shin-Nakamura Chemical Co., Ltd.).

[0285] As the polymerizable compound (particularly, an ethylenically unsaturated compound), one containing an ester bond is particularly preferred, as it provides excellent developability of the photosensitive composition layer after transfer. The ethylenically unsaturated compound containing an ester bond is not particularly limited as long as it contains an ester bond in the molecule. However, in terms of excellent effects of the present invention, an ethylenically unsaturated compound having a tetramethylolmethane structure or a trimethylolpropane structure is preferred, and tetramethylolmethane tri(meth)acrylate, tetramethylolmethane tetra(meth)acrylate, trimethylolpropane tri(meth)acrylate, or di(trimethylolpropane)tetraacrylate is more preferred. From the viewpoint of providing reliability, the ethylenically unsaturated compound preferably contains an ethylenically unsaturated compound having an aliphatic group having 6 to 20 carbon atoms and the above-mentioned ethylenically unsaturated compound having a tetramethylolmethane structure or a trimethylolpropane structure. Examples of ethylenically unsaturated compounds having an aliphatic structure with 6 or more carbon atoms include 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, and tricyclodecane dimethanol di(meth)acrylate.

[0286] One preferred embodiment of the polymerizable compound is a polymerizable compound having an aliphatic hydrocarbon ring structure (preferably a bifunctional ethylenically unsaturated compound). The polymerizable compound is preferably a polymerizable compound having a ring structure in which two or more aliphatic hydrocarbon rings are fused (preferably a structure selected from the group consisting of a tricyclodecane structure and a tricyclodecene structure), more preferably a bifunctional ethylenically unsaturated compound having a ring structure in which two or more aliphatic hydrocarbon rings are fused, and even more preferably tricyclodecane dimethanol di(meth)acrylate. The aliphatic hydrocarbon ring structure is preferably a cyclopentane structure, a cyclohexane structure, a tricyclodecane structure, a tricyclodecene structure, a norbornane structure, or an isoborone structure, in terms of achieving better effects of the present invention.

[0287] One preferred embodiment of the polymerizable compound is a compound having a bisphenol structure (preferably a bifunctional ethylenically unsaturated compound having a bisphenol structure). Of the bisphenol structures, a bisphenol A structure derived from bisphenol A (2,2-bis(4-hydroxyphenyl)propane) is particularly preferred. The polymerizable compound is preferably a compound having a bisphenol A structure (compound BPA1). Among these, the compound BPA1 is preferably a bifunctional ethylenically unsaturated compound having a bisphenol A structure (in other words, a compound (compound BPA2) having a bisphenol A structure and two ethylenically unsaturated groups), more preferably a (meth)acrylate compound having a bisphenol A structure and two (meth)acryloyl groups, and even more preferably 2,2-bis(4-((meth)acryloyloxypolyalkoxy)phenyl)propane. Specific examples of 2,2-bis(4-((meth)acryloyloxypolyalkoxy)phenyl)propane include the compounds exemplified in the description of the polymerizable compound B1. In one embodiment of the polymerizable compound, when the polymerizable compound contains the compound BPA2, the content of the compound BPA2 is preferably 80% by mass or more relative to the total mass of the polymerizable compound. The upper limit is not particularly limited, but is, for example, 100% by mass or less.

[0288] The molecular weight of the polymerizable compound is preferably from 200 to 3,000, more preferably from 250 to 2,600, still more preferably from 280 to 2,200, and particularly preferably from 300 to 2,200.

[0289] In one preferred embodiment of the photosensitive composition layer, the photosensitive composition layer preferably contains a bifunctional ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure and a specific polymer B having a structural unit having an aliphatic hydrocarbon ring.

[0290] In addition, as one of the preferred embodiments of the photosensitive composition layer, the photosensitive composition layer preferably contains a compound represented by Formula (M), a bifunctional ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure, and an ethylenically unsaturated compound having an acid group, more preferably contains 1,9-nonanediol diacrylate, tricyclodecane dimethanol diacrylate, and a polyfunctional ethylenically unsaturated compound having a carboxylic acid group, and even more preferably contains 1,9-nonanediol diacrylate, tricyclodecane dimethanol diacrylate, and a succinic acid modified product of dipentaerythritol pentaacrylate.

[0291] In addition, as one of the preferred embodiments of the photosensitive composition layer, the photosensitive composition layer preferably contains a compound represented by Formula (M), a bifunctional ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure, an ethylenically unsaturated compound having an acid group, and a thermally crosslinkable compound described below, and more preferably contains a compound represented by Formula (M), a bifunctional ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure, an ethylenically unsaturated compound having an acid group, and a blocked isocyanate compound described below.

[0292] In addition, as one of the preferred embodiments of the photosensitive composition layer, the photosensitive composition layer preferably contains a difunctional ethylenically unsaturated compound (preferably a difunctional (meth)acrylate compound) and a trifunctional or higher functional ethylenically unsaturated compound (preferably a trifunctional or higher functional (meth)acrylate compound). The mass ratio of the content of the difunctional ethylenically unsaturated compound to the content of the tri- or higher functional ethylenically unsaturated compound is preferably 10 / 90 to 90 / 10, more preferably 30 / 70 to 70 / 30. The content of the difunctional ethylenically unsaturated compound relative to the total amount of all ethylenically unsaturated compounds is preferably from 20 to 80% by mass, more preferably from 30 to 70% by mass. The content of the bifunctional ethylenically unsaturated compound in the photosensitive composition layer is preferably from 10 to 60% by mass, more preferably from 15 to 40% by mass.

[0293] In addition, as one of the preferred embodiments of the photosensitive composition layer, from the viewpoint of rust prevention, the photosensitive composition layer preferably contains a compound represented by formula (M) and a bifunctional ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure.

[0294] In addition, as one preferred embodiment of the photosensitive composition layer, from the viewpoints of substrate adhesion, suppression of development residues, and rust prevention, the photosensitive composition layer preferably contains a compound represented by formula (M) and an ethylenically unsaturated compound having an acid group, more preferably contains a compound represented by formula (M), a bifunctional ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure, and an ethylenically unsaturated compound having an acid group, still more preferably contains a compound represented by formula (M), a bifunctional ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure, a tri- or higher functional ethylenically unsaturated compound, and an ethylenically unsaturated compound having an acid group, and particularly preferably contains a compound represented by formula (M), a bifunctional ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure, a tri- or higher functional ethylenically unsaturated compound, an ethylenically unsaturated compound having an acid group, and a urethane (meth)acrylate compound.

[0295] Furthermore, as one preferred embodiment of the photosensitive composition layer, from the viewpoints of substrate adhesion, suppression of development residues, and rust prevention, the photosensitive composition layer preferably contains 1,9-nonanediol diacrylate and a polyfunctional ethylenically unsaturated compound having a carboxylic acid group, preferably contains 1,9-nonanediol diacrylate, tricyclodecane dimethanol diacrylate, and a polyfunctional ethylenically unsaturated compound having a carboxylic acid group, more preferably contains 1,9-nonanediol diacrylate, tricyclodecane dimethanol diacrylate, dipentaerythritol hexaacrylate, and an ethylenically unsaturated compound having a carboxylic acid group, and particularly preferably contains 1,9-nonanediol diacrylate, tricyclodecane dimethanol diacrylate, dipentaerythritol hexaacrylate, an ethylenically unsaturated compound having a carboxylic acid group, and a urethane acrylate compound.

[0296] The photosensitive composition layer may contain a monofunctional ethylenically unsaturated compound as the ethylenically unsaturated compound.

[0297] The polymerizable compound (particularly, the ethylenically unsaturated compound) may be used alone or in combination of two or more kinds. The content of the polymerizable compound (particularly, the ethylenically unsaturated compound) in the photosensitive composition layer is preferably 1 to 70 mass %, more preferably 5 to 70 mass %, even more preferably 5 to 60 mass %, and particularly preferably 5 to 50 mass %, relative to the total mass of the photosensitive composition layer.

[0298] <Polymerization initiator> The photosensitive composition layer contains a photopolymerization initiator. A photopolymerization initiator is a compound that initiates polymerization of a polymerizable compound when exposed to actinic rays such as ultraviolet light, visible light, and X-rays. The photopolymerization initiator is not particularly limited, and known photopolymerization initiators can be used. Examples of the photopolymerization initiator include a photoradical polymerization initiator and a photocationic polymerization initiator.

[0299] Of these, the photopolymerization initiator is preferably a photoradical polymerization initiator. Examples of the photoradical polymerization initiator include a photopolymerization initiator having an oxime ester structure (oxime ester-based photopolymerization initiator), a photopolymerization initiator having an α-aminoalkylphenone structure (α-aminoalkylphenone-based photopolymerization initiator), a photopolymerization initiator having an α-hydroxyalkylphenone structure (α-hydroxyalkylphenone-based photopolymerization initiator), a photopolymerization initiator having an acylphosphine oxide structure (acylphosphine oxide-based photopolymerization initiator), and a photopolymerization initiator having an N-phenylglycine structure (N-phenylglycine-based photopolymerization initiator).

[0300] The photoradical polymerization initiator preferably contains at least one selected from the group consisting of an oxime-based photopolymerization initiator, an α-aminoalkylphenone-based photopolymerization initiator, an α-hydroxyalkylphenone-based polymerization initiator, and an N-phenylglycine-based photopolymerization initiator, and more preferably contains at least one selected from the group consisting of an oxime-based photopolymerization initiator, an α-aminoalkylphenone-based photopolymerization initiator, and an N-phenylglycine-based photopolymerization initiator.

[0301] Further, the photoradical polymerization initiator also includes hexaarylbiimidazole derivatives (HABI). Examples of hexaarylbiimidazole derivatives include 2,4,5-triarylimidazole dimers and derivatives thereof, in which the two 2,4,5-triarylimidazole structures may be the same or different. Specific examples of the 2,4,5-triarylimidazole dimer and its derivatives 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.

[0302] Further, examples of the photoradical polymerization initiator include the polymerization initiators described in paragraphs

[0031] to

[0042] of JP-A No. 2011-095716 and paragraphs

[0064] to

[0081] of JP-A No. 2015-014783.

[0303] Commercially available photoradical polymerization initiators include 1-[4-(phenylthio)phenyl]-1,2-octanedione-2-(O-benzoyloxime) [trade name: IRGACURE® 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® OXE03 (manufactured by BASF), IRGACURE® OXE04 (manufactured by BASF), 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone [trade name: Omnirad® 379EG, manufactured by IGM Resins], and the like. 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 (registered trademark) 651, IGM Resins B.oxime esters [trade name: Lunar (registered trademark) 6, manufactured by DKSH Japan Co., Ltd.], 1-[4-(phenylthio)phenyl]-3-cyclopentylpropane-1,2-dione-2-(O-benzoyloxime) (trade name: TR-PBG-305, manufactured by Changzhou Strong Electronic New Materials Co., Ltd.), 1,2-propanedione, 3-cyclohexyl-1-[9-ethyl-6-(2-furanylcarbonyl)-9H-carbazol-3-yl]-, 2-(O-acetyloxime) (trade name: TR-PBG -326, manufactured by Changzhou Powerful Electronic New Materials Co., Ltd.), 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, manufactured by Changzhou Powerful Electronic New Materials Co., Ltd.), and APi-307 (1-(biphenyl-4-yl)-2-methyl-2-morpholinopropan-1-one, manufactured by Shenzhen UV-ChemTech Ltd.).

[0304] The photopolymerization initiator may be used alone or in combination of two or more kinds. When two or more types are used in combination, it is preferable to use an oxime-based photopolymerization initiator in combination with at least one selected from an α-aminoalkylphenone-based photopolymerization initiator and an α-hydroxyalkylphenone-based polymerization initiator. The content of the photopolymerization initiator is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and even more preferably 1.0% by mass or more, based on the total mass of the photosensitive composition layer, and the upper limit thereof is preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably 3% by mass or less, based on the total mass of the photosensitive composition layer.

[0305] <Heterocyclic compounds> The photosensitive composition layer may contain a heterocyclic compound. The heterocyclic ring contained in the heterocyclic compound may be either a monocyclic or polycyclic heterocyclic ring. Examples of heteroatoms contained in the heterocyclic compound include a nitrogen atom, an oxygen atom, and a sulfur atom. The heterocyclic compound preferably contains at least one atom selected from the group consisting of a nitrogen atom, an oxygen atom, and a sulfur atom, and more preferably contains a nitrogen atom.

[0306] Examples of heterocyclic compounds include triazole compounds, benzotriazole compounds, tetrazole compounds, thiadiazole compounds, triazine compounds, rhodanine compounds, thiazole compounds, benzothiazole compounds, benzimidazole compounds, benzoxazole compounds, and pyrimidine compounds. Among the above, the heterocyclic compound is preferably at least one compound selected from the group consisting of triazole compounds, benzotriazole compounds, tetrazole compounds, thiadiazole compounds, triazine compounds, rhodanine compounds, thiazole compounds, benzimidazole compounds, and benzoxazole compounds, and more preferably at least one compound selected from the group consisting of triazole compounds, benzotriazole compounds, tetrazole compounds, thiadiazole compounds, thiazole compounds, benzothiazole compounds, benzimidazole compounds, and benzoxazole compounds.

[0307] Preferable specific examples of the heterocyclic compounds are shown below. Examples of the triazole compounds and benzotriazole compounds include the following compounds.

[0308] [ka]

[0309] [ka]

[0310] Examples of the tetrazole compound include the following compounds.

[0311] [ka]

[0312] [ka]

[0313] Examples of the thiadiazole compound include the following compounds:

[0314] [ka]

[0315] Examples of the triazine compound include the following compounds:

[0316] [ka]

[0317] Examples of rhodanine compounds include the following compounds:

[0318] [ka]

[0319] Examples of the thiazole compound include the following compounds:

[0320] [ka]

[0321] Examples of the benzothiazole compound include the following compounds:

[0322] [ka]

[0323] Examples of the benzimidazole compound include the following compounds:

[0324] [ka]

[0325] [ka]

[0326] Examples of the benzoxazole compound include the following compounds:

[0327] [ka]

[0328] The heterocyclic compounds may be used alone or in combination of two or more. When the photosensitive composition layer contains a heterocyclic compound, the content of the heterocyclic compound is preferably 0.01 to 20.0 mass %, more preferably 0.10 to 10.0 mass %, still more preferably 0.30 to 8.0 mass %, and particularly preferably 0.50 to 5.0 mass %, relative to the total mass of the photosensitive composition layer.

[0329] <Aliphatic thiol compounds> The photosensitive composition layer may contain an aliphatic thiol compound. When the photosensitive composition layer contains an aliphatic thiol compound, the aliphatic thiol compound undergoes an ene-thiol reaction with the radical polymerizable compound having an ethylenically unsaturated group, thereby suppressing the cure shrinkage of the formed film and alleviating stress.

[0330] The aliphatic thiol compound is preferably a monofunctional aliphatic thiol compound or a polyfunctional aliphatic thiol compound (that is, a di- or higher functional aliphatic thiol compound).

[0331] Among the above, polyfunctional aliphatic thiol compounds are preferred as the aliphatic thiol compounds from the viewpoint of the adhesion of the pattern to be formed (particularly the adhesion after exposure).

[0332] In this specification, the term "polyfunctional aliphatic thiol compound" refers to an aliphatic compound having two or more thiol groups (also called "mercapto groups") in the molecule.

[0333] The polyfunctional aliphatic thiol compound is preferably a low molecular weight compound having a molecular weight of at least 100. Specifically, the molecular weight of the polyfunctional aliphatic thiol compound is more preferably 100 to 1,500, and even more preferably 150 to 1,000.

[0334] The number of functional groups in the polyfunctional aliphatic thiol compound is preferably 2 to 10, more preferably 2 to 8, and even more preferably 2 to 6, from the viewpoint of the adhesion of the pattern to be formed.

[0335] Examples of polyfunctional aliphatic thiol compounds include trimethylolpropane tris(3-mercaptobutyrate), 1,4-bis(3-mercaptobutyryloxy)butane, pentaerythritol tetrakis(3-mercaptobutyrate), 1,3,5-tris(3-mercaptobutyryloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, trimethylolethane tris(3-mercaptobutyrate), tris[(3-mercaptopropionyloxy)ethyl]isocyanurate, trimethylolpropane tris(3-mercaptopropionyloxy)ethyl ester), pentaerythritol tetrakis(3-mercaptopropionate), tetraethylene glycol bis(3-mercaptopropionate), dipentaerythritol hexakis(3-mercaptopropionate), ethylene glycol bisthiopropionate, 1,4-bis(3-mercaptobutyryloxy)butane, 1,2-ethanedithiol, 1,3-propanedithiol, 1,6-hexamethylenedithiol, 2,2'-(ethylenedithio)diethanethiol, meso-2,3-dimercaptosuccinic acid, and di(mercaptoethyl)ether.

[0336] Among the above, the polyfunctional aliphatic thiol compound is preferably at least one compound selected from the group consisting of trimethylolpropane tris(3-mercaptobutyrate), 1,4-bis(3-mercaptobutyryloxy)butane, and 1,3,5-tris(3-mercaptobutyryloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione.

[0337] Examples of monofunctional aliphatic thiol compounds include 1-octanethiol, 1-dodecanethiol, β-mercaptopropionic acid, methyl-3-mercaptopropionate, 2-ethylhexyl-3-mercaptopropionate, n-octyl-3-mercaptopropionate, methoxybutyl-3-mercaptopropionate, and stearyl-3-mercaptopropionate.

[0338] The photosensitive composition layer may contain one kind of aliphatic thiol compound alone, or may contain two or more kinds of aliphatic thiol compounds.

[0339] When the photosensitive composition layer contains an aliphatic thiol compound, the content of the aliphatic thiol compound is preferably 5% by mass or more, more preferably 5 to 50% by mass, even more preferably 5 to 30% by mass, and particularly preferably 8 to 20% by mass, relative to the total mass of the photosensitive composition layer.

[0340] <Thermal crosslinkable compound>

[0042] The photosensitive composition layer preferably contains a thermally crosslinkable compound from the viewpoints of the strength of the cured film obtained and the adhesiveness of the uncured film obtained. In this specification, a thermally crosslinkable compound having an ethylenically unsaturated group, which will be described later, is not considered to be an ethylenically unsaturated compound but is considered to be a thermally crosslinkable compound. Examples of the thermally crosslinkable compound include epoxy compounds, oxetane compounds, methylol compounds, and blocked isocyanate compounds. Among these, blocked isocyanate compounds are preferred in terms of the strength of the resulting cured film and the adhesiveness of the resulting uncured film. The blocked isocyanate compound reacts with a hydroxy group and a carboxy group. Therefore, for example, when at least one of the specific polymer B and the 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 function as a protective film tends to be enhanced. 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.

[0341] The dissociation temperature of the blocked isocyanate compound is not particularly limited, but is preferably 100 to 160°C, more preferably 130 to 150°C. The dissociation temperature of a blocked isocyanate means "the temperature of the endothermic peak accompanying the deprotection reaction of the blocked isocyanate when measured by DSC (Differential Scanning Calorimetry) analysis using a differential scanning calorimeter." 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.

[0342] 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 (compounds having a structure represented by -C(=N-OH)- in the molecule, such as formaldoxime, acetaldoxime, acetoxime, methyl ethyl ketoxime, and cyclohexanone oxime). Among these, as the blocking agent having a dissociation temperature of 100 to 160° C., at least one selected from oxime compounds is preferred from the viewpoint of storage stability, for example.

[0343] The blocked isocyanate compound preferably has an isocyanurate structure, for example, from the viewpoint of 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 isocyanuration. Among blocked isocyanate compounds having an isocyanurate structure, compounds having an oxime structure in which an oxime compound is used as a blocking agent are preferred because the dissociation temperature can be more easily adjusted to a preferred range and development residues can be reduced compared to compounds not having an oxime structure.

[0344] 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 radical polymerizable group being preferred. Examples of the polymerizable group include ethylenically unsaturated groups such as a (meth)acryloyloxy 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)acryloyloxy group, and even more preferably an acryloyloxy group.

[0345] 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).

[0346] The thermally crosslinkable compound may be used alone or in combination of two or more kinds. When the photosensitive composition layer contains a thermally crosslinkable compound, the content of the thermally crosslinkable compound is preferably 1 to 50 mass %, more preferably 5 to 30 mass %, based on the total mass of the photosensitive composition layer.

[0347] <Surfactant> The photosensitive composition layer may contain a surfactant. Examples of surfactants include those described in paragraph

[0017] of Japanese Patent No. 4502784 and paragraphs

[0060] to

[0071] of JP-A-2009-237362.

[0348] The surfactant is preferably a fluorine-based surfactant or a silicone-based surfactant. Commercially available fluorine-based surfactants include, for example, Megafac F-171, F-172, F-173, F-176, F-177, F-141, F-142, F-143, F-144, F-437, F-475, F-477, F-479, F-482, F-551-A, F-552, F-554, F-555-A, F-556, F-557, F-558, F-559, and F-5 60, F-561, F-565, F-563, F-568, F-575, F-780, EXP, MFS-330, R-41, R-41-LM, R-01, R-40, R-40-LM, RS-43, TF-1956, RS-90, R-94, RS-72-K, DS-21 (all manufactured by DIC Corporation), Fluorad FC430, FC431, FC171 (all manufactured by Sumitomo 3M Limited), Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, KH-40 (all manufactured by AGC Inc.), PolyFox PF636, PF656, PF6320, PF6520, PF7002 (all manufactured by OMNOVA), Futergent Examples include 710FM, 710FL, 610FM, 601AD, 601ADH2, 602A, 215M, 245F, 251, 212M, 250, 209F, 222F, 208G, 710LA, 710FS, 730LM, 650AC, and 681 (all manufactured by NEOS Corporation). Also suitable for use as fluorosurfactants are acrylic compounds that have a molecular structure with a functional group containing a fluorine atom, and when heated, the functional group containing the fluorine atom is cleaved, causing the fluorine atom to volatilize. Examples of such fluorosurfactants include the Megafac DS series manufactured by DIC Corporation (The Chemical Daily, February 22, 2016; The Nikkei Business Daily, February 23, 2016), such as Megafac DS-21. As the fluorine-based surfactant, it is also preferable to use a polymer of a fluorine atom-containing vinyl ether compound having a fluorinated alkyl group or a fluorinated alkylene ether group and a hydrophilic vinyl ether compound. Furthermore, a block polymer can also be used as the fluorine-based surfactant. Furthermore, as the fluorine-based surfactant, a fluorine-containing polymer compound containing a structural unit derived from a (meth)acrylate compound having a fluorine atom and a structural unit derived from a (meth)acrylate compound having two or more (preferably five or more) alkyleneoxy groups (preferably ethyleneoxy groups, propyleneoxy groups) can also be preferably used. As the fluorine-based surfactant, a fluorine-containing polymer having an ethylenically unsaturated bond-containing group in the side chain can also be used, such as Megafac RS-101, RS-102, RS-718K, and RS-72-K (all manufactured by DIC Corporation). From the viewpoint of improving environmental friendliness, it is preferable that the fluorosurfactant be a surfactant derived from an alternative material to compounds having a perfluoroalkyl group having seven or more carbon atoms, such as perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic acid (PFOS). Examples of nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane, and their ethoxylates and propoxylates (for example, glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid esters, Pluronic (registered trademark) L10, L31, L61, L62, 10R5, 17R2, 25R2 (all manufactured by BASF), Tetronic 304, 701, 704, 901, 904, 150R1 (all manufactured by BASF), and Solsperse 20000 (all manufactured by Lubrizol Nippon Co., Ltd.), NCW-101, NCW-1001, NCW-1002 (all manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), Paionin D-6112, D-6112-W, D-6315 (all manufactured by Takemoto Oil & Fat Co., Ltd.), Olfine E1010, Surfynol 104, 400, 440 (all manufactured by Nissin Chemical Industry Co., Ltd.), and the like.

[0349] Examples of silicone surfactants include linear polymers consisting of siloxane bonds and modified siloxane polymers in which organic groups have been introduced into the side chains or terminals.

[0350] Specific examples of surfactants include DOWSIL 8032 ADDITIVE, Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, and Toray Silicone SH8400 (all manufactured by Toray Dow Corning Co., Ltd.), as well as X-22-4952, X-22-4272, X-22-6266, KF-351A, K354L, KF-355A, and KF- 945, KF-640, KF-642, KF-643, X-22-6191, X-22-4515, KF-6004, KP-341, KF-6001, KF-6002 (all manufactured by Shin-Etsu Silicones Co., Ltd.), F-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (all manufactured by Momentive Performance Materials), BYK307, BYK323, BYK330 (all manufactured by BYK-Chemie), and the like.

[0351] The surfactants may be used alone or in combination of two or more. When the photosensitive composition layer contains a surfactant, the content of the surfactant is preferably 0.01 to 3.0 mass %, more preferably 0.01 to 1.0 mass %, and even more preferably 0.05 to 0.80 mass %, relative to the total mass of the photosensitive composition layer.

[0352] <Polymerization inhibitor> The photosensitive composition layer may contain a polymerization inhibitor. The polymerization inhibitor means a compound having the function of delaying or inhibiting a polymerization reaction. As the polymerization inhibitor, for example, a known compound used as a polymerization inhibitor can be used.

[0353] Examples of the polymerization inhibitor include phenothiazine compounds such as phenothiazine, bis-(1-dimethylbenzyl)phenothiazine, and 3,7-dioctylphenothiazine; bis[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionic acid][ethylenebis(oxyethylene)]2,4-bis[(laurylthio)methyl]-o-cresol, 1,3,5-tris(3,5-di-t-butyl-4-hydroxybenzyl), 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl), 2,4-bis-(n-octylthio)-6-(4-hydroxy-3,5-di-t-butylanilino)-1,3,5-triazine, and pentaerythritol tetrakis 3-(3,5-di-te nitroso compounds or salts thereof such as 4-nitrosophenol, N-nitrosodiphenylamine, N-nitrosocyclohexylhydroxylamine, and N-nitrosophenylhydroxylamine; quinone compounds such as methylhydroquinone, t-butylhydroquinone, 2,5-di-t-butylhydroquinone, and 4-benzoquinone; phenol compounds such as 4-methoxyphenol, 4-methoxy-1-naphthol, and t-butylcatechol; and metal salt compounds such as copper dibutyldithiocarbamate, copper diethyldithiocarbamate, manganese diethyldithiocarbamate, and manganese diphenyldithiocarbamate. Among these, in terms of achieving better effects of the present invention, the polymerization inhibitor is preferably at least one selected from the group consisting of phenothiazine compounds, nitroso compounds or salts thereof, and hindered phenol compounds, and more preferably phenothiazine, bis[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionic acid][ethylenebis(oxyethylene)]2,4-bis[(laurylthio)methyl]-o-cresol, 1,3,5-tris(3,5-di-t-butyl-4-hydroxybenzyl), and N-nitrosophenylhydroxylamine aluminum salt.

[0354] The polymerization inhibitor may be used alone or in combination of two or more kinds. When the photosensitive composition layer contains a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.001 to 5.0 mass%, more preferably 0.01 to 3.0 mass%, and even more preferably 0.02 to 2.0 mass%, relative to the total mass of the photosensitive composition layer. The content of the polymerization inhibitor is preferably 0.005 to 5.0 mass%, more preferably 0.01 to 3.0 mass%, and even more preferably 0.01 to 1.0 mass%, relative to the total mass of the polymerizable compounds.

[0355] <Hydrogen donor compounds> The photosensitive composition layer may contain a hydrogen donating compound. The hydrogen donor compound has the effect of further improving the sensitivity of the photopolymerization initiator to actinic rays and suppressing inhibition of polymerization of the polymerizable compound by oxygen.

[0356] Examples of hydrogen donor compounds include amines and amino acid compounds.

[0357] Examples of amines include compounds described in MRSander et al., Journal of Polymer Society, Vol. 10, p. 3173 (1972), JP-B-44-020189, JP-A-51-082102, JP-A-52-134692, JP-A-59-138205, JP-A-60-084305, JP-A-62-018537, JP-A-64-033104, and Research Disclosure No. 33825. More specific examples include 4,4'-bis(diethylamino)benzophenone, tris(4-dimethylaminophenyl)methane (also known as leuco crystal violet), triethanolamine, p-dimethylaminobenzoic acid ethyl ester, p-formyldimethylaniline, and p-methylthiodimethylaniline. Among these, at least one amine selected from the group consisting of 4,4'-bis(diethylamino)benzophenone and tris(4-dimethylaminophenyl)methane is preferred as the amine, as it provides better effects of the present invention.

[0358] Examples of the amino acid compound include N-phenylglycine, N-methyl-N-phenylglycine, and N-ethyl-N-phenylglycine. Among these, N-phenylglycine is preferred as the amino acid compound in that it provides a more excellent effect of the present invention.

[0359] Further, examples of the hydrogen donor compound include organometallic compounds (such as tributyltin acetate) described in JP-B-48-042965, hydrogen donors described in JP-B-55-034414, and sulfur compounds (such as trithiane) described in JP-A-6-308727.

[0360] The hydrogen donor compounds may be used alone or in combination of two or more. When the photosensitive composition layer contains a hydrogen donor compound, the content of the hydrogen donor compound is preferably 0.01 to 10.0 mass %, more preferably 0.01 to 8.0 mass %, and even more preferably 0.03 to 5.0 mass %, relative to the total mass of the photosensitive composition layer, from the viewpoint of improving the curing rate through a balance between the polymerization growth rate and chain transfer.

[0361] <Impurities, etc.> The photosensitive composition layer may contain a certain 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 these, halide ions, sodium ions, and potassium ions are likely to be mixed in as impurities, so it is preferable to set the contents to the following values.

[0362] The content of impurities in the photosensitive composition layer is preferably 80 ppm or less, more preferably 10 ppm or less, and even more preferably 2 ppm or less, by mass. The content of impurities in the photosensitive composition layer can be 1 ppb or more, or 0.1 ppm or more, by mass.

[0363] Methods for controlling the impurity content within the above range include selecting raw materials for the photosensitive composition layer that contain a small amount of impurities, preventing impurities from being mixed in during the formation of the photosensitive composition layer, and removing them by washing. By such methods, the amount of impurities can be controlled within the above range.

[0364] The amount of impurities can be determined by known methods such as ICP (Inductively Coupled Plasma) emission spectroscopy, atomic absorption spectroscopy, and ion chromatography.

[0365] 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 composition layer is preferably low. The content of these compounds in the photosensitive composition layer is preferably 100 ppm or less, more preferably 20 ppm or less, and even more preferably 4 ppm or less, by mass. The lower limit can be 10 ppb or more, and can be 100 ppb or more, by mass. The content of these compounds can be reduced in the same manner as for the metal impurities described above. Furthermore, they can be quantified by known measurement methods.

[0366] The content of water in the photosensitive composition layer is preferably from 0.01 to 1.0% by mass, more preferably from 0.05 to 0.5% by mass, from the viewpoint of improving reliability and lamination properties.

[0367] <Residual monomer> The photosensitive composition layer may contain residual monomers of the respective structural units of the alkali-soluble resin. 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, relative to the total mass of the alkali-soluble resin. Although there is no particular lower limit, it is preferably 1 ppm by mass or more, and more preferably 10 ppm by mass or more. From the viewpoints of patterning ability and reliability, the residual monomer content of each structural unit of the alkali-soluble resin 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, relative to the total mass of the photosensitive 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.

[0368] The amount of residual monomers in the synthesis of an alkali-soluble resin by a polymer reaction is also preferably within the above range. For example, when the alkali-soluble resin is synthesized by reacting glycidyl acrylate with a carboxylic acid side chain, the content of glycidyl acrylate is preferably within the above range. The amount of residual monomer can be measured by known methods such as liquid chromatography and gas chromatography.

[0369] <Other ingredients> The photosensitive composition layer may contain components other than those already described (hereinafter also referred to as "other components"). Examples of other components include colorants, antioxidants, and particles (e.g., metal oxide particles). Examples of other components include other additives described in paragraphs

[0058] to

[0071] of JP-A No. 2000-310706.

[0370] -particle- The particles are preferably metal oxide particles. The metals in the metal oxide particles also include metalloids such as B, Si, Ge, As, Sb, and Te. The average primary particle size of the particles is preferably from 1 to 200 nm, more preferably from 3 to 80 nm, from the viewpoint of the transparency of the cured film, for example. The average primary particle size of particles is calculated by measuring the particle sizes of 200 random particles using an electron microscope and calculating the arithmetic mean of the measurement results. If the particle shape is not spherical, the particle size is taken to be the longest side.

[0371] When the photosensitive composition layer contains particles, it may contain only one type of particles or two or more types of particles differing in metal species, size, etc. The photosensitive composition layer does not contain particles, or if it does contain particles, the particle content is preferably more than 0 mass% and not more than 35 mass%, relative to the total mass of the photosensitive composition layer; more preferably, it does not contain particles or the particle content is more than 0 mass% and not more than 10 mass%, relative to the total mass of the photosensitive composition layer; even more preferably, it does not contain particles or the particle content is more than 0 mass% and not more than 5 mass%, relative to the total mass of the photosensitive composition layer; even more preferably, it does not contain particles or the particle content is more than 0 mass% and not more than 1 mass%, relative to the total mass of the photosensitive composition layer; and it is particularly preferred that it does not contain particles.

[0372] -Coloring agent- The photosensitive composition layer may contain a small amount of a colorant (pigment, dye, etc.), but preferably does not substantially contain a colorant, for example, from the viewpoint of transparency. When the photosensitive composition layer contains a colorant, the content of the colorant is preferably less than 1% by mass, more preferably less than 0.1% by mass, based on the total mass of the photosensitive composition layer.

[0373] -Antioxidants- Examples of antioxidants include 3-pyrazolidones such as 1-phenyl-3-pyrazolidone (also known as phenidone), 1-phenyl-4,4-dimethyl-3-pyrazolidone, and 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone; polyhydroxybenzenes such as hydroquinone, catechol, pyrogallol, methylhydroquinone, and chlorohydroquinone; paramethylaminophenol, paraaminophenol, parahydroxyphenylglycine, and paraphenylenediamine. Among these, 3-pyrazolidones are preferred as the antioxidant, and 1-phenyl-3-pyrazolidone is more preferred, as they provide better effects of the present invention.

[0374] When the photosensitive composition layer contains an antioxidant, the content of the antioxidant is preferably 0.001% by mass or more, more preferably 0.005% by mass or more, and even more preferably 0.01% by mass or more, relative to the total mass of the photosensitive composition layer. There is no particular upper limit, but it is preferably 1% by mass or less.

[0375] <Thickness of Photosensitive Composition Layer> The thickness of the photosensitive composition layer is not particularly limited, but is often 30 μm or less, and is preferably 20 μm or less, more preferably 15 μm or less, even more preferably 10 μm or less, and particularly preferably 5.0 μm or less, in terms of providing superior effects of the present invention. The lower limit is preferably 0.60 μm or more, more preferably 1.5 μm or more, in terms of providing superior strength to the film obtained by curing the photosensitive composition layer. The thickness of the photosensitive composition layer can be calculated, for example, as the average value of measurements taken at any five points by cross-sectional observation using a scanning electron microscope (SEM).

[0376] <Refractive Index of Photosensitive Composition Layer> The refractive index of the photosensitive composition layer is preferably from 1.47 to 1.56, and more preferably from 1.49 to 1.54.

[0377] <Color of Photosensitive Composition Layer> The photosensitive composition layer is preferably achromatic. Specifically, the total reflection (incident angle 8°, light source: D-65 (2° visual field)) is preferably achromatic in the CIE1976 (L*, a*, b*) color space. * The value is preferably 10 to 90, and a * The value is preferably -1.0 to 1.0, and b * The value is preferably between -1.0 and 1.0.

[0378] The pattern obtained by curing the photosensitive composition layer (cured film of the photosensitive composition layer) is preferably achromatic. Specifically, total reflection (incident angle 8°, light source: D-65 (2° field of view)) is * The value is preferably 10 to 90, and the pattern a * The value is preferably -1.0 to 1.0, and the b * The value is preferably between -1.0 and 1.0.

[0379] <Moisture Permeability of Photosensitive Composition Layer> The moisture permeability of the pattern obtained by curing the photosensitive composition layer (cured film of the photosensitive composition layer) at a film thickness of 40 μm is set to 500 g / m from the viewpoint of rust prevention. 2 / 24hr or less is preferable, and 300g / m 2 / 24hr or less is more preferable, and 100g / m 2 It is more preferable that the time is 24 hours or less. The moisture permeability was measured by exposing the photosensitive composition layer to i-rays at a dose of 300 mJ / cm. 2 After exposure to light at 145° C. for 30 minutes, the photosensitive composition layer is cured and the cured film is measured.

[0380] <<Refractive index adjustment layer>> The transfer film preferably has a refractive index adjusting layer. The refractive index adjusting layer may be a known refractive index adjusting layer. Examples of materials contained in the refractive index adjusting layer include binder polymers, polymerizable compounds, metal salts, and particles. The method for controlling the refractive index of the refractive index adjusting layer is not particularly limited, and examples thereof include a method of using a resin having a predetermined refractive index alone, a method of using a resin and particles, and a method of using a complex of a metal salt and a resin.

[0381] Examples of the binder polymer and polymerizable compound include the binder polymer and polymerizable compound described above in the section "Photosensitive composition layer."

[0382] Examples of particles include metal oxide particles and metal particles. The type of metal oxide particles is not particularly limited, and known metal oxide particles can be used. The metals in the metal oxide particles include semimetals such as B, Si, Ge, As, Sb, and Te.

[0383] The average primary particle size of the particles is preferably from 1 to 200 nm, more preferably from 3 to 80 nm, from the viewpoint of the transparency of the cured film, for example. The average primary particle size of particles is calculated by measuring the particle sizes of 200 random particles using an electron microscope and calculating the arithmetic mean of the measurement results. If the particle shape is not spherical, the particle size is taken to be the longest side.

[0384] Specifically, the metal oxide particles are preferably at least one selected from the group consisting of zirconium oxide particles (ZrO2 particles), Nb2O5 particles, titanium oxide particles (TiO2 particles), silicon dioxide particles (SiO2 particles), and composite particles thereof. Among these, at least one type of metal oxide particles selected from the group consisting of zirconium oxide particles and titanium oxide particles is more preferred, for example, because the refractive index can be easily adjusted.

[0385] Commercially available metal oxide particles include calcined zirconium oxide particles (manufactured by CIK Nanotech Co., Ltd., product name: ZRPGM15WT%-F04), calcined zirconium oxide particles (manufactured by CIK Nanotech Co., Ltd., product name: ZRPGM15WT%-F74), calcined zirconium oxide particles (manufactured by CIK Nanotech Co., Ltd., product name: ZRPGM15WT%-F75), calcined zirconium oxide particles (manufactured by CIK Nanotech Co., Ltd., product name: ZRPGM15WT%-F76), zirconium oxide particles (Nanouse OZ-S30M, manufactured by Nissan Chemical Industries, Ltd.), and zirconium oxide particles (Nanouse OZ-S30K, manufactured by Nissan Chemical Industries, Ltd.).

[0386] The particles may be used alone or in combination of two or more types. The content of particles in the refractive index adjusting layer is preferably 1 to 95 mass %, more preferably 20 to 90 mass %, and even more preferably 40 to 85 mass %, based on the total mass of the refractive index adjusting layer. When titanium oxide is used as the metal oxide particles, the content of the titanium oxide particles is preferably 1 to 95 mass %, more preferably 20 to 90 mass %, and even more preferably 40 to 85 mass %, based on the total mass of the refractive index adjusting layer.

[0387] The refractive index of the refractive index-adjusting layer is preferably higher than the refractive index of the photosensitive composition layer. The refractive index of the refractive index-matching layer is preferably 1.50 or more, more preferably 1.55 or more, even more preferably 1.60 or more, and particularly preferably 1.65 or more. The upper limit of the refractive index of the refractive index-matching layer is preferably 2.10 or less, more preferably 1.85 or less, even more preferably 1.78 or less, and particularly preferably 1.74 or less.

[0388] The thickness of the refractive index adjusting layer is preferably from 50 to 500 nm, more preferably from 55 to 110 nm, and even more preferably from 60 to 100 nm. The thickness of the refractive index adjusting layer is calculated as the average value of measurements at any five points measured by cross-sectional observation using a scanning electron microscope (SEM).

[0389] <<Method for manufacturing transfer film according to the second embodiment>> The method for producing the transfer film of the second embodiment is not particularly limited, and any known method can be used. Examples of a method for manufacturing the transfer film 20 include a method including the steps of applying a photosensitive composition to the surface of the temporary support 11 to form a coating film, and then drying this coating film to form the photosensitive composition layer 13, and applying a composition for forming a refractive index adjusting layer to the surface of the photosensitive composition layer 13 to form a coating film, and then drying this coating film to form the refractive index adjusting layer 15.

[0390] The transfer film 20 is produced by pressing the protective film 17 onto the refractive index adjusting layer 15 of the laminate produced by the above-mentioned production method. As a manufacturing method for the transfer film of the second embodiment, it is preferable to include a step of providing a protective film 17 so that it is in contact with the side of the refractive index adjusting layer 15 opposite the side having the temporary support 11, thereby manufacturing a transfer film 20 comprising the temporary support 11, the photosensitive composition layer 13, the refractive index adjusting layer 15, and the protective film 17. After the transfer film 20 is manufactured by the above manufacturing method, the transfer film 20 may be wound up to produce and store a transfer film in a roll form. The transfer film in a roll form can be provided in that form as it is to the lamination step with a substrate in a roll-to-roll system described below.

[0391] Alternatively, the method for producing the transfer film 20 may include forming a refractive index adjusting layer 15 on a protective film 17, and then forming a photosensitive composition layer 13 on the surface of the refractive index adjusting layer 15. In addition, the method for manufacturing the above-mentioned transfer film 20 may be a method in which a photosensitive composition layer 13 is formed on a temporary support 11, a refractive index adjusting layer 15 is separately formed on a protective film 17, and the refractive index adjusting layer 15 is bonded to the photosensitive composition layer 13 to form the film.

[0392] <Photosensitive composition and method for forming photosensitive composition layer> Specifically, a preferred method for forming the photosensitive composition layer is to apply the photosensitive composition onto a temporary support to form a coating film, and then subject this coating film to a drying treatment at a predetermined temperature to form the photosensitive composition layer. The photosensitive composition preferably contains the various components forming the photosensitive composition layer described above and a solvent. Note that the preferred range of the content of each component in the photosensitive composition relative to the total solid content of the composition is the same as the preferred range of the content of each component relative to the total mass of the photosensitive composition layer described above.

[0393] The solvent is not particularly limited as long as it can dissolve or disperse each component other than the solvent, and known solvents can be used. Specifically, organic solvents are preferred. Examples of organic solvents include methyl ethyl ketone, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate (also known as 1-methoxy-2-propyl acetate), diethylene glycol ethyl methyl ether, cyclohexanone, methyl isobutyl ketone, ethyl lactate, methyl lactate, caprolactam, n-propanol, and 2-propanol.

[0394] Furthermore, as the solvent, an organic solvent having a boiling point of 180 to 250° C. (high boiling point solvent) can also be used, if necessary.

[0395] The solvents may be used alone or in combination of two or more. The total solid content of the photosensitive composition is preferably from 5 to 80 mass %, more preferably from 5 to 40 mass %, and even more preferably from 5 to 30 mass %, based on the total mass of the photosensitive composition. That is, the content of the solvent in the photosensitive composition is preferably 20 to 95 mass %, more preferably 60 to 95 mass %, and even more preferably 70 to 95 mass %, based on the total mass of the photosensitive composition.

[0396] The viscosity of the photosensitive composition at 25°C is, for example, preferably 1 to 50 mPa·s, more preferably 2 to 40 mPa·s, and even more preferably 3 to 30 mPa·s, from the viewpoint of coatability. The viscosity is measured using a viscometer. For example, a viscometer manufactured by Toki Sangyo Co., Ltd. (product name: VISCOMETER TV-22) can be suitably used. However, the viscometer is not limited to the above-mentioned viscometers.

[0397] The surface tension of the photosensitive composition at 25°C is preferably 5 to 100 mN / m, more preferably 10 to 80 mN / m, and even more preferably 15 to 40 mN / m, from the viewpoint of coatability. The surface tension is measured using a surface tensiometer. For example, a surface tensiometer manufactured by Kyowa Interface Science Co., Ltd. (trade name: Automatic Surface Tensiometer CBVP-Z) can be suitably used. However, the surface tensiometer is not limited to the above-mentioned surface tensiometer.

[0398] Examples of methods for applying the photosensitive composition include printing, spraying, roll coating, bar coating, curtain coating, spin coating, and die coating (that is, slit coating).

[0399] The method for drying the coating film of the photosensitive composition is preferably heat drying or vacuum drying. In this specification, "drying" means removing at least a part of the solvent contained in the composition.

[0400] <Composition for forming refractive index adjusting layer and method for forming refractive index adjusting layer> The composition for forming the refractive index adjusting layer preferably contains the various components for forming the refractive index adjusting layer described above and a solvent. Note that in the composition for forming the refractive index adjusting layer, the preferred range of the content of each component relative to the total solid content of the composition is the same as the preferred range of the content of each component relative to the total mass of the refractive index adjusting layer described above. The solvent is not particularly limited as long as it can dissolve or disperse the components contained in the refractive index adjusting layer, and at least one selected from the group consisting of water and water-miscible organic solvents is preferred, and water or a mixed solvent of water and a water-miscible organic solvent is more preferred. Examples of water-miscible organic solvents include alcohols having 1 to 3 carbon atoms, acetone, ethylene glycol, and glycerin, with alcohols having 1 to 3 carbon atoms being preferred, and methanol or ethanol being more preferred. The solvents may be used alone or in combination of two or more. The content of the solvent is preferably 50 to 2,500 parts by mass, more preferably 50 to 1,900 parts by mass, and even more preferably 100 to 900 parts by mass, relative to 100 parts by mass of the total solid content of the composition.

[0401] The method for forming the refractive index adjusting layer is not particularly limited as long as it is a method capable of forming a layer containing the above components, and examples thereof include known coating methods (slit coating, spin coating, curtain coating, inkjet coating, etc.).

[0402] Moreover, by laminating a protective film to the refractive index adjusting layer, the transfer film of the second embodiment can be produced. The method for attaching the protective film to the refractive index adjusting layer is not particularly limited, and known methods can be used. Examples of a device for laminating the protective film to the refractive index adjusting layer include known laminators such as a vacuum laminator and an auto-cut laminator. The laminator is preferably equipped with any heatable roller such as a rubber roller and is capable of applying pressure and heat.

[0403] [Method of manufacturing laminate] By using the above-mentioned transfer film, the composition layer can be transferred to a transfer-receiving body. In particular, the transfer film of the present invention is preferably used in the production of a touch panel. Among these, the method for producing a laminate of the present invention includes a lamination step of contacting a surface of a transfer film opposite to the temporary support with a substrate having a conductive portion and laminating them to obtain a substrate with a composition layer having a substrate, a conductive layer, a composition layer, and a temporary support in this order; an exposure step of pattern-exposing the composition layer; a development step of developing the exposed composition layer to form a protective film pattern that protects the conductive layer, Furthermore, the method for producing a laminate preferably includes a peeling step of peeling the temporary support from the substrate with the composition layer between the laminating step and the exposure step, or between the exposure step and the development step. The procedure of the above steps will be described in detail below.

[0404] [Lamination process] The laminating step is a step of contacting the surface of the transfer film opposite to the temporary support with a substrate having a conductive portion and laminating them together to obtain a substrate with a composition layer having a substrate, a conductive layer, a photosensitive composition layer, and a temporary support in this order. Note that if the transfer film has a protective film, the protective film is peeled off before the laminating step is carried out.

[0405] In the lamination, the conductive layer and the composition layer are pressed together so that their surfaces come into contact with each other. The method of pressure bonding is not particularly limited, and known transfer methods and lamination methods can be used. Among them, it is preferable to place the surface of the composition layer on a substrate having a conductive portion, and then apply pressure and heat using a roll or the like. For lamination, a known laminator such as a vacuum laminator or an auto-cut laminator can be used. The lamination temperature is not particularly limited, but is preferably 70 to 130°C, for example.

[0406] A substrate having a conductive layer has a conductive layer on a substrate, and an optional layer may be formed as necessary. That is, a substrate having a conductive layer is a conductive substrate having at least a substrate and a conductive layer disposed on the substrate.

[0407] Examples of the substrate include a resin substrate, a glass substrate, and a semiconductor substrate. A preferred embodiment of the substrate is described, for example, in paragraph

[0140] of International Publication No. 2018 / 155193, the contents of which are incorporated herein by reference. The resin substrate is preferably made of a cycloolefin polymer or polyimide, and has a thickness of preferably 5 μm to 200 μm, more preferably 10 to 100 μm.

[0408] From the viewpoints of 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. Furthermore, only one conductive layer may be disposed on the substrate, or two or more conductive layers may be disposed on the substrate. When two or more conductive layers are disposed, it is preferable that the conductive layers are made of different materials. A preferred embodiment of the conductive layer is described, for example, in paragraph

[0141] of WO 2018 / 155193, the contents of which are incorporated herein by reference.

[0409] The substrate having a conductive layer is preferably a substrate having at least one of a transparent electrode and a routed wiring. Such a substrate can be suitably used as a touch panel substrate. The transparent electrode can function favorably as an electrode for a touch panel, and is preferably made of a metal oxide film such as ITO (indium tin oxide) or IZO (indium zinc oxide), a metal mesh, or a thin metal wire such as silver nanowire. Examples of the thin metal wires include thin wires of silver, copper, etc. Among these, conductive silver materials such as silver mesh and silver nanowires are preferred.

[0410] The material of the lead wiring is preferably metal. Examples of metals that can be used for the wiring include gold, silver, copper, molybdenum, aluminum, titanium, chromium, zinc, and manganese, as well as alloys of two or more of these metal elements. The wiring is preferably made of copper, molybdenum, aluminum, or titanium, with copper being particularly preferred.

[0411] The touch panel electrode protective film formed using the photosensitive composition layer in the transfer film of the present invention is preferably provided so as to cover the electrodes, etc. directly or via another layer, for the purpose of protecting the electrodes, etc. (i.e., at least one of the touch panel electrodes and the touch panel wiring).

[0412] [Exposure process] The exposure step is a step of pattern-exposing the composition layer. Here, the term "pattern exposure" refers to a form of patterned exposure, that is, exposure in a form in which exposed areas and non-exposed areas exist. The positional relationship between the exposed and unexposed regions in the pattern exposure is not particularly limited and may be adjusted as appropriate. The composition layer may be exposed from the side opposite to the substrate, or from the substrate side of the composition layer.

[0413] The light source for pattern exposure can be appropriately selected and used as long as it can irradiate light in a wavelength range (e.g., 365 nm or 405 nm) that can at least cure the photosensitive composition layer. In particular, the dominant wavelength of the exposure light for pattern exposure is preferably 365 nm. The dominant wavelength is the wavelength with the highest intensity.

[0414] Examples of light sources include various lasers, light-emitting diodes (LEDs), ultra-high pressure mercury lamps, high pressure mercury lamps, and metal halide lamps. The exposure dose is 5 to 200 mJ / cm 2 is preferred, and 10 to 200 mJ / cm 2 is more preferred.

[0415] Preferred embodiments of the light source, exposure dose, and exposure method used for exposure are described, for example, in paragraphs

[0146] to

[0147] of WO 2018 / 155193, the contents of which are incorporated herein by reference.

[0416] By carrying out the exposure step and the development step described below, a protective film pattern that protects at least a part of the conductive layer is formed on the conductive layer on the substrate.

[0417] [Peeling process] The peeling step is a step of peeling the temporary support from the composition layer-carrying substrate 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.

[0418] [Development process] The development step is a step in which the exposed composition layer is developed to form a pattern. The composition layer can be developed using a developer. The developer is preferably an alkaline aqueous solution. Examples of alkaline compounds that can be contained in the alkaline aqueous solution include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, and choline (2-hydroxyethyltrimethylammonium hydroxide).

[0419] Examples of the development method include puddle development, shower development, spin development, and dip development.

[0420] In the present specification, examples of the developer that can be suitably used include the developer described in paragraph

[0194] of WO 2015 / 093271, and examples of the development method that can be suitably used include the development method described in paragraph

[0195] of WO 2015 / 093271.

[0421] [Post-exposure process and post-bake process] The method for producing the laminate may include a step of exposing the pattern obtained by the development step to light (post-exposure step) and / or a step of heating (post-baking step). When both the post-exposure step and the post-bake step are included, it is preferable to carry out the post-bake step after the post-exposure step. Post-exposure exposure dose: 100-5000mJ / cm 2 is preferred, and 200 to 3000 mJ / cm 2is more preferred. The post-baking temperature is preferably 80 to 250°C, more preferably 90 to 160°C. The post-baking time is preferably from 1 to 180 minutes, more preferably from 10 to 60 minutes.

[0422] [Uses of laminate] The laminate produced by the laminate production method of the present invention can be applied to various devices. Examples of devices equipped with the laminate include input devices, preferably touch panels, and more preferably capacitance touch panels. Furthermore, the input devices can be applied to display devices such as organic electroluminescence display devices and liquid crystal display devices. When the laminate is applied to a touch panel, the pattern formed from the composition layer is preferably used as a protective film for a touch panel electrode or a touch panel wiring. That is, the composition layer contained in the transfer film is preferably used to form a protective film for a touch panel electrode or a touch panel wiring.

[0423] [Circuit wiring manufacturing method] By using the transfer film described above, circuit wiring can also be produced. 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. In particular, the method for producing circuit wiring of the present invention includes a lamination step of bringing the surface of the transfer film opposite to the temporary support into contact with a substrate having a conductive layer to obtain a substrate with a composition layer having a substrate, a conductive layer, a composition layer, and a temporary support in this order. an exposure step of pattern-exposing the composition layer; a developing step of developing the exposed 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; Furthermore, the production method preferably includes a peeling step of peeling the temporary support from the substrate with the composition layer between the laminating step and the exposure step, or between the exposure step and the development step.

[0424] The specific steps of the method for manufacturing the circuit wiring will be described below. The laminating step, exposing step, developing step, and peeling step in the manufacturing method of circuit wiring are the same as the laminating step, exposing step, developing step, and peeling step in the manufacturing method of the laminate described above, and the preferred embodiments are also the same.

[0425] [Etching process] The method for manufacturing circuit wiring includes a step (etching step) of 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 (more preferably, a resin pattern manufactured by a manufacturing method including the laminating step, the exposing step, and the developing step) are laminated in this order. In the etching step, the resin pattern obtained from the photosensitive composition layer in the development step is used as an etching resist to etch the conductive layer. As the etching method, known methods can be applied, and examples thereof include the method described in paragraphs

[0209] to

[0210] of JP 2017-120435 A, the method described in paragraphs

[0048] to

[0054] of JP 2010-152155 A, a wet etching method in which the substrate is immersed in an etching solution, and a dry etching method such as plasma etching.

[0426] 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 acidic etching solutions include aqueous solutions of an acidic component selected from hydrochloric acid, sulfuric acid, nitric acid, acetic acid, hydrofluoric acid, oxalic acid, and phosphoric acid, and aqueous solutions 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 multiple acidic components. Examples of alkaline etching solutions include aqueous solutions of alkaline components selected from sodium hydroxide, potassium hydroxide, ammonia, organic amines, and salts of organic amines (e.g., tetramethylammonium hydroxide), as well as aqueous solutions of mixtures of alkaline components and salts (e.g., potassium permanganate). The alkaline component may be a combination of multiple alkaline components.

[0427] [Removal process] In the method for manufacturing 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 can be carried out as needed, 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 using a remover is preferred. The photosensitive composition layer can be removed by immersing the substrate having the remaining resin pattern in a stirring remover solution having a liquid temperature of preferably 30 to 80°C, more preferably 50 to 80°C, for 1 to 30 minutes.

[0428] Examples of the removal solution include a removal solution obtained by dissolving an inorganic or organic alkaline component 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 carried out by a known method such as a spray method, a shower method, or a puddle method using a removal solution.

[0429] [Other steps] The method for manufacturing a circuit wiring may include any steps (other steps) other than the steps described above. For example, examples include a process for reducing visible light reflectance described in paragraph

[0172] of WO 2019 / 022089, and a process for forming a new conductive layer on an insulating film described in paragraph

[0172] of WO 2019 / 022089, but are not limited to these processes.

[0430] <Step of reducing visible light reflectance> The method for manufacturing circuit wiring may include a step of performing a treatment to reduce the visible light reflectance of some or all of the plurality of conductive layers of the substrate. An example of a treatment for reducing the visible light reflectance is oxidation treatment. 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] ,

[0042] ,

[0048] , and

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

[0431] <Step of forming an insulating film, step of forming a new conductive layer on the surface of the insulating film> The method for manufacturing 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 include 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.

[0432] A preferred method for manufacturing circuit wiring involves using a substrate having multiple conductive layers on both surfaces of the substrate, and sequentially or simultaneously forming circuits on the conductive layers formed on both surfaces of the substrate. This configuration allows the formation of touch panel circuit wiring 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 preferred to form such touch panel circuit wiring from both surfaces of the substrate using a roll-to-roll process.

[0433] [Circuit wiring applications] The circuit wiring manufactured by the circuit wiring manufacturing method can be applied to various devices. Examples of devices equipped with the circuit wiring manufactured by the above manufacturing method include input devices, preferably touch panels, and more preferably capacitive touch panels. Furthermore, the input devices can be applied to display devices such as organic electroluminescence (EL) display devices and liquid crystal display devices. [Example]

[0434] The present invention will be described in more detail below with reference to examples. The materials, amounts used, ratios, treatment contents, treatment procedures, etc. shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the examples shown below. Unless otherwise specified, "parts" and "%" are by mass.

[0435] [Examples 1-1 to 1-18 and Comparative Examples 1-1 to 1-3] [Various components contained in the photosensitive composition] The various components used in the photosensitive composition for forming the photosensitive composition layer contained in the transfer films of Examples 1-1 to 1-18 and Comparative Examples 1-1 to 1-3 will be described below.

[0436] <<Polymer>> The polymer used was synthesized by the method described below. First, the GPC measurement conditions for the polymer will be explained below.

[0437] <GPC measurement of polymer> The weight average molecular weight (Mw), number average molecular weight (Mn) of the polymer, and the content ratio of a predetermined component were measured by gel permeation chromatography (GPC) under the following conditions.

[0438] (GPC conditions) Apparatus: Tosoh high-speed GPC apparatus HLC-8420GPC (product name), manufactured by Tosoh Corporation Guard column: Tosoh Corporation, HZ-L Separation column: Three columns of TSK gel Super HZM-N (product name) manufactured by Tosoh Corporation connected in series Measurement temperature: 40℃ Eluent: THF (tetrahydrofuran) Flow rate: Sample pump 0.35 mL / min, reference pump 0.175 mL / min Injection volume: 10μL Detector: differential refractometer GPC column calibration standard solution: Tosoh standard polystyrene

[0439] (Weight average molecular weight (Mw) and number average molecular weight (Mn)) The weight average molecular weight (Mw) and number average molecular weight (Mn) of the polymer were determined by the above-mentioned GPC measurement.

[0440] (Ratio of specified ingredients) The content ratio of components having a molecular weight equivalent to 5 or more times or 10 or more times the number average molecular weight (Mn) was calculated by observing the integrated molecular weight distribution curve (X axis: LogM, Y axis: integrated molecular weight distribution (%)) obtained by the above GPC measurement.

[0441] <Polymer synthesis> Polymer synthesis examples are described below, along with methods for synthesizing the polymers used in Examples 2-1 to 2-13 and Comparative Examples 2-R1 to 2-R4 in the latter part of this document. (Synthesis of polymers 1A and 1B) 124 g of propylene glycol monomethyl ether was placed in a flask, and a mixture of 12 g of methacrylic acid, 58 g of methyl methacrylate, 30 g of ethyl acrylate, and 0.45 g of V-601 (Fujifilm Wako Pure Chemical Industries, Ltd.) as a polymerization initiator was added dropwise over 4 hours at 80°C under a nitrogen stream. After the addition, the mixture was allowed to react at 80°C for 6 hours, and then diluted with propylene glycol monomethyl ether to obtain a polymer solution with a solids concentration of 25% by mass. This polymer was designated Polymer 1. The resulting polymer had a weight-average molecular weight of 63,700, a number-average molecular weight of 25,000, a content of components with a molecular weight at least five times the number-average molecular weight of 18.0%, and a content of components with a molecular weight at least 10 times the number-average molecular weight of 4.6%.

[0442] <High molecular weight component removal method A: synthesis of polymer 1A> While stirring 100 g of the resulting polymer 1 solution, hexane was added in small amounts until the turbidity reached 20 degrees. After stirring for 1 hour, the solution was filtered through a 0.1 micron tetrafluoroethylene filter, and the filtrate was concentrated to remove the hexane, yielding a polymer solution. This was designated polymer 1A. The resulting polymer had a weight-average molecular weight of 63,100, a number-average molecular weight of 24,700, a content of components with a molecular weight at least five times the number-average molecular weight of 16.2%, and a content of components with a molecular weight at least ten times the number-average molecular weight of 2.9%.

[0443] <High molecular weight component removal method B: synthesis of polymer 1B> To 100 g of the resulting polymer 1 solution, hexane was added in small amounts while stirring until the turbidity reached 50 degrees. After stirring for 1 hour, the solution was filtered through a 0.1 micron tetrafluoroethylene filter, and the filtrate was concentrated to remove the hexane, yielding a polymer solution. This was designated polymer 1B. The resulting polymer had a weight-average molecular weight of 63,000, a number-average molecular weight of 24,300, a content of components with a molecular weight at least five times the number-average molecular weight of 14.8%, and a content of components with a molecular weight at least 10 times the number-average molecular weight of 2.2%.

[0444] (Synthesis of polymers 2A and 2B) 124 g of propylene glycol monomethyl ether was placed in a flask, and a mixture of 30 g of methacrylic acid, 70 g of benzyl methacrylate, and 0.8 g of V-601 (Fujifilm Wako Pure Chemical Industries, Ltd.) as a polymerization initiator was added dropwise over 4 hours at 80°C under a nitrogen stream. After the addition, the mixture was allowed to react at 80°C for 6 hours, and then diluted with propylene glycol monomethyl ether to obtain a polymer solution with a solids concentration of 25% by mass. This was designated Polymer 2. Next, the above-mentioned high molecular weight component removal methods A and B were carried out in the same manner except that polymer 1 was changed to polymer 2, thereby obtaining polymers 2A and 2B. The weight average molecular weight, number average molecular weight, content ratio of components having a molecular weight equivalent to at least 5 times the number average molecular weight, content ratio of components having a molecular weight equivalent to at least 10 times the number average molecular weight, and acid value of the obtained polymers 2A and 2B are shown in Table 1.

[0445] (Synthesis of polymers 3A and 3B) 124 g of propylene glycol monomethyl ether was placed in a flask, and a mixture of 29 g of methacrylic acid, 19 g of methyl methacrylate, 52 g of styrene, and 0.45 g of V-601 (Fujifilm Wako Pure Chemical Industries, Ltd.) as a polymerization initiator was added dropwise over 4 hours at 80°C under a nitrogen stream. After the addition, the mixture was allowed to react at 80°C for 6 hours, and then diluted with propylene glycol monomethyl ether to obtain a polymer solution with a solids concentration of 25% by mass. This was designated Polymer 3. Next, the above-mentioned high molecular weight component removal methods A and B were carried out in the same manner except that polymer 1 was changed to polymer 3, thereby obtaining polymers 3A and 3B. The weight average molecular weight, number average molecular weight, content ratio of components having a molecular weight equivalent to at least 5 times the number average molecular weight, content ratio of components having a molecular weight equivalent to at least 10 times the number average molecular weight, and acid value of the obtained polymers 3A and 3B are shown in Table 1.

[0446] (Synthesis of polymers 4A and 4B) 201.2 g of propylene glycol monomethyl ether was placed in a flask and heated to 90°C under a nitrogen stream. A solution containing 172 g of styrene, 4.7 g of methyl methacrylate, 112.1 g of methacrylic acid, and 27.6 g of polymerization initiator V-601 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was added dropwise to the resulting solution over a period of 3 hours. After the addition was completed, 2.5 g of V-601 was added three times every hour. The reaction was then continued for another 3 hours. The mixture was then diluted with 160.7 g of propylene glycol monomethyl ether acetate and 233.3 g of propylene glycol monomethyl ether. Under an air stream, the reaction mixture was heated to 100°C, and 1.8 g of tetraethylammonium bromide and 0.86 g of p-methoxyphenol were added. 71.9 g of glycidyl methacrylate (manufactured by NOF Corporation, Blenmer GH) was added dropwise over a period of 20 minutes. This was reacted at 100° C. for 7 hours, and then diluted with propylene glycol monomethyl ether to obtain a solution of polymer 4 with a solid content concentration of 25% by mass. Next, the above-mentioned high molecular weight component removal methods A and B were carried out in the same manner except that polymer 1 was changed to polymer 4, thereby obtaining polymers 4A and 4B. The weight average molecular weight, number average molecular weight, content ratio of components having a molecular weight equivalent to at least 5 times the number average molecular weight, content ratio of components having a molecular weight equivalent to at least 10 times the number average molecular weight, and acid value of the obtained polymers 4A and 4B are shown in Table 1.

[0447] (Synthesis of polymers 5A and 5B) 405.7 g of propylene glycol monomethyl ether was placed in a flask and heated to 90°C under a nitrogen stream. A solution containing 106.6 g of styrene, 83.5 g of dicyclopentanyl methacrylate, 94.4 g of methacrylic acid, and 15.0 g of polymerization initiator V-601 (Fujifilm Wako Pure Chemical Industries, Ltd.) was added dropwise to the mixture over 3 hours. After the addition was completed, 2.1 g of V-601 was added three times every hour. The mixture was then allowed to react for another 3 hours. The mixture was then diluted with 162.1 g of propylene glycol monomethyl ether acetate and 32.6 g of propylene glycol monomethyl ether. Under an air stream, the reaction mixture was heated to 100°C, and 1.5 g of tetraethylammonium bromide and 0.71 g of p-methoxyphenol were added. 70.8 g of glycidyl methacrylate (NOF Corporation, Blenmer GH) was added dropwise over 20 minutes. This was reacted at 100° C. for 7 hours, and then diluted with propylene glycol monomethyl ether to obtain a solution of polymer 5 with a solid content concentration of 25% by mass. Next, the above-mentioned high molecular weight component removal methods A and B were carried out in the same manner except that polymer 1 was changed to polymer 5, thereby obtaining polymers 5A and 5B. The weight average molecular weight, number average molecular weight, content ratio of components having a molecular weight equivalent to at least 5 times the number average molecular weight, content ratio of components having a molecular weight equivalent to at least 10 times the number average molecular weight, and acid value of the obtained polymers 5A and 5B are shown in Table 1.

[0448] (Synthesis of polymers 6A and 6B) 238.7 g of propylene glycol monomethyl ether acetate and 180.1 g of propylene glycol monomethyl ether were placed in a flask and heated to 90°C under a nitrogen stream. A solution containing 165.2 g of cyclohexyl methacrylate, 4.1 g of methyl methacrylate, 84.1 g of methacrylic acid, and 8.2 g of polymerization initiator V-601 (Fujifilm Wako Pure Chemical Industries, Ltd.) was added dropwise to the mixture over a period of 3 hours. After the addition was complete, 1.8 g of V-601 was added three times every hour. The mixture was then allowed to react for another 3 hours. The mixture was then diluted with 153.7 g of propylene glycol monomethyl ether acetate. Under an air stream, the reaction mixture was heated to 100°C, and 1.5 g of tetraethylammonium bromide and 0.67 g of p-methoxyphenol were added. To this was added dropwise 63.1 g of glycidyl methacrylate (Blenmer GH manufactured by NOF Corporation) over 20 minutes, and the mixture was allowed to react at 100° C. for 7 hours, after which it was diluted with propylene glycol monomethyl ether to obtain a solution of polymer 6 with a solids concentration of 25% by mass. Next, the above-mentioned high molecular weight component removal methods A and B were carried out in the same manner except that polymer 1 was changed to polymer 6, thereby obtaining polymers 6A and 6B. The weight average molecular weight, number average molecular weight, content ratio of components having a molecular weight equivalent to at least 5 times the number average molecular weight, content ratio of components having a molecular weight equivalent to at least 10 times the number average molecular weight, and acid value of the obtained polymers 6A and 6B are shown in Table 1.

[0449] The specific structures of polymers 1 to 6 are shown below. In the following polymers 1 to 6, the numerical values ​​attached to each structural unit are in mass %.

[0450] [ka]

[0451] [Table 1]

[0452] <<Polymerizable compounds>> Polymerizable compound 1: Ethoxylated bisphenol A dimethacrylate (Arkema, SR-480) Polymerizable compound 2: Polypropylene glycol diacrylate (Toagosei Co., Ltd., M-270) Polymerizable compound 3: Trimethylolpropane triacrylate (A-TMPT, manufactured by Shin-Nakamura Chemical Co., Ltd.) Polymerizable compound 4: Dipentaerythritol hexaacrylate (A-DPH, manufactured by Shin-Nakamura Chemical Co., Ltd.) Polymerizable compound 5: m-phenoxybenzyl acrylate (synthesized from m-phenoxybenzyl alcohol and acrylic acid chloride)

[0453] <<Other ingredients>> Photopolymerization initiator 1: 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole (Tokyo Chemical Industry Co., Ltd.) Photopolymerization initiator 2: Irgacure OXE-02 (oxime ester photopolymerization initiator, manufactured by BASF Japan) Sensitizer: 4,4'-bis(diethylamino)benzophenone (Tokyo Chemical Industry Co., Ltd.) Dye: Leuco Crystal Violet (Tokyo Chemical Industry Co., Ltd.) Other ingredients (additive 1): N-phenylglycine (Tokyo Chemical Industry Co., Ltd.) Rust inhibitor: CBT-1 (manufactured by Johoku Chemical Industry Co., Ltd.) Polymerization inhibitor: TDP-G (Kawaguchi Chemical Industry Co., Ltd.) Antioxidant: Phenidone (Tokyo Chemical Industry Co., Ltd.) Surfactant: F-552 (DIC)

[0454] [Preparation of Photosensitive Composition] A photosensitive composition (solid content concentration: 25% by mass) was prepared by mixing the components according to the description in Table 2 and then adding methyl ethyl ketone. The numerical values ​​corresponding to the components listed in Table 2 represent the parts by mass of the solid content. The solid content refers to all components in the composition excluding the solvent (components that form the composition layer formed using the composition).

[0455] [Table 2]

[0456] [Preparation of Intermediate Layer Composition 1] Intermediate layer composition 1 was prepared by mixing the following components. Ion-exchanged water: 38.12 parts Methanol (Mitsubishi Gas Chemical Co., Ltd.): 57.17 parts Kuraray Poval PVA-205 (polyvinyl alcohol, manufactured by Kuraray Co., Ltd.): 3.22 parts Polyvinylpyrrolidone K-30 (manufactured by Nippon Shokubai Co., Ltd.): 1.49 parts Megafac F-444 (fluorine-based surfactant, manufactured by DIC Corporation): 0.0015 parts

[0457] [Preparation of Thermoplastic Resin Composition 1] Thermoplastic resin composition 1 was prepared by mixing the following components. Polymer A-2 (benzyl methacrylate / methacrylic acid (mass ratio 83 / 17) (solid concentration 30.0% propylene glycol monomethyl ether acetate solution): 42.85 parts B-1: Compound with the structure shown below: 0.08 parts C-1: Compound of the structure shown below: 0.32 parts D-3 (NK Ester A-DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.): 4.63 parts D-4 (8UX-015A, manufactured by Taisei Fine Chemical Co., Ltd.): 2.31 parts D-5 (Aronix TO-2349, manufactured by Toagosei Co., Ltd.): 0.77 parts Megafac F-551 (fluorine-based surfactant, manufactured by DIC Corporation): 0.03 parts MEK (methyl ethyl ketone, manufactured by Sankyo Chemical Co., Ltd.): 39.50 parts PGMEA (propylene glycol monomethyl ether acetate, Showa Denko K.K.): 9.51 parts

[0458] [ka]

[0459] [ka]

[0460] [Preparation of Photosensitive Transfer Film] Photosensitive transfer films were prepared so as to have the configurations shown in Table 3. Specifically, the following is the procedure. First, thermoplastic resin composition 1 was applied onto a temporary support PET film (Toray Industries, Inc., Lumirror 16QS62, thickness: 16 μm; arithmetic mean roughness Ra: 0.02 μm) using a slit nozzle so that the coating width would be 1.0 m and the layer thickness would be 4 μm after drying, and the coating was passed through a drying zone at 80°C for 40 seconds to form a thermoplastic resin layer (first layer). Then, intermediate layer composition 1 was applied onto the thermoplastic resin layer using a slit nozzle so that the coating width would be 1.0 m and the layer thickness would be 1.2 μm after drying, and the coating was passed through a drying zone at 80°C for 40 seconds to form an intermediate layer (second layer). Furthermore, the photosensitive composition shown in Table 3 was applied onto the intermediate layer using a slit nozzle so that the coating width would be 1.0 m and the layer thickness would be 3.0 μm after drying, and the coating was passed through a drying zone at 80°C for 40 seconds to form a negative photosensitive composition layer (third layer). A polyethylene film (OSM-N, manufactured by Tredegar) was pressed onto the film as a cover film to prepare a photosensitive transfer film, which was then wound up into a roll.

[0461] 〔evaluation〕 <Evaluation of development residue after storage> In the following evaluation, a polyethylene terephthalate (PET) substrate with a copper layer was used, which was prepared by forming a copper layer with a thickness of 200 nm on a 100 μm thick PET film by sputtering.

[0462] The photosensitive transfer film was unwound and laminated onto the copper-coated PET substrate at a roll temperature of 120°C, a linear pressure of 1.0 MPa, and a linear speed of 0.5 m / min. Without peeling off the temporary support, the film was exposed to an ultra-high pressure mercury lamp through a line-and-space (L / S = 6 μm / 6 μm) pattern mask. After leaving the film for 12 hours, the temporary support was peeled off and the film was developed. Development was performed using a 1.0% aqueous sodium carbonate solution at 25°C for 30 seconds by shower development. When a 6 μm line and space pattern was formed using the above method, the pattern shape and residue in the spaces were observed using a scanning electron microscope (SEM) and evaluated based on the following criteria. In practice, a rating of "C" or higher is preferable, with an "A" rating being most preferable. The results are shown in Table 3. (Evaluation criteria) "A": The pattern was rectangular and no development residue was observed. "B": The pattern had a slight footing shape, and no development residue was observed. "C": The pattern had a footing shape, and no development residue was observed. "D": The pattern had a trailing edge, and slight development residue was observed in the space areas. "E": The pattern had a trailing edge, and development residue was observed over the entire space area.

[0463] <Evaluation of line width uniformity (LWR) of copper wiring patterns> Using the pattern obtained in the evaluation of development residue after standing as a mask, the copper layer was etched using a copper etching solution (Cu-02, Kanto Chemical Co., Ltd.) Specifically, shower etching was performed at 27°C for 40 seconds. Next, the remaining resin pattern was peeled off using a stripping solution (Kanto Chemical Co., Ltd., KP-301) to obtain a copper wiring pattern. The copper wiring pattern was observed from above using an optical microscope to evaluate the line width uniformity (LWR) of the resulting copper pattern. Specifically, the line width was measured at a total of 50 random points, the standard deviation was determined, and 3σ was calculated. The smaller the value, the more uniform the line width and the better the characteristics. In practice, a rating of "C" or higher is preferable, with an "A" rating being the most preferable. The results are shown in Table 3. (Evaluation criteria) "A": Less than 200 nm "B": 200nm or more, less than 250nm "C": 250nm or more, less than 300nm "D": 300nm or more, less than 350nm "E": 350nm or more

[0464] In Table 3, the column "Content ratio (5 times or more)" indicates the content ratio (%) of components with a molecular weight equivalent to 5 times or more the number average molecular weight (Mn) of the polymer. "P" indicates a content ratio of 15.0% or less, and "N" indicates a content ratio of more than 15.0%. In Table 3, the "HABI Presence / Absence" column indicates whether the photosensitive composition (and photosensitive composition layer) contains a hexaarylbiimidazole derivative, with "P" indicating that it contains one and "N" indicating that it does not contain one. In Table 3, the column "Presence or absence of Bis-A" indicates whether the photosensitive composition (and photosensitive composition layer) contains a compound having a bisphenol A structure (compound BPA1), with "P" indicating that it contains it and "N" indicating that it does not contain it. In Table 3, the "Bis-A content" column indicates whether the photosensitive composition (and photosensitive composition layer) contains a compound (compound BPA2) having a bisphenol A structure and two ethylenically unsaturated groups in the molecule, and whether the content of compound BPA2 is 80 mass % or more relative to the total mass of the polymerizable compound. "P" indicates a case that corresponds to the above structure, and "N" indicates a case that does not correspond to the above structure. In Table 3, the column "Bifunctional or higher content" indicates whether the content of the compound having two or more ethylenically unsaturated groups in the molecule in the photosensitive composition (and the photosensitive composition layer) is 90 to 100% by mass relative to the total mass of the polymerizable compounds. "P" indicates a case that corresponds to the above structure, and "N" indicates a case that does not correspond to the above structure. In Table 3, the column "Content of trifunctional or more functional groups" indicates whether the content of the compound having three or more ethylenically unsaturated groups in the molecule in the photosensitive composition (and the photosensitive composition layer) is 0 to 20 mass % relative to the total mass of the polymerizable compounds. "P" indicates a case that corresponds to the above structure, and "N" indicates a case that does not correspond to the above structure. In Table 3, the column "Content of tetrafunctional or more functional groups" indicates whether the content of compounds having four or more ethylenically unsaturated groups in the molecule in the photosensitive composition (and photosensitive composition layer) is 0 to 10 mass % relative to the total mass of the polymerizable compounds. "P" indicates a case that corresponds to the above structure, and "N" indicates a case that does not correspond to the above structure. In Table 3, the column "Content of hexafunctional or higher functional groups" indicates whether the content of compounds having six or more ethylenically unsaturated groups in the molecule in the photosensitive composition (and the photosensitive composition layer) is less than 10 mass % relative to the total mass of the polymerizable compounds. "P" indicates a case that corresponds to the above structure, and "N" indicates a case that does not correspond to the above structure.

[0465] [Table 3]

[0466] From the results in Table 3, it was confirmed that the transfer films of the examples left little development residue even when subjected to development after exposure and subsequent storage. Furthermore, it was confirmed that when etching was performed using the cured film formed from the transfer film as an etching resist film, the LWR performance of the resulting copper pattern was also good. Furthermore, comparisons between Examples 1-1 and 1-2, between Examples 1-3 and 1-4, and between Examples 1-5 and 1-6 confirmed that when the polymer contained in the photosensitive composition layer satisfies all of the above-mentioned requirements 1 to 3, there is less development residue. Furthermore, a comparison of Examples 1-1 to 1-6 confirmed that when the polymer contained in the photosensitive composition layer contains a structural unit containing an aromatic ring, the LWR performance of the resulting copper pattern is more excellent. Furthermore, a comparison of Examples 1-6 to 1-18 confirmed that when the photosensitive composition layer contains a compound having a bisphenol A structure, there is less development residue and the LWR performance of the resulting copper pattern is better (see in particular the results of Example 1-12). Furthermore, a comparison of Examples 1-6 to 1-18 confirmed that when the content of the compound having a bisphenol A structure and two ethylenically unsaturated groups in the molecule in the photosensitive composition layer was 80% by mass or more, relative to the total mass of the polymerizable compounds, the LWR performance of the resulting copper pattern was more excellent (see, in particular, the results of Examples 1-7 to 1-9 and 1-15). Furthermore, a comparison of Examples 1-7 to 1-9 and 1-15 confirmed that when the content of the compound having six or more ethylenically unsaturated groups in the molecule was less than 10% by mass, relative to the total mass of the polymerizable compounds, the development residue was smaller (see, in particular, the result of Example 1-9). Furthermore, a comparison of Examples 1-7 to 1-9 and 1-15 confirmed that when the content of the compound having three or more ethylenically unsaturated groups in the molecule was 0 to 20% by mass, relative to the total mass of the polymerizable compounds, the development residue was smaller (see, in particular, the result of Example 1-15). Furthermore, a comparison of Examples 1-6 to 1-18 confirmed that when the photosensitive composition layer contained a hexaarylbiimidazole derivative, the LWR performance of the resulting copper pattern was more excellent (see, in particular, the result of Example 1-11). Furthermore, a comparison of Examples 1-6 to 1-18 confirmed that when the content of the compound having two or more ethylenically unsaturated groups in the molecule in the photosensitive composition layer is 90 to 100 mass% relative to the total mass of the polymerizable compound, the LWR performance of the obtained copper pattern is better (see, in particular, the result of Example 1-14). Furthermore, a comparison of Examples 1-6 to 1-18 confirmed that when the content of the compound having four or more ethylenically unsaturated groups in the molecule in the photosensitive composition layer is 0 to 10 mass% (preferably 0 mass% or more and less than 10 mass%) relative to the total mass of the polymerizable compound, the LWR performance of the obtained copper pattern is better (see in particular the result of Example 1-16).

[0467] [Examples 2-1 to 2-13 and Comparative Examples 2-1 to 2-4] [Various ingredients] The various components used in the photosensitive composition for forming the photosensitive composition layer contained in the transfer films of Examples 2-1 to 2-13 and Comparative Examples 2-1 to 2-4 will be described below.

[0468] <<Polymer>> The polymers used were the above-mentioned polymers 1, 1A, and 1B, polymers 4, 4A, and 4B, polymers 5, 5A, and 5B, and polymers 6, 6A, and 6B.

[0469] <<Polymerizable compounds>> A-DCP: Tricyclodecane dimethanol diacrylate (A-DCP manufactured by Shin-Nakamura Chemical Co., Ltd.) A-NOD-N: 1,9-nonanediol diacrylate (A-NOD-N manufactured by Shin-Nakamura Chemical Co., Ltd.) DPHA: Dipentaerythritol hexaacrylate (A-DPH manufactured by Shin-Nakamura Chemical Co., Ltd.) TO-2349: Dipentaerythritol polyacrylate modified with succinic acid, a 5-6 functional monomer (monomer with carboxyl groups) TMPT: Trimethylolpropane triacrylate (A-TMPT manufactured by Shin-Nakamura Chemical Co., Ltd.) DTMPT: Ditrimethylolpropane tetraacrylate (KAYARAD T-1420(T) manufactured by Nippon Kayaku Co., Ltd.)

[0470] <<Photopolymerization initiator>> OXE-02: Oxime ester photoinitiator (BASF, Irgacure OXE02) Omnirad 907: α-aminoalkylphenone photoinitiator (IGM Resins BV, Omnirad 907) OXE-01: Oxime ester photoinitiator (BASF, Irgacure OXE01) OXE-03: Oxime ester photoinitiator (BASF, Irgacure OXE03) Omnirad 379EG: α-aminoalkylphenone photoinitiator (IGM Resins BV, Omnirad 379EG) Compound Y: APi-307 (1-(biphenyl-4-yl)-2-methyl-2-morpholinopropan-1-one, manufactured by Shenzhen UV-ChemTech Ltd.)

[0471] <<Thermal crosslinkable compounds>> Blocked isocyanate 1: Duranate TPA-B80E (manufactured by Asahi Kasei Corporation) Blocked isocyanate 2: Compound with the following structure

[0472] [ka]

[0473] <<Other Ingredients>> N-phenylglycine: manufactured by Tokyo Chemical Industry Co., Ltd. Benzimidazole: manufactured by Tokyo Chemical Industry Co., Ltd. Isonicotinamide: manufactured by Tokyo Chemical Industry Co., Ltd. Tetrazole: 5-amino-1H-tetrazole (Chiyoda Chemical Co., Ltd., B6030) SMA EF-40: Styrene / maleic anhydride copolymer (4:1 molar ratio) (anhydride content: 1.94 mmol / g, Mw: 10500, Cray Valley) Megafac F551A: Fluorine-based surfactant (DIC Corporation, Megafac F551A)

[0474] [Preparation of Photosensitive Composition] A photosensitive composition (solid content concentration: 25% by mass) was prepared by mixing and dissolving each component in the formulation shown in Table 4 with propylene glycol monomethyl ether acetate / propylene glycol monomethyl ether / methyl ethyl ketone in a mass ratio of 18 / 60 / 22. The numerical values ​​corresponding to the components shown in Table 4 represent the parts by mass of the solid content. The solid content refers to all components in the composition excluding the solvent (components that form the composition layer formed using the composition).

[0475] [Table 4]

[0476] [Preparation of photosensitive transfer film 1] Photosensitive transfer films were prepared so as to have the configurations shown in Table 4. Specifically, the following is the procedure. <Formation of Photosensitive Composition Layer> The photosensitive composition shown in Table 3 was applied onto a 16 μm thick polyethylene terephthalate film (Toray, 16KS40) (temporary support) using a slit nozzle so that the thickness after drying would be 5.0 μm, and the coating was dried at 100°C for 2 minutes to form a photosensitive composition layer (first layer).

[0477] <Formation of refractive index adjustment layer> Next, a refractive index adjusting layer-forming composition having the following formulation 201 was applied onto the photosensitive composition layer so as to have a thickness of 70 nm after drying, and then dried at 80°C for 1 minute, followed by further drying at 110°C for 1 minute to form a refractive index adjusting layer (second layer). The refractive index adjusting layer had a thickness of 70 nm and a refractive index of 1.68. Note that Formulation 201 is prepared using a resin having an acid group and an aqueous ammonia solution, and the resin having an acid group is neutralized with the aqueous ammonia solution. That is, the refractive index adjustment layer forming composition contains an ammonium salt of a resin having an acid group.

[0478] ·Refractive index adjustment layer forming composition: Formulation 201 ·Acrylic resin (resin having an acid group, copolymer resin of methacrylic acid / methacrylic acid allyl, weight average molecular weight 25,000, composition ratio (molar ratio) = 40 / 60): 0.29 parts ·Aronix TO-2349 (monomer having a carboxylic acid group, manufactured by Toagosei Co., Ltd.): 0.04 parts ·Nano Use OZ-S30M (ZrO2 particles, solid content 30.5%, methanol 69.5%, refractive index 2.2, average particle size: a...

Claims

1. A transfer film having a temporary support and a composition layer, the composition layer includes a photosensitive composition layer, The photosensitive composition layer contains a polymer, a polymerizable compound, and a photopolymerization initiator that satisfy both of the following requirements 1 and 2: The transfer film, wherein the photopolymerization initiator comprises a hexaarylbiimidazole derivative. Requirement 1: The number average molecular weight, calculated as standard polystyrene, obtained by gel permeation chromatography is 3,000 to 50,000. Requirement 2: The content of components having a molecular weight equivalent to 10 times or more of the number average molecular weight, as determined from an integrated molecular weight distribution curve converted into standard polystyrene by gel permeation chromatography, is 3.0% or less.

2. The transfer film according to claim 1 , wherein the polymer further satisfies the following requirement 3: Requirement 3: The content ratio of components having a molecular weight equivalent to at least five times the number average molecular weight, as determined from an integrated molecular weight distribution curve in terms of standard polystyrene obtained by gel permeation chromatography, is 15.0% or less.

3. The transfer film according to claim 1 or 2, wherein the polymerizable compound comprises a compound BPA1 having a bisphenol A structure.

4. the compound BPA1 includes a compound BPA2 having a bisphenol A structure and two ethylenically unsaturated groups in the molecule; The transfer film according to claim 3 , wherein the content of the compound BPA2 is 80% by mass or more based on the total mass of the polymerizable compound.

5. 5. The transfer film according to claim 1, wherein the content of the compound having two or more ethylenically unsaturated groups in the molecule in the polymerizable compound is 90 to 100% by mass relative to the total mass of the polymerizable compound.

6. The transfer film according to any one of claims 1 to 5, wherein the content of the compound having three or more ethylenically unsaturated groups in the molecule in the polymerizable compound is 0 to 20 mass% relative to the total mass of the polymerizable compound.

7. 7. The transfer film according to claim 1, wherein the content of the compound having four or more ethylenically unsaturated groups in the molecule in the polymerizable compound is 0 to 10 mass% relative to the total mass of the polymerizable compound.

8. The transfer film according to any one of claims 1 to 7, wherein the polymer contains at least one of a structural unit having an aromatic group and a structural unit having an aliphatic hydrocarbon ring group.

9. The transfer film according to any one of claims 1 to 8, wherein the polymer comprises a structural unit having a polymerizable group.

10. The transfer film according to any one of claims 1 to 9, which is used for forming a protective film for a touch panel.

11. The transfer film according to any one of claims 1 to 9, which is used for forming an etching resist film.

12. a lamination 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 laminating the surface to obtain a composition layer-attached substrate having the substrate, the conductive layer, the composition layer, and the temporary support in this order; an exposure step of pattern-exposing the composition layer; a developing step of developing the exposed composition layer to form a protective film pattern that protects the conductive layer; The method for producing a laminate further comprises a peeling step of peeling the temporary support from the composition layer-formed substrate between the laminating step and the exposing step, or between the exposing step and the developing step.

13. The method for producing a laminate according to claim 12 , wherein the substrate having the conductive layer is a substrate having at least one of a touch panel electrode and a touch panel wiring.

14. a lamination step of bringing a surface of the transfer film according to any one of claims 1 to 9 opposite to the temporary support into contact with a substrate having a conductive layer to obtain a composition layer-attached substrate having the substrate, the conductive layer, the composition layer, and the temporary support in this order; an exposure step of pattern-exposing the composition layer; a developing step of developing the exposed 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 composition layer between the laminating step and the exposure step, or between the exposure step and the development step.

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