Method for manufacturing resin pattern, method for manufacturing circuit wiring, method for manufacturing touch panel, and photosensitive transfer member

Abstract

Provided are: a resin pattern manufacturing method for forming a resin pattern on a substrate using a photosensitive transfer member having a temporary support and a photosensitive resin layer, wherein the pattern width at the portion of the resin pattern in contact with the substrate is at least 0.2 μm larger than the pattern width at the position where the height is 90% of the maximum height of the resin pattern; a circuit wiring manufacturing method; a touch panel manufacturing method; and a photosensitive transfer member comprising a temporary support and a photosensitive resin layer, wherein when a resin pattern A having a pattern width of 6 μm at the position where the height is 90% of the maximum height is formed on a substrate, the pattern width of the resin pattern A at the portion in contact with the substrate is at least 6.2 μm, in the cross section of the resin pattern A in the width direction.

Description

[Technical field]

[0001] The present disclosure relates to a method for producing a resin pattern, a method for producing circuit wiring, a method for producing a touch panel, and a photosensitive transfer member. [Background technology]

[0002] In display devices (such as organic electroluminescence (EL) display devices and liquid crystal display devices) equipped with a touch panel such as a capacitance-type input device, conductive layer patterns such as an electrode pattern corresponding to the sensor of the visible area, and wiring of the peripheral wiring portion and the extraction wiring portion are provided inside the touch panel. Generally, in forming a patterned layer, the number of steps required to obtain a desired pattern shape is small, and therefore a method is widely used in which a layer of a photosensitive resin composition provided on a substrate using a photosensitive transfer member is exposed through a mask having a desired pattern and then developed.

[0003] Furthermore, as conventional photosensitive resin compositions, those described in JP-A-2014-209173 and JP-A-2011-209426 are known. Japanese Patent Application Laid-Open No. 2014-209173 describes a photosensitive resin composition comprising (A) an acid-modified photosensitive epoxy resin and (B) a non-photosensitive carboxylic acid resin having a styrene skeleton and a weight-average molecular weight of 10,000 to 50,000.

[0004] Japanese Patent Application Laid-Open No. 2011-209426 describes a photosensitive resin composition comprising an alkali-soluble resin, a compound having a quinone diazide structure, and a nitrogen-containing heterocyclic compound having at least one structure selected from the group consisting of a pyrrole structure, an isoxazole structure, a thiazole structure, an isothiazole structure, a pyridine structure, an indole structure, a quinoline structure, and an isoquinoline structure. Summary of the Invention [Problem to be solved by the invention]

[0005] An object of one embodiment of the present invention is to provide a method for producing a resin pattern having excellent resolution. Another problem to be solved by another embodiment of the present invention is to provide a method for manufacturing circuit wiring and a method for manufacturing a touch panel, which are excellent in resolution. Furthermore, a problem to be solved by another embodiment of the present invention is to provide a photosensitive transfer member having excellent resolution. [Means for solving the problem]

[0006] Means for solving the above problems include the following aspects. <1> A method for manufacturing a resin pattern, which forms a resin pattern on a substrate using a photosensitive transfer member having a temporary support and a photosensitive resin layer, wherein the pattern width at a portion of the resin pattern in contact with the substrate is 0.2 μm or more larger than the pattern width at a position that is 90% of the maximum height of the resin pattern from the substrate. <2> The thickness of the photosensitive resin layer is 8 μm or less. <1> 2. A method for producing a resin pattern according to claim 1 . <3> The thickness of the temporary support is 25 μm or less. <1> or <2> 2. A method for producing a resin pattern according to claim 1 . <4> The value obtained by subtracting the pattern width at a position corresponding to 90% of the maximum height of the resin pattern from the pattern width at the portion of the resin pattern in contact with the substrate is 0.2 μm or more and 2.4 μm or less. <1> ~ <3> 13. A method for producing a resin pattern according to any one of the above items. <5> The photosensitive resin layer contains a polymerizable compound and a binder polymer. <1> ~ <4> 13. A method for producing a resin pattern according to any one of the above items. <6> The ratio Mm / Mb of the content Mm of the polymerizable compound to the content Mb of the binder polymer in the photosensitive resin layer is 0.9 or less. <5> 2. A method for producing a resin pattern according to claim 1 . <7> The polymerizable compound in the photosensitive resin layer contains a (meth)acrylic compound, and the content of the acrylic compound relative to the total mass of the (meth)acrylic compound contained in the photosensitive resin layer is 60 mass % or less. <5> or <6> 2. A method for producing a resin pattern according to claim 1 . <8> The resin pattern to be manufactured includes a resin pattern having a pattern width of 6 μm or less. <1> ~ <7> 13. A method for producing a resin pattern according to any one of the above items. <9> the substrate has a conductive layer on a surface on which the resin pattern is formed, <1> ~ <8> 13. A method for producing a circuit wiring, comprising: a step of etching the conductive layer in an area where the resin pattern is not arranged in a laminate having the resin pattern on the substrate produced by the method for producing a resin pattern described in any one of claims 1 to 12, to form a circuit wiring. <10> the substrate has a conductive layer on a surface on which the resin pattern is formed, <1> ~ <8> 2. A method for manufacturing a touch panel, comprising the step of: etching the conductive layer in an area where the resin pattern is not disposed in a laminate having the resin pattern on the substrate manufactured by the method for manufacturing a resin pattern described in any one of claims 1 to 11, to form wiring for a touch panel. <11> A photosensitive transfer member having a temporary support and a photosensitive resin layer, wherein when a resin pattern A having a pattern width of 6 μm at a position that is 90% of the maximum height from the substrate is formed on a substrate using the photosensitive transfer member, the pattern width of the resin pattern A at a cross section in the width direction at the portion in contact with the substrate is 6.2 μm or more. Effect of the Invention

[0007] According to one embodiment of the present invention, a method for producing a resin pattern having excellent resolution can be provided. According to another embodiment of the present invention, a method for manufacturing a circuit wiring having excellent resolution and a method for manufacturing a touch panel can be provided. Furthermore, according to another embodiment of the present invention, a photosensitive transfer member having excellent resolution can be provided. [Brief description of the drawings]

[0008] [Figure 1] FIG. 1 is a schematic cross-sectional view in the width direction of a resin pattern formed in a method for producing a resin pattern according to the present disclosure. [Diagram 2] FIG. 2 is a schematic diagram showing an example of the layer structure of a photosensitive transfer member used in the present disclosure. [Diagram 3] FIG. 3 is a schematic diagram showing pattern A. [Figure 4] FIG. 4 is a schematic diagram showing pattern B. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0009] The present disclosure will be described below with reference to the accompanying drawings, in which reference numerals may be omitted. In addition, in this specification, a numerical range expressed using "to" means a range that includes the numerical values ​​before and after "to" as the lower limit and upper limit. In addition, in this specification, "(meth)acrylic" refers to both or either of acrylic and methacrylic, and "(meth)acrylate" refers to both or either of acrylate and methacrylate. Furthermore, in this specification, when a plurality of substances corresponding to each component are present in the composition, the amount of each component in the composition means the total amount of the corresponding substances present in the composition, unless otherwise specified. 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. In the description of groups (atomic groups) in this specification, when there is no indication of substituted or unsubstituted, the term encompasses both unsubstituted and substituted groups. For example, the term "alkyl group" encompasses not only alkyl groups without a substituent (unsubstituted alkyl groups) but also alkyl groups with a substituent (substituted alkyl groups). In this specification, unless otherwise specified, "exposure" includes not only exposure using light, but also drawing using particle beams such as electron beams and ion beams. In addition, examples of light used for exposure generally include the bright line spectrum of a mercury lamp, far ultraviolet light represented by an excimer laser, extreme ultraviolet light (EUV light), X-rays, electron beams, and other actinic rays (active energy rays). In addition, chemical structural formulas in this specification may be described as simplified structural formulas in which hydrogen atoms are omitted. In the present disclosure, "mass %" and "weight %" are synonymous, and "parts by mass" and "parts by weight" are synonymous. Also, in the present disclosure, combinations of two or more preferred aspects are more preferred aspects. In addition, unless otherwise specified, the weight average molecular weight (Mw) and number average molecular weight (Mn) in the present disclosure are molecular weights detected by a gel permeation chromatography (GPC) analyzer using columns of TSKgel GMHxL, TSKgel G4000HxL, or TSKgel G2000HxL (all product names manufactured by Tosoh Corporation) in a solvent of THF (tetrahydrofuran) and a differential refractometer, and converted using polystyrene as a standard substance.

[0010] [Method of manufacturing resin patterns] The method for producing a resin pattern according to the present disclosure is a method for producing a resin pattern on a substrate using a photosensitive transfer member having a temporary support and a photosensitive resin layer, wherein in a cross section of the resin pattern in the width direction, the pattern width at a portion of the resin pattern in contact with the substrate is 0.2 μm or more larger than the pattern width at a position corresponding to 90% of the maximum height of the resin pattern from the substrate.

[0011] In order to achieve higher definition of photosensitive resin compositions, reduction in film thickness has been investigated. In the case of thin-film resists, if they are developed, etched, or otherwise processed under the same conditions as conventional thick-film resists, excessive development and etching may occur, resulting in an undesirable shape (undercut, peeling, uneven shapes, etc.). In particular, if etching is excessive, the etching may progress deep into the lower part of the resist (so-called side etching), causing damage to the resist layer itself and causing the wiring to disappear, making it difficult to miniaturize the resin pattern. On the other hand, resists are generally required to have a rectangular shape to ensure etching linearity and uniformity of the linear shape, and are designed to obtain good linearity by, for example, extending the etching time. However, when the resist is thinned as described above, it becomes difficult to perform etching for a long time.

[0012] The present inventors have found that the resolution is insufficient in conventional methods for producing a resin pattern that forms a cross-sectional shape of a pattern. As a result of extensive investigations, the present inventors have found that the method for producing a resin pattern having the above-mentioned configuration provides excellent resolution. Although the detailed mechanism by which the above effect is manifested is unknown, it is presumed that, in a cross section of the resin pattern in the width direction, the pattern width at the portion of the resin pattern in contact with the substrate is 0.2 μm or more larger than the pattern width at a position that is 90% of the maximum height of the resin pattern from the substrate. Therefore, during etching using the resin pattern, since the width of the portion of the resin pattern in contact with the substrate is large, the progress of side etching can be slowed down, and even with a small etching pattern, the occurrence of etching defects such as pattern thinning and breakage can be suppressed, resulting in an etching pattern with excellent resolution (also simply referred to as "resolution").

[0013] Furthermore, in order to prevent etching defects, the etching resist is usually required to have a rectangular shape without residue or tailing. On the other hand, the method for producing a resin pattern according to the present disclosure is designed to deliberately design the resist shape after development to have a trailing edge, thereby slowing down the etching rate and preventing excessive etching. In other words, the method for producing a resin pattern according to the present disclosure is an invention having a technical concept opposite to that of conventional negative resist designs.

[0014] The method for producing a resin pattern according to the present disclosure is a method for producing a resin pattern, which forms a resin pattern on a substrate using a photosensitive transfer member having a temporary support and a photosensitive resin layer. A preferred embodiment of the photosensitive transfer member used in the present disclosure will be described later. The photosensitive transfer member used in the method for producing a resin pattern according to the present disclosure is preferably a negative-type photosensitive transfer member. Furthermore, the resin pattern produced by the method for producing a resin pattern according to the present disclosure can be suitably used as an etching resist.

[0015] In the method for producing a resin pattern according to the present disclosure, the width of the resin pattern at a portion where the resin pattern contacts the substrate is 0.2 μm or more larger than the width of the resin pattern at a position corresponding to 90% of the maximum height of the resin pattern from the substrate in a cross section in the width direction of the resin pattern. When the width is 0.2 μm or more larger, the progression of side edges during etching can be delayed, resulting in excellent resolution. Furthermore, in the method for producing a resin pattern according to the present disclosure, in a cross section of the resin pattern in the width direction, the value obtained by subtracting the pattern width at a position corresponding to 90% of the maximum height of the resin pattern from the pattern width at the portion of the resin pattern in contact with the substrate (the value of the pattern width at the portion of the resin pattern in contact with the substrate - the pattern width at a position corresponding to 90% of the maximum height of the resin pattern) is, from the viewpoints of resolution and linearity, preferably from 0.2 μm to 3.0 μm, more preferably from 0.2 μm to 2.4 μm, even more preferably from 0.3 μm to 2.0 μm, and particularly preferably from 0.4 μm to 2.0 μm.

[0016] In the present disclosure, the method for measuring the pattern width at 90% of the maximum height of the resin pattern from the substrate in the cross section in the width direction of the resin pattern and the pattern width at the portion of the resin pattern in contact with the substrate is as follows: the substrate having the resin pattern is cut in the width direction of the resin pattern, and the cut resin pattern and substrate are observed from the cut surface side by a scanning electron microscope to measure each pattern width. Note that the pattern width at 90% of the maximum height of the resin pattern and the pattern width at the portion of the resin pattern in contact with the substrate are average values ​​of measurements at 10 points.

[0017] In the present disclosure, "cross section of the resin pattern in the width direction" refers to a cross section in a plane parallel to the width and thickness directions of the substrate, for example, a cross section in a plane perpendicular to the line direction of a resin pattern that is a line and space. In addition, in the present disclosure, "a position at X% of the maximum height of the resin pattern in the cross section of the resin pattern in the width direction" refers to a position at a height from the substrate that is X% of the maximum height of the resin pattern in the cross section of the resin pattern in the width direction. Furthermore, in the present disclosure, it is preferable that the resin pattern has a hardness higher than that of the uncured photosensitive resin layer.

[0018] FIG. 1 is a schematic cross-sectional view in the width direction of a resin pattern formed in a method for producing a resin pattern according to the present disclosure. 1 has footing portions 4a on both sides of the resin pattern 4 near the portion in contact with the substrate 2. In addition, in Fig. 1, the height of 90% of the maximum height of the resin pattern 4 from the substrate 2 is H90, the pattern width at the position of 90% of the maximum height of the resin pattern 4 is L1, and the pattern width at the portion of the resin pattern 4 in contact with the substrate 2 is L2.

[0019] Furthermore, in the method for producing a resin pattern according to the present disclosure, when a resin pattern A having a pattern width of 6 μm at a position that is 90% of the maximum height from the substrate is formed on a substrate, the pattern width of the resin pattern A in a cross section in the width direction at the portion in contact with the substrate is, from the viewpoints of resolution and linearity, preferably 6.2 μm or more, more preferably 6.2 μm or more and 9.0 μm or less, even more preferably 6.2 μm or more and 8.4 μm or less, particularly preferably 6.3 μm or more and 8.0 μm or less, and most preferably 6.4 μm or more and 8.0 μm or less.

[0020] In the method for producing a resin pattern according to the present disclosure, it is not necessary for all of the resin patterns to be resin patterns in which, in a cross section in the width direction of the resin pattern, the pattern width at the portion in contact with the substrate is 0.2 μm or more larger than the pattern width at 90% of the maximum height from the substrate. Of the resin patterns produced using the photosensitive transfer member observed in a direction perpendicular to the surface direction of the substrate, the proportion of resin patterns in which, in a cross section in the width direction of the resin pattern, the pattern width at the portion in contact with the substrate is 0.2 μm or more larger than the pattern width at 90% of the maximum height of the resin pattern is preferably 50 area % or more, more preferably 80 area % or more, and particularly preferably 90 area % or more.

[0021] Furthermore, in the method for producing a resin pattern according to the present disclosure, in a cross section of the resin pattern in the width direction, the value of the pattern width at a position that is 90% of the maximum height of the resin pattern minus the pattern width at a position that is 50% of the maximum height of the resin pattern is, from the viewpoints of resolution and linearity, preferably from -0.5 μm to 1.0 μm, more preferably from -0.2 μm to 0.5 μm, even more preferably from -0.2 μm to 0.2 μm, and particularly preferably from -0.1 μm to 0.1 μm.

[0022] From the viewpoints of resolution and linearity, the resin pattern produced by the resin pattern production method according to the present disclosure is preferably a resin pattern in which, in a cross section in the width direction of the resin pattern, the pattern width gradually increases from a position of 5% to 40% of the maximum height of the resin pattern toward the substrate, more preferably a resin pattern in which the pattern width gradually increases from a position of 10% to 30% of the maximum height of the resin pattern toward the substrate, and particularly preferably a resin pattern in which the pattern width gradually increases from a position of 15% to 25% of the maximum height of the resin pattern toward the substrate.

[0023] Furthermore, in the method for producing a resin pattern according to the present disclosure, in a cross section of the resin pattern in the width direction, the value of the pattern width at a position that is 90% of the maximum height of the resin pattern from the substrate minus the pattern width at a position that is 5% of the maximum height of the resin pattern from the substrate is, from the viewpoints of resolution and linearity, preferably from 0.1 μm to 2.5 μm, more preferably from 0.1 μm to 2.0 μm, even more preferably from 0.15 μm to 1.8 μm, and particularly preferably from 0.2 μm to 1.5 μm.

[0024] From the viewpoint of better exerting the effects of the present disclosure, the resin pattern produced by the resin pattern producing method according to the present disclosure preferably includes a resin pattern having a pattern width of 10 μm or less, more preferably includes a resin pattern having a pattern width of 8 μm or less, even more preferably includes a resin pattern having a pattern width of 6 μm or less, and particularly preferably includes a resin pattern having a pattern width of 1 μm or more and 6 μm or less. Moreover, from the viewpoint of further exerting the effects of the present disclosure, the resin pattern produced by the method for producing a resin pattern according to the present disclosure preferably has a line and space pattern. Furthermore, from the viewpoint of further exerting the effects of the present disclosure, the resin pattern produced by the method for producing a resin pattern according to the present disclosure is preferably an etching resist pattern for forming wiring, more preferably an etching resist pattern for circuit wiring, and particularly preferably an etching resist pattern for circuit wiring including wiring having a width of 6 μm or less.

[0025] The maximum height of the resin pattern produced by the resin pattern production method according to the present disclosure is also related to the thickness of the photosensitive resin layer described below, but from the viewpoint of better exerting the effects of the present disclosure, it is preferably 20 μm or less, more preferably 10 μm or less, even more preferably 8 μm or less, and particularly preferably 2 μm or more and 8 μm or less.

[0026] Furthermore, it is preferable that the resin pattern produced by the method for producing a resin pattern according to the present disclosure includes a resin pattern in which the value of the pattern width at a position that is 90% of the maximum height of the resin pattern from the substrate / the maximum height of the resin pattern is in the following numerical range: In order to better exert the effects of the present disclosure, the value of the pattern width at a position that is 90% of the maximum height of the resin pattern from the substrate / the maximum height of the resin pattern is preferably 2 or less, more preferably 1.5 or less, even more preferably 1 or less, and particularly preferably 0.5 or more and 0.8 or less.

[0027] The method for producing a resin pattern according to the present disclosure is a method for producing a resin pattern, which forms a resin pattern on a substrate using a photosensitive transfer member having a temporary support and a photosensitive resin layer. As a method for producing a resin pattern, a method including, in this order, a step of bonding a photosensitive transfer member and a substrate (preferably a substrate having conductivity) by contacting the substrate with the second surface of the photosensitive resin layer, i.e., the surface not facing the temporary support (hereinafter also referred to as the "bonding step"), a step of exposing the photosensitive resin layer to a pattern (hereinafter also referred to as the "exposure step"), and a step of developing the exposed photosensitive resin layer to form a resin pattern (hereinafter also referred to as the "development step").

[0028] <Lamination process> The method for producing the resin pattern preferably includes a lamination step. In the lamination step, it is preferable to bring a substrate (or a conductive layer, if a conductive layer is provided on the surface of the substrate) into contact with the second surface of the photosensitive resin layer, and to press the photosensitive transfer member and the substrate together. In the above embodiment, the adhesion between the second surface of the photosensitive resin layer and the substrate is improved, and therefore the photosensitive transfer member can be suitably used as an etching resist when etching the conductive layer of the patterned photosensitive resin layer after exposure and development.

[0029] When the photosensitive transfer member has a cover film, the cover film may be removed from the surface of the photosensitive resin layer before lamination. In addition, in the case where the photosensitive transfer member further comprises a layer other than the cover film (e.g., a high refractive index layer and / or a low refractive index layer) on the surface of the photosensitive resin layer that does not face the temporary support, the bonding process is carried out in such a manner that the surface of the photosensitive resin layer that does not have the temporary support is bonded to the substrate via that layer.

[0030] The method for bonding the substrate and the photosensitive transfer member by pressure is not particularly limited, and known transfer methods and lamination methods can be used. The photosensitive transfer member is preferably laminated to the substrate by placing the substrate on the second surface side of the photosensitive resin layer and applying pressure and heat using a roll or other means. For the lamination, a known laminator such as a laminator, a vacuum laminator, or an autocut laminator that can further increase productivity can be used.

[0031] The method for producing a resin pattern and the method for producing a circuit wiring, which include the lamination step, are preferably carried out by a roll-to-roll method. The roll-to-roll method will be described below. The roll-to-roll method refers to a method in which a substrate that can be wound up and unwound is used as the substrate, and includes a step of unwinding the substrate or a structure including the substrate (also referred to as an "unwinding step") before any step included in the method for manufacturing a resin pattern or a method for manufacturing a circuit wiring, and a step of winding up the substrate or the structure including the substrate (also referred to as a "winding step") after any step, in which at least any step (preferably all steps, or all steps other than the heating step) is performed while the substrate or the structure including the substrate is being transported. The unwinding method in the unwinding step and the winding method in the winding step are not particularly limited, and any known method may be used in a production method that employs a roll-to-roll system.

[0032] <Substrate> As the substrate used in the method for producing a resin pattern according to the present disclosure, any known substrate may be used, but a substrate having a conductive layer is preferred, and a substrate having a conductive layer on the surface thereof is more preferred. The substrate may have any layer other than the conductive layer, if necessary.

[0033] Examples of the base material constituting the substrate include glass, silicon, and films. The base material constituting the substrate is preferably transparent. In this specification, the term "transparent" means that the transmittance of light with a wavelength of 400 nm to 700 nm is 80% or more. The refractive index of the substrate constituting the substrate is preferably 1.50 to 1.52.

[0034] The transparent glass substrate may be a tempered glass such as Gorilla Glass manufactured by Corning Inc. In addition, the transparent glass substrate may be made of the materials described in JP-A-2010-86684, JP-A-2010-152809, and JP-A-2010-257492.

[0035] When a film substrate is used as the substrate, it is preferable to use a film substrate having small optical distortion and / or high transparency. Examples of such a film substrate include polyethylene terephthalate (PET), polyethylene naphthalate, polycarbonate, triacetyl cellulose, and cycloolefin polymer.

[0036] When the substrate is produced by a roll-to-roll method, a film substrate is preferable. When a circuit wiring for a touch panel is produced by a roll-to-roll method, the substrate is preferably a sheet-shaped resin composition.

[0037] The conductive layer of the substrate may be a conductive layer used for general circuit wiring or touch panel wiring. From the viewpoints of electrical conductivity and fine line formability, the conductive layer is preferably at least one layer selected from the group consisting of a metal layer, a conductive metal oxide layer, a graphene layer, a carbon nanotube layer, and a conductive polymer layer, more preferably a metal layer, and even more preferably a copper layer or a silver layer. The substrate may have one conductive layer or two or more conductive layers. When the substrate has two or more conductive layers, the conductive layers are preferably made of different materials.

[0038] Materials for the conductive layer include metals and conductive metal oxides. Metals include Al, Zn, Cu, Fe, Ni, Cr, Mo, Ag and Au. Examples of conductive metal oxides include indium tin oxide (ITO), indium zinc oxide (IZO), and SiO2. In this specification, "conductive" means a material having a volume resistivity of 1×10 6 The volume resistivity of conductive metal oxides is less than 1×10 4 Less than Ωcm is preferred.

[0039] When a resin pattern is produced using a substrate having a plurality of conductive layers, at least one of the plurality of conductive layers preferably contains a conductive metal oxide. The conductive layer is preferably an electrode pattern corresponding to a sensor of a visual recognition portion used in a capacitive touch panel or wiring of a peripheral extraction portion.

[0040] <Exposure process> The method for producing a resin pattern preferably includes, after the lamination step, a step of pattern-exposing the photosensitive resin layer (exposure step).

[0041] The detailed arrangement and specific size of the pattern in the pattern exposure are not particularly limited. In order to improve the display quality of a display device (e.g., a touch panel) equipped with an input device having a circuit wiring manufactured by the manufacturing method for circuit wiring and to reduce the area occupied by the lead wiring, at least a part of the pattern (preferably the electrode pattern of the touch panel and / or the lead wiring part) preferably includes a thin line having a width of 20 μm or less, more preferably includes a thin line having a width of 10 μm or less.

[0042] The light source used for exposure can be appropriately selected and used as long as it irradiates light with a wavelength (e.g., 365 nm or 405 nm) that can expose the photosensitive resin layer. Specific examples include ultra-high pressure mercury lamps, high pressure mercury lamps, metal halide lamps, and LEDs (Light Emitting Diodes).

[0043] The exposure dose was 5 mJ / cm 2 ~200mJ / cm 2 is preferred, and 10 mJ / cm 2 ~100mJ / cm 2 is more preferred.

[0044] In the exposure step, the temporary support may be peeled off from the photosensitive resin layer and then pattern exposure may be performed, or the temporary support may be peeled off after pattern exposure via the temporary support. In order to prevent contamination of the photosensitive resin layer due to contact between the photosensitive resin layer and the mask, and to avoid the influence of foreign matter attached to the mask on the exposure, it is preferable to perform pattern exposure via the temporary support. The pattern exposure may be exposure via a mask, or may be direct exposure using an exposure means such as a laser.

[0045] <Developing process> The method for producing a resin pattern preferably includes, after the above-mentioned exposure step, a step of developing the exposed photosensitive resin layer to form a resin pattern (development step). When the photosensitive transfer member has a thermoplastic resin and an intermediate layer, the thermoplastic resin layer and the intermediate layer in the non-exposed area are removed together with the photosensitive resin layer in the non-exposed area in the development step. In addition, the thermoplastic resin layer and the intermediate layer in the exposed area may also be removed in a form dissolved or dispersed in the developer in the development step.

[0046] In the development step, the exposed photosensitive resin layer can be developed using a developer. The developer is not particularly limited as long as it can remove the non-image areas (non-exposed areas) of the photosensitive resin layer, and known developers such as the developer described in JP-A-5-72724 can be used. The developer is preferably an aqueous alkaline developer containing a compound having a pKa of 7 to 13 at a concentration of 0.05 mol / L to 5 mol / L (liter). The developer may contain a water-soluble organic solvent and / or a surfactant. The developer is also preferably the developer described in paragraph 0194 of WO2015 / 093271.

[0047] The development method is not particularly limited, and may be any of paddle development, shower development, shower and spin development, and dip development. Shower development is a development treatment in which a developer is sprayed by shower onto the photosensitive resin layer after exposure to remove the unexposed area. After the development step, it is preferable to remove development residues by spraying a cleaning agent by showering and scrubbing with a brush. The temperature of the developer is not particularly limited, but is preferably from 20°C to 40°C.

[0048] <Cover film peeling process> When the photosensitive transfer member has a cover film, the method for producing a resin pattern preferably includes a step of peeling off the cover film from the photosensitive transfer member. The method for peeling off the cover film is not limited, and a known method can be applied.

[0049] <Other processes> The method for producing a resin pattern may include any steps (other steps) other than the steps described above, such as, but not limited to, the following steps.

[0050] The photosensitive transfer member used in the present disclosure will now be described in detail.

[0051] <Photosensitive transfer member> The photosensitive transfer member used in the present disclosure includes at least a temporary support and a photosensitive resin layer. In the photosensitive transfer member, the temporary support and the photosensitive resin layer may be laminated directly without any other layer therebetween, or may be laminated via another layer. Also, another layer may be laminated on the surface of the photosensitive resin layer opposite to the surface facing the temporary support. Examples of layers other than the temporary support and the photosensitive resin layer include a thermoplastic resin layer, an intermediate layer, and a cover film.

[0052] [Temporary Support] The photosensitive transfer member used in this disclosure includes a temporary support. The temporary support is a peelable support that supports the photosensitive resin layer or the laminate including the photosensitive resin layer.

[0053] The temporary support preferably has light transmittance from the viewpoint of enabling exposure of the photosensitive resin layer through the temporary support when the photosensitive resin layer is subjected to patternwise exposure. In this specification, "having light transmittance" means that the transmittance of light of the wavelength used for patternwise exposure is 50% or more. From the viewpoint of improving the exposure sensitivity of the photosensitive resin layer, the temporary support preferably has a transmittance of 60% or more, more preferably 70% or more, for light having a wavelength used for pattern exposure (more preferably a wavelength of 365 nm). The transmittance of the layer of the photosensitive transfer member is the ratio of the intensity of the emitted light that passes through the layer to the intensity of the incident light when the light is incident in a direction perpendicular to the main surface of the layer (thickness direction), and is measured using an MCPD Series manufactured by Otsuka Electronics Co., Ltd.

[0054] Examples of materials constituting the temporary support include a glass substrate, a resin film, and paper. From the viewpoints of strength, flexibility, and light transmittance, a resin film is preferred. Examples of the resin film include a polyethylene terephthalate (PET) film, a cellulose triacetate film, a polystyrene film, and a polycarbonate film. Among these, a PET film is preferable, and a biaxially stretched PET film is more preferable.

[0055] The thickness (layer thickness) of the temporary support is not particularly limited, and may be selected according to the material from the standpoints of strength as a support, flexibility required for bonding to a substrate for forming circuit wiring, and light transmittance required in the initial exposure step. The thickness of the temporary support is preferably in the range of 5 μm to 100 μm, and from the viewpoints of ease of handling and versatility, more preferably in the range of 10 μm to 50 μm, further preferably in the range of 10 μm to 20 μm, particularly preferably in the range of 10 μm to 16 μm. The thickness of the temporary support is preferably 50 μm or less, and more preferably 25 μm or less, from the viewpoints of resolution and linearity when exposure is performed through the temporary support.

[0056] Furthermore, the film used as the temporary support is preferably free from deformations such as wrinkles, scratches, defects, and the like. From the viewpoint of pattern formability during pattern exposure through the temporary support and the transparency of the temporary support, it is preferable that the number of fine particles, foreign matter, defects, precipitates, etc. contained in the temporary support is small. The number of fine particles, foreign matter, and defects with a diameter of 1 μm or more is 50 / 10 mm. 2 It is preferable that the number of pieces is less than 10 pieces / 10 mm. 2 More preferably, 3 pieces / 10 mm or less. 2 More preferably, 0 pieces / 10 mm or less. 2 It is particularly preferred that:

[0057] Preferred embodiments of the temporary support are described, for example, in paragraphs 0017 to 0018 of JP 2014-85643 A, paragraphs 0019 to 0026 of JP 2016-27363 A, paragraphs 0041 to 0057 of WO 2012 / 081680 A, paragraphs 0029 to 0040 of WO 2018 / 179370 A, and paragraphs 0012 to 0032 of JP 2019-101405 A, the contents of which are incorporated herein by reference.

[0058] [Photosensitive resin layer] The photosensitive transfer member used in the present disclosure comprises a photosensitive resin layer.

[0059] The photosensitive resin layer is preferably a negative type photosensitive resin layer in which the solubility of the exposed portion in a developer is reduced by exposure and the non-exposed portion is removed by development. However, the photosensitive resin layer is not limited to a negative type photosensitive resin layer, and may be a positive type photosensitive resin layer in which the solubility of the exposed portion in a developer is increased by exposure and the exposed portion is removed by development.

[0060] The photosensitive resin layer preferably contains a polymerizable compound and a binder polymer, more preferably contains a polymerizable compound, a binder polymer, and a photopolymerization initiator, and particularly preferably contains polymer A, a polymerizable compound, and a photopolymerization initiator. The photosensitive resin layer preferably contains, based on the total mass of the photosensitive resin layer, 10% by mass to 90% by mass of the binder polymer, 5% by mass to 70% by mass of the polymerizable compound, and 0.01% by mass to 20% by mass of the photopolymerization initiator. Each component will be described in turn below.

[0061] (Binder polymer) The photosensitive resin layer preferably contains a binder polymer. The binder polymer is not particularly limited, and suitable examples thereof include known binder polymers used in etching resists. Moreover, examples of the binder polymer include alkali-soluble polymers. The alkali-soluble polymer is preferably an alkali-soluble polymer having an acid group. Among these, the binder polymer is preferably the polymer A described below.

[0062] -Polymer A- As the binder polymer, it is preferable to contain polymer A. The polymer A is preferably an alkali-soluble polymer. The alkali-soluble polymer includes polymers that are easily soluble in alkaline substances.

[0063] The acid value of polymer A is preferably 220 mgKOH / g or less, more preferably less than 200 mgKOH / g, and even more preferably less than 190 mgKOH / g, from the viewpoint of suppressing swelling of the photosensitive resin layer by the developer and thereby achieving superior resolution. The lower limit of the acid value of polymer A is not particularly limited, but from the viewpoint of better developability, it is preferably 60 mgKOH / g or more, more preferably 120 mgKOH / g or more, even more preferably 150 mgKOH / g or more, and particularly preferably 170 mgKOH / g or more.

[0064] The acid value is the mass [mg] of potassium hydroxide required to neutralize 1 g of a sample, and is expressed in units of mgKOH / g in this specification. The acid value can be calculated, for example, from the average content of acid groups in a compound. The acid value of the polymer A may be adjusted by changing the type of structural unit constituting the polymer A and the content of the structural unit containing an acid group.

[0065] The weight average molecular weight of the polymer A is preferably 5,000 to 500,000. The weight average molecular weight of 500,000 or less is preferable from the viewpoint of improving resolution and developability. The weight average molecular weight is more preferably 100,000 or less, even more preferably 60,000 or less, and particularly preferably 50,000 or less. On the other hand, the weight average molecular weight of 5,000 or more is preferable from the viewpoint of controlling the properties of the development aggregate and the properties of the unexposed film such as edge fuse property and cut chip property when the film is made into a photosensitive resin laminate. The weight average molecular weight is more preferably 10,000 or more, even more preferably 20,000 or more, and particularly preferably 30,000 or more. The edge fuse property refers to the degree of the tendency of the photosensitive resin layer to protrude from the end face of the roll when the photosensitive transfer member is wound into a roll. The cut chip property refers to the degree of the tendency of the chip to fly when the unexposed film is cut with a cutter. If these chips adhere to the upper surface of the photosensitive resin laminate, they will be transferred to a mask in a subsequent exposure step, causing defective products. The polydispersity of polymer A is preferably 1.0 to 6.0, more preferably 1.0 to 5.0, even more preferably 1.0 to 4.0, and even more preferably 1.0 to 3.0. In the present disclosure, the molecular weight is a value measured using gel permeation chromatography. The polydispersity is the ratio of the weight average molecular weight to the number average molecular weight (weight average molecular weight / number average molecular weight).

[0066] From the viewpoint of suppressing line width thickening and deterioration of resolution when the focal position is shifted during exposure, the photosensitive resin layer preferably contains a monomer component having an aromatic hydrocarbon group as the polymer A. Examples of such aromatic hydrocarbon groups include substituted or unsubstituted phenyl groups and substituted or unsubstituted aralkyl groups. The content of the monomer component having an aromatic hydrocarbon group in the polymer A is preferably 20% by mass or more, more preferably 30% by mass or more, even more preferably 40% by mass or more, particularly preferably 45% by mass or more, and most preferably 50% by mass or more, based on the total mass of all monomer components. The upper limit is not particularly limited, but is preferably 95% by mass or less, more preferably 85% by mass or less. In the case where multiple types of polymer A are contained, the content of the monomer component having an aromatic hydrocarbon group was calculated as a weight average value.

[0067] Examples of the monomer having an aromatic hydrocarbon group include a monomer having an aralkyl group, styrene, and a polymerizable styrene derivative (e.g., methylstyrene, vinyltoluene, tert-butoxystyrene, acetoxystyrene, 4-vinylbenzoic acid, styrene dimer, styrene trimer, etc.). Among them, a monomer having an aralkyl group or styrene is preferred. In one embodiment, when the monomer component having an aromatic hydrocarbon group in the polymer A is styrene, the content of the styrene monomer component is preferably 20% by mass to 50% by mass, more preferably 25% by mass to 45% by mass, further preferably 30% by mass to 40% by mass, and particularly preferably 30% by mass to 35% by mass, based on the total mass of all the monomer components.

[0068] 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.

[0069] An example of the monomer having a phenylalkyl group is phenylethyl (meth)acrylate.

[0070] 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. Among these, benzyl (meth)acrylate is preferred. In one embodiment, when the monomer component having an aromatic hydrocarbon group in the polymer A is benzyl (meth)acrylate, the content of the benzyl (meth)acrylate monomer component is preferably 50% by mass to 95% by mass, more preferably 60% by mass to 90% by mass, further preferably 70% by mass to 90% by mass, and particularly preferably 75% by mass to 90% by mass, based on the total mass of all monomer components.

[0071] The polymer A containing a monomer component having an aromatic hydrocarbon group is preferably obtained by polymerizing a monomer having an aromatic hydrocarbon group with at least one type of a first monomer described below and / or at least one type of a second monomer described below.

[0072] The polymer A not containing a monomer component having an aromatic hydrocarbon group is preferably obtained by polymerizing at least one type of first monomer described later, and more preferably obtained by copolymerizing at least one type of first monomer with at least one type of second monomer described later.

[0073] 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 first monomer in polymer A is preferably 5% by mass to 50% by mass, more preferably 10% by mass to 40% by mass, and even more preferably 15% by mass to 30% by mass, based on the total mass of all monomer components.

[0074] In this specification, "(meth)acrylic acid" means acrylic acid or methacrylic acid, "(meth)acryloyl group" means acryloyl group or methacryloyl group, and "(meth)acrylate" means "acrylate" or "methacrylate".

[0075] The copolymerization ratio of the first monomer is preferably 10% by mass to 50% by mass based on the total mass of all monomer components. The copolymerization ratio of 10% by mass or more is preferable from the viewpoint of achieving good developability and controlling edge fusing properties, and is more preferably 15% by mass or more, and even more preferably 20% by mass or more. The copolymerization ratio of 50% by mass or less is preferable from the viewpoint of high resolution and foot shape of the resist pattern, and furthermore from the viewpoint of chemical resistance of the resist pattern, and from these viewpoints, it is more preferably 35% by mass or less, even more preferably 30% by mass or less, and particularly preferably 27% by mass or less.

[0076] The second monomer is a monomer that is non-acidic and has at least one polymerizable unsaturated group in the molecule. Examples of the second monomer include (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, cyclohexyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate; esters of vinyl alcohol such as vinyl acetate; and (meth)acrylonitrile. Among them, methyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and n-butyl (meth)acrylate are preferred, and methyl (meth)acrylate is particularly preferred. The content of the second monomer in polymer A is preferably 5% by mass to 60% by mass, more preferably 15% by mass to 50% by mass, and even more preferably 20% by mass to 45% by mass, based on the total mass of all monomer components.

[0077] It is preferable to contain a monomer having an aralkyl group and / or styrene as a monomer from the viewpoint of suppressing line width thickening and deterioration of resolution when the focal position is shifted during exposure. For example, a copolymer containing methacrylic acid, benzyl methacrylate, and styrene, or a copolymer containing methacrylic acid, methyl methacrylate, benzyl methacrylate, and styrene is preferable. In one embodiment, the polymer A is preferably a polymer containing 25% to 40% by mass of a monomer component having an aromatic hydrocarbon group, 20% to 35% by mass of a first monomer component, and 30% to 45% by mass of a second monomer component. In another embodiment, the polymer A is preferably a polymer containing 70% to 90% by mass of a monomer component having an aromatic hydrocarbon group, and 10% to 25% by mass of the first monomer component.

[0078] The polymer A may have a linear structure, a branched structure, or an alicyclic structure in the side chain. By using a monomer containing a group having a branched structure in the side chain, or a monomer containing a group having an alicyclic structure in the side chain, a branched structure or an alicyclic structure can be introduced into the side chain of the polymer A. The group having an alicyclic structure may be monocyclic or polycyclic.

[0079] Specific examples of monomers containing a group having a branched structure in the side chain include isopropyl (meth)acrylate, isobutyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, isoamyl (meth)acrylate, tert-amyl (meth)acrylate, sec-amyl (meth)acrylate, 2-octyl (meth)acrylate, 3-octyl (meth)acrylate, and tert-octyl (meth)acrylate, etc. Among these, isopropyl (meth)acrylate, isobutyl (meth)acrylate, and tert-butyl methacrylate are preferred, and isopropyl methacrylate or tert-butyl methacrylate is more preferred.

[0080] Specific examples of the monomer containing a group having an alicyclic structure in the side chain include a monomer having a monocyclic aliphatic hydrocarbon group, a monomer having a polycyclic aliphatic hydrocarbon group, and a (meth)acrylate having an alicyclic hydrocarbon group having 5 to 20 carbon atoms. More specific examples include (bicyclo[2.2.1]heptyl-2)(meth)acrylate, 1-adamantyl (meth)acrylate, 2-adamantyl (meth)acrylate, 3-methyl-1-adamantyl (meth)acrylate, 3,5-dimethyl-1-adamantyl (meth)acrylate, 3-ethyladamantyl (meth)acrylate, 3-methyl-5-ethyl-1-adamantyl (meth)acrylate, 3,5,8-triethyl-1-adamantyl (meth)acrylate, 3,5-dimethyl-8-ethyl-1-adamantyl (meth)acrylate, 2-methyl-2-adamantyl (meth)acrylate, 2-ethyl-2-adamantyl (meth)acrylate, 3-hydroxy-2-(meth)acrylate, 2-methyl-2-(meth)acrylate, 2-ethyl-2-(meth)acrylate, 2-hydroxy ... Examples of such acrylates include 1-adamantyl (meth)acrylate, octahydro-4,7-menthanoinden-5-yl (meth)acrylate, octahydro-4,7-menthanoinden-1-ylmethyl (meth)acrylate, 1-menthyl (meth)acrylate, tricyclodecane (meth)acrylate, 3-hydroxy-2,6,6-trimethyl-bicyclo[3.1.1]heptyl (meth)acrylate, 3,7,7-trimethyl-4-hydroxy-bicyclo[4.1.0]heptyl (meth)acrylate, (nor)bornyl (meth)acrylate, isobornyl (meth)acrylate, fenchyl (meth)acrylate, 2,2,5-trimethylcyclohexyl (meth)acrylate, and cyclohexyl (meth)acrylate.Among these (meth)acrylic acid esters, cyclohexyl (meth)acrylate, (nor)bornyl (meth)acrylate, isobornyl (meth)acrylate, 1-adamantyl (meth)acrylate, 2-adamantyl (meth)acrylate, fenchyl (meth)acrylate, 1-menthyl (meth)acrylate, or tricyclodecane (meth)acrylate is preferred, and cyclohexyl (meth)acrylate, (nor)bornyl (meth)acrylate, isobornyl (meth)acrylate, 2-adamantyl (meth)acrylate, or tricyclodecane (meth)acrylate is more preferred.

[0081] The polymer A may be used alone or in combination of two or more. When using in combination of two or more, it is preferable to use two types of polymer A containing a monomer component having an aromatic hydrocarbon group as a mixture, or to use a polymer A containing a monomer component having an aromatic hydrocarbon group and a polymer A not containing a monomer component having an aromatic hydrocarbon group as a mixture. In the latter case, the proportion of the polymer A containing a monomer component having an aromatic hydrocarbon group is preferably 50% by mass or more, more preferably 70% by mass or more, more preferably 80% by mass or more, and more preferably 90% by mass or more, based on the total amount of the polymer A.

[0082] The synthesis of polymer A is preferably carried out by adding an appropriate amount of a radical polymerization initiator such as benzoyl peroxide or azoisobutyronitrile to a solution obtained by diluting one or more of the monomers described above with a solvent such as acetone, methyl ethyl ketone, or isopropanol, and heating and stirring the solution. In some cases, the synthesis is carried out while dropping a part of the mixture into the reaction solution. After the reaction is completed, further solvent may be added to adjust the concentration to the desired level. As a synthesis method, bulk polymerization, suspension polymerization, or emulsion polymerization may be used in addition to solution polymerization.

[0083] The glass transition temperature Tg of the polymer A is preferably 30° C. or more and 135° C. or less. By using the polymer A having a Tg of 135° C. or less in the photosensitive resin layer, it is possible to suppress line width thickening and deterioration of resolution when the focal position is shifted during exposure. From this viewpoint, the Tg of the polymer A is more preferably 130° C. or less, further preferably 120° C. or less, and particularly preferably 110° C. or less. In addition, it is preferable to use the polymer A having a Tg of 30° C. or more from the viewpoint of improving edge fuse resistance. From this viewpoint, the Tg of the polymer A is more preferably 40° C. or more, further preferably 50° C. or more, particularly preferably 60° C. or more, and most preferably 70° C. or more.

[0084] The photosensitive resin layer may contain a resin other than the polymer A. Examples of resins other than polymer A include acrylic resins, styrene-acrylic copolymers (with the styrene content being 40 mass% or less), polyurethane resins, polyvinyl alcohol, polyvinyl formal, polyamide resins, polyester resins, polyamide resins, epoxy resins, polyacetal resins, polyhydroxystyrene resins, polyimide resins, polybenzoxazole resins, polysiloxane resins, polyethyleneimines, polyallylamine, and polyalkylene glycols.

[0085] The binder polymer may be used alone or in combination of two or more kinds. The ratio of the binder polymer to the total mass of the photosensitive resin layer is preferably in the range of 10% by mass to 90% by mass, more preferably 30% by mass to 70% by mass, and even more preferably 40% by mass to 60% by mass. It is preferable to set the ratio of the binder polymer to the photosensitive resin layer to 90% by mass or less from the viewpoint of controlling the development time. On the other hand, it is preferable to set the ratio of the binder polymer to the photosensitive resin layer to 10% by mass or more from the viewpoint of improving edge fuse resistance.

[0086] (polymerizable compound) The photosensitive resin layer preferably contains a polymerizable compound. In this specification, the term "polymerizable compound" refers to a compound that undergoes polymerization under the action of a polymerization initiator described below, and is different from the binder polymer described above.

[0087] The polymerizable compound is preferably an ethylenically unsaturated compound. The ethylenically unsaturated compound is a component that contributes to the photosensitivity (that is, photocurability) of the negative photosensitive resin layer and the strength of the cured film. Also, an ethylenically unsaturated compound is a compound having one or more ethylenically unsaturated groups. The photosensitive resin layer preferably contains, as the ethylenically unsaturated compound, a di- or higher functional ethylenically unsaturated compound. Here, the di- or higher functional ethylenically unsaturated compound means a compound having two or more ethylenically unsaturated groups in one molecule. The ethylenically unsaturated group is more preferably a (meth)acryloyl group. As the ethylenically unsaturated compound, a (meth)acrylate compound is preferred.

[0088] The photosensitive resin layer preferably contains a polymerizable compound having a polymerizable group. The polymerizable group of the polymerizable compound is not particularly limited as long as it is a group that participates in a polymerization reaction, and examples thereof include groups having an ethylenically unsaturated group, such as a vinyl group, an acryloyl group, a methacryloyl group, a styryl group, and a maleimide group; and groups having a cationic polymerizable group, such as an epoxy group and an oxetane group. The polymerizable group is preferably a group having an ethylenically unsaturated group, and more preferably an acryloyl group or a methacryloyl group.

[0089] As the polymerizable compound, a compound having one or more ethylenically unsaturated groups (ethylenically unsaturated compound) is preferred, and a compound having two or more ethylenically unsaturated groups in one molecule (polyfunctional ethylenically unsaturated compound) is more preferred, in that the photosensitivity of the photosensitive resin layer is superior. From the viewpoint of obtaining superior resolution and peelability, the number of ethylenically unsaturated groups that the ethylenically unsaturated compound has in one molecule is preferably 6 or less, more preferably 3 or less, and even more preferably 2 or less.

[0090] The photosensitive resin layer preferably contains a bifunctional or trifunctional ethylenically unsaturated compound having two or three ethylenically unsaturated groups in one molecule, and more preferably contains a bifunctional ethylenically unsaturated compound having two ethylenically unsaturated groups in one molecule, in that the photosensitive resin layer has a better balance between photosensitivity, resolution, and peelability. The content of the bifunctional ethylenically unsaturated compound relative to the content of the polymerizable compound in the photosensitive resin layer is preferably 60% by mass or more, more preferably more than 70% by mass, and even more preferably 90% by mass or more, from the viewpoint of excellent peelability. The upper limit is not particularly limited, and may be 100% by mass. That is, all of the polymerizable compounds contained in the photosensitive resin layer may be bifunctional ethylenically unsaturated compounds. Moreover, the ethylenically unsaturated compound is preferably a (meth)acrylate compound having a (meth)acryloyl group as a polymerizable group.

[0091] -Polymerizable compound B1- The photosensitive resin layer preferably contains a polymerizable compound B1 having an aromatic ring and two ethylenically unsaturated groups. The polymerizable compound B1 is a bifunctional ethylenically unsaturated compound having one or more aromatic rings in one molecule among the above-mentioned polymerizable compounds.

[0092] In the photosensitive resin layer, the mass ratio of the content of the polymerizable compound B1 to the content of the polymerizable compound is preferably 40% by mass or more, more preferably 50% by mass or more, even more preferably 55% by mass or more, and particularly preferably 60% by mass or more, from the viewpoint of superior resolution. The upper limit is not particularly limited, but from the viewpoint of peelability, it is preferably 99% by mass or less, more preferably 95% by mass or less, even more preferably 90% by mass or less, and particularly preferably 85% by mass or less.

[0093] The aromatic ring of the polymerizable compound B1 includes, for example, aromatic hydrocarbon rings such as benzene ring, naphthalene ring and anthracene ring, aromatic heterocycles such as thiophene ring, furan ring, pyrrole ring, imidazole ring, triazole ring and pyridine ring, and condensed rings thereof, and is preferably aromatic hydrocarbon ring, more preferably benzene ring.The aromatic ring may have a substituent. The polymerizable compound B1 may have only one aromatic ring, or may have two or more aromatic rings.

[0094] The polymerizable compound B1 preferably has a bisphenol structure, since this suppresses swelling of the photosensitive resin layer due to a developer, thereby improving the resolution. Examples of the bisphenol structure include a bisphenol A structure derived from bisphenol A (2,2-bis(4-hydroxyphenyl)propane), a bisphenol F structure derived from bisphenol F (2,2-bis(4-hydroxyphenyl)methane), and a bisphenol B structure derived from bisphenol B (2,2-bis(4-hydroxyphenyl)butane), with the bisphenol A structure being preferred.

[0095] An example of the polymerizable compound B1 having a bisphenol structure is a compound having a bisphenol structure and two polymerizable groups (preferably (meth)acryloyl groups) bonded to both ends of the bisphenol structure. Both ends of the bisphenol structure may be directly bonded to the two polymerizable groups, or may be bonded via one or more alkyleneoxy groups. The alkyleneoxy groups added to both ends of the bisphenol structure are preferably ethyleneoxy or propyleneoxy, more preferably ethyleneoxy. 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 JP2016-224162A, the contents of which are incorporated herein by reference.

[0096] As the polymerizable compound B1, a bifunctional ethylenically unsaturated compound having a bisphenol A structure is preferable, and 2,2-bis(4-((meth)acryloxypolyalkoxy)phenyl)propane is more preferable. Examples of 2,2-bis(4-((meth)acryloxypolyalkoxy)phenyl)propane include 2,2-bis(4-(methacryloxydiethoxy)phenyl)propane (FA-324M, Hitachi Chemical Co., Ltd.), 2,2-bis(4-(methacryloxyethoxypropoxy)phenyl)propane, 2,2-bis(4-(methacryloxypentaethoxy)phenyl)propane (BPE-500, Shin-Nakamura Chemical Co., Ltd.), and 2,2-bis(4-(methacryloxydodecaethoxy)phenyl)propane. Examples of the ethoxylated bisphenol A diacrylate include 2,2-bis(4-(tetrapropoxy)phenyl)propane (FA-3200MY, manufactured by Hitachi Chemical Co., Ltd.), 2,2-bis(4-(methacryloxypentadecaethoxy)phenyl)propane (BPE-1300, manufactured by Shin-Nakamura Chemical Co., Ltd.), 2,2-bis(4-(methacryloxydiethoxy)phenyl)propane (BPE-200, manufactured by Shin-Nakamura Chemical Co., Ltd.), and ethoxylated (10) bisphenol A diacrylate (NK Ester A-BPE-10, manufactured by Shin-Nakamura Chemical Co., Ltd.).

[0097] The polymerizable compound B1 is represented by the following general formula (I):

[0098] [ka]

[0099] {In the formula, R1 and R2 each independently represent a hydrogen atom or a methyl group, A is C2H4, B is 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, and the arrangement of the repeating units -(AO)- and -(BO)- may be random or block. In the case of a block, either -(AO)- or -(BO)- may be on the bisphenyl group side.} It is possible to use a compound represented by the following formula: In one embodiment, n1+n2+n3+n4 is preferably an integer of 2 to 20, more preferably an integer of 2 to 16, and even more preferably an integer of 4 to 12. Furthermore, n2+n4 is preferably an integer of 0 to 10, more preferably an integer of 0 to 4, even more preferably an integer of 0 to 2, and particularly preferably 0.

[0100] The polymerizable compound B1 may be used alone or in combination of two or more kinds. The content of the polymerizable compound B1 in the photosensitive resin layer is preferably 10% by mass or more, more preferably 20% by mass or more, based on the total mass of the photosensitive resin layer, from the viewpoint of better resolution. The upper limit is not particularly limited, but is preferably 70% by mass or less, more preferably 60% by mass or less, from the viewpoint of transferability and edge fusion (phenomenon in which the photosensitive resin oozes out from the edge of the transfer member).

[0101] The photosensitive resin layer may contain a polymerizable compound other than the above-mentioned polymerizable compound B1. The polymerizable compound other than the polymerizable compound B1 is not particularly limited and can be appropriately selected from known compounds. For example, a compound having one ethylenically unsaturated group in one molecule (monofunctional ethylenically unsaturated compound), a bifunctional ethylenically unsaturated compound without an aromatic ring, and a trifunctional or higher ethylenically unsaturated compound can be mentioned.

[0102] Examples of monofunctional ethylenically unsaturated compounds include ethyl (meth)acrylate, ethylhexyl (meth)acrylate, 2-(meth)acryloyloxyethyl succinate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, and phenoxyethyl (meth)acrylate.

[0103] Examples of difunctional ethylenically unsaturated compounds having no aromatic ring include alkylene glycol di(meth)acrylate, polyalkylene glycol di(meth)acrylate, urethane di(meth)acrylate, and trimethylolpropane diacrylate. Examples of alkylene glycol di(meth)acrylates include tricyclodecane dimethanol diacrylate (A-DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.), tricyclodecane dimethanol dimethacrylate (DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.), 1,9-nonanediol diacrylate (A-NOD-N, manufactured by Shin-Nakamura Chemical Co., Ltd.), 1,6-hexanediol diacrylate (A-HD-N, manufactured by Shin-Nakamura Chemical Co., Ltd.), ethylene glycol dimethacrylate, 1,10-decanediol diacrylate, and neopentyl glycol di(meth)acrylate. Examples of polyalkylene glycol di(meth)acrylates include polyethylene glycol di(meth)acrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, and polypropylene glycol di(meth)acrylate. Examples of urethane di(meth)acrylate include propylene oxide modified urethane di(meth)acrylate, and ethylene oxide and propylene oxide modified urethane di(meth)acrylate. Commercially available products include 8UX-015A (manufactured by Taisei Fine Chemical Co., Ltd.), UA-32P (manufactured by Shin-Nakamura Chemical Co., Ltd.), and UA-1100H (manufactured by Shin-Nakamura Chemical Co., Ltd.).

[0104] Examples of the trifunctional or higher ethylenically unsaturated compound include dipentaerythritol (tri / tetra / penta / hexa)(meth)acrylate, pentaerythritol (tri / tetra)(meth)acrylate, trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, trimethylolethane tri ... Examples of the alkylene acrylate include acrylate, isocyanuric acid tri(meth)acrylate, glycerin tri(meth)acrylate, and alkylene oxide modified products thereof. Here, "(tri / tetra / penta / hexa)(meth)acrylate" is a concept that includes tri(meth)acrylate, tetra(meth)acrylate, penta(meth)acrylate, and hexa(meth)acrylate, and "(tri / tetra)(meth)acrylate" is a concept that includes tri(meth)acrylate and tetra(meth)acrylate. In one embodiment, the photosensitive resin layer preferably contains the above-mentioned polymerizable compound B1 and a trifunctional or higher ethylenically unsaturated compound, and more preferably contains the above-mentioned polymerizable compound B1 and two or more trifunctional or higher ethylenically unsaturated compounds. In this case, the mass ratio of the polymerizable compound B1 to the trifunctional or higher ethylenically unsaturated compound is preferably (total mass of the polymerizable compound B1):(total mass of the trifunctional or higher ethylenically unsaturated compound)=1:1 to 5:1, more preferably 1.2:1 to 4:1, and even more preferably 1.5:1 to 3:1. In one embodiment, the photosensitive resin layer preferably contains the above-mentioned polymerizable compound B1 and two or more kinds of trifunctional ethylenically unsaturated compounds.

[0105] Examples of alkylene oxide modified trifunctional or higher ethylenically unsaturated compounds include caprolactone modified (meth)acrylate compounds (KAYARAD (registered trademark) DPCA-20 manufactured by Nippon Kayaku Co., Ltd., A-9300-1CL manufactured by Shin-Nakamura Chemical Co., Ltd., etc.), alkylene oxide modified (meth)acrylate compounds (KAYARAD RP-1040 manufactured by Nippon Kayaku Co., Ltd., ATM-35E and A-9300 manufactured by Shin-Nakamura Chemical Co., Ltd., EBECRYL (registered trademark) manufactured by Daicel-Allnex Corporation), etc. No. 135, etc.), ethoxylated glycerin triacrylate (A-GLY-9E, etc., manufactured by Shin-Nakamura Chemical Co., Ltd.), 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.).

[0106] As the polymerizable compound other than the polymerizable compound B1, the polymerizable compounds having an acid group described in paragraphs 0025 to 0030 of JP-A No. 2004-239942 may be used.

[0107] From the viewpoints of resolution and linearity, the ratio Mm / Mb of the polymerizable compound content Mm to the binder polymer content Mb in the photosensitive resin layer is preferably 1.0 or less, more preferably 0.9 or less, and particularly preferably 0.5 or more and 0.9 or less. From the viewpoints of curability and resolution, the polymerizable compound in the photosensitive resin layer preferably contains a (meth)acrylic compound. Further, from the viewpoints of curability, resolution and linearity, it is more preferable that the polymerizable compound in the photosensitive resin layer contains a (meth)acrylic compound, and the content of the acrylic compound relative to the total mass of the (meth)acrylic compound contained in the photosensitive resin layer is 60 mass% or less. The lower limit of the content of the acrylic compound is not particularly limited, and is, for example, 0.1 mass%.

[0108] The polymerizable compounds may be used alone or in combination of two or more kinds. The content of the polymerizable compound in the photosensitive resin layer is preferably 10% by mass to 70% by mass, more preferably 20% by mass to 60% by mass, and further preferably 20% by mass to 50% by mass, based on the total mass of the photosensitive resin layer.

[0109] The weight average molecular weight (Mw) of the polymerizable compound including the polymerizable compound B1 is preferably from 200 to 3,000, more preferably from 280 to 2,200, and further preferably from 300 to 2,200.

[0110] (Other Ingredients) The photosensitive resin layer may contain components other than the binder polymer and the polymerizable compound.

[0111] -Photopolymerization initiator- The photosensitive resin layer preferably contains a photopolymerization initiator. A photopolymerization initiator is a compound that initiates polymerization of a polymerizable compound when exposed to active light such as ultraviolet light, visible light, and X-rays. The photopolymerization initiator is not particularly limited, and any known photopolymerization initiator can be used. Examples of the photopolymerization initiator include a photoradical polymerization initiator and a photocationic polymerization initiator, and a photoradical polymerization initiator is preferred.

[0112] Examples of the photoradical polymerization initiator include a photopolymerization initiator having an oxime ester structure, a photopolymerization initiator having an α-aminoalkylphenone structure, a photopolymerization initiator having an α-hydroxyalkylphenone structure, a photopolymerization initiator having an acylphosphine oxide structure, and a photopolymerization initiator having an N-phenylglycine structure.

[0113] From the viewpoints of photosensitivity, visibility of exposed and non-exposed areas, and resolution, the photosensitive resin layer preferably contains at least one photoradical polymerization initiator selected from the group consisting of 2,4,5-triarylimidazole dimers and derivatives thereof. Note that the two 2,4,5-triarylimidazole structures in the 2,4,5-triarylimidazole dimer and derivatives thereof may be the same or different. Examples of derivatives of 2,4,5-triarylimidazole dimers include 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(o-chlorophenyl)-4,5-di(methoxyphenyl)imidazole dimer, 2-(o-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(o-methoxyphenyl)-4,5-diphenylimidazole dimer, and 2-(p-methoxyphenyl)-4,5-diphenylimidazole dimer.

[0114] As the photoradical polymerization initiator, for example, the polymerization initiators described in paragraphs 0031 to 0042 of JP-A No. 2011-95716 and paragraphs 0064 to 0081 of JP-A No. 2015-14783 may be used.

[0115] 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 Co., Ltd.), benzophenone, TAZ-111 (trade name: manufactured by Midori Chemical Co., Ltd.), Irgacure OXE01, OXE02, OXE03, OXE04 (manufactured by BASF), Omnirad 651 and 369 (trade names: 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.).

[0116] Commercially available photoradical polymerization initiators include, for example, 1-[4-(phenylthio)phenyl]-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), 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone (trade name: Omnirad 379EG, manufactured by IGM Resins BV), 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one (trade name: Omnirad 907, manufactured by IGM Resins BV), 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)benzyl]phenyl}-2-methylpropan-1-one (trade name: Omnirad 127, manufactured by IGM Resins BV), 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone-1 (trade name: Omnirad 369, manufactured by IGM Resins BV), 2-hydroxy-2-methyl-1-phenylpropan-1-one (trade name: Omnirad 1173, manufactured by IGM Resins BV), 1-hydroxycyclohexyl phenyl ketone (trade name: Omnirad 184, manufactured by IGM Resins BV), 2,2-dimethoxy-1,2-diphenylethan-1-one (trade name: Omnirad 651, manufactured by IGM Resins BV), 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 BVExamples of photopolymerization initiators include oxime ester-based photopolymerization initiators (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.).

[0117] In addition, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbisimidazole (2-(2-chlorophenyl)-4,5-diphenylimidazole dimer) (product name: B-IMD, manufactured by Kurogane Kasei Co., Ltd.) can also be used.

[0118] In this specification, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbisimidazole (2-(2-chlorophenyl)-4,5-diphenylimidazole dimer) is referred to as B-CIM or B-IMD.

[0119] A photocationic polymerization initiator (photoacid generator) is a compound that generates an acid when exposed to actinic rays. As the photocationic polymerization initiator, a compound that responds to actinic rays having a wavelength of 300 nm or more, preferably 300 to 450 nm, and generates an acid is preferred, but the chemical structure is not limited. In addition, even if a photocationic polymerization initiator is not directly sensitive to actinic rays having a wavelength of 300 nm or more, it can be preferably used in combination with a sensitizer as long as it responds to actinic rays having a wavelength of 300 nm or more and generates an acid when used in combination with a sensitizer. As the photocationic polymerization initiator, a photocationic polymerization initiator that generates an acid having a pKa of 4 or less is preferable, a photocationic polymerization initiator that generates an acid having a pKa of 3 or less is more preferable, and a photocationic polymerization initiator that generates an acid having a pKa of 2 or less is particularly preferable. The lower limit of the pKa is not particularly set, but is preferably, for example, -10.0 or more.

[0120] The photocationic polymerization initiator includes an ionic photocationic polymerization initiator and a nonionic photocationic polymerization initiator. Examples of the ionic photocationic polymerization initiator include onium salt compounds such as diaryliodonium salts and triarylsulfonium salts, as well as quaternary ammonium salts. As the ionic photocationic polymerization initiator, the ionic photocationic polymerization initiators described in paragraphs 0114 to 0133 of JP-A-2014-85643 may be used.

[0121] Examples of nonionic photocationic polymerization initiators include trichloromethyl-s-triazines, diazomethane compounds, imide sulfonate compounds, and oxime sulfonate compounds. As trichloromethyl-s-triazines, diazomethane compounds, and imide sulfonate compounds, compounds described in paragraphs 0083 to 0088 of JP 2011-221494 A may be used. As oxime sulfonate compounds, compounds described in paragraphs 0084 to 0088 of WO 2018 / 179640 may be used.

[0122] The photosensitive resin layer preferably contains a photoradical polymerization initiator, and more preferably contains at least one selected from the group consisting of 2,4,5-triarylimidazole dimers and derivatives thereof.

[0123] The photosensitive resin layer may contain one type of photopolymerization initiator alone, or may contain two or more types of photopolymerization initiators. The content of the photopolymerization initiator in the photosensitive resin layer is not particularly limited, but is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and even more preferably 1.0% by mass or more, based on the total mass of the photosensitive resin layer. The upper limit is not particularly limited, but is preferably 10% by mass or less, and more preferably 5% by mass or less, based on the total mass of the photosensitive resin layer.

[0124] -Dye- From the viewpoints of visibility of exposed and unexposed parts, pattern visibility after development, and resolution, the photosensitive resin layer preferably contains a dye (also simply referred to as "dye N") whose maximum absorption wavelength in the wavelength range of 400 nm to 780 nm during color development is 450 nm or more and whose maximum absorption wavelength changes depending on an acid, a base, or a radical. When dye N is contained, the adhesion with adjacent layers (for example, a temporary support and an intermediate layer) is improved, and the resolution is more excellent, although the detailed mechanism is unknown.

[0125] In this specification, the dye "whose maximum absorption wavelength changes due to an acid, a base, or a radical" may mean any of an embodiment in which a dye in a colored state is decolorized by an acid, a base, or a radical, a dye in a decolorized state is colored by an acid, a base, or a radical, and a dye in a colored state is changed to a colored state of another hue. Specifically, the dye N may be a compound that changes from a decolorized state to a colored state by exposure to light, or may be a compound that changes from a colored state to a decolored state by exposure to light. In this case, the dye may be a dye whose colored or decolored state changes when an acid, base, or radical is generated and acts in the photosensitive resin layer by exposure to light, or a dye whose colored or decolored state changes when the state (e.g., pH) in the photosensitive resin layer changes due to an acid, base, or radical. Alternatively, the dye may be a dye whose colored or decolored state changes when it is directly stimulated by an acid, base, or radical without exposure to light.

[0126] Among these, from the viewpoints of visibility and resolution of exposed and unexposed areas, dye N is preferably a dye whose maximum absorption wavelength changes in response to an acid or a radical, and more preferably a dye whose maximum absorption wavelength changes in response to a radical. From the viewpoints of visibility of exposed and unexposed areas and resolution, the photosensitive resin layer preferably contains both a dye N whose maximum absorption wavelength changes due to radicals, and a photoradical polymerization initiator. From the viewpoint of visibility of exposed and unexposed areas, dye N is preferably a dye that develops color in response to an acid, a base, or a radical.

[0127] An example of the color-developing mechanism of dye N in the present disclosure is an embodiment in which a photoradical polymerization initiator, a cationic photopolymerization initiator (photoacid generator), or a photobase generator is added to a photosensitive resin layer, and after exposure, a radical-reactive dye, an acid-reactive dye, or a base-reactive dye (e.g., a leuco dye) develops color due to a radical, acid, or base generated from the photoradical polymerization initiator, the photocationic photopolymerization initiator, or the photobase generator.

[0128] 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 nm to 780 nm upon color development, more preferably 550 nm to 700 nm, and even more preferably 550 nm to 650 nm. Furthermore, dye N may have only one maximum absorption wavelength in the wavelength range of 400 nm to 780 nm when it develops color, or may have two or more maximum absorption wavelengths. When dye N has two or more maximum absorption wavelengths in the wavelength range of 400 nm to 780 nm when it develops color, the maximum absorption wavelength having the highest absorbance among the two or more maximum absorption wavelengths may be 450 nm or more.

[0129] The maximum absorption wavelength of dye N is obtained by measuring the transmission spectrum of a solution containing dye N (liquid temperature 25°C) in the range of 400 nm to 780 nm using a spectrophotometer UV3100 (manufactured by Shimadzu Corporation) in an atmospheric environment and detecting the wavelength at which the light intensity is minimum (maximum absorption wavelength).

[0130] Examples of the dye that develops or loses color upon exposure to light include leuco compounds. Examples of dyes that are decolorized by exposure to light include leuco compounds, diarylmethane dyes, oxazine dyes, xanthene dyes, iminonaphthoquinone dyes, azomethine dyes, and anthraquinone dyes. As the dye N, a leuco compound is preferable from the viewpoint of visibility of exposed and non-exposed areas.

[0131] Examples of the leuco compound include leuco compounds having a triarylmethane skeleton (triarylmethane-based dyes), leuco compounds having a spiropyran skeleton (spiropyran-based dyes), leuco compounds having a fluoran skeleton (fluoran-based dyes), leuco compounds having a diarylmethane skeleton (diarylmethane-based dyes), leuco compounds having a rhodamine lactam skeleton (rhodamine lactam-based dyes), leuco compounds having an indolylphthalide skeleton (indolylphthalide-based dyes), and leuco compounds having a leucoauramine skeleton (leucoauramine-based dyes). Among these, triarylmethane dyes or fluoran dyes are preferred, and leuco compounds having a triphenylmethane skeleton (triphenylmethane dyes) or fluoran dyes are more preferred.

[0132] From the viewpoint of visibility of the exposed and non-exposed parts, the leuco compound preferably has a lactone ring, a sultine ring, or a sultone ring. This allows the lactone ring, the sultine ring, or the sultone ring of the leuco compound to react with a radical generated from a photoradical polymerization initiator or an acid generated from a photocationic polymerization initiator, thereby changing the leuco compound to a ring-closed state to cause discoloration, or changing the leuco compound to a ring-open state to cause color development. The leuco compound is preferably a compound having a lactone ring, a sultine ring, or a sultone ring, which is opened by a radical or an acid to develop color, and more preferably a compound having a lactone ring, which is opened by a radical or an acid to develop color.

[0133] 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-naphthalenesulfonate, Victoria Pure Blue BOH (manufactured by Hodogaya Chemical Industry Co., Ltd.), Oil Blue #603 (manufactured by Orient Chemical Industry Co., Ltd.), Oil Pink #312 (manufactured by Orient Chemical Industry Co., Ltd.), Oil Red 5B (manufactured by Orient Chemical Industry Co., Ltd.), Oil Scarlet #308 (manufactured by Orient Chemical Industry Co., Ltd.), Examples of the oil-soluble pigments that can be used include Orient Chemical Industry Co., Ltd.), Oil Red OG (Orient Chemical Industry Co., Ltd.), Oil Red RR (Orient Chemical Industry Co., Ltd.), Oil Green #502 (Orient Chemical Industry Co., Ltd.), Spiron Red BEH Special (Hodogaya Chemical Industry Co., Ltd.), m-Cresol Purple, Cresol Red, Rhodamine B, Rhodamine 6G, Sulforhodamine B, Auramine, 4-p-diethylaminophenyliminonaphthoquinone, 2-carboxyanilino-4-p-diethylaminophenyliminonaphthoquinone, 2-carboxystearylamino-4-pN,N-bis(hydroxyethyl)amino-phenyliminonaphthoquinone, 1-phenyl-3-methyl-4-p-diethylaminophenylimino-5-pyrazolone, and 1-β-naphthyl-4-p-diethylaminophenylimino-5-pyrazolone.

[0134] Specific examples of the leuco compound among the dyes N include p,p',p"-hexamethyltriaminotriphenylmethane (leuco crystal violet), Pergascript Blue SRB (manufactured by Ciba-Geigy), crystal violet lactone, malachite green lactone, benzoyl leucomethylene blue, 2-(N-phenyl-N-methylamino)-6-(Np-tolyl-N-ethyl)aminofluoran, 2-anilino-3-methyl-6-(N-ethyl-p-toluidino)fluoran, 3,6-dimethoxyfluoran, 3-(N,N-diethylamino)-5-methyl-7-(N,N-dibenzylamino)fluoran, 3-(N-cyclohexyl-N-methylamino)-6-(N-cyclohexyl-N-methylamino)fluoran, and the like. -methyl-7-anilinofluoran, 3-(N,N-diethylamino)-6-methyl-7-anilinofluoran, 3-(N,N-diethylamino)-6-methyl-7-xylidinofluoran, 3-(N,N-diethylamino)-6-methyl-7-chlorofluoran, 3-(N,N-diethylamino)-6-methoxy-7-aminofluoran, 3-(N,N-diethylamino)-7-(4-chloroanilino)fluoran, 3-(N,N-diethylamino)-7-chlorofluoran, 3-(N,N-diethylamino)- 3-(N,N-diethylamino)-7-benzylaminofluoran, 3-(N,N-diethylamino)-7,8-benzofluoran, 3-(N,N-dibutylamino)-6-methyl-7-anilinofluoran, 3-(N,N-dibutylamino)-6-methyl-7-xylidinofluoran, 3-piperidino-6-methyl-7-anilinofluoran, 3-pyrrolidino-6-methyl-7-anilinofluoran, 3,3-bis(1-ethyl-2-methylindol-3-yl)phthalide, 3,3-bis(1-n-butyl-2-methylindol-3-yl)phthalide 3-(4-diethylamino-2-ethoxyphenyl)-3-(1-ethyl-2-methylindol-3-yl)phthalide, 3,3-bis(p-dimethylaminophenyl)-6-dimethylaminophthalide, 3-(4-diethylamino-2-ethoxyphenyl)-3-(1-ethyl-2-methylindol-3-yl)phthalide, 3-(4-diethylaminophenyl)-3-(1-ethyl-2-methylindol-3-yl)phthalide, and 3',6'-bis(diphenylamino)spiroisobenzofuran-1(3H),9'-[9H]xanthen-3-one.

[0135] From the viewpoints of visibility of exposed and unexposed areas, pattern visibility after development, and resolution, dye N is preferably a dye whose maximum absorption wavelength changes in response to radicals, and more preferably a dye that develops color in response to radicals. As dye N, leuco crystal violet, crystal violet lactone, brilliant green, or Victoria Pure Blue-naphthalenesulfonate is preferred.

[0136] The dye N may be used alone or in combination of two or more kinds. From the viewpoints of visibility of exposed and unexposed areas, pattern visibility after development, and resolution, the content of dye N is preferably 0.1 mass % or more, more preferably 0.1 mass % to 10 mass %, even more preferably 0.1 mass % to 5 mass %, and particularly preferably 0.1 mass % to 1 mass %, relative to the total mass of the photosensitive resin layer.

[0137] The content of dye N means the content of dye when all of dye N contained in the photosensitive resin layer is in a color-developing state. A method for quantifying the content of dye N will be described below using a dye that develops color by radicals as an example. A solution was prepared by dissolving 0.001 g and 0.01 g of the dye in 100 mL of methyl ethyl ketone. A photoradical polymerization initiator Irgacure OXE01 (product name, BASF Japan Ltd.) was added to each of the obtained solutions, and radicals were generated by irradiating with 365 nm light. All of the dyes are allowed to develop color, and then the absorbance of each solution at a liquid temperature of 25° C. is measured in an air atmosphere using a spectrophotometer (UV3100, manufactured by Shimadzu Corporation), and a calibration curve is created. Next, the absorbance of the solution in which all the dyes have been colored is measured in the same manner as above, except that the photosensitive resin layer 3g is dissolved in methyl ethyl ketone instead of the dye. The content of the dye contained in the photosensitive resin layer is calculated based on the calibration curve from the absorbance of the solution containing the photosensitive resin layer obtained.

[0138] -Surfactants- From the viewpoint of thickness uniformity, the photosensitive resin layer preferably contains a surfactant. Examples of the surfactant include anionic surfactants, cationic surfactants, nonionic surfactants, and amphoteric surfactants, with nonionic surfactants being preferred.

[0139] Examples of nonionic surfactants include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenyl ethers, higher fatty acid diesters of polyoxyethylene glycol, silicone-based nonionic surfactants, and fluorine-based nonionic surfactants.

[0140] The photosensitive resin layer preferably contains a fluorine-based nonionic surfactant in terms of better resolution. It is believed that the inclusion of a fluorine-based nonionic surfactant in the photosensitive resin layer suppresses the penetration of the etching solution into the photosensitive resin layer, thereby reducing side etching.

[0141] Commercially available fluorine-based nonionic surfactants include, for example, Megafac F-551, F-552 and F-554 (all manufactured by DIC Corporation).

[0142] In addition, examples of commercially available fluorine-based surfactants include 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-555-A, F-556, F-557, F-558, F-559, F-560, F-561, F-565, F-563, F-564, F-565-B, F-565-C, F-565-D ... 568, F-575, F-780, EXP, MFS-330, MFS-578, MFS-579, MFS-586, MFS-587, 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), Fluorard 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 710FL, 710FM, 610FM, 601AD, 601ADH2, 602A, 215M, 245F, 251, 212M, 250, 209F, 222F, 208G, 710LA, 710FS, 730LM, 650AC, 681, 683 (all manufactured by NEOS Co., Ltd.), etc. Examples include:

[0143] Also suitable for use as the fluorosurfactant are acrylic compounds that have a molecular structure with a functional group containing a fluorine atom, and when heat is applied, the functional group containing the fluorine atom is broken and the fluorine atom volatilizes. Examples of such fluorosurfactants include the Megafac DS series manufactured by DIC Corporation (The Chemical Daily (February 22, 2016), Nikkei Business Daily (February 23, 2016)), such as Megafac DS-21.

[0144] 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.

[0145] Furthermore, as the fluorosurfactant, a block polymer can also be used.

[0146] In addition, 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.

[0147] 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).

[0148] From the viewpoint of improving environmental compatibility, it is preferable that the fluorosurfactant be a surfactant derived from an alternative material to compounds having a linear perfluoroalkyl group having 7 or more carbon atoms, such as perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic acid (PFOS).

[0149] Examples of nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane, and 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, sorbitan fatty acid esters, Pluronic 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 Co., Ltd.), Olfine E1010, Surfynol 104, 400, 440 (all manufactured by Nissin Chemical Industry Co., Ltd.), and the like.

[0150] Examples of silicone surfactants include linear polymers formed from siloxane bonds, and modified siloxane polymers in which organic groups have been introduced into the side chains or ends.

[0151] Specific examples of silicone 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).

[0152] As the surfactant, the surfactants described in paragraphs 0120 to 0125 of International Publication No. 2018 / 179640, the surfactants described in paragraph 0017 of Japanese Patent No. 4,502,784, and the surfactants described in paragraphs 0060 to 0071 of JP-A-2009-237362 can also be used.

[0153] The photosensitive resin layer may contain one type of surfactant alone, or may contain two or more types of surfactants. The content of the surfactant is preferably from 0.001% by mass to 10% by mass, and more preferably from 0.01% by mass to 3% by mass, based on the total mass of the photosensitive resin layer.

[0154] -Additives- The photosensitive resin layer may contain known additives, if necessary, in addition to the above components. Examples of the additives include radical polymerization inhibitors, sensitizers, plasticizers, heterocyclic compounds, benzotriazoles, carboxybenzotriazoles, resins other than polymer A, and solvents. The photosensitive resin layer may contain one type of each additive alone, or two or more types.

[0155] The photosensitive resin layer may contain a radical polymerization inhibitor. Examples of the radical polymerization inhibitor include the thermal polymerization inhibitors described in paragraph 0018 of Japanese Patent No. 4502784. Among them, phenothiazine, phenoxazine, or 4-methoxyphenol is preferable. Other radical polymerization inhibitors include naphthylamine, cuprous chloride, nitrosophenylhydroxyamine aluminum salt, diphenylnitrosamine, etc. In order not to impair the sensitivity of the photosensitive resin layer, it is preferable to use nitrosophenylhydroxyamine aluminum salt as the radical polymerization inhibitor.

[0156] 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.

[0157] 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, N-(N,N-di-2-ethylhexyl)aminoethylenecarboxybenzotriazole, etc. Examples of carboxybenzotriazoles that can be used include commercially available products such as CBT-1 (Johoku Chemical Industry Co., Ltd., trade name).

[0158] The total content of the radical polymerization inhibitor, benzotriazoles, and carboxybenzotriazoles is preferably 0.01% by mass to 3% by mass, and more preferably 0.05% by mass to 1% by mass, when the total mass of the photosensitive resin layer is taken as 100% by mass. A content of 0.01% by mass or more is preferable from the viewpoint of imparting storage stability to the photosensitive resin layer. On the other hand, a content of 3% by mass or less is preferable from the viewpoint of maintaining sensitivity and suppressing discoloration of the dye.

[0159] The photosensitive resin layer may contain a sensitizer. The sensitizer is not particularly limited, and known sensitizers, dyes and pigments can be used. Examples of the sensitizer include dialkylaminobenzophenone compounds, pyrazoline compounds, anthracene compounds, coumarin compounds, xanthone compounds, thioxanthone compounds, acridone compounds, oxazole compounds, benzoxazole compounds, thiazole compounds, benzothiazole compounds, triazole compounds (e.g., 1,2,4-triazole), stilbene compounds, triazine compounds, thiophene compounds, naphthalimide compounds, triarylamine compounds and aminoacridine compounds.

[0160] The photosensitive resin layer may contain one type of sensitizer alone, or may contain two or more types of sensitizers. When the photosensitive resin layer contains a sensitizer, the content of the sensitizer can be appropriately selected depending on the purpose. From the viewpoints of improving the sensitivity to the light source and improving the curing speed by balancing the polymerization rate and chain transfer, the content of the sensitizer is preferably 0.01% by mass to 5% by mass, and more preferably 0.05% by mass to 1% by mass, relative to the total mass of the photosensitive resin layer.

[0161] The photosensitive resin 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 0097-0103 and 0111-0118 of WO 2018 / 179640.

[0162] The photosensitive resin layer may contain a solvent. When the photosensitive resin layer is formed from a photosensitive resin composition containing a solvent, the solvent may remain in the photosensitive resin layer.

[0163] The photosensitive resin layer may further contain known additives such as metal oxide particles, antioxidants, dispersants, acid multipliers, development accelerators, conductive fibers, thermal radical polymerization initiators, thermal acid generators, ultraviolet absorbers, thickeners, crosslinking agents, and organic or inorganic suspending agents. Additives contained in the photosensitive resin layer are described in paragraphs

[0165] to

[0184] of JP2014-85643A, the contents of which are incorporated herein by reference.

[0164] <Physical properties, etc.> The thickness of the photosensitive resin layer is preferably 0.1 μm to 300 μm, more preferably 0.2 μm to 100 μm, even more preferably 0.5 μm to 50 μm, even more preferably 0.5 μm to 15 μm, particularly preferably 0.5 μm to 10 μm, and most preferably 0.5 μm to 8 μm, which can improve the developability of the photosensitive resin layer and the resolution. In one embodiment, the thickness is preferably 0.5 μm to 5 μm, more preferably 0.5 μm to 4 μm, and even more preferably 0.5 μm to 3 μm. Furthermore, from the viewpoint of linearity, the thickness of the photosensitive resin layer is preferably 10 μm or less, more preferably 8 μm or less, further preferably 6 μm or less, and particularly preferably 1 μm or more and 4 μm or less. The thickness of each layer of the photosensitive transfer member is measured by observing a cross section perpendicular to the main surface of the photosensitive transfer member using a scanning electron microscope (SEM), measuring the thickness of each layer at 10 or more points based on the obtained observation image, and calculating the average value.

[0165] From the viewpoint of superior adhesion, the transmittance of the photosensitive resin 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.

[0166] <Formation method> The method for forming the photosensitive resin layer is not particularly limited as long as it is a method capable of forming a layer containing the above components. Examples of methods for forming the photosensitive resin layer include a method in which a photosensitive resin composition containing a binder polymer, a polymerizable compound, a solvent, etc. is prepared, the photosensitive resin composition is applied to a surface of a temporary support or the like, and the coating film of the photosensitive resin composition is dried to form the photosensitive resin layer.

[0167] Examples of the photosensitive resin composition used to form the photosensitive resin layer include compositions containing a binder polymer, a polymerizable compound, the above-mentioned optional components, and a solvent. The photosensitive resin composition preferably contains a solvent in order to adjust the viscosity of the photosensitive resin composition and facilitate the formation of the photosensitive resin layer.

[0168] (solvent) The solvent contained in the photosensitive resin composition is not particularly limited as long as it can dissolve or disperse the binder polymer, the polymerizable compound, and the above-mentioned optional components, and any known solvent can be used. Examples of the solvent 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, amide solvents, lactone solvents, and mixed solvents containing two or more of these. When preparing a photosensitive transfer member having a temporary support, a thermoplastic resin layer, an intermediate layer, and a photosensitive resin layer, the photosensitive resin composition preferably contains at least one selected from the group consisting of an alkylene glycol ether solvent and an alkylene glycol ether acetate solvent. Among them, a mixed solvent containing at least one selected from the group consisting of an alkylene glycol ether solvent and an alkylene glycol ether acetate solvent, and at least one selected from the group consisting of a ketone solvent and a cyclic ether solvent is more preferable, and a mixed solvent containing at least three of an alkylene glycol ether solvent and an alkylene glycol ether acetate solvent, a ketone solvent, and a cyclic ether solvent is even more preferable.

[0169] Examples of alkylene glycol ether solvents include ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, propylene glycol monoalkyl ethers, propylene glycol dialkyl ethers, diethylene glycol dialkyl ethers, dipropylene glycol monoalkyl ethers, and dipropylene glycol dialkyl ethers. Examples of alkylene glycol ether acetate solvents include 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 JP-A-2018-177889 may be used, the contents of which are incorporated herein by reference.

[0170] The photosensitive resin composition may contain one type of solvent alone, or may contain two or more types of solvents. The content of the solvent when applying the photosensitive resin composition is preferably 50 to 1,900 parts by mass, and more preferably 100 to 900 parts by mass, per 100 parts by mass of the total solid content in the photosensitive resin composition.

[0171] The method for preparing the photosensitive resin composition is not particularly limited, and examples thereof include a method in which each component is dissolved in the above-mentioned solvent to prepare a solution in advance, and the obtained solutions are mixed in a predetermined ratio to prepare the photosensitive resin composition. The photosensitive resin composition is preferably filtered using a filter having a pore size of 0.2 μm to 30 μm before forming a photosensitive resin layer.

[0172] The method for applying the photosensitive resin composition is not particularly limited, and may be any known method, such as slit coating, spin coating, curtain coating, or inkjet coating. The photosensitive resin layer may be formed by applying a photosensitive resin composition onto a cover film described below and drying it.

[0173] [Thermoplastic resin layer] The photosensitive transfer member may include a thermoplastic resin layer. The photosensitive transfer member preferably has a thermoplastic resin layer between the temporary support and the photosensitive resin layer, because the photosensitive transfer member has a thermoplastic resin layer between the temporary support and the photosensitive resin layer, which improves the conformability to the substrate in the bonding step, suppresses the inclusion of air bubbles between the substrate and the photosensitive transfer member, and improves the adhesion to an adjacent layer (e.g., temporary support).

[0174] <Ingredients> (alkali soluble resin) The thermoplastic resin layer contains an alkali-soluble resin as a thermoplastic resin. In this specification, the term "alkali-soluble" means that the solubility in 100 g of a 1% by mass aqueous solution of sodium carbonate at 22°C is 0.1 g or more. Examples of the alkali-soluble resin include acrylic resin, polystyrene resin, styrene-acrylic copolymer, polyurethane resin, polyvinyl alcohol, polyvinyl formal, polyamide resin, polyester resin, polyamide resin, epoxy resin, polyacetal resin, polyhydroxystyrene resin, polyimide resin, polybenzoxazole resin, polysiloxane resin, polyethyleneimine, polyallylamine, and polyalkylene glycol.

[0175] As the alkali-soluble resin, from the viewpoints of developability and adhesion to adjacent layers, an acrylic resin is preferred. Here, the acrylic resin refers to a resin having at least one type of structural unit selected from the group consisting of structural units derived from (meth)acrylic acid, structural units derived from (meth)acrylic acid esters, and structural units derived from (meth)acrylic acid amides. The acrylic resin preferably contains a total content of constituent units derived from (meth)acrylic acid, constituent units derived from (meth)acrylic acid ester, and constituent units derived from (meth)acrylic acid amide of 50 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 esters is preferably 30% by mass to 100% by mass, and more preferably 50% by mass to 100% by mass, relative to the total mass of the acrylic resin.

[0176] 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 the 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 carboxy group-containing acrylic resin having an acid value of 60 mgKOH / g or more. The upper limit of the acid value of the alkali-soluble resin is not particularly limited, but is preferably 200 mgKOH / g or less, and more preferably 150 mgKOH / g or less.

[0177] 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 of the alkali-soluble resin include a carboxy group-containing acrylic resin having an acid value of 60 mgKOH / g or more among the polymers described in paragraph 0025 of JP-A-2011-95716, a carboxy group-containing acrylic resin having an acid value of 60 mgKOH / g or more among the polymers described in paragraphs 0033 to 0052 of JP-A-2010-237589, and a carboxy group-containing acrylic resin having an acid value of 60 mgKOH / g or more among the binder polymers described in paragraphs 0053 to 0068 of JP-A-2016-224162. The copolymerization ratio of the structural unit having a carboxy group in the carboxy group-containing acrylic resin is preferably 5% by mass to 50% by mass, more preferably 10% by mass to 40% by mass, and even more preferably 12% by mass to 30% by mass, based on the total mass of the acrylic resin. As the alkali-soluble resin, from the viewpoints of developability and adhesion to adjacent layers, an acrylic resin having a structural unit derived from (meth)acrylic acid is particularly preferred.

[0178] The alkali-soluble resin may have a reactive group. The reactive group may be any group capable of addition polymerization, and examples of the reactive group include ethylenically unsaturated groups, polycondensable groups such as hydroxyl groups and carboxyl groups, and polyaddition reactive groups such as epoxy groups and (blocked) isocyanate groups.

[0179] 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.

[0180] The thermoplastic resin layer may contain one type of alkali-soluble resin alone or two or more types of alkali-soluble resins. From the viewpoints of developability and adhesion to adjacent layers, the content of the alkali-soluble resin is preferably 10% by mass to 99% by mass, more preferably 20% by mass to 90% by mass, even more preferably 40% by mass to 80% by mass, and particularly preferably 50% by mass to 70% by mass, relative to the total mass of the thermoplastic resin layer.

[0181] (dye) The thermoplastic resin layer preferably contains a dye (also simply referred to as "dye B") that has a maximum absorption wavelength of 450 nm or more in the wavelength range of 400 nm to 780 nm when colored and whose maximum absorption wavelength changes depending on an acid, a base, or a radical. The preferred embodiments of dye B are the same as the preferred embodiments of dye N, except for the points described below.

[0182] From the viewpoints of visibility of exposed and unexposed areas and resolution, dye B is preferably a dye whose maximum absorption wavelength changes in response to an acid or a radical, and more preferably a dye whose maximum absorption wavelength changes in response to an acid. From the viewpoints of visibility and resolution of exposed and unexposed areas, it is preferable that the thermoplastic layer contains both a dye, as dye B, whose maximum absorption wavelength changes in response to acid, and a compound that generates acid when exposed to light, as described below.

[0183] The dye B may be used alone or in combination of two or more kinds. From the viewpoint of visibility of exposed and non-exposed areas, the content of dye B is preferably 0.2 mass% or more, more preferably 0.2 mass% to 6 mass%, even more preferably 0.2 mass% to 5 mass%, and particularly preferably 0.25 mass% to 3.0 mass%, relative to the total mass of the thermoplastic resin layer.

[0184] Here, the content of dye B means the content of dye when all of dye B contained in the thermoplastic resin layer is in a colored state. A method for quantifying the content of dye B will be described below using a dye that develops color by radicals as an example. Prepare solutions by dissolving 0.001 g and 0.01 g of dye in 100 mL of methyl ethyl ketone. Add a photoradical polymerization initiator Irgacure OXE01 (product name, BASF Japan Co., Ltd.) to each of the obtained solutions, and irradiate with 365 nm light to generate radicals and make all the dyes colored. Then, measure the absorbance of each solution at a liquid temperature of 25°C using a spectrophotometer (UV3100, manufactured by Shimadzu Corporation) in an air atmosphere, and create a calibration curve. Next, the absorbance of the solution in which all the dye has been colored 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 calibration curve from the absorbance of the solution containing the thermoplastic resin layer obtained.

[0185] (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 upon exposure to actinic rays such as ultraviolet light and visible light. Known photoacid generators, photobase generators, and photoradical polymerization initiators (photoradical generators) can be used as the compound C. Among them, photoacid generators are preferred.

[0186] -Photoacid generator- From the viewpoint of resolution, the thermoplastic resin layer preferably contains a photoacid generator. Examples of the photoacid generator include the above-mentioned cationic photopolymerization initiators which may be contained in the photosensitive resin layer, and preferred aspects are also the same except for the points described below.

[0187] From the viewpoints of sensitivity and resolution, the photoacid generator preferably contains at least one compound selected from the group consisting of an onium salt compound and an oxime sulfonate compound, and from the viewpoints of sensitivity, resolution and adhesion, it is more preferable that the photoacid generator contains an oxime sulfonate compound. As the photoacid generator, a photoacid generator having the following structure is also preferred.

[0188] [ka]

[0189] -Photoradical polymerization initiator- The thermoplastic resin layer may contain a photoradical polymerization initiator (photoradical polymerization initiator). As the photoradical polymerization initiator, the above-mentioned photoradical polymerization initiators which may be contained in the photosensitive resin layer can be mentioned, and the preferred embodiments are also the same.

[0190] -Photobase generator- The thermoplastic resin layer may contain a photobase generator. The photobase generator is not particularly limited as long as it is a known photobase generator, and examples thereof include 2-nitrobenzylcyclohexylcarbamate, triphenylmethanol, O-carbamoylhydroxylamide, O-carbamoyloxime, [[(2,6-dinitrobenzyl)oxy]carbonyl]cyclohexylamine, bis[[(2-nitrobenzyl)oxy]carbonyl]hexane 1,6-diamine, 4-(methylthiobenzoyl)-1-methyl-1-morpholinoethane, (4-morpholinobenzoyl)- Examples of suitable dimethylamino compounds include 1-benzyl-1-dimethylaminopropane, N-(2-nitrobenzyloxycarbonyl)pyrrolidine, hexaamminecobalt(III) tris(triphenylmethylborate), 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone, 2,6-dimethyl-3,5-diacetyl-4-(2-nitrophenyl)-1,4-dihydropyridine, and 2,6-dimethyl-3,5-diacetyl-4-(2,4-dinitrophenyl)-1,4-dihydropyridine.

[0191] The thermoplastic resin layer may contain one type of compound C alone, or may contain two or more types. The content of compound C is preferably 0.1 to 10% by mass, and 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 non-exposed areas.

[0192] (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 (Mw) in the case of an oligomer or polymer) than the alkali-soluble resin. The molecular weight (weight average molecular weight (Mw)) 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. The alkyleneoxy group contained in the plasticizer more preferably has a polyethyleneoxy structure or a polypropyleneoxy structure.

[0193] From the viewpoints of resolution and storage stability, the plasticizer preferably contains a (meth)acrylate compound. From the viewpoints of compatibility, resolution, and adhesion to adjacent layers, it is more preferable that the alkali-soluble resin is an acrylic resin and the plasticizer contains a (meth)acrylate compound. Examples of the (meth)acrylate compound used as the plasticizer include the (meth)acrylate compounds described above as the polymerizable compound contained in the photosensitive resin layer. In the photosensitive transfer member, when the thermoplastic resin layer and the photosensitive resin layer are laminated in direct contact with each other, it is preferable that both the thermoplastic resin layer and the photosensitive resin layer contain the same (meth)acrylate compound, because the thermoplastic resin layer and the photosensitive resin layer each contain the same (meth)acrylate compound, which suppresses component diffusion between the layers and improves storage stability.

[0194] 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 to adjacent layers. In addition, the (meth)acrylate compound used as a plasticizer is preferably a polyfunctional (meth)acrylate compound having two or more (meth)acryloyl groups in one molecule, from the viewpoints of resolution, adhesion to adjacent layers, and developability. Furthermore, as the (meth)acrylate compound used as the plasticizer, a (meth)acrylate compound having an acid group or a urethane (meth)acrylate compound is also preferred.

[0195] The thermoplastic resin layer may contain one type of plasticizer alone, or may contain two or more types of plasticizers. From the viewpoints of resolution, adhesion to adjacent layers, and developability, the content of the plasticizer is preferably 1% by mass to 70% by mass, more preferably 10% by mass to 60% by mass, and particularly preferably 20% by mass to 50% by mass, relative to the total mass of the thermoplastic resin layer.

[0196] (Surfactant) From the viewpoint of thickness uniformity, the thermoplastic resin layer preferably contains a surfactant. As the surfactant, the surfactant which may be contained in the photosensitive resin layer described above can be mentioned, and the preferred embodiments are also the same.

[0197] The thermoplastic resin layer may contain one type of surfactant alone, or may contain two or more types of surfactants. The content of the surfactant is preferably from 0.001% by mass to 10% by mass, and more preferably from 0.01% by mass to 3% by mass, based on the total mass of the thermoplastic resin layer.

[0198] (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 resin layer described above.

[0199] The thermoplastic resin layer may contain one type of sensitizer alone or two or more types of sensitizers. The content of the sensitizer can be appropriately selected depending on the purpose, but from the viewpoints of improving sensitivity to the light source and visibility of exposed and non-exposed areas, it is preferably in the range of 0.01 mass % to 5 mass %, and more preferably in the range of 0.05 mass % to 1 mass %, relative to the total mass of the thermoplastic resin layer.

[0200] (Additives, etc.) The thermoplastic resin layer may contain known additives, if necessary, in addition to the above components. In addition, the thermoplastic resin layer is described in paragraphs

[0189] to

[0193] of JP2014-85643A, the contents of which are incorporated herein by reference.

[0201] <Physical properties, etc.> 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 with adjacent layers. The upper limit is not particularly limited, but is preferably 20 μm or less, more preferably 10 μm or less, and even more preferably 5 μm or less, from the viewpoint of developability and resolution.

[0202] <Formation method> 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-mentioned components. Examples of methods for forming the thermoplastic resin layer include a method in which a thermoplastic resin composition containing the above-mentioned components and a solvent is prepared, the thermoplastic resin composition is applied to a surface of a temporary support or the like, and a coating of the thermoplastic resin composition is dried to form the layer. The thermoplastic resin composition preferably contains a solvent in order to adjust the viscosity of the thermoplastic resin composition and facilitate the formation of the thermoplastic resin layer.

[0203] (solvent) The solvent contained in the thermoplastic resin composition is not particularly limited as long as it can dissolve or disperse the above-mentioned components contained in the thermoplastic resin layer. As the solvent contained in the thermoplastic resin composition, the solvent which may be contained in the photosensitive resin composition described above can be mentioned, and the preferred embodiments are also the same.

[0204] The solvent contained in the thermoplastic resin composition may be one type alone or two or more types. The content of the solvent when applying the thermoplastic resin composition is preferably 50 to 1,900 parts by mass, and more preferably 100 to 900 parts by mass, per 100 parts by mass of the total solid content in the thermoplastic resin composition.

[0205] The preparation of the thermoplastic resin composition and the formation of the thermoplastic resin layer may be carried out in accordance with the above-mentioned method for preparing the photosensitive resin composition and the method for forming the photosensitive resin layer. For example, a solution is prepared in advance by dissolving each component contained in the thermoplastic resin layer in the above-mentioned solvent, and the obtained solutions are mixed in a predetermined ratio to prepare a thermoplastic resin composition, and then, The obtained thermoplastic resin composition is applied to the surface of a temporary support, and the coating of the thermoplastic resin composition is dried to form a thermoplastic resin layer. Alternatively, after forming a photosensitive resin layer and an intermediate layer on a cover film described below, a thermoplastic resin layer may be formed on the surface of the intermediate layer.

[0206] [Middle class] The photosensitive transfer member preferably has an intermediate layer between the thermoplastic resin layer and the photosensitive resin layer, which can prevent the components from mixing when applying multiple layers and during storage after application. The intermediate layer is preferably a water-soluble layer from the viewpoints of developability and suppressing mixing of components when applying a plurality of layers and during storage after application. In this specification, the term "water-soluble" means that the solubility in 100 g of water having a liquid temperature of 22°C and a pH of 7.0 is 0.1 g or more.

[0207] The intermediate layer may be an oxygen-blocking layer having an oxygen-blocking function, which is described as a "separation layer" in JP-A-5-72724. When the intermediate layer is an oxygen-blocking layer, the sensitivity during exposure is improved, the time load of the exposure machine is reduced, and productivity is improved, which is preferable. The oxygen barrier layer used as the intermediate layer may be appropriately selected from known layers described in the above publications, etc. Among them, an oxygen barrier layer that exhibits low oxygen permeability and disperses or dissolves in water or an alkaline aqueous solution (a 1% by mass aqueous solution of sodium carbonate at 22° C.) is preferred.

[0208] The intermediate layer preferably contains a resin. Examples of resins contained in the intermediate layer 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. The resin contained in the intermediate layer is preferably a water-soluble resin. In addition, from the viewpoint of suppressing mixing of components between multiple layers, it is preferable that the resin contained in the intermediate layer is a resin different from both the polymer A contained in the photosensitive resin layer and the thermoplastic resin (alkali-soluble resin) contained in the thermoplastic resin layer.

[0209] From the viewpoints of oxygen barrier properties and suppressing mixing of components when multiple layers are applied and during storage after application, the intermediate layer preferably contains polyvinyl alcohol, and more preferably contains both polyvinyl alcohol and polyvinylpyrrolidone.

[0210] The intermediate layer may contain one type of the above resin alone, or may contain two or more types. The resin content in the intermediate layer is not particularly limited, but from the viewpoints of oxygen barrier properties and suppressing mixing of components when multiple layers are applied and during storage after application, the resin content is preferably 50% by mass to 100% by mass, more preferably 70% by mass to 100% by mass, even more preferably 80% by mass to 100% by mass, and particularly preferably 90% by mass to 100% by mass, relative to the total mass of the intermediate layer. Furthermore, the intermediate layer may contain additives such as a surfactant, if necessary.

[0211] The thickness of the intermediate layer is not particularly limited, but is preferably 0.1 μm to 5 μm, and more preferably 0.5 μm to 3 μm. When the thickness of the intermediate layer is within the above range, the oxygen barrier properties are not reduced, mixing of components can be suppressed when multiple layers are applied and during storage after application, and an increase in the time required to remove the intermediate layer during development can be suppressed.

[0212] The method for forming the intermediate layer is not particularly limited, and examples thereof include a method in which an intermediate layer composition containing the above-mentioned resin and any additives is prepared, applied to the surface of a thermoplastic resin layer or a photosensitive resin layer, and the coating of the intermediate layer composition is dried to form an intermediate layer. The intermediate layer composition preferably contains a solvent in order to adjust the viscosity of the intermediate layer composition and to facilitate the formation of the intermediate layer.

[0213] The solvent contained in the intermediate layer composition is not particularly limited as long as it is capable of dissolving or dispersing the above-mentioned 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 the water-miscible organic solvent 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.

[0214] [Cover film] The photosensitive transfer member preferably includes a cover film in contact with the surface of the photosensitive resin layer that does not face the temporary support. Hereinafter, in this specification, the surface of the photosensitive resin layer facing the temporary support is also referred to as the "first surface", and the surface opposite to the first surface is also referred to as the "second surface".

[0215] Materials constituting the cover film include resin films and paper, with resin films being preferred from the standpoints of strength and flexibility. Examples of the resin film include a polyethylene film, a polypropylene film, a polyethylene terephthalate film, a cellulose triacetate film, a polystyrene film, and a polycarbonate film. Among these, a polyethylene film, a polypropylene film, or a polyethylene terephthalate film is preferable.

[0216] The thickness (layer thickness) of the cover film is not particularly limited, but is preferably from 5 μm to 100 μm, and more preferably from 10 to 50 μm. The arithmetic mean roughness Ra value of the surface of the cover film in contact with the photosensitive resin layer (hereinafter also simply referred to as the "surface of the cover film") is preferably 0.3 μm or less, more preferably 0.1 μm or less, and even more preferably 0.05 μm or less, from the viewpoint of superior resolution. It is believed that the uniformity of the layer thickness of the photosensitive resin layer and the formed resin pattern is improved by the Ra value of the surface of the cover film being within the above range. There is no particular lower limit for the Ra value of the surface of the cover film, but it is preferably 0.001 μm or more.

[0217] The Ra value of the surface of the cover film is measured by the following method. Using a three-dimensional optical profiler (New View7300, manufactured by Zygo), the surface of the cover film is measured under the following conditions to obtain a surface profile of the optical film. The measurement and analysis software used is Microscope Application of MetroPro ver8.3.2. Next, the Surface Map screen is displayed in the analysis software, and histogram data is obtained in the Surface Map screen. From the obtained histogram data, the arithmetic mean roughness is calculated, and the Ra value of the cover film surface is obtained. When a cover film is attached to the photosensitive transfer member, the cover film is peeled off from the photosensitive transfer member, and the Ra value of the surface on the peeled side may be measured.

[0218] The photosensitive transfer member may include layers other than the layers described above (hereinafter, also referred to as "other layers"). Examples of the other layers include a contrast enhancement layer. The contrast enhancement layer is described in paragraph 0134 of WO 2018 / 179640. The other layers are described in paragraphs 0194 to 0196 of JP 2014-85643 A. The contents of these publications are incorporated herein by reference.

[0219] In order to better exert the effects of the present disclosure, the total thickness of each layer in the photosensitive transfer member, excluding the temporary support and the cover film, is preferably 20 μm or less, more preferably 10 μm or less, even more preferably 8 μm or less, and particularly preferably 2 μm or more and 8 μm or less. In addition, from the viewpoint of better exerting the effects of the present disclosure, the total thickness of the photosensitive resin layer, intermediate layer and thermoplastic resin layer in the photosensitive transfer member is preferably 20 μm or less, more preferably 10 μm or less, even more preferably 8 μm or less, and particularly preferably 2 μm or more and 8 μm or less.

[0220] [Method of Manufacturing Photosensitive Transfer Member] The method for producing the photosensitive transfer member used in the present disclosure is not particularly limited, and any known production method, for example, any known method for forming each layer, can be used. Hereinafter, a method for producing a photosensitive transfer member used in the present disclosure will be described with reference to Fig. 2. However, the photosensitive transfer member used in the present disclosure is not limited to the one having the configuration shown in Fig. 2. Fig. 2 is a schematic diagram showing an example of the configuration of a photosensitive transfer member used in the present disclosure. The photosensitive transfer member 100 shown in Fig. 2 has a configuration in which a temporary support 10, a thermoplastic resin layer 12, an intermediate layer 14, a photosensitive resin layer 16, and a cover film 18 are laminated in this order.

[0221] Examples of a method for manufacturing the above-mentioned photosensitive transfer member 100 include a method including the steps of applying a thermoplastic resin composition to the surface of the temporary support 10 and then drying the coating of the thermoplastic resin composition to form a thermoplastic resin layer 12, applying an intermediate layer composition to the surface of the thermoplastic resin layer 12 and then drying the coating of the intermediate layer composition to form an intermediate layer 14, and applying a photosensitive resin composition containing a binder polymer and a polymerizable compound to the surface of the intermediate layer 14 and then drying the coating of the photosensitive resin composition to form a photosensitive resin layer 16. In the above manufacturing method, it is preferable to use a thermoplastic resin composition containing at least one selected from the group consisting of an alkylene glycol ether solvent and an alkylene glycol ether acetate solvent, an intermediate layer composition containing at least one selected from the group consisting of water and a water-miscible organic solvent, and a photosensitive resin composition containing a binder polymer, a polymerizable compound, and at least one selected from the group consisting of an alkylene glycol ether solvent and an alkylene glycol ether acetate solvent. This can suppress mixing of the components contained in the thermoplastic resin layer 12 and the components contained in the intermediate layer 14 during the application of the intermediate layer composition to the surface of the thermoplastic resin layer 12 and / or the storage period of a laminate having a coating film of the intermediate layer composition, and can also suppress mixing of the components contained in the intermediate layer 14 and the components contained in the photosensitive resin layer 16 during the application of the photosensitive resin composition to the surface of the intermediate layer 14 and / or the storage period of a laminate having a coating film of the photosensitive resin composition.

[0222] A cover film 18 is pressure-bonded to the photosensitive resin layer 16 of the laminate produced by the above-mentioned production method, thereby producing a photosensitive transfer member 100. The manufacturing method of the photosensitive transfer member used in the present disclosure preferably includes a step of providing a cover film 18 in contact with the second surface of the photosensitive resin layer 16, thereby manufacturing a photosensitive transfer member 100 having a temporary support 10, a thermoplastic resin layer 12, an intermediate layer 14, a photosensitive resin layer 16 and a cover film 18. After the photosensitive transfer member 100 is manufactured by the above-mentioned manufacturing method, a photosensitive transfer member in a roll form may be manufactured and stored by winding up the photosensitive transfer member 100. The photosensitive transfer member in a roll form can be provided in its original form to a lamination step with a substrate in a roll-to-roll system described later.

[0223] [Circuit wiring manufacturing method] The method for producing a circuit wiring according to the present disclosure is not particularly limited as long as it is a method for producing a circuit wiring that includes the method for producing a resin pattern according to the present disclosure. As a method for manufacturing circuit wiring, a method is preferred in which the substrate has a conductive layer on the surface on which the resin pattern is formed, and the substrate has resin patterns manufactured by the method for manufacturing a resin pattern according to the present disclosure laminated in this order, the method including a step of etching the conductive layer in an area where the resin pattern is not arranged (hereinafter also referred to as an "etching step"). This is more preferred when using a resin pattern manufactured by a manufacturing method including the lamination step, the exposure step, and the development step. Below, each step included in the method for manufacturing circuit wiring will be explained, but unless otherwise specified, the contents explained for each step included in the method for manufacturing resin patterns also apply to each step included in the method for manufacturing circuit wiring.

[0224] [Etching process] The method for manufacturing circuit wiring preferably includes a step (etching step) of etching the conductive layer in an area where the resin pattern is not disposed in a laminate in which a substrate, a conductive layer, and a resin pattern (more preferably a resin pattern manufactured by a manufacturing method including the lamination step, the exposure step, and the development step) are laminated in this order. "Etching the conductive layer in an area where the resin pattern is not disposed" specifically means etching the conductive layer to remove a part of the conductive layer on which the resin pattern is not disposed.

[0225] In the etching process, the conductive layer is etched using the resin pattern formed from the photosensitive resin layer as an etching resist. As the etching method, known methods can be applied, for example, 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 can be mentioned.

[0226] The etching solution used in the wet etching may be an acidic or alkaline etching solution that is appropriately selected depending on the target to be etched. Examples of the acidic etching solution include an aqueous solution of an acidic component selected from hydrochloric acid, sulfuric acid, nitric acid, acetic acid, hydrofluoric acid, oxalic acid, and phosphoric acid, and an aqueous solution of a mixture of an acidic component and a salt selected from ferric chloride, ammonium fluoride, and potassium permanganate. The acidic component may be a combination of a plurality of acidic components. Examples of the alkaline etching solution include an aqueous solution of an alkaline component selected from sodium hydroxide, potassium hydroxide, ammonia, organic amines, and salts of organic amines (e.g., tetramethylammonium hydroxide), and an aqueous solution of a mixture of an alkaline component and a salt (e.g., potassium permanganate). The alkaline component may be a combination of a plurality of alkaline components.

[0227] [Removal process] In the method for producing circuit wiring, it is preferable to carry out a step of removing the remaining resin pattern (removal step). The removal step is not particularly limited and may be carried out as necessary, but is preferably carried out after the etching step. The method for removing the remaining resin pattern is not particularly limited, but includes a method of removing it by chemical treatment, and a method of removing it by using a removing liquid is preferable. The photosensitive resin layer can be removed by immersing the substrate having the remaining resin pattern in a stirring removal liquid having a liquid temperature of preferably 30°C to 80°C, more preferably 50°C to 80°C, for 1 minute to 30 minutes.

[0228] Examples of the removal liquid include removal liquids in which an inorganic or organic alkaline component is dissolved in water, dimethyl sulfoxide, N-methylpyrrolidone, or a mixture thereof. Examples of the inorganic alkaline component include sodium hydroxide and potassium hydroxide. Examples of the organic alkaline component include primary amine compounds, secondary amine compounds, tertiary amine compounds, and quaternary ammonium salt compounds. Alternatively, the removal may be performed by a known method such as a spray method, a shower method, or a paddle method using a removal liquid.

[0229] [Other steps] The method for producing a circuit wiring may include any steps (other steps) other than the steps described above, such as, but not limited to, the following steps. Moreover, examples of the exposure step, development step and other steps that can be applied to the method for producing circuit wiring include the steps described in paragraphs 0035 to 0051 of JP-A No. 2006-23696.

[0230] <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 multiple conductive layers of the substrate. Examples of treatments for reducing the visible light reflectance include oxidation treatments. When the substrate has a conductive layer containing copper, the visible light reflectance of the conductive layer can be reduced by oxidizing the copper to copper oxide and blackening the conductive layer. Treatments for reducing visible light reflectance are described in paragraphs 0017 to 0025 of JP 2014-150118 A, and paragraphs 0041, 0042, 0048, and 0058 of JP 2013-206315 A, and the contents of these publications are incorporated herein by reference.

[0231] <Step of forming an insulating film, step of forming a new conductive layer on the surface of the insulating film> The method for producing the circuit wiring preferably includes the steps of forming an insulating film on the surface of the circuit wiring, and forming a new conductive layer on the surface of the insulating film. By the above steps, a second electrode pattern insulated from the first electrode pattern can be formed. The step of forming the insulating film is not particularly limited, and may be a known method for forming a permanent film. Alternatively, an insulating film having a desired pattern may be formed by photolithography using a photosensitive material having insulating properties. The step of forming a new conductive layer on the insulating film is not particularly limited, and for example, a new conductive layer having a desired pattern may be formed by photolithography using a photosensitive material having conductivity.

[0232] In the method for producing the circuit wiring, a substrate having a plurality of conductive layers on both surfaces of the substrate is used, and circuits are formed on the conductive layers formed on both surfaces of the substrate, either sequentially or simultaneously. With this configuration, a touch panel circuit wiring can be formed in which a first conductive pattern is formed on one surface of the substrate and a second conductive pattern is formed on the other surface of the substrate. It is also preferable to form the touch panel circuit wiring having such a configuration from both sides of the substrate by roll-to-roll.

[0233] [Circuit wiring applications] The circuit wiring manufactured by the manufacturing method of the circuit wiring can be applied to various devices. An example of a device having the circuit wiring manufactured by the manufacturing method is an input device, preferably a touch panel, more preferably a capacitive touch panel. The input device can also be applied to a display device such as an organic EL display device and a liquid crystal display device.

[0234] [Touch panel manufacturing method] The method for producing a touch panel according to the present disclosure is not particularly limited as long as it is a method for producing circuit wiring that includes the method for producing a resin pattern according to the present disclosure. As a method for manufacturing a touch panel, the above-mentioned substrate has a conductive layer on the surface on which the resin pattern is formed, and in a laminate in which resin patterns manufactured using the above-mentioned photosensitive transfer member are laminated in this order, a method including a step of forming wiring for a touch panel by etching the conductive layer in an area where the resin pattern is not arranged is preferred, and this is more preferred when using a resin pattern manufactured by a manufacturing method including the above-mentioned lamination step, the above-mentioned exposure step, and the above-mentioned development step.

[0235] Specific aspects of each step in the method for manufacturing a touch panel, and the order in which each step is performed, are as described above in the sections "Method for manufacturing a resin pattern" and "Method for manufacturing a circuit wiring", and preferred aspects are also the same. The method for manufacturing the touch panel may refer to a known method for manufacturing a touch panel, except that the wiring for the touch panel is formed by the above-mentioned method. Furthermore, the method for manufacturing a touch panel may include any steps (other steps) other than those described above.

[0236] An example of a mask pattern used in manufacturing a touch panel is shown in FIG. 3 and FIG. In pattern A shown in FIG. 3 and pattern B shown in FIG. 4, SL and G are non-image areas (light-shielding areas), and DL is an imaginary representation of an alignment frame. In a method for manufacturing a touch panel, for example, a photosensitive resin layer is exposed through a mask having pattern A shown in FIG. 3 to manufacture a touch panel in which circuit wiring having pattern A corresponding to SL and G is formed. Specifically, it can be manufactured by the method shown in FIG. 1 of WO 2016 / 190405. In one example of the manufactured touch panel, G is a portion where a transparent electrode (electrode for touch panel) is formed, and SL is a portion where wiring of a peripheral extraction portion is formed.

[0237] The above-mentioned method for producing a touch panel produces a touch panel having at least a wiring for a touch panel. The touch panel preferably has a transparent substrate, an electrode, and an insulating layer or a protective layer. Examples of detection methods for touch panels include known methods such as a resistive film method, a capacitive method, an ultrasonic method, an electromagnetic induction method, and an optical method, etc. Among these, the capacitive method is preferred.

[0238] Examples of touch panel types include the so-called in-cell type (e.g., those shown in Figures 5, 6, 7, and 8 of JP-T 2012-517051), the so-called on-cell type (e.g., those shown in Figure 19 of JP-A 2013-168125 and those shown in Figures 1 and 5 of JP-A 2012-89102), the OGS (One Glass Solution) type, the TOL (Touch-on-Lens) type (e.g., those shown in Figure 2 of JP-A 2013-54727), various out-cell types (so-called GG, G1 / G2, GFF, GF2, GF1, G1F, etc.), and other configurations (e.g., those shown in Figure 6 of JP-A 2013-164871). An example of the touch panel is described in paragraph 0229 of JP2017-120345A.

[0239] [Photosensitive transfer material] The photosensitive transfer member according to the present disclosure is a photosensitive transfer member having a temporary support and a photosensitive resin layer, and when the photosensitive transfer member is used to form a resin pattern A on a substrate, the pattern width of the resin pattern A at a portion in contact with the substrate in a cross section in the width direction of the resin pattern A is 6.2 μm or more. Preferred aspects of the photosensitive transfer member according to the present disclosure are the same as the preferred aspects of the photosensitive transfer member used in the method for producing a resin pattern according to the present disclosure described above, except as described below.

[0240] In the photosensitive transfer member of the present disclosure, when a resin pattern A having a pattern width of 6 μm at a position that is 90% of the maximum height from the substrate is formed on a substrate, the pattern width of the resin pattern A in a cross section in the width direction at the portion in contact with the substrate is, from the viewpoints of resolution and linearity, preferably 6.2 μm or more and 9.0 μm or less, more preferably 6.2 μm or more and 8.4 μm or less, even more preferably 6.3 μm or more and 8.0 μm or less, and particularly preferably 6.4 μm or more and 8.0 μm or less. EXAMPLES

[0241] The following examples further illustrate the embodiments of the present invention. The materials, amounts, ratios, processing contents, and processing procedures shown in the following examples can be changed as appropriate without departing from the spirit of the embodiments of the present invention. Therefore, the scope of the embodiments of the present invention is not limited to the specific examples shown below. Unless otherwise specified, "parts" and "%" are based on mass.

[0242] (Examples 1 to 9 and Comparative Examples 1 to 3) <Preparation of Photosensitive Transfer Member> - Formation of thermoplastic resin layer - A PET film having a thickness of 25 μm was prepared as a temporary support. The following thermoplastic resin composition was applied to the surface of the temporary support using a slit nozzle so that the coating width was 1.0 m and the layer thickness after drying was 4.0 μm. The formed coating of the thermoplastic resin composition was dried at 80° C. for 40 seconds to form a thermoplastic resin layer.

[0243] <<Thermoplastic resin composition>> A thermoplastic resin composition was prepared by mixing the following components. Copolymer of benzyl methacrylate, methacrylic acid and acrylic acid (solid concentration 30.0%, Mw 30,000, acid value 153 mg KOH / g): 42.85 parts NK Ester A-DCP (tricyclodecane dimethanol diacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.): 4.63 parts 8UX-015A (polyfunctional urethane acrylate compound, manufactured by Taisei Fine Chemical Co., Ltd.): 2.31 parts Aronix TO-2349 (polyfunctional acrylate compound having a carboxy group, manufactured by Toagosei Co., Ltd.): 0.77 parts Compound with the structure shown below (photoacid generator, compound synthesized according to the method described in paragraph 0227 of JP2013-47765A): 0.32 parts

[0244] [ka]

[0245] Compound with the structure shown below (coloring agent that changes color when exposed to acid): 0.08 parts

[0246] [ka]

[0247] E-1 (Megafac F552 (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

[0248] - Formation of the intermediate layer - The intermediate layer composition was applied to the surface of the formed thermoplastic resin layer using a slit nozzle so that the coating width was 1.0 m and the layer thickness after drying was 1.2 μm. The coating of the intermediate layer composition was dried at 80° C. for 40 seconds to form an intermediate layer.

[0249] <<Interlayer composition>> An intermediate layer composition was prepared by mixing the following components: Ion-exchanged water: 38.12 parts Methanol (manufactured by 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 nonionic surfactant, manufactured by DIC Corporation): 0.0015 parts

[0250] - Formation of photosensitive resin layer - On the surface of the formed intermediate layer, any one of the photosensitive resin compositions A-1 to A-7 or AH-1 to AH-3 described in Table 1 was applied using a slit nozzle so that the coating width was 1.0 m and the layer thickness after drying was the thickness described in Table 1. The coating film of any one of the photosensitive resin compositions A-1 to A-7 or AH-1 to AH-3 was dried at 80° C. for 40 seconds to form a photosensitive resin layer.

[0251] [Table 1]

[0252] The compositions of the photosensitive resin compositions A-1 to A-7 and AH-1 to AH-3 used are shown in Table 2 below.

[0253] [Table 2]

[0254] In Table 2, "Mm / Mb" represents the ratio Mm / Mb of the polymerizable compound content Mm to the binder polymer content Mb in the photosensitive resin layer, and "acrylic compound content" represents the acrylic compound content relative to the total mass of (meth)acrylic compounds contained in the photosensitive resin layer, expressed in mass %.

[0255] Details of the abbreviations in Table 2 are shown below. BPE-500: Ethoxylated (10 molar equivalents) bisphenol A dimethacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.) BPE-200: Ethoxylated (4 molar equivalents) bisphenol A dimethacrylate (Shin-Nakamura Chemical Co., Ltd.) M-270: Polypropylene glycol diacrylate (n = approx. 12) (manufactured by Toagosei Co., Ltd.) A-TMPT: Trimethylolpropane triacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.) SR-454: Ethoxylated trimethylolpropane triacrylate (Arkema) SR-502: Ethoxylated (9 molar equivalents) trimethylolpropane triacrylate (Arkema) A-9300-CL1: ε-caprolactone modified tris-(2-acryloxyethyl) isocyanurate (manufactured by Shin-Nakamura Chemical Co., Ltd.) B-CIM: 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-bisimidazole (polymerization initiator, manufactured by Kurogane Kasei Co., Ltd.) SB-PI 701: 4,4'-bis(diethylamino)benzophenone (sensitizer, Sanyo Trading Co., Ltd.) CBT-1: Carboxybenzotriazole (rust inhibitor, manufactured by Johoku Chemical Industry Co., Ltd.) TDP-G: Phenothiazine (polymerization inhibitor, manufactured by Kawaguchi Chemical Industry Co., Ltd.) Irganox245: ethylene bis(oxyethylene)bis(3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate) (polymerization inhibitor, manufactured by BASF) F-552: Fluorine-based surfactant (DIC Corporation)

[0256] -Attaching the cover film- A PET film (manufactured by Toray Industries, Inc., Lumirror 16QS62, arithmetic mean roughness (Ra value) 0.02 μm) was pressure-bonded as a cover film to the surface of the formed photosensitive resin layer to prepare a photosensitive transfer member for each example. The obtained photosensitive transfer member was wound up to prepare a roll-shaped photosensitive transfer member.

[0257] <Preparation of Laminate> The cover films of the photosensitive transfer members F-1 to F-9, FH-1, and FH-2 prepared above were peeled off, and the peeled surface of the photosensitive transfer member was brought into contact with a copper substrate. The copper substrate was prepared by sputtering copper onto a PET film to form a copper layer of 200 μm in thickness, and laminated under the following lamination conditions to obtain a laminate. -Lamination conditions- Copper board temperature: 40℃ Rubber roller temperature: 110℃ Linear pressure: 3N / cm Conveying speed: 2m / min

[0258] <Exposure> Next, an exposure mask having an exposure pattern of line & space = 6 μm / 6 μm was attached to the temporary support on the side of the laminate where the photosensitive transfer member was laminated, and the resist pattern was exposed through the exposure mask using a proximity type exposure machine (manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.) equipped with an ultra-high pressure mercury lamp, with an exposure amount such that the width of the height at a position 90% of the maximum height of the resist pattern was 6 μm.

[0259] <Development> Thereafter, the temporary support was peeled off from the exposed laminate, and the laminate was developed using a 1.0% aqueous sodium carbonate solution at 26° C. for 30 seconds. Next, a cleaning treatment was carried out using pure water at 26° C. for 30 seconds. Next, air was blown onto the surface to remove moisture, thereby producing a substrate having a resin pattern. The developing process and the washing process were carried out using a shower type developing machine, and the spray pressure was 0.08 MPa.

[0260] <Etching and peeling> The copper layer of the substrate having the resin pattern was shower-etched for 60 seconds using a copper etching solution (Cu-02, manufactured by Kanto Chemical Co., Ltd.) at 25°C. Thereafter, the resin pattern was removed by shower stripping using a stripping solution (KP-301, manufactured by Kanto Chemical Co., Ltd.) at 60° C. for 2 minutes, thereby producing a circuit wiring A.

[0261] <Measurement of resist line width in exposed area> The substrate having the resin pattern thus produced was cut along a plane perpendicular to the line direction of the line pattern. The cross section of the line pattern was observed from the cross section side using a scanning electron microscope (SEM), and the width of the resist was measured. In addition, the layer thickness of the non-exposed area of ​​the same sample as above was measured.

[0262] <Evaluation> -Resolution evaluation- Using a circuit wiring pattern mask with lines and spaces of various widths, wiring samples were prepared after removing the resist in the same manner as above. The wiring portions of the obtained wiring samples were observed with an optical microscope, and the resolution was evaluated according to the width of the thinnest line that was resolved, using the following evaluation criteria. A: The thinnest line that can be resolved is 6 μm or less in width. B: The width of the thinnest resolved line is greater than 6 μm and less than 10 μm. C: The thinnest resolved line width is greater than 10 μm.

[0263] - Linearity evaluation - The width of the wiring was measured at 20 randomly selected points on the wiring sample. The standard deviation σ was calculated from the obtained line width data, and the standard deviation σ was multiplied by three to define LWR (Line Width Roughness) as an index of pattern linearity. By definition, the smaller the LWR, the smaller the line width fluctuation, which is preferable. A: LWR value is 200nm or less B: LWR value is greater than 200 nm and less than 300 nm C: LWR value is greater than 300 nm

[0264] Example 10 A substrate having a resin pattern and circuit wiring A were produced in the same manner as in Example 5, except that during the above exposure, the exposure pattern of lines and spaces = 6 μm / 6 μm was changed to an exposure pattern of lines and spaces = 8 μm / 8 μm. Moreover, evaluation was carried out in the same manner as in Example 5.

[0265] Example 11 A substrate having a resin pattern and circuit wiring A were produced in the same manner as in Example 5, except that during the above exposure, the exposure pattern of lines and spaces = 6 μm / 6 μm was changed to an exposure pattern of lines and spaces = 4 μm / 4 μm. Moreover, evaluation was carried out in the same manner as in Example 5.

[0266] Example 12 During the above development, the development conditions were changed from using a 1.0% aqueous sodium carbonate solution at 26°C for 30 seconds to using a 1.2% aqueous potassium carbonate solution at 30°C for 30 seconds, in the same manner as in Example 5, except that a substrate having a resin pattern and a circuit wiring A were produced. Moreover, evaluation was carried out in the same manner as in Example 5.

[0267] [Table 3]

[0268] As shown in Table 3 above, the resin pattern manufacturing methods and photosensitive transfer members of Examples 1 to 12 have superior resolution of the obtained etching patterns such as wiring, compared to the resin pattern manufacturing methods and photosensitive transfer members of Comparative Examples 1 to 3. Furthermore, as shown in Table 3 above, the resin pattern production methods and photosensitive transfer members of Examples 1 to 12 provide etching patterns with excellent linearity.

[0269] The disclosure of Japanese Patent Application No. 2020-017720, filed on February 5, 2020, is incorporated herein by reference in its entirety. In addition, all documents, patent applications, and technical standards described herein are incorporated herein by reference to the same extent as if each individual document, patent application, and technical standard was specifically and individually indicated to be incorporated by reference.

Claims

1. A method for producing a resin pattern, comprising the steps of: forming a resin pattern on a substrate using a photosensitive transfer member having a temporary support and a photosensitive resin layer, the method comprising the steps of: In a cross section in a width direction of the resin pattern, a value obtained by subtracting a pattern width at a position corresponding to 90% of a maximum height of the resin pattern from a pattern width at a portion of the resin pattern in contact with the substrate is 0.2 μm or more and 2.4 μm or less, the photosensitive resin layer is a single-layer negative photosensitive resin layer, and contains a polymerizable compound, a binder polymer, and a photopolymerization initiator; the binder polymer comprises a copolymer of (meth)acrylic acid and at least one monomer which is non-acidic and has at least one polymerizable unsaturated group in the molecule; The resin pattern to be produced includes a resin pattern having a pattern width of 6 μm or less, the polymerizable compound in the photosensitive resin layer contains a (meth)acrylic compound, The content of the acrylic compound relative to the total mass of the (meth)acrylic compound contained in the photosensitive resin layer is 60 mass% or less. A method for producing a resin pattern.

2. 2. The method for producing a resin pattern according to claim 1, wherein the photosensitive resin layer has a thickness of 8 [mu]m or less.

3. 3. The method for producing a resin pattern according to claim 1, wherein the temporary support has a thickness of 25 μm or less.

4. 4. The method for producing a resin pattern according to claim 1, wherein a ratio Mm / Mb of a content Mm of the polymerizable compound to a content Mb of the binder polymer in the photosensitive resin layer is 0.9 or less.

5. the substrate has a conductive layer on a surface on which the resin pattern is formed, A method for manufacturing a resin pattern according to any one of claims 1 to 4, comprising the step of etching the conductive layer in an area where the resin pattern is not disposed to form a circuit wiring in a laminate having the resin pattern on the substrate manufactured by the method for manufacturing a resin pattern according to any one of claims 1 to 4. A method for manufacturing circuit wiring.

6. the substrate has a conductive layer on a surface on which the resin pattern is formed, The method includes the step of forming wiring for a touch panel by etching the conductive layer in an area where the resin pattern is not arranged in a laminate having the resin pattern on the substrate manufactured by the method for manufacturing a resin pattern according to any one of claims 1 to 4. A method for manufacturing a touch panel.

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