Photosensitive transfer material, method for manufacturing a resin pattern, method for manufacturing a laminate, method for manufacturing a circuit wiring, and method for manufacturing an electronic device

Abstract

A photosensitive transfer material is provided that comprises a temporary support body and a photosensitive layer, wherein the photosensitive layer contains a polymerization initiator and a polymerizable compound, the polymerization initiator either contains a radical polymerization initiator and a cation polymerization initiator or contains a polymerization initiator that generates a radical and an acid, and the polymerizable compound contains a radical polymerizable compound and a cation polymerizable compound; also provided are a resin pattern manufacturing method that uses the photosensitive transfer material, a laminate manufacturing method, a circuit wiring manufacturing method and an electronic device manufacturing method.

Description

[Technical Field]

[0001] The present disclosure relates to a photosensitive transfer material, a method for producing a resin pattern, a method for producing a laminate, a method for producing circuit wiring, and a method for producing an electronic device. [Background technology]

[0002] In display devices (such as organic electroluminescence (EL) display devices and liquid crystal display devices) equipped with touch panels such as capacitance-type input devices, conductive layer patterns such as electrode patterns corresponding to the sensors of the visible area, and wiring for 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 formed on a substrate using a photosensitive transfer material is exposed to light through a mask having a desired pattern, and then developed.

[0003] Furthermore, as a conventional photosensitive resin laminate, one described in JP-A-2019-133143 is known. JP 2019-133143 A describes a photosensitive resin laminate for exposure after support film peeling, which comprises a support film and a photosensitive resin composition layer disposed on the support film and containing a photosensitive resin composition, wherein the photosensitive resin composition contains (A) an alkali-soluble polymer, (B) a compound reactive with a photoinitiator, and (C) a photoinitiator. A 0.4 mm thick copper-clad laminate laminated with a 35 μm rolled copper foil is jet-scrubbed using a #400 abrasive and then preheated to 60 ° C., and the photosensitive resin laminate is laminated to the copper-clad laminate using a hot roll laminator at a roll temperature of 105 ° C., an air pressure of 0.35 MPa, and a lamination speed of 1.5 m / min. Then, the following conditions (1) and (2) are met: (1) Exposing the support film surface to light using an exposure device with the focal position adjusted, and peeling the support film from the photosensitive resin composition layer after exposure; (2) Peeling off the support film, and then exposing the film using an exposure device with the focus adjusted to the area that was previously the surface of the support film. and then using a fine particle alkaline developer, spray a 1% by mass Na2CO3 aqueous solution at 30°C for twice the minimum developing time to remove unexposed areas, rinse with pure water for the same time as the developing time, remove water with an air knife, and then dry with hot air to obtain a resist pattern in which the difference in the minimum patternable independent fine line width between the first resist pattern obtained by exposure under the above condition (1) and the second resist pattern obtained by exposure under the above condition (2) is 5 μm or less, The exposure apparatus includes: (a) an exposure device with an exposure light peak wavelength of 350 to 370 nm; (b) an exposure device with a peak wavelength of exposure light of 400 to 410 nm; (c) an exposure device in which the peak wavelengths of the exposure light are 360 ​​to 380 nm and 390 to 410 nm, and the wavelength intensity ratio is 360 to 380 nm:390 to 410 nm=30:70; and (d) Mercury short arc lamp The photosensitive resin laminate for exposure after peeling off the support film is described. Summary of the Invention [Problem to be solved by the invention]

[0004] The problem to be solved by one embodiment of the present invention is to provide a photosensitive transfer material that has excellent resolution even when the photosensitive layer is directly exposed without using a temporary support. Another problem to be solved by other embodiments of the present invention is to provide a method for manufacturing a resin pattern using the above-mentioned photosensitive transfer material, a method for manufacturing a laminate, a method for manufacturing circuit wiring, and a method for manufacturing an electronic device. [Means for solving the problem]

[0005] The means for solving the above problems include the following aspects. <1> A photosensitive transfer material having a temporary support and a photosensitive layer, wherein the photosensitive layer contains a polymerization initiator and a polymerizable compound, the polymerization initiator contains a radical polymerization initiator and a cationic polymerization initiator, or contains a polymerization initiator that generates radicals and an acid, and the polymerizable compound contains a radical polymerizable compound and a cationic polymerizable compound. <2> The pKa of the acid generated from the cationic polymerization initiator or the polymerization initiator that generates radicals and an acid is −5 or less. <1> The photosensitive transfer material according to claim 1. <3> The polymerization initiator includes a radical polymerization initiator and a cationic polymerization initiator. <1> or <2> The photosensitive transfer material according to claim 1. <4> The molecular weight or weight average molecular weight of the radical polymerizable compound is 2,000 or less. <1> ~ <3> 10. The photosensitive transfer material according to any one of the above items. <5> The molecular weight or weight average molecular weight of the cationic polymerizable compound is 2,000 or less. <1> ~ <4> 10. The photosensitive transfer material according to any one of the above items. <6> The radical polymerizable compound includes a radical polymerizable compound having two or more functionalities. <1> ~ <5> 10. The photosensitive transfer material according to any one of the above items. <7> The radical polymerizable compound includes a radical polymerizable compound having three or more functional groups. <1> ~ <6> 10. The photosensitive transfer material according to any one of the above items. <8> The radical polymerizable compound includes a radical polymerizable compound having a polyethylene oxide structure. <1> ~ <7> 10. The photosensitive transfer material according to any one of the above items. <9> An intermediate layer is further provided between the temporary support and the photosensitive layer. <1> ~ <8> 10. The photosensitive transfer material according to any one of the above items. <10> <1> ~ <9> a step of bonding the photosensitive transfer material described in any one of the above items to the substrate so that the photosensitive layer side of the photosensitive transfer material is in contact with the substrate; a step of peeling off the temporary support; and a step of exposing and developing the exposed photosensitive layer to form a pattern, in this order. <11> <1> ~ <9> A method for manufacturing a laminate, comprising, in this order, a step of bonding the photosensitive transfer material described in any one of the above items to a substrate so that the photosensitive layer side of the photosensitive transfer material contacts the substrate, a step of peeling off the temporary support, and a step of exposing and developing the exposed photosensitive layer to form a pattern. <12> <1> ~ <9> a step of bonding the photosensitive transfer material described in any one of the above to a substrate having a conductive layer so that the photosensitive layer side of the photosensitive transfer material is in contact with the conductive layer of the substrate; a step of peeling off the temporary support; a step of exposing and developing the exposed photosensitive layer to form a pattern; and a step of etching the conductive layer in an area where the pattern is not arranged. <13> <1> ~ <9> a step of bonding the photosensitive transfer material described in any one of the above to a substrate having a conductive layer so that the photosensitive layer side of the photosensitive transfer material is in contact with the conductive layer of the substrate; a step of peeling off the temporary support; a step of exposing and developing the exposed photosensitive layer to form a pattern; and a step of etching the conductive layer in an area where the pattern is not arranged. [Effects of the Invention]

[0006] According to one embodiment of the present invention, it is possible to provide a photosensitive transfer material that is excellent in resolution even when the photosensitive layer is directly exposed without using a temporary support. According to other embodiments of the present invention, there can be provided a method for producing a resin pattern using the above-mentioned photosensitive transfer material, a method for producing a laminate, a method for producing circuit wiring, and a method for producing an electronic device. [Brief explanation of the drawings]

[0007] [Figure 1] FIG. 1 is a schematic diagram showing an example of the configuration of a photosensitive transfer material. [Figure 2] FIG. 2 is a schematic plan view showing pattern A. [Figure 3] FIG. 3 is a schematic plan view showing pattern B. DETAILED DESCRIPTION OF THE INVENTION

[0008] The present disclosure will be described below with reference to the accompanying drawings, in which reference numerals may be omitted. Furthermore, in this specification, a numerical range expressed using "to" means a range that includes the numerical values ​​before and after "to" as the lower and upper limits. In addition, in this specification, "(meth)acrylic" represents both or either of acrylic and methacrylic, "(meth)acrylate" represents both or either of acrylate and methacrylate, and "(meth)acryloyl" represents both or either of acryloyl and methacryloyl. Furthermore, in this specification, the amount of each component in a composition means the total amount of the corresponding substances present in the composition, unless otherwise specified, when multiple substances corresponding to each component are present in the composition. 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 a notation does not specify whether the group is substituted or unsubstituted, it 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, light used for exposure generally includes the bright line spectrum of a mercury lamp, far ultraviolet light typified by excimer lasers, 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 written as simplified structural formulas in which hydrogen atoms are omitted. In the present disclosure, "% by mass" and "% by weight" are synonymous, and "parts by mass" and "parts by weight" are synonymous. Also, in the present disclosure, a combination of two or more preferred embodiments is a more preferred embodiment. Furthermore, unless otherwise specified, the weight-average molecular weight (Mw) and number-average molecular weight (Mn) in the present disclosure are molecular weights determined by gel permeation chromatography (GPC) using columns of TSKgel GMHxL, TSKgel G4000HxL, or TSKgel G2000HxL (all trade names manufactured by Tosoh Corporation), detection with a differential refractometer using THF (tetrahydrofuran) as a solvent, and conversion using polystyrene as a standard substance. As used herein, the term "total solid content" refers to the total mass of the components of the composition excluding the solvent. As described above, the term "solid content" refers to the components excluding the solvent, and may be solid or liquid at 25°C, for example.

[0009] (Photosensitive transfer material) The photosensitive transfer material according to the present disclosure has a temporary support and a photosensitive layer, the photosensitive layer containing a polymerization initiator and a polymerizable compound, the polymerization initiator containing a radical polymerization initiator and a cationic polymerization initiator, or a polymerization initiator that generates radicals and an acid, and the polymerizable compound containing a radical polymerizable compound and a cationic polymerizable compound.

[0010] The present inventors have discovered that in a conventional wiring formation process using a photosensitive transfer material, when a photosensitive layer bonded to a substrate is exposed to light after the temporary support is peeled off, oxygen present in the atmosphere penetrates into the photosensitive layer, inhibiting polymerization and reducing resolution. As a result of detailed investigations by the present inventors, the present inventors have found that by adopting the above-mentioned embodiment, excellent resolution can be achieved even when the photosensitive layer is directly exposed without using a temporary support. In the photosensitive transfer material according to the present disclosure, not only a radical polymerization reaction, in which the radicals that are the polymerization initiation species are easily deactivated by oxygen, but also a cationic polymerization reaction, in which oxygen has little effect on polymerization, is used in combination, thereby making it possible to produce a photosensitive layer that is less susceptible to the effects of polymerization inhibition by oxygen, and it is estimated that the photosensitive layer will have excellent resolution even when exposed directly without a temporary support.

[0011] The photosensitive transfer material according to the present disclosure preferably has a temporary support and a photosensitive layer in this order, and a temporary support, a photosensitive layer, and a protective film in this order. The photosensitive transfer material according to the present disclosure may also have other layers between the temporary support and the photosensitive layer, between the photosensitive layer and the protective film, or the like. Furthermore, the photosensitive transfer material according to the present disclosure preferably further has an intermediate layer between the temporary support and the photosensitive layer. The photosensitive transfer material according to the present disclosure is preferably a roll-shaped photosensitive transfer material from the viewpoint of further exerting the effects of the present disclosure.

[0012] An example of an embodiment of the photosensitive transfer material according to the present disclosure is shown below, but the present disclosure is not limited thereto. (1) "Temporary support / photosensitive layer / refractive index adjusting layer / protective film" (2) "Temporary support / photosensitive layer / protective film" (3) "Temporary support / intermediate layer / photosensitive layer / protective film" (4) "Temporary support / thermoplastic resin layer / intermediate layer / photosensitive layer / protective film" In each of the above configurations, the photosensitive layer is preferably a negative photosensitive layer. It is also preferable that the photosensitive layer is a colored resin layer. The photosensitive transfer material according to the present disclosure is preferably used as a photosensitive transfer material for etching resist. When used as a photosensitive transfer material for etching resist, the photosensitive transfer material preferably has the configurations (2) to (4) described above.

[0013] In the photosensitive transfer material, when the photosensitive layer further has other layers on the side opposite the temporary support side, the total thickness of the other layers arranged on the side opposite the temporary support side of the photosensitive layer is preferably 0.1% to 30% of the thickness of the photosensitive layer, and more preferably 0.1% to 20%.

[0014] Hereinafter, the photosensitive transfer material according to the present disclosure will be described with reference to a specific embodiment.

[0015] An example of the photosensitive transfer material will be described below. The photosensitive transfer material 20 shown in FIG. 1 has a temporary support 11, a transfer layer 12 including a thermoplastic resin layer 13, an intermediate layer 15 and a photosensitive layer 17, and a protective film 19 in this order. Furthermore, the photosensitive transfer material 20 shown in FIG. 1 has a configuration in which the thermoplastic resin layer 13 and the intermediate layer 15 are arranged, but the thermoplastic resin layer 13 and the intermediate layer 15 do not necessarily have to be arranged. Each element constituting the photosensitive transfer material will be described below.

[0016] [Temporary support] The photosensitive transfer material used in the present disclosure has a temporary support. The temporary support is a peelable support that supports the photosensitive layer or a laminate including the photosensitive layer.

[0017] The temporary support preferably has optical transparency so that the photosensitive layer can be exposed through the temporary support when the photosensitive layer is subjected to patternwise exposure. In this specification, "having optical transparency" 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 layer, the temporary support preferably has a transmittance of 60% or more, more preferably 70% or more, for light of the wavelength used for pattern exposure (more preferably a wavelength of 365 nm). The transmittance of the layer of the photosensitive transfer material is the ratio of the intensity of the emitted light that has passed through the layer to the intensity of the incident light when light is incident in a direction perpendicular to the main surface of the layer (thickness direction), and is measured using the MCPD Series manufactured by Otsuka Electronics Co., Ltd.

[0018] Examples of materials constituting the temporary support include a glass substrate, a resin film, and paper, with a resin film being preferred from the viewpoints of strength, flexibility, and light transmittance. Examples of the resin film include a polyethylene terephthalate (PET) film, a cellulose triacetate film, a polystyrene film, and a polycarbonate film. Of these, a PET film is preferred, and a biaxially stretched PET film is more preferred.

[0019] The thickness (layer thickness) of the temporary support is not particularly limited, and may be selected according to the material from the viewpoints of the strength as a support, the flexibility required for bonding to the circuit wiring formation substrate, and the 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 viewpoint 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, more preferably 25 μm or less, and particularly preferably 20 μm or less, from the viewpoint of defect suppression, resolution, and linearity of the resin pattern.

[0020] Furthermore, it is preferable that the film used as the temporary support is free from deformations such as wrinkles, scratches, defects, and the like. From the viewpoint of pattern formation during pattern exposure through the temporary support and the transparency of the temporary support, it is preferable that the number of fine particles, foreign matter, 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 Preferably, it is 10 pieces / 10 mm or less. 2It is more preferable that the number is less than 3 / 10 mm. 2 More preferably, it is 0 pieces / 10 mm or less. 2 It is particularly preferred that:

[0021] From the viewpoints of suppressing defects in the resin pattern, resolution, and transparency of the temporary support, it is preferable that the haze of the temporary support is small. Specifically, the haze value of the temporary support is preferably 2% or less, more preferably 1.5% or less, even more preferably less than 1.0%, and particularly preferably 0.5% or less. The haze value in the present disclosure is measured using a haze meter (NDH-2000, manufactured by Nippon Denshoku Industries Co., Ltd.) according to a method in accordance with JIS K 7105:1981.

[0022] A layer containing fine particles (lubricant layer) may be provided on the surface of the temporary support to improve handling properties. The lubricant layer may be provided on one side or both sides of the temporary support. The diameter of the particles contained in the lubricant layer may be, for example, 0.05 μm to 0.8 μm. The thickness of the lubricant layer may be, for example, 0.05 μm to 1.0 μm.

[0023] From the viewpoints of transportability, suppression of defects in the resin pattern, and resolution, it is preferable that the arithmetic mean roughness Ra of the surface of the temporary support opposite to the photosensitive layer side is equal to or greater than the arithmetic mean roughness Ra of the surface of the temporary support facing the photosensitive layer. The arithmetic mean roughness Ra of the surface of the temporary support opposite to the photosensitive layer side is preferably 100 nm or less, more preferably 50 nm or less, even more preferably 20 nm or less, and particularly preferably 10 nm or less, from the viewpoints of transportability, suppression of defects in the resin pattern, and resolution. The arithmetic mean roughness Ra of the surface of the temporary support facing the photosensitive layer is preferably 100 nm or less, more preferably 50 nm or less, even more preferably 20 nm or less, and particularly preferably 10 nm or less, from the viewpoints of releasability of the temporary support, suppression of defects in the resin pattern, and resolution. Furthermore, the value of the arithmetic mean roughness Ra of the surface of the temporary support opposite to the photosensitive layer side - the arithmetic mean roughness Ra of the surface of the temporary support facing the photosensitive layer is preferably 0 nm to 10 nm, more preferably 0 nm to 5 nm, from the viewpoints of transportability, suppression of defects in the resin pattern, and resolution.

[0024] The arithmetic mean roughness Ra of the surface of the temporary support or protective film in the present disclosure is measured by the following method. Using a three-dimensional optical profiler (New View 7300, manufactured by Zygo), the surface of the temporary support or protective film is measured under the following conditions to obtain a surface profile of the film. The measurement and analysis software used was MetroPro ver. 8.3.2 Microscope Application. Next, the Surface Map screen was displayed in the analysis software, and histogram data was obtained from the Surface Map screen. From the obtained histogram data, the arithmetic mean roughness was calculated, and the Ra value of the surface of the temporary support or protective film was obtained. When a temporary support or a protective film is attached to the photosensitive layer or the like, the temporary support or the protective film may be peeled off from the photosensitive layer, and the Ra value of the surface on the peeled side may be measured.

[0025] The peeling force of the temporary support, specifically the peeling force between the temporary support and the photosensitive layer or the thermoplastic resin layer, is preferably 0.5 mN / mm or more, and more preferably 0.5 mN / mm to 2.0 mN / mm, from the viewpoint of suppressing peeling of the temporary support caused by adhesion between stacked laminates when the wound-up laminate is transported again by the roll-to-roll method.

[0026] The peel strength of the temporary support in the present disclosure is measured as follows. A copper layer with a thickness of 200 nm is formed on a polyethylene terephthalate (PET) film with a thickness of 100 μm by sputtering to prepare a PET substrate with a copper layer. The protective film was peeled off from the prepared photosensitive transfer material and laminated onto the copper-layered PET substrate under lamination conditions of a laminating roll temperature of 100°C, a linear pressure of 0.6 MPa, and a linear speed (lamination speed) of 1.0 m / min. Next, tape (PRINTACK, manufactured by Nitto Denko Corporation) was applied to the surface of the temporary support, and the laminate consisting of at least the temporary support and photosensitive layer on the copper-layered PET substrate was cut into a 70 mm x 10 mm sample. The PET substrate side of the sample was fixed onto a sample stand. Using a tension / compression testing machine (SV-55, manufactured by Imada Seisakusho Co., Ltd.), the tape is pulled in a 180-degree direction at 5.5 mm / sec to peel the photosensitive layer or thermoplastic resin layer from the temporary support, and the force required for peeling (peeling force) or adhesion force is measured.

[0027] Preferred embodiments of the temporary support are described, for example, in paragraphs 0017 to 0018 of JP-A-2014-85643, paragraphs 0019 to 0026 of JP-A-2016-27363, paragraphs 0041 to 0057 of WO 2012 / 081680, paragraphs 0029 to 0040 of WO 2018 / 179370, and paragraphs 0012 to 0032 of JP-A-2019-101405, the contents of which are incorporated herein by reference.

[0028] [Photosensitive layer] The photosensitive transfer material according to the present disclosure has a photosensitive layer, and the photosensitive layer contains a polymerization initiator and a polymerizable compound, the polymerization initiator contains a radical polymerization initiator and a cationic polymerization initiator, or contains a polymerization initiator that generates radicals and an acid, and the polymerizable compound contains a radical polymerizable compound and a cationic polymerizable compound. The photosensitive layer is a negative-working photosensitive layer. The photosensitive layer preferably contains an alkali-soluble resin, a polymerizable compound, and a polymerization initiator, and more preferably contains, based on the total mass of the photosensitive layer, 10% by mass to 90% by mass of the alkali-soluble resin; 5% by mass to 70% by mass of the polymerizable compound; and 0.01% by mass to 20% by mass of the polymerization initiator. Each component will be explained in turn below.

[0029] <Polymerization initiator> The photosensitive layer contains a polymerization initiator, and the polymerization initiator contains a radical polymerization initiator and a cationic polymerization initiator, or contains a polymerization initiator that generates radicals and an acid. The polymerization initiator is preferably a photopolymerization initiator. A photopolymerization initiator is a compound that initiates polymerization of a polymerizable compound when exposed to actinic rays such as ultraviolet light, visible light, and X-rays. The photopolymerization initiator is not particularly limited, and known photopolymerization initiators can be used. Examples of the photopolymerization initiator include a photoradical polymerization initiator and a photocationic polymerization initiator. In particular, from the viewpoints of resolution and pattern formability, the photosensitive layer preferably contains a radical polymerization initiator and a cationic polymerization initiator, and more preferably contains a photoradical polymerization initiator and a photocationic polymerization initiator.

[0030] Furthermore, the pKa of the acid generated from the cationic polymerization initiator or the polymerization initiator that generates radicals and an acid is preferably 0 or less, more preferably -2 or less, even more preferably -5 or less, and particularly preferably -10 to -30, from the viewpoints of resolution and pattern formability.

[0031] The pKa of an acid in the present disclosure can be calculated using Advanced Chemistry Development (ACD / Labs) Software V11.02 (1994-2014 ACD / Labs) or can be a value described in the literature (for example, J. Phys. Chem. A 2011, 115, 6641-6645, etc.). In addition, if the calculated value differs from the value in the literature, the calculated value takes precedence.

[0032] 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, a photopolymerization initiator having an N-phenylglycine structure, and a biimidazole compound.

[0033] As the photoradical polymerization initiator, for example, 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.

[0034] Examples of the photoradical polymerization initiator include ethyl dimethylaminobenzoate (DBE, CAS No. 10287-53-3), benzoin methyl ether, anisyl (p,p'-dimethoxybenzyl), TAZ-110 (trade name: manufactured by Midori Chemical Industry Co., Ltd.), benzophenone, TAZ-111 (trade name: manufactured by Midori Chemical Industry Co., Ltd.), IrgacureOXE01, OXE02, OXE03, OXE04 (manufactured by BASF), Omnirad651 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.).

[0035] 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), and 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one (trade name: Omnirad 907, IGM Resins BV), 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)benzyl]phenyl}-2-methylpropan-1-one (trade name: Omnirad 127, IGM Resins BV), 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone-1 (trade name: Omnirad 369, IGM Resins BV), 2-hydroxy-2-methyl-1-phenylpropan-1-one (trade name: Omnirad 1173, IGM Resins BV), 1-hydroxycyclohexyl phenyl ketone (trade name: Omnirad 184, IGM Resins BV), 2,2-dimethoxy-1,2-diphenylethan-1-one (trade name: Omnirad 651, 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 BV)Examples of photopolymerization initiators include an oxime ester-based photopolymerization initiator (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.).

[0036] A photocationic polymerization initiator (photoacid generator) is a compound that generates an acid when exposed to actinic rays. The photocationic polymerization initiator is preferably a compound that responds to actinic rays with a wavelength of 300 nm or more, preferably 300 to 450 nm, and generates an acid, but the chemical structure is not limited. Furthermore, even if a photocationic polymerization initiator is not directly sensitive to actinic rays with 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 with a wavelength of 300 nm or more and generates an acid when used in combination with a sensitizer.

[0037] Examples of the photocationic polymerization initiator include an ionic photocationic polymerization initiator and a nonionic photocationic polymerization initiator. Examples of the ionic photocationic polymerization initiator include onium salt compounds such as diaryliodonium salts and triarylsulfonium salts, and quaternary ammonium salts. As the ionic photocationic polymerization initiator, the ionic photocationic polymerization initiators described in paragraphs 0114 to 0133 of JP-A No. 2014-85643 may be used.

[0038] Examples of nonionic photocationic polymerization initiators include trichloromethyl-s-triazines, diazomethane compounds, imide sulfonate compounds, and oxime sulfonate compounds. Examples of trichloromethyl-s-triazines, diazomethane compounds, and imide sulfonate compounds include the compounds described in paragraphs 0083 to 0088 of JP 2011-221494 A. Examples of oxime sulfonate compounds include the compounds described in paragraphs 0084 to 0088 of WO 2018 / 179640 A.

[0039] The polymerization initiator that generates radicals and an acid is a compound that can generate both a radical and an acid from one compound, and examples thereof include oxime sulfonate compounds, iodonium compounds, and compounds having a radical-generating structure and an acid-generating structure. As the polymerization initiator, a polymerization initiator that generates radicals and an acid may be used in combination with a radical polymerization initiator, a cationic polymerization initiator, or a combination of a radical polymerization initiator and a cationic polymerization initiator.

[0040] The photosensitive layer may contain one type of radical polymerization initiator alone or two or more types of radical polymerization initiators. The content of the radical polymerization initiator in the photosensitive layer is not particularly limited, but from the viewpoints of resolution and pattern formability, it is preferably 0.1% by mass or more, more preferably 0.25% by mass or more, and even more preferably 0.5% by mass or more, based on the total mass of the photosensitive layer. The upper limit is not particularly limited, but it is preferably 10% by mass or less, more preferably 5% by mass or less, based on the total mass of the photosensitive layer.

[0041] The photosensitive layer may contain one type of cationic polymerization initiator alone or two or more types of cationic polymerization initiators. The content of the cationic polymerization initiator in the photosensitive layer is not particularly limited, but from the viewpoints of resolution and pattern formability, it is preferably 0.1% by mass or more, more preferably 0.25% by mass or more, and even more preferably 0.5% by mass or more, based on the total mass of the photosensitive layer. The upper limit is not particularly limited, but it is preferably 10% by mass or less, more preferably 5% by mass or less, based on the total mass of the photosensitive layer.

[0042] From the viewpoints of resolution and pattern formability, the mass ratio Mri / Mci of the radical polymerization initiator content Mri to the cationic polymerization initiator content Mci in the photosensitive layer is preferably 0.2 to 5, more preferably 0.5 to 2, even more preferably 0.66 to 1.5, and particularly preferably 0.8 to 1.2.

[0043] The photosensitive layer may contain one type of polymerization initiator that generates radicals and acids, or may contain two or more types of polymerization initiators. The content of the radical- and acid-generating polymerization initiator in the photosensitive layer is not particularly limited, but from the viewpoints of resolution and pattern formability, it 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 layer. The upper limit is not particularly limited, but it is preferably 20% by mass or less, more preferably 10% by mass or less, based on the total mass of the photosensitive layer.

[0044] The total content of the polymerization initiator in the photosensitive layer is not particularly limited, but from the viewpoints of resolution and pattern formability, it 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 layer. The upper limit is not particularly limited, but it is preferably 20% by mass or less, more preferably 10% by mass or less, based on the total mass of the photosensitive layer.

[0045] <Polymerizable compound> The photosensitive layer contains a polymerizable compound, and the polymerizable compound includes a radically polymerizable compound and a cationically polymerizable compound. In this specification, the term "polymerizable compound" refers to a compound that polymerizes under the action of the above-mentioned polymerization initiator, and is different from the alkali-soluble resin described below.

[0046] The polymerizable group contained in the polymerizable compound is not particularly limited as long as it is a group that participates in a polymerization reaction, and examples thereof include groups having an ethylenically unsaturated group such as a vinyl group, an acryloyl group, a methacryloyl group, a styryl group, and a maleimide group; and groups having a cationically polymerizable group such as an epoxy group and an oxetane group. Furthermore, the polymerizable compound may include, in addition to the radical polymerizable compound and the cationically polymerizable compound, a compound having a radical polymerizable group and a cationically polymerizable group different from the radical polymerizable group.

[0047] <<Radical polymerizable compounds>> The photosensitive layer contains a radically polymerizable compound. The radically polymerizable group in the radically polymerizable compound is preferably an ethylenically unsaturated group, more preferably an acryloyl group or a methacryloyl group. The radical polymerizable compound preferably contains an ethylenically unsaturated compound, and more preferably contains a (meth)acrylate compound. An ethylenically unsaturated compound is a compound that has one or more ethylenically unsaturated groups.

[0048] From the viewpoint of resolution and pattern formability, the radical polymerizable compound preferably contains a difunctional or higher functional radical polymerizable compound, and more preferably contains a trifunctional or higher functional radical polymerizable compound. Furthermore, from the viewpoints of resolution and pattern formability, the radical polymerizable compound preferably contains a bifunctional radical polymerizable compound and a trifunctional or higher functional radical polymerizable compound, and more preferably contains a bifunctional radical polymerizable compound and a trifunctional radical polymerizable compound. Here, the term "bifunctional or higher functional radically polymerizable compound" refers to a compound having two or more radically polymerizable groups in one molecule.

[0049] The radical polymerizable compound preferably contains a compound having two or more ethylenically unsaturated groups in one molecule (a polyfunctional ethylenically unsaturated compound) in that the photosensitive layer has better photosensitivity. In terms of achieving better resolution and releasability, the number of ethylenically unsaturated groups that the ethylenically unsaturated compound has in one molecule is preferably 6 or less, and more preferably 3 or less.

[0050] The photosensitive 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 order to achieve a better balance between the photosensitivity, resolution, and peelability of the photosensitive layer. The content of the bifunctional ethylenically unsaturated compound relative to the total content of the ethylenically unsaturated compound in the photosensitive 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 ethylenically unsaturated compounds contained in the photosensitive layer may be bifunctional ethylenically unsaturated compounds.

[0051] From the viewpoints of resolution and pattern formability, the radical polymerizable compound preferably contains a radical polymerizable compound having a polyalkylene oxide structure, and more preferably contains a radical polymerizable compound having a polyethylene oxide structure. Preferred examples of the radically polymerizable compound having a polyalkylene oxide structure include polyalkylene glycol di(meth)acrylate and alkylene oxide modified products, which will be described later.

[0052] -Ethylenically unsaturated compounds B1- The photosensitive layer preferably contains an ethylenically unsaturated compound B1 having an aromatic ring and two ethylenically unsaturated groups. The ethylenically unsaturated compound B1 is a bifunctional ethylenically unsaturated compound having one or more aromatic rings in one molecule, among the above-mentioned ethylenically unsaturated compounds.

[0053] In the photosensitive layer, the mass ratio of the content of the ethylenically unsaturated compound B1 to the content of the ethylenically unsaturated 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.

[0054] The aromatic ring of the ethylenically unsaturated compound B1 may be, for example, an aromatic hydrocarbon ring such as a benzene ring, a naphthalene ring, or an anthracene ring, or an aromatic heterocycle such as a thiophene ring, a furan ring, a pyrrole ring, an imidazole ring, a triazole ring, or a pyridine ring, or a condensed ring thereof, and is preferably an aromatic hydrocarbon ring, and more preferably a benzene ring.The aromatic ring may have a substituent. The ethylenically unsaturated compound B1 may have only one aromatic ring, or may have two or more aromatic rings.

[0055] The ethylenically unsaturated compound B1 preferably has a bisphenol structure, since this inhibits swelling of the photosensitive layer due to the 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.

[0056] Examples of the ethylenically unsaturated compound B1 having a bisphenol structure include a compound having a bisphenol structure and two polymerizable groups (preferably (meth)acryloyl groups) bonded to both ends of the bisphenol structure. The two polymerizable groups may be bonded to both ends of the bisphenol structure directly or via one or more alkyleneoxy groups. The alkyleneoxy groups added to both ends of the bisphenol structure are preferably ethyleneoxy groups or propyleneoxy groups, more preferably ethyleneoxy groups. The number of alkyleneoxy groups added to the bisphenol structure is not particularly limited, but is preferably 4 to 16, more preferably 6 to 14 per molecule. The ethylenically unsaturated compound B1 having a bisphenol structure is described in paragraphs 0072 to 0080 of JP 2016-224162 A, the contents of which are incorporated herein by reference.

[0057] As the ethylenically unsaturated compound B1, a bifunctional ethylenically unsaturated compound having a bisphenol A structure is preferred, and 2,2-bis(4-((meth)acryloxypolyalkoxy)phenyl)propane is more preferred. Examples of 2,2-bis(4-((meth)acryloxypolyalkoxy)phenyl)propane include 2,2-bis(4-(methacryloxydiethoxy)phenyl)propane (FA-324M, manufactured by Hitachi Chemical Co., Ltd.), 2,2-bis(4-(methacryloxyethoxypropoxy)phenyl)propane, 2,2-bis(4-(methacryloxypentaethoxy)phenyl)propane (BPE-500, manufactured by Shin-Nakamura Chemical Co., Ltd.), and 2,2-bis(4-(methacryloxydodecaethoxy)phenyl)propane. Examples of the ethoxylated bisphenol A diacrylate include 2,2-bis(4-(methacryloxypentadecaethoxy)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.).

[0058] As the ethylenically unsaturated compound B1, a compound represented by the following formula (Bis) can be used.

[0059] [ka]

[0060] In formula (Bis), 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 -(AO)- and -(BO)- repeating units may be random or block. In the case of block, either -(AO)- or -(BO)- may be on the bisphenol structure side. In one embodiment, n1+n2+n3+n4 is preferably an integer of 2 to 20, more preferably an integer of 2 to 16, and even more preferably an integer of 4 to 12. Furthermore, n2+n4 is preferably an integer of 0 to 10, more preferably an integer of 0 to 4, even more preferably an integer of 0 to 2, and particularly preferably 0.

[0061] The ethylenically unsaturated compound B1 may be used alone or in combination of two or more kinds. The content of the ethylenically unsaturated compound B1 in the photosensitive layer is preferably 10% by mass or more, more preferably 20% by mass or more, based on the total mass of the photosensitive layer, from the viewpoint of better resolution. The upper limit is not particularly limited, but from the viewpoint of transferability and edge fusion (a phenomenon in which components in the photosensitive layer bleed out from the edge of the photosensitive transfer material), it is preferably 70% by mass or less, more preferably 60% by mass or less.

[0062] The photosensitive layer may contain an ethylenically unsaturated compound other than the above-mentioned ethylenically unsaturated compound B1. The ethylenically unsaturated compound other than the ethylenically unsaturated compound B1 is not particularly limited and can be appropriately selected from known compounds, such as a compound having one ethylenically unsaturated group in one molecule (monofunctional ethylenically unsaturated compound), a bifunctional ethylenically unsaturated compound having no aromatic ring, and a trifunctional or higher ethylenically unsaturated compound.

[0063] 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.

[0064] Examples of bifunctional 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)acrylates include propylene oxide-modified urethane di(meth)acrylates and ethylene oxide and propylene oxide-modified urethane di(meth)acrylates. 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.).

[0065] Examples of tri- or higher functional ethylenically unsaturated compounds include dipentaerythritol (tri / tetra / penta / hexa)(meth)acrylate, pentaerythritol (tri / tetra)(meth)acrylate, trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, trimethylolethane tri(meth)acrylate, isocyanuric acid tri(meth)acrylate, glycerin tri(meth)acrylate, and alkylene oxide-modified products thereof. Here, "(tri / tetra / penta / hexa)(meth)acrylate" is a concept that encompasses tri(meth)acrylate, tetra(meth)acrylate, penta(meth)acrylate, and hexa(meth)acrylate, and "(tri / tetra)(meth)acrylate" is a concept that encompasses tri(meth)acrylate and tetra(meth)acrylate. In one embodiment, the photosensitive layer preferably contains the above-described ethylenically unsaturated compound B1 and a tri- or higher functional ethylenically unsaturated compound, and more preferably contains the above-described ethylenically unsaturated compound B1 and two or more tri- or higher functional ethylenically unsaturated compounds. In this case, the mass ratio of the ethylenically unsaturated compound B1 to the tri- or higher functional ethylenically unsaturated compounds is preferably (total mass of the ethylenically unsaturated compound B1):(total mass of the tri- or higher functional ethylenically unsaturated compounds)=1:1 to 5:1, more preferably 1.2:1 to 4:1, and even more preferably 1.5:1 to 3:1. In one embodiment, the photosensitive layer preferably contains the above-mentioned ethylenically unsaturated compound B1 and two or more trifunctional ethylenically unsaturated compounds.

[0066] 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), and the like. 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.).

[0067] Furthermore, as the ethylenically unsaturated compound other than the ethylenically unsaturated compound B1, the ethylenically unsaturated compounds having an acid group described in paragraphs 0025 to 0030 of JP-A No. 2004-239942 may be used.

[0068] From the viewpoint of resolution and linearity, the ratio Mm / Mb of the content Mm of the ethylenically unsaturated compound in the photosensitive layer to the content Mb of the alkali-soluble resin is preferably 1.0 or less, more preferably 0.9 or less, and particularly preferably 0.5 or more and 0.9 or less. Moreover, the ethylenically unsaturated compound in the photosensitive layer preferably contains a (meth)acrylic compound from the viewpoints of curability and resolution. Furthermore, from the viewpoints of curability, resolution, and linearity, it is more preferable that the ethylenically unsaturated compound in the photosensitive layer contains a (meth)acrylic compound, and that the content of the acrylic compound relative to the total mass of the (meth)acrylic compounds contained in the photosensitive layer is 60 mass% or less.

[0069] The molecular weight or weight average molecular weight (weight average molecular weight (Mw) when there is a distribution) of the radical polymerizable compound is preferably 3,000 or less, more preferably 2,000 or less, further preferably 100 to 1,500, and particularly preferably 200 to 1,000, from the viewpoints of resolution and pattern formability.

[0070] The radical polymerizable compounds may be used alone or in combination of two or more, but it is preferable to use two or more. From the viewpoints of resolution and pattern formability, the content of the radical polymerizable compound in the photosensitive layer is preferably 5% by mass to 65% by mass, more preferably 8% by mass to 50% by mass, and particularly preferably 10% by mass to 30% by mass, relative to the total mass of the photosensitive layer.

[0071] <<Cationic polymerizable compounds>> The photosensitive layer contains a cationically polymerizable compound. The cationically polymerizable group in the cationically polymerizable compound is preferably a cyclic ether group, an allyl group, or a vinyl ether group, more preferably a cyclic ether group, and particularly preferably an epoxy group or an oxetanyl group. As the cationically polymerizable compound, a cyclic ether compound, an allyl compound, or a vinyl ether compound is preferred, a cyclic ether compound is more preferred, and an epoxy compound or an oxetane compound is particularly preferred.

[0072] From the viewpoint of resolution and pattern formability, the cationically polymerizable compound preferably contains a bifunctional or higher functional cationically polymerizable compound, and more preferably contains a trifunctional or higher functional cationically polymerizable compound. Furthermore, from the viewpoints of resolution and pattern formability, the cationically polymerizable compound preferably contains a bifunctional cationically polymerizable compound and a trifunctional or higher functional cationically polymerizable compound, and more preferably contains a bifunctional cationically polymerizable compound and a trifunctional or tetrafunctional cationically polymerizable compound. Here, the bifunctional or higher functional cationically polymerizable compound means a compound having two or more cationically polymerizable groups in one molecule.

[0073] As the cationically polymerizable compound, known cationically polymerizable compounds such as epoxy compounds, oxetane compounds, allyl compounds, oxazoline compounds, vinyl ether compounds, and vinyl ester compounds can be used. Among these, from the viewpoints of curability, resolution, and pattern formability, it is preferable that the composition contains an epoxy compound, an oxetane compound, an allyl compound, or a vinyl ether compound, it is more preferable that the composition contains an epoxy compound or an oxetane compound, and it is particularly preferable that the composition contains an epoxy compound or an oxetane compound. From the viewpoints of curability, resolution, and pattern formability, the cationically polymerizable compound preferably contains a monomer having 2 to 20 cationically polymerizable groups, more preferably contains a monomer having 2 to 12 cationically polymerizable groups, and particularly preferably contains a monomer having 2 to 6 cationically polymerizable groups.

[0074] Examples of the cationically polymerizable compound include epoxy compounds, vinyl ether compounds, and oxetane compounds described in JP-A Nos. 6-9714, 2001-31892, 2001-40068, 2001-55507, 2001-310938, 2001-310937, and 2001-220526.

[0075] The epoxy compound includes aromatic epoxides, alicyclic epoxides, aliphatic epoxides, and the like. Examples of aromatic epoxides include di- or polyglycidyl ethers of bisphenol A or its alkylene oxide adducts, and di- or polyglycidyl ethers of hydrogenated bisphenol A or its alkylene oxide adducts. Examples of alkylene oxides include ethylene oxide and propylene oxide. Preferred examples of the alicyclic epoxide include cyclohexene oxide- or cyclopentene oxide-containing compounds obtained by epoxidizing a compound having at least one cycloalkane ring, such as a cyclohexene ring or a cyclopentene ring, with a suitable oxidizing agent, such as hydrogen peroxide or a peracid. Examples of aliphatic epoxides include di- or polyglycidyl ethers of aliphatic polyhydric alcohols or their alkylene oxide adducts. Typical examples include diglycidyl ethers of alkylene glycols such as diglycidyl ether of ethylene glycol, diglycidyl ether of propylene glycol, or diglycidyl ether of 1,6-hexanediol; polyglycidyl ethers of polyhydric alcohols such as di- or triglycidyl ethers of glycerin or its alkylene oxide adducts; and diglycidyl ethers of polyalkylene glycols, typified by diglycidyl ethers of polyethylene glycol or its alkylene oxide adducts, and diglycidyl ethers of polypropylene glycol or its alkylene oxide adducts. Examples of alkylene oxides include ethylene oxide and propylene oxide. As the epoxy compound, a compound having an isocyanuric ring such as triglycidyl isocyanurate is preferably used.

[0076] The oxetane compound may be any compound having an oxetanyl group, and for example, the oxetane compounds described in JP-A Nos. 2001-220526, 2001-310937, and 2003-341217 can be used. Further, examples of compounds having 1 to 4 oxetane rings in the molecule include compounds represented by general formulas (1) to (4) described in paragraphs 0037 to 0051 of JP-A No. 2007-91946.

[0077] As the allyl compound, known allyl compounds can be used. Specific examples of allyl compounds include triallyl isocyanurate, diallyl phthalate, triallyl trimellitate, diethylene glycol bisallyl carbonate, trimethylolpropane diallyl ether, trimethylolpropane triallyl ether, pentaerythritol triallyl ether, pentaerythritol tetraallyl ether, 1,1,2,2-tetraallyloxyethane, diarylidene pentaerythritol, triallyl cyanurate, 1,2,4-trivinylcyclohexane, 1,4-butanediol diallyl ether, nonanediol diallyl ether, 1,4-cyclohexane dimethanol diallyl ether, and triethylene glycol diallyl ether. Examples of such vinyl ethers include methylolpropane trivinyl ether, trimethylolpropane trivinyl ether, pentaerythritol tetravinyl ether, diallyl ether of bisphenol S, divinylbenzene, divinylbiphenyl, 1,3-diisopropenylbenzene, 1,4-diisopropenylbenzene, 1,3-bis(allyloxy)adamantane, 1,3-bis(vinyloxy)adamantane, 1,3,5-tris(allyloxy)adamantane, 1,3,5-tris(vinyloxy)adamantane, dicyclopentadiene, vinylcyclohexene, 1,5-hexadiene, 1,9-decadiene, diallyl ether, bisphenol A diallyl ether, and 2,5-diallylphenol allyl ether.

[0078] Examples of vinyl ether compounds include di- or trivinyl ether compounds such as ethylene glycol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, propylene glycol divinyl ether, dipropylene glycol divinyl ether, butanediol divinyl ether, hexanediol divinyl ether, cyclohexanedimethanol divinyl ether, and trimethylolpropane trivinyl ether; and monovinyl ether compounds such as ethyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, octadecyl vinyl ether, cyclohexyl vinyl ether, hydroxybutyl vinyl ether, 2-ethylhexyl vinyl ether, cyclohexanedimethanol monovinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, isopropenyl vinyl ether, dodecyl vinyl ether, diethylene glycol monovinyl ether, and octadecyl vinyl ether.

[0079] The molecular weight or weight average molecular weight (weight average molecular weight (Mw) when there is a distribution) of the cationically polymerizable compound is preferably 3,000 or less, more preferably 2,000 or less, further preferably 50 to 1,500, and particularly preferably 100 to 1,000, from the viewpoints of resolution and pattern formability.

[0080] The cationically polymerizable compounds may be used alone or in combination of two or more, but it is preferable to use two or more. From the viewpoints of resolution and pattern formability, the content of the cationically polymerizable compound in the photosensitive layer is preferably 5% by mass to 65% by mass, more preferably 8% by mass to 50% by mass, and particularly preferably 10% by mass to 30% by mass, relative to the total mass of the photosensitive layer.

[0081] The mass ratio Mrm / Mcm of the content Mrm of the radical polymerizable compound to the content Mcm of the cationically polymerizable compound in the photosensitive layer is preferably 0.2 to 5, more preferably 0.5 to 2, even more preferably 0.66 to 1.5, and particularly preferably 0.8 to 1.2, from the viewpoints of resolution and pattern formability.

[0082] From the viewpoints of resolution and pattern formability, the total content of the polymerizable compounds in the photosensitive layer is preferably 10% by mass to 70% by mass, more preferably 20% by mass to 60% by mass, and even more preferably 20% by mass to 50% by mass, relative to the total mass of the photosensitive layer.

[0083] <Alkali-soluble resin> The photosensitive layer preferably contains an alkali-soluble resin. In this specification, "alkali-soluble" means that the solubility in 100 g of a 1% by mass aqueous solution of sodium carbonate at a liquid temperature of 22°C is 0.1 g or more. The alkali-soluble resin is not particularly limited, and suitable examples include known alkali-soluble resins used in etching resists. The alkali-soluble resin is preferably a binder polymer. The alkali-soluble resin is preferably an alkali-soluble resin having an acid group. Among these, the alkali-soluble resin is preferably polymer A, which will be described later.

[0084] -Polymer A- The alkali-soluble resin preferably contains polymer A. 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, in order to suppress swelling of the photosensitive layer by the developer and thereby obtain better 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.

[0085] The acid value is the mass [mg] of potassium hydroxide required to neutralize 1 g of sample. In this specification, the unit is expressed as mgKOH / g. The acid value can be calculated, for example, from the average content of acid groups in the compound. The acid value of polymer A may be adjusted by changing the type of structural unit constituting polymer A and the content of structural units containing an acid group.

[0086] The weight-average molecular weight of polymer A is preferably 5,000 to 500,000. A weight-average molecular weight of 500,000 or less is preferred from the viewpoint of improving resolution and developability. A weight-average molecular weight of 100,000 or less is more preferred, 60,000 or less is even more preferred, and 50,000 or less is particularly preferred. On the other hand, a weight-average molecular weight of 5,000 or more is preferred from the viewpoint of controlling the properties of developed aggregates and the properties of the unexposed film, such as edge fusing and cut-chip resistance, when formed into a photosensitive resin laminate. A weight-average molecular weight of 10,000 or more is more preferred, 20,000 or more is even more preferred, and 30,000 or more is particularly preferred. Edge fusing refers to the degree to which the photosensitive layer protrudes from the edge of a roll when the photosensitive transfer material is wound into a roll. Cut-chip resistance refers to the degree to which chips fly off 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, resulting in 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).

[0087] From the viewpoint of suppressing line width thickening and deterioration of resolution when the focal position is shifted during exposure, the photosensitive layer preferably contains a monomer component having an aromatic hydrocarbon group as 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 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. While there is no particular upper limit, it is preferably 95% by mass or less, more preferably 85% by mass or less. When multiple types of polymer A are contained, the content of the monomer component having an aromatic hydrocarbon group is determined as a weight average value.

[0088] Examples of the monomer having an aromatic hydrocarbon group include a monomer having an aralkyl group, styrene, and polymerizable styrene derivatives (e.g., methylstyrene, vinyltoluene, tert-butoxystyrene, acetoxystyrene, 4-vinylbenzoic acid, styrene dimer, styrene trimer, etc.). Among these, a monomer having an aralkyl group or styrene is preferred. In one embodiment, when the monomer component having an aromatic hydrocarbon group in 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, even more 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 monomer components.

[0089] 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.

[0090] Examples of the monomer having a phenylalkyl group include phenylethyl (meth)acrylate.

[0091] Examples of the monomer having a benzyl group include (meth)acrylates having a benzyl group, such as benzyl (meth)acrylate and chlorobenzyl (meth)acrylate; and vinyl monomers having a benzyl group, such as vinylbenzyl chloride and vinylbenzyl alcohol. Of these, benzyl (meth)acrylate is preferred. In one embodiment, when the monomer component having an aromatic hydrocarbon group in 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, even more 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.

[0092] 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 kind of first monomer described below and / or at least one kind of second monomer described below.

[0093] The polymer A, which does not contain a monomer component having an aromatic hydrocarbon group, is preferably obtained by polymerizing at least one type of first monomer described below, and more preferably by copolymerizing at least one type of first monomer with at least one type of second monomer described below.

[0094] The first monomer is a monomer having a carboxy group in the molecule. Examples of the first monomer include (meth)acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, 4-vinylbenzoic acid, maleic anhydride, and maleic acid half ester. Among these, (meth)acrylic acid is 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.

[0095] 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. A copolymerization ratio of 10% by mass or more is preferred from the viewpoints of achieving good developability and controlling edge fusing, and is more preferably 15% by mass or more, and even more preferably 20% by mass or more. A copolymerization ratio of 50% by mass or less is preferred from the viewpoints of high resolution and foot shape of the resist pattern, and furthermore chemical resistance of the resist pattern; from these viewpoints, a copolymerization ratio of 35% by mass or less is more preferred, more preferably 30% by mass or less, and particularly preferably 27% by mass or less is particularly preferred.

[0096] The second monomer is non-acidic and has at least one polymerizable unsaturated group in the molecule. Examples of the second monomer include (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, cyclohexyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate; vinyl alcohol esters such as vinyl acetate; and (meth)acrylonitrile. Among these, methyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and n-butyl (meth)acrylate are preferred, with methyl (meth)acrylate being 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.

[0097] 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, 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, 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.

[0098] The polymer A may have a branched structure or 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 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. Specific examples of monomers containing a group having a branched structure in the side chain include i-propyl (meth)acrylate, i-butyl (meth)acrylate, s-butyl (meth)acrylate, t-butyl (meth)acrylate, i-amyl (meth)acrylate, t-amyl (meth)acrylate, sec-iso-amyl (meth)acrylate, 2-octyl (meth)acrylate, 3-octyl (meth)acrylate, t-octyl (meth)acrylate, etc. Among these, i-propyl (meth)acrylate, i-butyl (meth)acrylate, or t-butyl methacrylate is preferred, and i-propyl methacrylate or t-butyl methacrylate is more preferred. Examples of the monomer containing a group having an alicyclic structure in the side chain include a monomer having a monocyclic aliphatic hydrocarbon group and a monomer having a polycyclic aliphatic hydrocarbon group, and include 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 ... hydroxy-1-adamantyl (meth)acrylate, octahydro-4,7-menthanoinden-5-yl (meth)acrylate, octahydro-4,7-menthanoinden-1-ylmethyl (meth)acrylate, 1-menthyl (meth)acrylate, tricyclodecane (meth)acrylate, 3-hydroxy-2,6,6-trimethyl-bicyclo[3.1.1]heptyl (meth)acrylate, 3,7,7-trimethyl-4-hydroxybicyclo[4.1.0]heptyl (meth)acrylate, (nor)bornyl (meth)acrylate, isobornyl (meth)acrylate, fenchyl (meth)acrylate, 2,2,5-trimethylcyclohexyl (meth)acrylate, cyclohexyl (meth)acrylate, and the like.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 particularly preferred.

[0099] The polymer A may be used singly or in a mixture of two or more. When a mixture of two or more types is used, it is preferable to use a mixture of two polymers A containing a monomer component having an aromatic hydrocarbon group, or to use a mixture of 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. 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, preferably 80% by mass or more, and more preferably 90% by mass or more, based on the total amount of the polymer A.

[0100] 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 prepared by diluting one or more of the monomers described above with a solvent such as acetone, methyl ethyl ketone, or isopropanol, and then heating and stirring the mixture. The synthesis may be carried out while adding a portion of the mixture dropwise to the reaction solution. After the reaction is complete, 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.

[0101] The glass transition temperature Tg of the polymer A is preferably 30°C or higher and 135°C or lower. By using a polymer A having a Tg of 135°C or lower in the photosensitive 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 lower, even more preferably 120°C or lower, and particularly preferably 110°C or lower. Furthermore, using a polymer A having a Tg of 30°C or higher is preferable from the viewpoint of improving edge fuse resistance. From this viewpoint, the Tg of the polymer A is more preferably 40°C or higher, even more preferably 50°C or higher, particularly preferably 60°C or higher, and most preferably 70°C or higher.

[0102] The photosensitive layer may contain a resin other than the alkali-soluble resin. Examples of resins other than alkali-soluble resins include acrylic resins, styrene-acrylic copolymers (with a styrene content of 40% by 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, polyethyleneimine, polyallylamine, and polyalkylene glycols.

[0103] The alkali-soluble resins may be used alone or in combination of two or more. The proportion of the alkali-soluble resin relative to the total mass of the photosensitive 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. Setting the proportion of the alkali-soluble resin relative to the photosensitive layer to 90% by mass or less is preferred from the viewpoint of controlling the development time. On the other hand, setting the proportion of the alkali-soluble resin relative to the photosensitive layer to 10% by mass or more is preferred from the viewpoint of improving edge fuse resistance.

[0104] <Dye> From the viewpoints of the visibility of exposed and unexposed areas, the pattern visibility after development, and resolution, the photosensitive layer preferably contains a dye, and more 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 in response to an acid, a base, or a radical. When dye N is contained, adhesion to adjacent layers (for example, the temporary support and the first resin layer) is improved, resulting in better resolution, although the detailed mechanism is unknown.

[0105] In this specification, the expression "the maximum absorption wavelength of a dye changes in response to an acid, a base, or a radical" may mean any of an embodiment in which a dye in a colored state is decolorized by an acid, a base, or a radical, an embodiment in which a dye in a decolorized state develops color by an acid, a base, or a radical, and an embodiment in which a dye in a colored state changes to a colored state of another hue. Specifically, dye N may be a compound that changes from a decolorized state to a color upon exposure, or a compound that changes from a colored state to a decolorized state upon exposure. In this case, the dye may be one whose color-developing or decolorizing state changes when an acid, base, or radical is generated and acts within the photosensitive layer upon exposure, or one whose color-developing or decolorizing state changes when an acid, base, or radical changes the state (e.g., pH) within the photosensitive layer. Alternatively, the dye may be one whose color-developing or decolorizing state changes upon direct stimulation by an acid, base, or radical without exposure.

[0106] Among these, from the viewpoints of the visibility and resolution of exposed and unexposed areas, dye N is preferably a dye whose maximum absorption wavelength changes in response to an acid or a radical, and more preferably a dye whose maximum absorption wavelength changes in response to a radical. From the viewpoint of the visibility of exposed and unexposed areas and resolution, the photosensitive layer preferably contains both a dye whose maximum absorption wavelength changes in response to radicals as dye N, 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.

[0107] 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 the photosensitive layer, and after exposure, a radical-reactive dye, an acid-reactive dye, or a base-reactive dye (e.g., a leuco dye) develops color due to a radical, acid, or base generated from the photoradical polymerization initiator, the cationic photopolymerization initiator, or the photobase generator.

[0108] 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 or two or more maximum absorption wavelengths in the wavelength range of 400 nm to 780 nm when it develops color. When dye N has two or more maximum absorption wavelengths in the wavelength range of 400 nm to 780 nm when it develops color, it is sufficient that the maximum absorption wavelength with the highest absorbance among the two or more maximum absorption wavelengths is 450 nm or longer.

[0109] The maximum absorption wavelength of dye N can be obtained by measuring the transmission spectrum of a solution containing dye N (liquid temperature 25°C) in the range of 400 nm to 780 nm using a spectrophotometer UV3100 (Shimadzu Corporation) in an atmospheric environment and detecting the wavelength at which the light intensity is minimum (maximum absorption wavelength).

[0110] Examples of dyes that develop or lose color upon exposure include leuco compounds. Examples of dyes that are decolorized by exposure include leuco compounds, diarylmethane dyes, oxazine dyes, xanthene dyes, iminonaphthoquinone dyes, azomethine dyes, and anthraquinone dyes. As the dye N, a leuco compound is preferred from the viewpoint of visibility of exposed and unexposed areas.

[0111] Examples of leuco compounds include leuco compounds having a triarylmethane skeleton (triarylmethane-based dyes), leuco compounds having a spiropyran skeleton (spiropyran-based dyes), leuco compounds having a fluoran skeleton (fluoran-based dyes), leuco compounds having a diarylmethane skeleton (diarylmethane-based dyes), leuco compounds having a rhodamine lactam skeleton (rhodamine lactam-based dyes), leuco compounds having an indolylphthalide skeleton (indolylphthalide-based dyes), and leuco compounds having a leucoauramine skeleton (leucoauramine-based dyes). Among these, triarylmethane dyes or fluoran dyes are preferred, and leuco compounds having a triphenylmethane skeleton (triphenylmethane dyes) or fluoran dyes are more preferred.

[0112] From the viewpoint of visibility of exposed and unexposed areas, the leuco compound preferably has a lactone ring, a sultine ring, or a sultone ring. This allows the lactone ring, sultine ring, or sultone ring of the leuco compound to react with a radical generated from a photoradical polymerization initiator or an acid generated from a photocationic polymerization initiator, thereby converting the leuco compound into a ring-closed state and thereby discoloring, or converting the leuco compound into a ring-open state and thereby developing a color. The leuco compound is preferably a compound having a lactone ring, a sultine ring, or a sultone ring, which develops a color upon ring-opening of the lactone ring, the sultine ring, or the sultone ring by a radical or an acid, and more preferably a compound having a lactone ring, which develops a color upon ring-opening of the lactone ring by a radical or an acid.

[0113] Examples of the dye N include the following dyes and leuco compounds. Specific examples of dyes among the dyes N include brilliant green, ethyl violet, methyl green, crystal violet, basic fuchsin, methyl violet 2B, quinaldine red, rose bengal, metanil yellow, thymolsulfophthalein, xylenol blue, methyl orange, paramethyl red, Congo red, benzopurpurin 4B, α-naphthyl red, Nile blue 2B, Nile blue A, methyl violet, malachite green, parafuchsin, Victoria Pure Blue naphthalene sulfonate, Victoria Pure Blue BOH (manufactured by Hodogaya Chemical Co., Ltd.), Oil Blue #603 (manufactured by Orient Chemical Industries Co., Ltd.), Oil Pink #312 (manufactured by Orient Chemical Industries Co., Ltd.), Oil Red 5B (manufactured by Orient Chemical Industries Co., Ltd.), and Oil Scarlet #308 (manufactured by Orient Chemical Industries Co., Ltd.). Examples of the oxidizing agent include Orient Chemical Industry Co., Ltd.), Oil Red OG (Orient Chemical Industry Co., Ltd.), Oil Red RR (Orient Chemical Industry Co., Ltd.), Oil Green #502 (Orient Chemical Industry Co., Ltd.), Spiron Red BEH Special (Hodogaya Chemical Co., Ltd.), m-cresol purple, cresol red, rhodamine B, rhodamine 6G, sulforhodamine B, auramine, 4-p-diethylaminophenyliminonaphthoquinone, 2-carboxyanilino-4-p-diethylaminophenyliminonaphthoquinone, 2-carboxystearylamino-4-pN,N-bis(hydroxyethyl)amino-phenyliminonaphthoquinone, 1-phenyl-3-methyl-4-p-diethylaminophenylimino-5-pyrazolone, and 1-β-naphthyl-4-p-diethylaminophenylimino-5-pyrazolone.

[0114] Specific examples of leuco compounds among the dyes N include p,p',p"-hexamethyltriaminotriphenylmethane (leuco crystal violet), Pergascript Blue SRB (manufactured by Ciba-Geigy), crystal violet lactone, malachite green lactone, benzoyl leucomethylene blue, 2-(N-phenyl-N-methylamino)-6-(Np-tolyl-N-ethyl)aminofluoran, 2-anilino-3-methyl-6-(N-ethyl-p-toluidino)fluoran, 3,6-dimethoxyfluoran, 3-(N,N-diethylamino)-5-methyl-7-(N,N-dibenzylamino)fluoran, and 3-(N-cyclohexyl-N-methylamino)-6 -methyl-7-anilinofluoran, 3-(N,N-diethylamino)-6-methyl-7-anilinofluoran, 3-(N,N-diethylamino)-6-methyl-7-xylidinofluoran, 3-(N,N-diethylamino)-6-methyl-7-chlorofluoran, 3-(N,N-diethylamino)-6-methoxy-7-aminofluoran, 3-(N,N-diethylamino)-7-(4-chloroanilino)fluoran, 3-(N,N-diethylamino)-7-chlorofluoran, 3-(N,N-diethylamino)-7-(4-chloroanilino)fluoran, 3-(N,N-diethylamino)-7-chlorofluoran, 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-diethylaminophenyl)-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.

[0115] From the viewpoints of the visibility of exposed and unexposed areas, the 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 the dye N, leuco crystal violet, crystal violet lactone, brilliant green, or Victoria Pure Blue-naphthalene sulfonate is preferred.

[0116] The dyes may be used alone or in combination of two or more. From the viewpoints of visibility of exposed and unexposed areas, pattern visibility after development, and resolution, the content of the dye is preferably 0.1% by mass or more, more preferably 0.1% by mass to 10% by mass, even more preferably 0.1% by mass to 5% by mass, and particularly preferably 0.1% by mass to 1% by mass, relative to the total mass of the photosensitive layer. Furthermore, from the viewpoints of the visibility of exposed and unexposed areas, the pattern visibility after development, and resolution, the content of dye N is preferably 0.1% by mass or more, more preferably 0.1% by mass to 10% by mass, even more preferably 0.1% by mass to 5% by mass, and particularly preferably 0.1% by mass to 1% by mass, relative to the total mass of the photosensitive layer.

[0117] The content of dye N means the content of dye when all of dye N contained in the photosensitive layer is in a color-developing state. A method for quantifying the content of dye N will be explained below using a dye that develops color by radicals as an example. Two solutions were prepared by dissolving 0.001 g or 0.01 g of dye in 100 mL of methyl ethyl ketone. The photoradical polymerization initiator Irgacure OXE01 (BASF Japan Ltd.) was added to each solution, and radicals were generated by irradiating with 365 nm light, causing all dyes to develop color. The absorbance of each solution was then measured at 25°C using a spectrophotometer (UV3100, Shimadzu Corporation) under atmospheric conditions, and a calibration curve was created. Next, the absorbance of the solution in which all the dye has developed is measured in the same manner as above, except that 3 g of the photosensitive layer is dissolved in methyl ethyl ketone instead of the dye.The content of the dye contained in the photosensitive layer is calculated based on the absorbance of the obtained solution containing the photosensitive layer and a calibration curve.

[0118] <Thermal crosslinkable compound> From the viewpoints of the strength of the cured film obtained and the adhesiveness of the uncured film obtained, the photosensitive layer preferably contains a thermally crosslinkable compound. In this specification, a thermally crosslinkable compound having an ethylenically unsaturated group, which will be described later, is not considered to be a polymerizable compound but is considered to be a thermally crosslinkable compound. Examples of the thermally crosslinkable compound include methylol compounds and blocked isocyanate compounds. Among these, blocked isocyanate compounds are preferred from the viewpoints of the strength of the resulting cured film and the adhesiveness of the resulting uncured film. Since the blocked isocyanate compound reacts with a hydroxy group and a carboxy group, for example, when a resin and / or a polymerizable compound has at least one of a hydroxy group and a carboxy group, the hydrophilicity of the formed film tends to decrease, and the functionality of the film obtained by curing the photosensitive layer when used as a protective film tends to be enhanced. The blocked isocyanate compound refers to a compound having a structure in which the isocyanate group of an isocyanate is protected (so-called masked) with a blocking agent.

[0119] The dissociation temperature of the blocked isocyanate compound is not particularly limited, but is preferably 100°C to 160°C, and more preferably 130°C to 150°C. The dissociation temperature of a blocked isocyanate means "the temperature of the endothermic peak accompanying the deprotection reaction of the blocked isocyanate when measured by DSC (Differential Scanning Calorimetry) analysis using a differential scanning calorimeter." As the differential scanning calorimeter, for example, a differential scanning calorimeter (model: DSC6200) manufactured by Seiko Instruments Inc. can be suitably used. However, the differential scanning calorimeter is not limited to this.

[0120] Examples of blocking agents having a dissociation temperature of 100°C to 160°C include active methylene compounds [malonic acid diesters (dimethyl malonate, diethyl malonate, di-n-butyl malonate, di-2-ethylhexyl malonate, etc.)] and oxime compounds (compounds having a structure represented by -C(=N-OH)- in the molecule, such as formaldoxime, acetaldoxime, acetoxime, methylethylketoxime, and cyclohexanoneoxime). Among these, the blocking agent having a dissociation temperature of 100° C. to 160° C. preferably contains an oxime compound, for example, from the viewpoint of storage stability.

[0121] The blocked isocyanate compound preferably has an isocyanurate structure, for example, from the viewpoint of improving the brittleness of the film and improving the adhesive strength to the transfer target. A blocked isocyanate compound having an isocyanurate structure can be obtained, for example, by protecting hexamethylene diisocyanate by isocyanuration. Among blocked isocyanate compounds having an isocyanurate structure, compounds having an oxime structure in which an oxime compound is used as a blocking agent are preferred from the viewpoints that the dissociation temperature can be more easily adjusted to a preferred range and development residues can be reduced compared to compounds not having an oxime structure.

[0122] The blocked isocyanate compound may have a polymerizable group. The polymerizable group is not particularly limited, and any known polymerizable group can be used, with a radical polymerizable group being preferred. Examples of the polymerizable group include ethylenically unsaturated groups such as a (meth)acryloxy group, a (meth)acrylamide group and a styryl group, and groups having an epoxy group such as a glycidyl group. Among these, the polymerizable group is preferably an ethylenically unsaturated group, more preferably a (meth)acryloxy group, and even more preferably an acryloxy group.

[0123] As the blocked isocyanate compound, commercially available products can be used. Examples of commercially available blocked isocyanate compounds include Karenz (registered trademark) AOI-BM, Karenz (registered trademark) MOI-BM, Karenz (registered trademark) MOI-BP, and the like (all manufactured by Showa Denko K.K.), and the blocked Duranate series (e.g., Duranate (registered trademark) TPA-B80E, Duranate (registered trademark) WT32-B75P, and the like, manufactured by Asahi Kasei Chemicals Corporation). Furthermore, as the blocked isocyanate compound, a compound having the following structure can also be used.

[0124] [ka]

[0125] The thermally crosslinkable compounds may be used alone or in combination of two or more. When the photosensitive layer contains a thermally crosslinkable compound, the content of the thermally crosslinkable compound is preferably 1% by mass to 50% by mass, more preferably 5% by mass to 30% by mass, based on the total mass of the photosensitive layer.

[0126] <Other ingredients> The photosensitive layer may contain components other than the above-mentioned alkali-soluble resin, polymerization initiator, polymerizable compound, dye, and thermally crosslinkable compound.

[0127] -Surfactants- From the viewpoint of thickness uniformity, the photosensitive layer preferably contains a surfactant. Examples of surfactants include anionic surfactants, cationic surfactants, nonionic surfactants, and amphoteric surfactants, with nonionic surfactants being preferred. Examples of surfactants include those described in paragraph 0017 of Japanese Patent No. 4502784 and paragraphs 0060 to 0071 of JP-A No. 2009-237362.

[0128] The surfactant is preferably a fluorine-based surfactant or a silicone-based surfactant. Commercially available fluorine-based surfactants include, for example, Megafac (trade name) F-171, F-172, F-173, F-176, F-177, F-141, F-142, F-143, F-144, F-437, F-444, F-475, F-477, F-479, F-482, F-551-A, F-552, F-554, F-555-A, F-556, F-557, F-558, F-559, F-560, F-561, F- 565, F-563, F-568, F-575, F-780, EXP.MFS-330, EXP.MFS-578, EXP.MFS-578-2, EXP.MFS-579, EXP.MFS-586, EXP. MFS-587, EXP.MFS-628, EXP.MFS-631, EXP.MFS-603, R-41, R-41-LM, R-01, R-40, R-40-LM, RS-43, TF-1956, RS-90, R-94, RS-72-K, DS-21 (all manufactured by DIC Corporation), Fluorard (trade name) FC430, FC431, FC171 (all manufactured by Sumitomo 3M Limited), Surflon (trade name) S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, KH-40 (all manufactured by AGC Corporation), PolyFox (trade name) PF636, PF656, Examples include PF6320, PF6520, PF7002 (all manufactured by OMNOVA), Futergent (trade name) 710FL, 710FM, 610FM, 601AD, 601ADH2, 602A, 215M, 245F, 251, 212M, 250, 209F, 222F, 208G, 710LA, 710FS, 730LM, 650AC, 681, 683 (all manufactured by NEOS Corporation), and U-120E (Unichem Co., Ltd.). In addition, acrylic compounds that have a molecular structure with a functional group containing a fluorine atom and that volatilize when heated by cleaving the functional group containing the fluorine atom can also be used as the fluorosurfactant. Examples of such fluorosurfactants include the Megafac (trade name) DS series manufactured by DIC Corporation (The Chemical Daily, February 22, 2016; The Nikkei Business Daily, February 23, 2016), such as Megafac (trade name) DS-21.

[0129] It is also preferable to use, as the fluorine-based surfactant, a polymer of a fluorine atom-containing vinyl ether compound having a fluorinated alkyl group or a fluorinated alkylene ether group and a hydrophilic vinyl ether compound. The fluorine-based surfactant may also be a block polymer. 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) may also be preferably used. The fluorine-based surfactant may also be a fluorine-containing polymer having an ethylenically unsaturated group in the side chain, such as Megafac (trade name) RS-101, RS-102, RS-718K, or RS-72-K (all manufactured by DIC Corporation).

[0130] Examples of nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane, and their ethoxylates and propoxylates (for example, glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, and sorbitan fatty acid esters. Specific examples include Pluronic (trade name) L10, L31, L61, L62, 10R5, 17R2, and 25R2 (all manufactured by BASF), Tetronic (trade name) 304, 701, 704, 901, 904, and 150R1, and HYDROPALAT WE 3323 (all manufactured by BASF), Solsperse (trade name) 20000 (all manufactured by Lubrizol Nippon Co., Ltd.), NCW-101, NCW-1001, NCW-1002 (all manufactured by Fujifilm Wako Pure Chemical Industries Co., Ltd.), Paionin (trade name) D-1105, D-6112, D-6112-W, D-6315 (all manufactured by Takemoto Oil & Fat Co., Ltd.), Olfine E1010, Surfynol 104, 400, 440 (all manufactured by Nissin Chemical Industry Co., Ltd.), and the like. In addition, in recent years, there have been concerns about the environmental compatibility of compounds having a linear perfluoroalkyl group with seven or more carbon atoms, so it is preferable to use surfactants that use alternative materials to perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic acid (PFOS).

[0131] Examples of silicone surfactants include linear polymers consisting of siloxane bonds and modified siloxane polymers in which organic groups have been introduced into the side chains or terminals. Specific examples of silicone surfactants include EXP.S-309-2, EXP.S-315, EXP.S-503-2, and EXP.S-505-2 (all manufactured by DIC Corporation), DOWSIL (trade name) 8032 ADDITIVE, Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, and Toray Silicone SH8400 (all manufactured by Dow Corning Toray Co., Ltd.), as well as X-22-4952, X-22-4272, and X-22 -6266, KF-351A, K354L, KF-355A, KF-945, KF-640, KF-642, KF-643, X-22-6191, X-22-4515, KF-6004, KP- 341, KF-6001, KF-6002, KP-101, KP-103, KP-104, KP-105, KP-106, KP-109, KP-112, KP-120, KP-121, KP-1 24, KP-125, KP-301, KP-306, KP-310, KP-322, KP-323, KP-327, KP-341, KP-368, KP-369, KP-611, KP-620, KP-621, KP-626, KP-652 (all manufactured by Shin-Etsu Chemical Co., Ltd.), F-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (all manufactured by Momenty Examples of such acrylic acid esters include BYK300, BYK306, BYK307, BYK310, BYK320, BYK323, BYK325, BYK330, BYK313, BYK315N, BYK331, BYK333, BYK345, BYK347, BYK348, BYK349, BYK370, BYK377, and BYK378 (all manufactured by BYK-Chemie).

[0132] The photosensitive layer may contain one type of surfactant alone or 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, relative to the total mass of the photosensitive layer.

[0133] -Additives- In addition to the above components, the photosensitive layer may contain known additives as necessary. Examples of additives include polymerization inhibitors, sensitizers, plasticizers, heterocyclic compounds, benzotriazoles, carboxybenzotriazoles, pyridines (such as isonicotinamide), purine bases (such as adenine), and solvents. The photosensitive layer may contain one type of each additive alone or two or more types.

[0134] The photosensitive layer may contain a polymerization inhibitor, and the polymerization inhibitor is preferably a radical polymerization inhibitor. Examples of the polymerization inhibitor include the thermal polymerization inhibitors described in paragraph 0018 of Japanese Patent No. 4502784. Among these, phenothiazine, phenoxazine, and 4-methoxyphenol are preferred. Other polymerization inhibitors include naphthylamine, cuprous chloride, nitrosophenylhydroxyamine aluminum salt, and diphenylnitrosamine. In order to avoid impairing the sensitivity of the photosensitive resin composition, it is preferable to use nitrosophenylhydroxyamine aluminum salt as the polymerization inhibitor.

[0135] 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.

[0136] 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 (trade name, manufactured by Johoku Chemical Industry Co., Ltd.).

[0137] The total content of the 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, relative to the total mass of the photosensitive layer. A content of 0.01% by mass or more is preferred from the viewpoint of imparting storage stability to the photosensitive resin composition. On the other hand, a content of 3% by mass or less is preferred from the viewpoint of maintaining sensitivity and suppressing discoloration of the dye.

[0138] The photosensitive 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.

[0139] The photosensitive layer may contain one type of sensitizer alone or two or more types of sensitizers. When the photosensitive layer contains a sensitizer, the content of the sensitizer can be appropriately selected depending on the purpose. From the viewpoints of improving sensitivity to the light source and improving the curing rate by balancing the polymerization rate and chain transfer, the content is preferably 0.01% 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 layer.

[0140] The photosensitive layer may contain at least one selected from the group consisting of plasticizers and heterocyclic compounds. Examples of the plasticizer and heterocyclic compound include the compounds described in paragraphs 0097 to 0103 and 0111 to 0118 of WO 2018 / 179640.

[0141] The photosensitive layer may contain a solvent. When the photosensitive layer is formed using a photosensitive resin composition containing a solvent, the solvent may remain in the photosensitive layer.

[0142] The photosensitive 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, crosslinkers, and organic or inorganic suspending agents. Additives contained in the photosensitive layer are described in paragraphs 0165 to 0184 of JP-A No. 2014-85643, the contents of which are incorporated herein by reference.

[0143] <Impurities, etc.> The photosensitive layer may contain a certain amount of impurities. Specific examples of impurities include sodium, potassium, magnesium, calcium, iron, manganese, copper, aluminum, titanium, chromium, cobalt, nickel, zinc, tin, halogens, and ions thereof. Among these, halide ions, sodium ions, and potassium ions are likely to be mixed in as impurities, so it is preferable to set the contents to the following ranges.

[0144] The content of impurities in the photosensitive layer is preferably 80 ppm or less, more preferably 10 ppm or less, and even more preferably 2 ppm or less, by mass. The content of impurities can be 1 ppb or more, or may be 0.1 ppm or more, by mass.

[0145] Methods for controlling the impurity content within the above range include selecting raw materials for the composition that contain a small amount of impurities, preventing impurities from being mixed in during the preparation of the photosensitive layer, and removing impurities by washing.

[0146] The amount of impurities can be determined by known methods such as ICP (Inductively Coupled Plasma) emission spectroscopy, atomic absorption spectroscopy, and ion chromatography.

[0147] The content of compounds such as benzene, formaldehyde, trichloroethylene, 1,3-butadiene, carbon tetrachloride, chloroform, N,N-dimethylformamide, N,N-dimethylacetamide, and hexane in the photosensitive layer is preferably small, and the content of these compounds relative to the total mass of the photosensitive layer is preferably 100 ppm or less, more preferably 20 ppm or less, and even more preferably 4 ppm or less, by mass. The lower limit, based on mass, can be 10 ppb or more, or 100 ppb or more, based on the total mass of the photosensitive layer. The content of these compounds can be reduced in the same manner as for the metal impurities described above. Furthermore, they can be quantified by known measurement methods.

[0148] The water content in the photosensitive layer is preferably 0.01% by mass to 1.0% by mass, and more preferably 0.05% by mass to 0.5% by mass, from the viewpoint of improving reliability and lamination properties.

[0149] <Residual monomer> The photosensitive layer may contain residual monomers corresponding to the respective structural units of the alkali-soluble resin. From the viewpoints of patterning property and reliability, the content of the residual monomer is preferably 5,000 ppm by mass or less, more preferably 2,000 ppm by mass or less, and even more preferably 500 ppm by mass or less, relative to the total mass of the alkali-soluble resin. Although there is no particular lower limit, it is preferably 1 ppm by mass or more, and more preferably 10 ppm by mass or more. From the viewpoints of patterning ability and reliability, the residual monomer content of each structural unit of the alkali-soluble resin is preferably 3,000 ppm by mass or less, more preferably 600 ppm by mass or less, and even more preferably 100 ppm by mass or less, relative to the total mass of the photosensitive layer. Although there is no particular lower limit, it is preferably 0.1 ppm by mass or more, and more preferably 1 ppm by mass or more.

[0150] The amount of residual monomers in the synthesis of an alkali-soluble resin by a polymer reaction is also preferably within the above range. For example, when the alkali-soluble resin is synthesized by reacting glycidyl acrylate with a carboxylic acid side chain, the content of glycidyl acrylate is preferably within the above range. The amount of residual monomer can be measured by known methods such as liquid chromatography and gas chromatography.

[0151] <Physical properties etc.> The thickness of the photosensitive 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, still 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 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 resolution, the thickness of the photosensitive layer is preferably 10 μm or less, and more preferably 8 μm or less. The thickness of each layer of the photosensitive transfer material is measured by observing a cross section of the photosensitive transfer material in a direction perpendicular to the main surface with a scanning electron microscope (SEM), measuring the thickness of each layer at 10 or more points based on the obtained observation image, and calculating the average value.

[0152] In order to obtain superior adhesion, the transmittance of the photosensitive 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 upper limit, but it is preferably 99.9% or less.

[0153] <Formation method> The method for forming the photosensitive layer is not particularly limited as long as it is a method that can form a layer containing the above components. Examples of methods for forming the photosensitive layer include a method in which a photosensitive resin composition containing an alkali-soluble resin, an ethylenically unsaturated compound, a photopolymerization initiator, a solvent, etc. is prepared, the photosensitive resin composition is applied to the surface of a temporary support or the like, and the coating film of the photosensitive resin composition is dried to form the photosensitive layer.

[0154] Examples of the photosensitive resin composition used to form the photosensitive layer include compositions containing an alkali-soluble resin, an ethylenically unsaturated compound, a photopolymerization initiator, 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 layer.

[0155] -solvent- The solvent contained in the photosensitive resin composition is not particularly limited as long as it can dissolve or disperse the alkali-soluble resin, the ethylenically unsaturated compound, the photopolymerization initiator, 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 material including a temporary support, a thermoplastic resin layer, an intermediate layer, a photosensitive layer, and a protective film, the photosensitive resin composition preferably contains at least one solvent selected from the group consisting of alkylene glycol ether solvents and alkylene glycol ether acetate solvents. Among these, a mixed solvent containing at least one solvent selected from the group consisting of alkylene glycol ether solvents and alkylene glycol ether acetate solvents and at least one solvent selected from the group consisting of ketone solvents and cyclic ether solvents is more preferred, and a mixed solvent containing at least three solvents: at least one solvent selected from the group consisting of alkylene glycol ether solvents and alkylene glycol ether acetate solvents, a ketone solvent, and a cyclic ether solvent is even more preferred.

[0156] 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 Japanese Patent Application Laid-Open No. 2018-177889 may be used, the contents of which are incorporated herein by reference.

[0157] The photosensitive resin composition may contain one type of solvent alone or 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, more preferably 100 to 900 parts by mass, relative to 100 parts by mass of the total solid content in the photosensitive resin composition.

[0158] The method for preparing the photosensitive resin composition is not particularly limited, and examples thereof include a method in which solutions of the components are dissolved in the above-mentioned solvents in advance, and the resulting solutions are mixed in a predetermined ratio to prepare the photosensitive resin composition. The photosensitive resin composition is preferably filtered using a filter with a pore size of 0.2 μm to 30 μm before forming the photosensitive layer.

[0159] 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 layer may also be formed by applying a photosensitive resin composition onto a protective film described below and drying it.

[0160] In addition, the photosensitive transfer material according to the present disclosure preferably has another layer between the temporary support and the photosensitive layer, from the viewpoints of resolution and releasability of the temporary support. Preferred examples of the other layers include an intermediate layer, a thermoplastic resin layer, and a protective film. Among these, it is preferable that the other layer include an intermediate layer, and it is more preferable that the other layer include a thermoplastic resin layer and an intermediate layer.

[0161] [Middle class] The photosensitive transfer material preferably has an intermediate layer between the temporary support and the photosensitive layer, or, if the photosensitive transfer material has a thermoplastic resin layer described below, between the thermoplastic resin layer and the photosensitive layer. The intermediate layer can prevent components from mixing when forming multiple layers and during storage.

[0162] The intermediate layer is preferably a water-soluble layer from the viewpoints of developability and suppressing mixing of components when coating multiple layers and during storage after coating. In the present disclosure, "water-soluble" means that the solubility in 100 g of water at pH 7.0 and a liquid temperature of 22°C is 0.1 g or more.

[0163] An example of the intermediate layer is an oxygen-blocking layer having an oxygen-blocking function, which is described as a "separation layer" in JP-A-5-72724. The oxygen-blocking layer used as the intermediate layer improves sensitivity during exposure and reduces the time load on the exposure machine, thereby improving productivity. The oxygen-blocking layer used as the intermediate layer may be appropriately selected from known layers. The oxygen-blocking layer used as the intermediate layer preferably exhibits low oxygen permeability and is dispersible or soluble in water or an alkaline aqueous solution (a 1% by mass aqueous solution of sodium carbonate at 22°C).

[0164] The intermediate layer preferably contains a resin. Examples of the resin 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.

[0165] 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 negative photosensitive layer and the thermoplastic resin (alkali-soluble resin) contained in the thermoplastic resin layer.

[0166] From the viewpoints of oxygen blocking properties, developability, resolution, and pattern formability, the intermediate layer preferably contains a water-soluble compound, and more preferably contains a water-soluble resin. The water-soluble compound is not particularly limited, but from the viewpoints of oxygen blocking properties, developability, resolution, and pattern formability, it is preferably one or more compounds selected from the group consisting of water-soluble cellulose derivatives, polyhydric alcohols, oxide adducts of polyhydric alcohols, polyethers, phenol derivatives, and amide compounds, more preferably at least one water-soluble resin selected from the group consisting of polyvinyl alcohol, polyvinylpyrrolidone, hydroxypropyl cellulose, and hydroxypropyl methylcellulose, even more preferably at least two water-soluble resins selected from the group consisting of polyvinyl alcohol, polyvinylpyrrolidone, hydroxypropyl cellulose, and hydroxypropyl methylcellulose, and particularly preferably at least three water-soluble resins selected from the group consisting of polyvinyl alcohol, polyvinylpyrrolidone, hydroxypropyl cellulose, and hydroxypropyl methylcellulose. Examples of water-soluble resins include water-soluble cellulose derivatives, polyvinyl alcohol, polyvinylpyrrolidone, acrylamide resins, (meth)acrylate resins, polyethylene oxide resins, gelatin, vinyl ether resins, polyamide resins, and copolymers thereof. Among these, the water-soluble compound preferably contains polyvinyl alcohol, and more preferably is polyvinyl alcohol, from the viewpoints of oxygen blocking properties, developability, resolution, and pattern formability. The degree of hydrolysis of polyvinyl alcohol is not particularly limited, but is preferably 73 mol % to 99 mol % from the viewpoints of oxygen blocking properties, developability, resolution, and pattern formability. In addition, from the viewpoints of oxygen blocking properties, developability, resolution, and pattern formability, it is preferable that the polyvinyl alcohol contains ethylene as a monomer unit.

[0167] The method for measuring the degree of hydrolysis is not particularly limited, and it can be measured, for example, by the method described in JIS K 6726:1994.

[0168] From the viewpoints of oxygen barrier properties and suppressing mixing of components when applying multiple layers and during storage after application, the intermediate layer preferably contains polyvinyl alcohol, and more preferably contains polyvinyl alcohol and polyvinylpyrrolidone.

[0169] The intermediate layer may contain one type of resin alone, or two or more types of resins.

[0170] The content of the water-soluble compound in the intermediate layer 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, from the viewpoints of oxygen blocking properties and suppressing mixing of components when multiple layers are applied and during storage after application.

[0171] The intermediate layer may also contain additives, such as surfactants, if necessary.

[0172] The thickness of the intermediate layer is not limited. The average thickness of the intermediate layer 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 during formation of multiple layers and during storage can be suppressed, and an increase in the time required to remove the intermediate layer during development can be suppressed.

[0173] The method for forming the intermediate layer is not limited as long as it is a method capable of forming a layer containing the above-mentioned components. Examples of the method for forming the intermediate layer include a method in which an intermediate layer composition is applied to the surface of a thermoplastic resin layer or a negative photosensitive layer, and then the coating film of the intermediate layer composition is dried.

[0174] Examples of intermediate layer compositions include compositions containing a resin and optional additives. The intermediate layer composition preferably contains a solvent to adjust the viscosity of the intermediate layer composition and facilitate the formation of the intermediate layer. The solvent is not limited as long as it can dissolve or disperse the resin. The solvent 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.

[0175] Examples of water-miscible organic solvents include alcohols having 1 to 3 carbon atoms, acetone, ethylene glycol, and glycerin. The water-miscible organic solvent is preferably an alcohol having 1 to 3 carbon atoms, more preferably methanol or ethanol.

[0176] [Thermoplastic resin layer] The photosensitive transfer material according to the present disclosure may have a thermoplastic resin layer. The photosensitive transfer material preferably has a thermoplastic resin layer between the temporary support and the photosensitive layer. By having a thermoplastic resin layer between the temporary support and the photosensitive layer, the photosensitive transfer material has improved conformability to the adherend, and the inclusion of air bubbles between the adherend and the photosensitive transfer material is suppressed, resulting in improved adhesion between the layers.

[0177] The thermoplastic resin layer preferably contains an alkali-soluble resin as the thermoplastic resin.

[0178] Examples of alkali-soluble resins include acrylic resins, polystyrene resins, styrene-acrylic copolymers, polyurethane resins, polyvinyl alcohol, polyvinyl formal, polyamide resins, polyester resins, polyamide resins, epoxy resins, polyacetal resins, polyhydroxystyrene resins, polyimide resins, polybenzoxazole resins, polysiloxane resins, polyethyleneimine, polyallylamine, and polyalkylene glycols.

[0179] The alkali-soluble resin is preferably an acrylic resin from the viewpoints of developability and adhesion to a layer adjacent to the thermoplastic resin layer. Here, "acrylic resin" refers to a resin having at least one selected from the group consisting of a structural unit derived from (meth)acrylic acid, a structural unit derived from a (meth)acrylic acid ester, and a structural unit derived from a (meth)acrylic acid amide.

[0180] In the acrylic resin, the total content of the structural units derived from (meth)acrylic acid, the structural units derived from (meth)acrylic acid esters, and the structural units derived from (meth)acrylic acid amides is preferably 50% by mass or more relative to the total mass of the acrylic resin. In the acrylic resin, 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.

[0181] The alkali-soluble resin is preferably a polymer having an acid group, such as a carboxy group, a sulfo group, a phosphate group, or a phosphonate group, with the carboxy group being preferred.

[0182] From the viewpoint of developability, the alkali-soluble resin is preferably an alkali-soluble resin having an acid value of 60 mgKOH / g or more, and more preferably a carboxyl group-containing acrylic resin having an acid value of 60 mgKOH / g or more. There is no upper limit to the acid value. The acid value of the alkali-soluble resin is preferably 200 mgKOH / g or less, and more preferably 150 mgKOH / g or less.

[0183] The carboxyl group-containing acrylic resin having an acid value of 60 mgKOH / g or more is not limited and can be appropriately selected from known resins. Examples of the carboxyl group-containing acrylic resin having an acid value of 60 mgKOH / g or more include the carboxyl 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, the carboxyl 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 the carboxyl 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.

[0184] The content of structural units 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 particularly preferably 12% by mass to 30% by mass, relative to the total mass of the carboxy group-containing acrylic resin.

[0185] From the viewpoints of developability and adhesion to a layer adjacent to the thermoplastic resin layer, the alkali-soluble resin is particularly preferably an acrylic resin having a structural unit derived from (meth)acrylic acid.

[0186] The alkali-soluble resin may have a reactive group. The reactive group may be, for example, a group capable of addition polymerization. Examples of the reactive group include an ethylenically unsaturated group, a polycondensable group (e.g., a hydroxy group and a carboxy group), and a polyaddition reactive group (e.g., an epoxy group and a (blocked) isocyanate group).

[0187] 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 particularly preferably from 20,000 to 50,000.

[0188] The thermoplastic resin layer may contain one kind of alkali-soluble resin alone, or two or more kinds of alkali-soluble resins.

[0189] From the viewpoints of developability and adhesion to layers adjacent to the thermoplastic resin layer, 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.

[0190] The thermoplastic resin layer preferably contains a dye (hereinafter sometimes referred to as "dye B") 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 in response to an acid, a base, or a radical. Preferred aspects of dye B are the same as those of dye N described above, except for the points described below.

[0191] From the viewpoints of the visibility of the exposed area, the visibility of the unexposed area, and the 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.

[0192] From the viewpoints of the visibility of exposed areas, the visibility of unexposed areas, and resolution, the thermoplastic layer preferably contains, as dye B, a dye whose maximum absorption wavelength changes in response to acid, and a compound that generates acid when exposed to light, as described below.

[0193] The thermoplastic resin layer may contain one type of dye B alone, or two or more types of dye B.

[0194] From the viewpoint of visibility of exposed areas and visibility of unexposed 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.

[0195] Here, the content of dye B refers to the content of dye when all of the dye B contained in the thermoplastic resin layer is in a colored state. Below, we will explain the method for quantifying the content of dye B using a dye that develops color through radicals as an example. Two solutions were prepared by dissolving dye (0.001 g) and dye (0.01 g) in methyl ethyl ketone (100 mL). IRGACURE OXE-01 (BASF) was added to each solution as a photoradical polymerization initiator, and then irradiated with 365 nm light to generate radicals and color all of the dyes. Next, the absorbance of each solution was measured at a liquid temperature of 25°C under atmospheric conditions using a spectrophotometer (UV3100, Shimadzu Corporation), and a calibration curve was created. Next, the absorbance of the solution in which all of the dyes had developed color was measured using the same method as above, except that thermoplastic resin layer (0.1 g) was dissolved in methyl ethyl ketone instead of the dye. The amount of the dye contained in the thermoplastic resin layer is calculated from the absorbance of the obtained solution containing the thermoplastic resin layer based on a calibration curve.

[0196] The thermoplastic resin layer may contain a compound that generates an acid, a base, or a radical when exposed to light (hereinafter, may be referred to as "compound C"). Compound C is preferably a compound that generates an acid, a base, or a radical when exposed to actinic rays (e.g., ultraviolet light and visible light). Examples of compound C include known photoacid generators, photobase generators, and photoradical polymerization initiators (photoradical generators). Compound C is preferably a photoacid generator.

[0197] From the viewpoint of resolution, the thermoplastic resin layer preferably contains a photoacid generator, such as the cationic photopolymerization initiator that may be contained in the negative-type photosensitive layer described above, and preferred embodiments are the same except for the points described below.

[0198] From the viewpoints of sensitivity and resolution, the photoacid generator preferably contains at least one 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.

[0199] The photoacid generator is also preferably a photoacid generator having the following structure:

[0200] [ka]

[0201] The thermoplastic resin layer may contain a photobase generator, such as 2-nitrobenzyl cyclohexyl carbamate, 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)-1-benzyl-1-diamine, 4-(methylthiobenzoyl)-1-methyl-1-morpholinoethane, 4-(methylthio ... methylaminopropane, 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.

[0202] The thermoplastic resin layer may contain a photoradical polymerization initiator. Examples of the photoradical polymerization initiator include the photoradical polymerization initiators that may be contained in the negative-type photosensitive layer described above, and preferred embodiments are also the same.

[0203] The thermoplastic resin layer may contain one or more types of compound C.

[0204] From the viewpoints of visibility of exposed areas, visibility of unexposed areas, and resolution, the content of compound C is preferably 0.1% by mass to 10% by mass, and more preferably 0.5% by mass to 5% by mass, relative to the total mass of the thermoplastic resin layer.

[0205] The thermoplastic resin layer preferably contains a plasticizer from the viewpoints of resolution, adhesion to layers adjacent to the thermoplastic resin layer, and developability.

[0206] The molecular weight of the plasticizer (when it is an oligomer or polymer, this refers to the weight average molecular weight (Mw); the same applies hereinafter in this paragraph) is preferably smaller than the molecular weight of the alkali-soluble resin. The molecular weight of the plasticizer is preferably 200 to 2,000.

[0207] The plasticizer is not limited as long as it is a compound that is compatible with the alkali-soluble resin and exhibits plasticity. From the viewpoint of imparting plasticity, the plasticizer is preferably a compound having an alkyleneoxy group in the molecule, more preferably a polyalkylene glycol compound. The alkyleneoxy group contained in the plasticizer preferably has a polyethyleneoxy structure or a polypropyleneoxy structure.

[0208] 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 a layer adjacent to the thermoplastic resin layer, it is more preferable that the alkali-soluble resin is an acrylic resin and the plasticizer contains a (meth)acrylate compound.

[0209] Examples of (meth)acrylate compounds used as plasticizers include the (meth)acrylate compounds described above in the section on ethylenically unsaturated compounds. In the photosensitive transfer material, when a thermoplastic resin layer and a negative photosensitive layer are disposed in direct contact with each other, it is preferable that the thermoplastic resin layer and the negative photosensitive layer each contain the same (meth)acrylate compound. This is because the thermoplastic resin layer and the negative photosensitive layer each contain the same (meth)acrylate compound, which suppresses component diffusion between the layers and improves storage stability.

[0210] 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 layers adjacent to the thermoplastic resin layer.

[0211] In one embodiment, the (meth)acrylate compound used as a plasticizer is preferably a (meth)acrylate compound having two or more (meth)acryloyl groups in one molecule, from the viewpoints of resolution, adhesion to a layer adjacent to the thermoplastic resin layer, and developability.

[0212] In one embodiment, the (meth)acrylate compound used as the plasticizer is preferably a (meth)acrylate compound having an acid group or a urethane (meth)acrylate compound.

[0213] The thermoplastic resin layer may contain one kind of plasticizer alone or two or more kinds of plasticizers.

[0214] From the viewpoints of resolution, adhesion to layers adjacent to the thermoplastic resin layer, 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.

[0215] From the viewpoint of thickness uniformity, the thermoplastic resin layer preferably contains a surfactant. Examples of the surfactant include the surfactants that may be contained in the negative-type photosensitive layer described above, and preferred embodiments are also the same.

[0216] The thermoplastic resin layer may contain one or more types of surfactants.

[0217] The content of the surfactant is preferably 0.001% by mass to 10% by mass, and more preferably 0.01% by mass to 3% by mass, relative to the total mass of the thermoplastic resin layer.

[0218] The thermoplastic resin layer may contain a sensitizer, such as the sensitizers that may be contained in the negative-type photosensitive layer.

[0219] The thermoplastic resin layer may contain one or more types of sensitizers.

[0220] From the viewpoints of improving sensitivity to the light source, visibility of the exposed areas, and visibility of the unexposed areas, 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 thermoplastic resin layer.

[0221] The thermoplastic resin layer may contain known additives in addition to the above components, if necessary.

[0222] The thermoplastic resin layer is described in paragraphs 0189 to 0193 of JP 2014-85643 A, the contents of which are incorporated herein by reference.

[0223] The thickness of the thermoplastic resin layer is not limited. From the viewpoint of adhesion to the layer adjacent to the thermoplastic resin layer, the average thickness of the thermoplastic resin layer is preferably 1 μm or more, and more preferably 2 μm or more. The upper limit of the average thickness of the thermoplastic resin layer is not limited. From the viewpoint of developability and resolution, the average thickness of the thermoplastic resin layer is preferably 20 μm or less, more preferably 10 μm or less, and particularly preferably 5 μm or less.

[0224] The method for forming the thermoplastic resin layer is not limited as long as it is a method capable of forming a layer containing the above-mentioned components. Examples of the method for forming the thermoplastic resin layer include a method of applying a thermoplastic resin composition to the surface of a temporary support and drying the coating film of the thermoplastic resin composition.

[0225] The thermoplastic resin composition may be, for example, a composition containing the above-mentioned components. The thermoplastic resin composition preferably contains a solvent to adjust the viscosity of the thermoplastic resin composition and facilitate the formation of the thermoplastic resin layer.

[0226] The solvent contained in the thermoplastic resin composition is not limited as long as it can dissolve or disperse the components contained in the thermoplastic resin layer. Examples of the solvent include the solvents that may be contained in the photosensitive resin composition described above, and preferred embodiments are also the same.

[0227] The thermoplastic resin composition may contain one solvent alone or two or more solvents.

[0228] The content of the solvent in the thermoplastic resin composition is preferably 50 to 1,900 parts by mass, and more preferably 100 to 900 parts by mass, relative to 100 parts by mass of the total solid content in the thermoplastic resin composition.

[0229] 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 negative photosensitive layer. For example, a solution in which each component contained in the thermoplastic resin layer is dissolved in a solvent is prepared in advance, and the resulting solutions are mixed in a predetermined ratio to prepare a thermoplastic resin composition. The resulting thermoplastic resin composition is then 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, a negative photosensitive layer may be formed on a protective film, and then a thermoplastic resin layer may be formed on the surface of the negative photosensitive layer.

[0230] [Protective film] The photosensitive transfer material has a protective film. It is preferable that the photosensitive layer and the protective film are in direct contact with each other.

[0231] Materials constituting the protective film include resin films and paper, with resin films being preferred from the viewpoints 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 preferred.

[0232] The thickness (layer thickness) of the protective film is not particularly limited, but is preferably 5 μm to 100 μm, more preferably 10 μm to 50 μm. From the viewpoints of transportability, suppression of defects in the resin pattern, and resolution, the arithmetic mean roughness Ra of the surface of the protective film opposite the photosensitive layer side is preferably equal to or less than the arithmetic mean roughness Ra of the surface of the protective film facing the photosensitive layer, and more preferably is smaller than the arithmetic mean roughness Ra of the surface of the protective film facing the photosensitive layer. The arithmetic mean roughness Ra of the surface of the protective film opposite to the photosensitive layer side is preferably 300 nm or less, more preferably 100 nm or less, even more preferably 70 nm or less, and particularly preferably 50 nm or less, from the viewpoint of transportability and winding ability. Furthermore, the arithmetic mean roughness Ra of the surface of the protective film facing the photosensitive layer is preferably 300 nm or less, more preferably 100 nm or less, even more preferably 70 nm or less, and particularly preferably 50 nm or less, from the viewpoint of superior resolution. It is believed that when the Ra value of the surface of the protective film is within the above range, the uniformity of the layer thickness of the photosensitive layer and the formed resin pattern is improved. The lower limit of the Ra value of the surface of the protective film is not particularly limited, but is preferably 1 nm or more, more preferably 10 nm or more, and particularly preferably 20 nm or more, on each of both surfaces. The peel strength of the protective film is preferably smaller than that of the temporary support.

[0233] The photosensitive transfer material may include layers other than the above-mentioned layers (hereinafter also referred to as "other layers"), such as 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.

[0234] The total thickness of the photosensitive transfer material is preferably 5 μm to 55 μm, more preferably 10 μm to 50 μm, and particularly preferably 20 μm to 40 μm. The total thickness of the photosensitive transfer material is measured by a method similar to the method for measuring the thickness of each layer described above. In order to better demonstrate the effects of the present disclosure, the total thickness of each layer in the photosensitive transfer material, excluding the temporary support and the protective 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. Furthermore, from the viewpoint of further exerting the effects of the present disclosure, the total thickness of the photosensitive layer, intermediate layer, and thermoplastic resin layer in the photosensitive transfer material 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.

[0235] [Method for producing photosensitive transfer material] The method for producing the photosensitive transfer material according to the present disclosure is not particularly limited, and known production methods, for example, known methods for forming each layer, can be used. Hereinafter, a method for producing a photosensitive transfer material according to the present disclosure will be described with reference to Fig. 1. However, the photosensitive transfer material according to the present disclosure is not limited to the configuration shown in Fig. 1. Fig. 1 is a schematic cross-sectional view showing an example of the layer structure of one embodiment of the photosensitive transfer material according to the present disclosure. The photosensitive transfer material 20 shown in Fig. 1 has a structure in which a temporary support 11, a thermoplastic resin layer 13, an intermediate layer 15, a photosensitive layer 17, and a protective film 19 are laminated in this order.

[0236] Examples of methods for producing the photosensitive transfer material 20 include the steps of applying a thermoplastic resin composition to the surface of the temporary support 11 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 13 and then drying the coating of the intermediate layer composition to form an intermediate layer 15, and applying a photosensitive resin composition containing a polymerization initiator and a polymerizable compound to the surface of the intermediate layer 15 and then drying the coating of the photosensitive resin composition to form a photosensitive layer 16. In the above-mentioned manufacturing method, it is preferable to use a thermoplastic resin composition containing at least one solvent selected from the group consisting of alkylene glycol ether solvents and alkylene glycol ether acetate solvents, an intermediate layer composition containing at least one solvent selected from the group consisting of water and water-miscible organic solvents, and a photosensitive resin composition containing a binder polymer, an ethylenically unsaturated compound, and at least one solvent selected from the group consisting of alkylene glycol ether solvents and alkylene glycol ether acetate solvents. This can prevent mixing of the components contained in the thermoplastic resin layer 13 and the intermediate layer 15 during application of the intermediate layer composition to the surface of the thermoplastic resin layer 13 and / or during storage of a laminate having a coating film of the intermediate layer composition. Furthermore, it can prevent mixing of the components contained in the intermediate layer 15 and the photosensitive layer 16 during application of the photosensitive resin composition to the surface of the intermediate layer 15 and / or during storage of a laminate having a coating film of the photosensitive resin composition.

[0237] A protective film 19 is pressed onto the photosensitive layer 17 of the laminate produced by the above-described production method, thereby producing a photosensitive transfer material 20. The method for producing the photosensitive transfer material used in the present disclosure preferably includes a step of providing a protective film 19 in contact with the second surface of the photosensitive layer 17, thereby producing a photosensitive transfer material 20 comprising a temporary support 11, a thermoplastic resin layer 13, an intermediate layer 15, a photosensitive layer 17, and a protective film 19. After producing the photosensitive transfer material 20 by the above-described production method, a roll-form photosensitive transfer material may be produced and stored by winding up the photosensitive transfer material 20. The roll-form photosensitive transfer material can be provided in its original form for the step of laminating the photosensitive transfer material to a substrate in a roll-to-roll system, which will be described later.

[0238] The photosensitive transfer material according to the present disclosure can be suitably used in various applications requiring precision microfabrication by photolithography. After patterning the photosensitive layer, etching may be performed using the photosensitive layer as a coating, or electroforming, mainly involving electroplating, may be performed. The cured film obtained by patterning may also be used as a permanent film, for example, as an interlayer insulating film, a wiring protective film, or a wiring protective film having an index matching layer. The photosensitive transfer material according to the present disclosure can also be suitably used in applications such as various wiring formation applications for semiconductor packages, printed circuit boards, and sensor substrates, touch panels, electromagnetic wave shielding materials, conductive films such as film heaters, liquid crystal sealants, and the formation of structures in the fields of micromachines or microelectronics.

[0239] In addition, the photosensitive transfer material according to the present disclosure also preferably has an embodiment in which the photosensitive layer is a colored resin layer containing a pigment. In addition to the above-mentioned applications, the colored resin layer is suitable for applications such as forming colored pixels or black matrices of color filters used in liquid crystal display devices (LCDs) and solid-state imaging devices (e.g., CCDs (charge-coupled devices) and CMOSs ​​(complementary metal oxide semiconductors)). The aspects of the colored resin layer other than the pigment are the same as those described above.

[0240] <Pigments> The photosensitive layer may be a colored resin layer containing a pigment. In order to protect the liquid crystal display window of recent electronic devices, a cover glass having a black frame-shaped light-shielding layer formed on the periphery of the back surface of a transparent glass substrate or the like is sometimes attached. A colored resin layer can be used to form such a light-shielding layer. The pigment may be appropriately selected according to the desired hue, and may be selected from black pigments, white pigments, and pigments of chromatic colors other than black and white. In particular, when a black pattern is to be formed, a black pigment is preferably selected as the pigment.

[0241] As the black pigment, any known black pigment (organic pigment, inorganic pigment, etc.) can be appropriately selected as long as the effects of the present disclosure are not impaired. Among them, from the viewpoint of optical density, suitable black pigments include, for example, carbon black, titanium oxide, titanium carbide, iron oxide, titanium oxide, and graphite, with carbon black being particularly preferred. As the carbon black, from the viewpoint of surface resistance, carbon black at least a portion of the surface of which is coated with a resin is preferred.

[0242] From the viewpoint of dispersion stability, the particle size of the black pigment is preferably 0.001 μm to 0.1 μm, more preferably 0.01 μm to 0.08 μm, in terms of number average particle size. Here, the particle size refers to the diameter of a circle whose area is equal to the area of ​​a pigment particle, calculated from a photograph of the pigment particle taken with an electron microscope, and the number average particle size is the average value obtained by calculating the particle size for 100 random particles and averaging the particle sizes of the 100 particles.

[0243] As a pigment other than black pigments, the white pigments described in paragraphs 0015 and 0114 of JP-A No. 2005-007765 can be used. Specifically, among the white pigments, inorganic pigments such as titanium oxide, zinc oxide, lithopone, precipitated calcium carbonate, white carbon, aluminum oxide, aluminum hydroxide, and barium sulfate are preferred, titanium oxide or zinc oxide is more preferred, and titanium oxide is even more preferred. As the inorganic pigment, rutile or anatase titanium oxide is more preferred, and rutile titanium oxide is particularly preferred. The surface of titanium oxide may be subjected to a silica treatment, alumina treatment, titania treatment, zirconia treatment, or organic treatment, or may be subjected to two or more of these treatments, which suppresses the catalytic activity of titanium oxide and improves heat resistance, fading resistance, etc. From the viewpoint of reducing the thickness of the photosensitive layer after heating, the surface treatment of the titanium oxide is preferably at least one of alumina treatment and zirconia treatment, and particularly preferably both alumina treatment and zirconia treatment.

[0244] Furthermore, when the photosensitive layer is a colored resin layer, it is also preferable that the photosensitive layer further contains a chromatic pigment other than a black pigment and a white pigment, from the viewpoint of transferability. When a chromatic pigment is contained, the particle size of the chromatic pigment is preferably 0.1 μm or less, and more preferably 0.08 μm or less, in terms of better dispersibility. Examples of chromatic pigments include Victoria Pure Blue BO (Color Index (CI) 42595), Auramine (CI 41000), Fat Black HB (CI 26150), Monolight Yellow GT (CI Pigment Yellow 12), Permanent Yellow GR (CI Pigment Yellow 17), Permanent Yellow HR (CI Pigment Yellow 83), Permanent Carmine FBB (CI Pigment Red 146), Hoster Balm Red ESB (CI Pigment Violet 19), Permanent Ruby FBH (CI Pigment Red 11), Fastel Pink B Supra (CI Pigment Red 81), Monastral Fast Blue (CI Pigment Red 146), and Permanent Yellow GR (CI Pigment Yellow 17). Examples of pigments that can be used include CI Pigment Blue 15), Monolight Fast Black B (CI Pigment Black 1) and Carbon, CI Pigment Red 97, CI Pigment Red 122, CI Pigment Red 149, CI Pigment Red 168, CI Pigment Red 177, CI Pigment Red 180, CI Pigment Red 192, CI Pigment Red 215, CI Pigment Green 7, CI Pigment Blue 15:1, CI Pigment Blue 15:4, CI Pigment Blue 22, CI Pigment Blue 60, CI Pigment Blue 64, and CI Pigment Violet 23. Of these, CI Pigment Red 177 is preferred.

[0245] When the photosensitive layer contains a pigment, the content of the pigment is preferably more than 3% by mass and not more than 40% by mass, more preferably more than 3% by mass and not more than 35% by mass, even more preferably more than 5% by mass and not more than 35% by mass, and particularly preferably 10% by mass or more and not more than 35% by mass, relative to the total mass of the photosensitive layer.

[0246] When the photosensitive layer contains pigments other than black pigments (white pigments and chromatic pigments), the content of the pigments other than black pigments is preferably 30% by mass or less, more preferably 1% by mass to 20% by mass, and even more preferably 3% by mass to 15% by mass, relative to the black pigment.

[0247] In addition, when the photosensitive layer contains a black pigment and is formed from a photosensitive resin composition, the black pigment (preferably carbon black) is preferably introduced into the photosensitive resin composition in the form of a pigment dispersion. The dispersion may be prepared by premixing a black pigment and a pigment dispersant, adding the resulting mixture to an organic solvent (or vehicle), and dispersing the mixture using a disperser. The pigment dispersant may be selected depending on the pigment and solvent, and commercially available dispersants may be used, for example. The vehicle refers to the medium in which the pigment is dispersed when a pigment dispersion is prepared. The vehicle is liquid and includes a binder component that maintains the black pigment in a dispersed state and a solvent component (organic solvent) that dissolves and dilutes the binder component.

[0248] The dispersing machine is not particularly limited, and examples thereof include known dispersing machines such as a kneader, a roll mill, an attritor, a super mill, a dissolver, a homomixer, and a sand mill. Furthermore, fine pulverization may be performed by utilizing frictional force through mechanical grinding. For details about dispersing machines and fine pulverization, please refer to the descriptions in "Pigment Dictionary" (Kunizo Asakura, 1st Edition, Asakura Shoten, 2000, pp. 438 and 310).

[0249] (Method for manufacturing a resin pattern, a laminate, and a circuit wiring) The method for producing a resin pattern according to the present disclosure is a method for producing a resin pattern in which a resin pattern is formed on a substrate using the photosensitive transfer material according to the present disclosure. A preferred method for producing a resin pattern according to the present disclosure is a method that includes, in this order, a step of bonding the photosensitive transfer material according to the present disclosure to the substrate so that the photosensitive layer side of the photosensitive transfer material is in contact with the substrate (hereinafter also referred to as the "bonding step"); a step of peeling off the temporary support (hereinafter also referred to as the "temporary support peeling step"); and a step of exposing and developing the exposed photosensitive layer to form a pattern (hereinafter also referred to as the "pattern formation step"). Furthermore, the method for producing a resin pattern according to the present disclosure preferably includes a step of peeling off the protective film (hereinafter also referred to as a "protective film peeling step") before the laminating step.

[0250] The method for producing a laminate according to the present disclosure is a method for producing a laminate having a resin pattern on a substrate using the photosensitive transfer material according to the present disclosure. A preferred method for manufacturing a laminate according to the present disclosure includes, in this order: a step of bonding the photosensitive transfer material according to the present disclosure to the substrate so that the photosensitive layer side of the photosensitive transfer material is in contact with the substrate; a step of peeling off the temporary support; and a step of exposing and developing the exposed photosensitive layer to form a pattern. Furthermore, the method for producing a laminate according to the present disclosure preferably includes a step of peeling off the protective film before the bonding step.

[0251] The method for producing circuit wiring according to the present disclosure is not particularly limited as long as it is a method that uses the photosensitive transfer material according to the present disclosure. A preferred method for manufacturing circuit wiring according to the present disclosure includes, in this order, a step of bonding the photosensitive transfer material according to the present disclosure to a substrate so that the photosensitive layer side of the photosensitive transfer material is in contact with the conductive layer of the substrate having a conductive layer; a step of peeling off the temporary support; a step of exposing and developing the exposed photosensitive layer to form a pattern; and a step of etching the conductive layer in areas where the pattern is not arranged (hereinafter also referred to as the "etching step"). Furthermore, the method for producing circuit wiring according to the present disclosure preferably includes a step of peeling off the protective film before the laminating step. Below, we will explain each step included in the method for manufacturing a resin pattern, the method for manufacturing a laminate, and the method for manufacturing circuit wiring.Unless otherwise specified, the contents explained for each step included in the method for manufacturing a resin pattern or the method for manufacturing a laminate also apply to each step included in the method for manufacturing circuit wiring.

[0252] <Protective film peeling process> The method for producing a resin pattern or the method for producing a laminate preferably includes a step of peeling the protective film from the photosensitive transfer material according to the present disclosure. The method for peeling the protective film is not limited, and known methods can be applied.

[0253] <Laminating process> The method for producing a resin pattern or the method for producing a laminate preferably include a laminating step. In the lamination step, it is preferable to bring a substrate (or the conductive layer, if a conductive layer is provided on the surface of the substrate) into contact with the outermost layer of the photosensitive transfer material on the side having the photosensitive layer relative to the temporary support, and to press the photosensitive transfer material and the substrate together. In this embodiment, the adhesion between the outermost layer of the photosensitive transfer material on the side having the photosensitive layer relative to the temporary support and the substrate is improved, so that the patterned photosensitive layer after exposure and development can be suitably used as an etching resist when etching the conductive layer.

[0254] Furthermore, in the case where the photosensitive transfer material further comprises a layer other than the protective film (for example, a high refractive index layer and / or a low refractive index layer) on the surface of the photosensitive layer that does not face the temporary support, the lamination process is carried out in such a manner that the surface of the photosensitive layer that does not have the temporary support is laminated to the substrate via that layer.

[0255] The method for pressing the substrate and the photosensitive transfer material together is not particularly limited, and known transfer methods and lamination methods can be used. The photosensitive transfer material is preferably bonded to the substrate by superposing the outermost layer of the photosensitive transfer material on the temporary support on the substrate, the outermost layer having the photosensitive layer, and the substrate, and applying pressure and heat using a roll, etc. For the bonding, known laminators such as a laminator, a vacuum laminator, and an auto-cut laminator that can further increase productivity can be used. The lamination temperature is not particularly limited, but is preferably 70°C to 130°C, for example.

[0256] The method for producing a resin pattern and the method for producing a laminate, which include the lamination step, are preferably carried out by a roll-to-roll system. The roll-to-roll method will be described below. The roll-to-roll method is 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 of the steps included in the resin pattern manufacturing method or the etching method, and a step of winding up the substrate or a structure including the substrate (also referred to as a "winding step") after any of the steps, and at least any of the steps (preferably all of the steps, or all of the steps except the heating step) are 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 manufacturing method that employs a roll-to-roll system.

[0257] <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. Examples of the substrate include a resin substrate, a glass substrate, and a semiconductor substrate. Preferred embodiments of the substrate include, for example, those described in paragraph 0140 of International Publication No. 2018 / 155193, the contents of which are incorporated herein by reference.

[0258] Examples of the base material that constitutes the substrate include glass, silicon, and film. The base material constituting the substrate is preferably transparent. In this specification, "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.

[0259] Examples of transparent glass substrates include tempered glass, such as Gorilla Glass from Corning Inc. Furthermore, materials used in JP-A-2010-86684, JP-A-2010-152809, and JP-A-2010-257492 can be used as the transparent glass substrate.

[0260] When a film substrate is used as the substrate, it is preferable to use a film substrate with small optical distortion and / or high transparency, such as polyethylene terephthalate (PET), polyethylene naphthalate, polycarbonate, triacetyl cellulose, and cycloolefin polymer.

[0261] When the substrate is produced by a roll-to-roll method, a film substrate is preferred. When circuit wiring for a touch panel is produced by a roll-to-roll method, the substrate is preferably a sheet-shaped resin composition.

[0262] 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, and when having two or more conductive layers, it is preferable that the conductive layers are made of different materials.

[0263] 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 ITO (indium tin oxide), IZO (indium zinc oxide), and SiO2. In this specification, "electrically 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 Preferably less than Ωcm.

[0264] 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 in a visual recognition section used in a capacitance type touch panel or wiring in a peripheral extraction section. Preferred embodiments of the conductive layer are described, for example, in paragraph 0141 of International Publication No. 2018 / 155193, the contents of which are incorporated herein by reference.

[0265] The substrate having a conductive layer is preferably a substrate having at least one of a transparent electrode and a lead wiring. Such a substrate can be suitably used as a touch panel substrate. The transparent electrode can function favorably as an electrode for a touch panel, and is preferably made of a metal oxide film such as ITO (indium tin oxide) or IZO (indium zinc oxide), a metal mesh, or a thin metal wire such as silver nanowire. Examples of the thin metal wires include thin wires of silver, copper, etc. Among these, conductive silver materials such as silver mesh and silver nanowires are preferred.

[0266] The material of the lead wiring is preferably metal. Examples of metals that can be used for the wiring include gold, silver, copper, molybdenum, aluminum, titanium, chromium, zinc, and manganese, as well as alloys of two or more of these metal elements. The wiring is preferably made of copper, molybdenum, aluminum, or titanium, with copper being particularly preferred.

[0267] The touch panel electrode protective film formed using the photosensitive transfer material according to the present disclosure is preferably provided to cover the electrodes, etc. (i.e., at least one of the touch panel electrodes and the touch panel wiring), either directly or via another layer, for the purpose of protecting the electrodes, etc.

[0268] <Temporary support peeling process> The method for producing a resin pattern or the method for producing a laminate preferably includes a temporary support peeling step of peeling off the temporary support between the laminating step and the exposure step. The method for peeling off the temporary support is not particularly limited, and a mechanism similar to the cover film peeling mechanism described in paragraphs 0161 to 0162 of JP-A No. 2010-072589 can be used.

[0269] <Pattern formation process> The method for producing a resin pattern or a laminate preferably includes, after the laminating step, a step of subjecting the exposed photosensitive layer to an exposure treatment and a development treatment to form a pattern (pattern forming step). The exposure process is a patterned exposure process (also called "pattern exposure"), that is, an exposure process in which exposed areas and non-exposed areas exist. The positional relationship between the exposed and unexposed regions in the pattern exposure is not particularly limited and may be adjusted as appropriate.

[0270] The detailed arrangement and specific size of the pattern in the pattern exposure are not particularly limited. For example, in order to improve the display quality of a display device (e.g., a touch panel) equipped with an input device having circuit wiring manufactured by an etching method and to reduce the area occupied by the lead wiring, at least a part of the pattern (preferably the electrode pattern and / or the lead wiring of the touch panel) preferably includes thin lines having a width of 20 μm or less, more preferably thin lines having a width of 10 μm or less.

[0271] 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 layer. Specific examples include ultra-high pressure mercury lamps, high pressure mercury lamps, metal halide lamps, and LEDs (light emitting diodes). The exposure dose is 5 mJ / cm 2 ~200mJ / cm 2 is preferred, and 10 mJ / cm 2 ~100mJ / cm 2 is more preferred. Preferred embodiments of the light source, exposure dose, and exposure method used for exposure are described, for example, in paragraphs 0146 to 0147 of WO 2018 / 155193, the contents of which are incorporated herein by reference.

[0272] In the exposure step, pattern exposure may be performed after peeling the temporary support from the photosensitive layer, or pattern exposure may be performed via the temporary support before peeling the temporary support, and then the temporary support may be peeled off. If the temporary support is peeled off before exposure, the mask may be exposed in contact with the photosensitive layer, or in close proximity without contact. If exposure is performed without peeling the temporary support, the mask may be exposed in contact with the temporary support, or in close proximity without contact. To prevent mask contamination due to contact between the photosensitive 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 without peeling the temporary support. The exposure method can be appropriately selected from contact exposure in the case of contact exposure, and proximity exposure, lens-based or mirror-based projection exposure, and direct exposure using an exposure laser, etc., in the case of lens-based or mirror-based projection exposure. In the case of lens-based or mirror-based projection exposure, an exposure machine with an appropriate lens numerical aperture (NA) can be used depending on the required resolution and depth of focus. In the case of the direct exposure method, the image may be drawn directly on the photosensitive layer, or the photosensitive layer may be exposed by reduction projection through a lens. The exposure may be carried out not only in the atmosphere but also under reduced pressure or vacuum, and may be carried out by interposing a liquid such as water between the light source and the photosensitive layer.

[0273] In the pattern formation step, after exposure, the exposed photosensitive layer is subjected to a development treatment to form a pattern.

[0274] The exposed photosensitive layer in the pattern forming step can be developed using a developer. The developer is not particularly limited as long as it can remove the non-image areas of the photosensitive layer, and known developers such as the developer described in JP-A No. 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. Examples of alkaline compounds that can be contained in the alkaline aqueous solution include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, and choline (2-hydroxyethyltrimethylammonium hydroxide). Preferred examples of the developer include the developer described in paragraph 0194 of WO 2015 / 093271. Suitable development methods include, for example, the development method described in paragraph 0195 of WO 2015 / 093271.

[0275] The development method is not particularly limited, and may be any of puddle development, shower development, shower and spin development, and dip development. Shower development is a development treatment in which a developer is sprayed onto the photosensitive layer after exposure in a shower to remove non-image areas. After the pattern forming 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 20°C to 40°C.

[0276] <Post-exposure process and post-bake process> The method for producing a resin pattern or the method for producing a laminate may include a step of exposing the resin pattern obtained by the above-mentioned development step (post-exposure step) and / or a step of heating (post-baking step). When both the post-exposure step and the post-bake step are included, it is preferable to carry out the post-bake step after the post-exposure step.

[0277] <Etching process> The method for manufacturing the circuit wiring preferably includes a step of etching the conductive layer in the region where the pattern is not arranged (etching step).

[0278] In the etching step, the resin pattern formed from the photosensitive layer is used as an etching resist to etch the conductive layer. 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.

[0279] The etching solution used in the wet etching may be an acidic or alkaline etching solution that is appropriately selected depending on the target to be etched. Examples of acidic etching solutions include aqueous solutions of an acidic component selected from hydrochloric acid, sulfuric acid, nitric acid, acetic acid, hydrofluoric acid, oxalic acid, and phosphoric acid, and aqueous solutions of a mixture of an acidic component and a salt selected from ferric chloride, ammonium fluoride, and potassium permanganate. The acidic component may be a combination of multiple acidic components. Examples of alkaline etching solutions include aqueous solutions of alkaline components selected from sodium hydroxide, potassium hydroxide, ammonia, organic amines, and salts of organic amines (e.g., tetramethylammonium hydroxide), as well as aqueous solutions of mixtures of alkaline components and salts (e.g., potassium permanganate). The alkaline component may be a combination of multiple alkaline components.

[0280] <Removal process> In the method for manufacturing circuit wiring, it is preferable to carry out a step of removing the remaining resin pattern (removal step). The removal step is not particularly limited and can be carried out as needed, but is preferably carried out after the etching step. The method for removing the remaining resin pattern is not particularly limited, but includes a method of removing it by chemical treatment, and a method of removing it using a remover is preferred. The photosensitive layer can be removed by immersing the substrate with the remaining resin pattern in a stirring removal solution, preferably at a temperature of 30°C to 80°C, more preferably 50°C to 80°C, for 1 minute to 30 minutes.

[0281] Examples of the removal solution include a removal solution obtained by dissolving an inorganic or organic alkaline component in water, dimethyl sulfoxide, N-methylpyrrolidone, or a mixture thereof. Examples of the inorganic alkaline component include sodium hydroxide and potassium hydroxide. Examples of the organic alkaline component include primary amine compounds, secondary amine compounds, tertiary amine compounds, and quaternary ammonium salt compounds. Alternatively, the removal may be carried out by a known method such as a spray method, a shower method, or a puddle method using a removal solution.

[0282] <Other processes> The methods for producing a resin pattern, a laminate, and a circuit wiring may include any steps (other steps) other than those described above. For example, the following steps can be mentioned, but the present invention is not limited to these steps. Furthermore, examples of pattern forming steps and other steps that can be applied to the method for manufacturing circuit wiring include the steps described in paragraphs 0035 to 0051 of JP-A No. 2006-23696. Furthermore, other processes include, for example, a process of reducing visible light reflectance as described in paragraph 0172 of WO 2019 / 022089, a process of forming a new conductive layer on the insulating film as described in paragraph 0172 of WO 2019 / 022089, and the like, but are not limited to these processes.

[0283] -Process to reduce visible light reflectance- The method for manufacturing circuit wiring may include a step of performing a treatment to reduce the visible light reflectance of some or all of the plurality of conductive layers of the substrate. An example of a treatment for reducing the visible light reflectance is oxidation treatment. When the substrate has a conductive layer containing copper, the visible light reflectance of the conductive layer can be reduced by oxidizing the copper to copper oxide and blackening the conductive layer. Treatments for reducing visible light reflectance are described in paragraphs 0017 to 0025 of JP 2014-150118 A and paragraphs 0041, 0042, 0048, and 0058 of JP 2013-206315 A, and the contents of these publications are incorporated herein by reference.

[0284] - A process for forming an insulating film, and a process for forming a new conductive layer on the surface of the insulating film - The method for manufacturing the circuit wiring preferably includes the steps of forming an insulating film on the surface of the circuit wiring, and forming a new conductive layer on the surface of the insulating film. By the above steps, a second electrode pattern insulated from the first electrode pattern can be formed. The step of forming the insulating film is not particularly limited, and may include a known method for forming a permanent film. Alternatively, an insulating film having a desired pattern may be formed by photolithography using a photosensitive material having insulating properties. The step of forming a new conductive layer on the insulating film is not particularly limited, and for example, a new conductive layer having a desired pattern may be formed by photolithography using a photosensitive material having conductivity.

[0285] A preferred method for manufacturing circuit wiring is to use a substrate having multiple conductive layers on both surfaces of the substrate, and to sequentially or simultaneously form circuits on the conductive layers formed on both surfaces of the substrate. This configuration allows the formation of touch panel circuit wiring in which a first conductive pattern is formed on one surface of the substrate and a second conductive pattern is formed on the other surface. It is also preferred to form such touch panel circuit wiring from both surfaces of the substrate using a roll-to-roll process.

[0286] <Application> The resin pattern produced by the resin pattern production method according to the present disclosure, the laminate produced by the laminate production method according to the present disclosure, and the circuit wiring produced by the circuit wiring production method according to the present disclosure can be applied to various devices. Examples of devices including the laminate include input devices, and the like, preferably touch panels, more preferably capacitive touch panels. Furthermore, the input devices can be applied to display devices such as organic electroluminescence display devices and liquid crystal display devices. When the laminate is applied to a touch panel, the formed resin pattern is preferably used as a protective film for electrodes or wiring for a touch panel. That is, the photosensitive transfer material according to the present disclosure is preferably used to form an electrode protective film for a touch panel or wiring for a touch panel.

[0287] (Electronic device manufacturing method) The method for producing an electronic device according to the present disclosure is not particularly limited as long as it is a method that uses a photosensitive transfer material according to the present disclosure. A preferred method for manufacturing an electronic device according to the present disclosure includes, in this order, a step of bonding the photosensitive transfer material according to the present disclosure to a substrate so that the photosensitive layer side of the photosensitive transfer material is in contact with the conductive layer of the substrate having a conductive layer; a step of peeling off the temporary support; a step of exposing and developing the exposed photosensitive layer to form a pattern; and a step of etching the conductive layer in areas where the pattern is not arranged. The method for producing an electronic device according to the present disclosure preferably includes a step of peeling off the protective film before the bonding step.

[0288] Specific aspects of each step in the method for manufacturing an electronic device, and the order in which each step is performed, etc., are as described above in the sections "Method for manufacturing a resin pattern" and "Etching method," and preferred aspects are also the same. The method for manufacturing an electronic device may refer to known methods for manufacturing an electronic device, except that the wiring for an electronic device is formed by the above-mentioned method. Furthermore, the method for manufacturing an electronic device may include any steps (other steps) other than those described above.

[0289] The electronic device is not particularly limited, but suitable examples include semiconductor packages, printed circuit boards, various wiring formation applications for sensor substrates, touch panels, electromagnetic wave shielding materials, conductive films such as film heaters, liquid crystal sealing materials, and structures in the fields of micromachines or microelectronics. The resin pattern is preferably used as a permanent film in the electronic device, such as an interlayer insulating film, a wiring protective film, or a wiring protective film having an index matching layer. Among these, a touch panel is particularly suitable as an electronic device.

[0290] An example of a mask pattern used in manufacturing a touch panel is shown in FIGS. In pattern A shown in FIG. 2 and pattern B shown in FIG. 3, GR denotes a non-image area (light-shielding area), EX denotes an image area (exposed area), and DL denotes a virtual alignment frame. In a touch panel manufacturing method, for example, by exposing the photosensitive layer through a mask having pattern A shown in FIG. 2, a touch panel can be manufactured in which circuit wiring having pattern A corresponding to EX is formed. Specifically, it can be manufactured by the method described in FIG. 1 of WO 2016 / 190405. In one example of the manufactured touch panel, the central portion of the exposed area EX (the pattern portion where the lines are connected) is the area where a transparent electrode (touch panel electrode) is formed, and the peripheral portion (thin line portion) of the exposed area EX is the area where wiring for the peripheral extraction section is formed.

[0291] By the above-described method for manufacturing an electronic device, an electronic device having at least wiring for an electronic device is manufactured, and preferably, for example, a touch panel having at least wiring for a touch panel is manufactured. The touch panel preferably includes a transparent substrate, electrodes, 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 capacitance method, an ultrasonic method, an electromagnetic induction method, and an optical method, among which the capacitance method is preferred.

[0292] Examples of touch panel types include so-called in-cell types (for example, those shown in Figures 5, 6, 7, and 8 of JP-A-2012-517051), so-called on-cell types (for example, those shown in Figure 19 of JP-A-2013-168125 and those shown in Figures 1 and 5 of JP-A-2012-89102), OGS (One Glass Solution) types, TOL (Touch-on-Lens) types (for example, those shown in Figure 2 of JP-A-2013-54727), various out-cell types (so-called GG, G1 / G2, GFF, GF2, GF1, and G1F, etc.), and other configurations (for example, those shown in Figure 6 of JP-A-2013-164871). An example of a touch panel is described in paragraph 0229 of JP 2017-120435 A. [Example]

[0293] The following examples further illustrate the embodiments of the present invention. The materials, amounts used, ratios, processing details, processing procedures, etc. 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.

[0294] <Polymer> In the following synthesis examples, the following abbreviations represent the following compounds, respectively. St: Styrene (Fujifilm Wako Pure Chemical Industries, Ltd.) MAA: methacrylic acid (Fujifilm Wako Pure Chemical Industries, Ltd.) MMA: Methyl methacrylate (Fujifilm Wako Pure Chemical Industries, Ltd.) PGMEA: Propylene glycol monomethyl ether acetate (Showa Denko K.K.) V-601: Dimethyl 2,2'-azobis(2-methylpropionate) (Fujifilm Wako Pure Chemical Industries, Ltd.)

[0295] <Synthesis of Polymer A-1> PGMEA (116.5 parts) was placed in a three-necked flask and heated to 90°C under a nitrogen atmosphere. A solution containing St (52.0 parts), MMA (19.0 parts), MAA (29.0 parts), V-601 (4.0 parts), and PGMEA (116.5 parts) was added dropwise over 2 hours to the three-necked flask solution maintained at 90°C ± 2°C. After completion of the addition, the mixture was stirred at 90°C ± 2°C for 2 hours to obtain Polymer A-1 (solids concentration 30.0%).

[0296] Polymer A-2: Resin having the structure shown below (weight average molecular weight (Mw): 18,000, acid value: 95 mg KOH / g, solid content: 30.0% PGMEA solution) In the formula below, the numbers to the right of the parentheses represent the molar ratio of each constituent unit.

[0297] [ka]

[0298] <Polymerizable compound> B-1: NK Ester BPE-500 (ethoxylated bisphenol A dimethacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.) B-2: Aronix M-270 (polypropylene glycol diacrylate, manufactured by Toagosei Co., Ltd.) B-3: Diglycidyl ether of polyethylene glycol with an average of 5 moles of ethylene oxide added to each end of bisphenol A (glycidyl ether of the above BPE-500 (in which the dimethacryloxy group is converted to a diglycidyl ether group)) B-4: Tetraglycidyl ether of polyethylene glycol with an average of 9 moles of ethylene oxide added to pentaerythritol B-5: 3-ethyl-3-{[(3-ethyloxetan-3-yl)methoxy]methyl}oxetane B-6: SR454 (3-mol ethoxylated trimethylolpropane triacrylate, manufactured by Sartomer Corporation)

[0299] <Polymerization initiator (photoacid generator (photocationic polymerization initiator) and photoradical polymerization initiator), and sensitizer> C-1: Compound with the structure shown below (photoacid generator, pKa of generated tosylic acid: -2.6, compound described in paragraph 0227 of JP2013-47765A, synthesized according to the method described in paragraph 0227)

[0300] [ka]

[0301] C-2: BIMD (photoradical polymerization initiator, 2-(2-chlorophenyl)-4,5-diphenylimidazole dimer, B-CIM manufactured by Hampford) C-3: EAB-F (sensitizer, 4,4'-bis(diethylamino)benzophenone, manufactured by Tokyo Chemical Industry Co., Ltd.) C-4: CPI-101A (photoacid generator, triarylsulfonium hexafluoroantimonate compound, pKa of generated hexafluoroantimonate: -25, manufactured by San-Apro Co., Ltd.) C-5: N-phenylcarbamoylmethyl-N-carboxymethylaniline (sensitizer, Fujifilm Wako Pure Chemical Industries, Ltd.): 0.02 parts

[0302] <Additives> D-1: CBT-1 (carboxybenzotriazole, manufactured by Johoku Chemical Industry Co., Ltd.) D-2: LCV (Leuco Crystal Violet, manufactured by Yamada Chemical Industries Co., Ltd.) D-3: Phenothiazine (Seiko Chemical Co., Ltd.) D-4: 4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone (Fujifilm Wako Pure Chemical Industries, Ltd.)

[0303] <Surfactant> E-1: Megafac F-552 (fluorine-based surfactant, manufactured by DIC Corporation) E-2: Megafac F-444 (fluorine-based surfactant, manufactured by DIC Corporation)

[0304] <Water-soluble resin> F-1: Kuraray Poval PVA-4-88LA (polyvinyl alcohol, saponification degree 88, manufactured by Kuraray Co., Ltd.) F-2: Polyvinylpyrrolidone K-30 (manufactured by Nippon Shokubai Co., Ltd.) F-3: Metolose 60SH (hydroxypropyl methylcellulose, manufactured by Shin-Etsu Chemical Co., Ltd.)

[0305] <Preparation of Photosensitive Composition 1> The following components were mixed to prepare Photosensitive Composition 1. The unit of the amount of each component is parts by mass. A-1 (solid content concentration 30.0%): 25.2 parts B-1 (NK Ester BPE-500, ethoxylated bisphenol A dimethacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.): 1.4 parts B-2 (Aronix M-270, polypropylene glycol diacrylate, manufactured by Toagosei Co., Ltd.): 0.29 parts B-3 (diglycidyl ether of polyethylene glycol in which an average of 5 moles of ethylene oxide are added to each end of bisphenol A): 1.85 parts B-4 (tetraglycidyl ether of polyethylene glycol in which an average of 9 moles of ethylene oxide is added to pentaerythritol): 0.62 parts B-5 (3-ethyl-3-{[(3-ethyloxetan-3-yl)methoxy]methyl}oxetane): 0.62 parts B-6 (SR454, 3-mol ethoxylated trimethylolpropane triacrylate, manufactured by Sartomer Corporation): 1.4 parts C-2 (BIMD, photoradical polymerization initiator, 2-(2-chlorophenyl)-4,5-diphenylimidazole dimer, B-CIM manufactured by Hampford): 0.52 parts C-3 (EAB-F, sensitizer, 4,4'-bis(diethylamino)benzophenone, manufactured by Tokyo Chemical Industry Co., Ltd.): 0.045 parts C-4 (CPI-101A, photoacid generator, triarylsulfonium hexafluoroantimonate compound, pKa of generated acid: -25, manufactured by San-Apro Co., Ltd.): 0.52 parts C-5 (sensitizer, N-phenylcarbamoylmethyl-N-carboxymethylaniline, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.): 0.02 parts D-1 (CBT-1, manufactured by Johoku Chemical Industry Co., Ltd.): 0.015 parts D-2 (LCV, Leuco Crystal Violet, manufactured by Yamada Chemical Co., Ltd., a radical-coloring dye): 0.06 parts D-3 (phenothiazine, manufactured by Seiko Chemical Co., Ltd.): 0.04 parts D-4 (sensitizer, 4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.): 0.002 parts E-1 (Megafac F-552, manufactured by DIC Corporation): 0.048 parts Methyl ethyl ketone (manufactured by Sankyo Chemical Co., Ltd.): 43.8 parts PGMEA (Showa Denko K.K.): 19.7 parts Propylene glycol monomethyl ether (MFG, manufactured by Nippon Nyukazai Co., Ltd.): 3.89 parts

[0306] <Preparation of Intermediate Layer Composition> The following components were mixed to prepare an intermediate layer composition. Ion-exchanged water: 38.12 parts Methanol (Mitsubishi Gas Chemical Co., Ltd.): 57.17 parts F-1 (Kuraray Poval PVA-4-88LA, polyvinyl alcohol, manufactured by Kuraray Co., Ltd.): 3.22 parts F-2 (Polyvinylpyrrolidone K-30, manufactured by Nippon Shokubai Co., Ltd.): 1.49 parts F-3 (Metolose 60SH, manufactured by Shin-Etsu Chemical Co., Ltd.): 0.04 parts E-2 (Megafac F-444, fluorine-based surfactant, manufactured by DIC Corporation): 0.001 part

[0307] Example 1 <Preparation of photosensitive transfer material> Intermediate layer composition 1 was applied using a slit nozzle onto a 16 μm thick polyethylene terephthalate film (Lumirror 16QS62, manufactured by Toray Industries, Inc.) serving as a temporary support to a coating width of 1.0 m and a layer thickness of 1.1 μm, and the film was passed through a drying zone at 80° C. for 40 seconds to form an intermediate layer, so as to have the configuration shown in Table 1 below. Furthermore, photosensitive resin composition 1 was applied onto the intermediate layer using a slit nozzle to a coating width of 1.0 m and a layer thickness of 5.0 μm, and the film was passed through a drying zone at 80° C. for 40 seconds to form a photosensitive layer.

[0308] <Performance evaluation> A polyethylene terephthalate (PET) substrate with a copper layer was used, which was prepared by sputtering a copper layer with a thickness of 200 nm on a 100 μm thick PET film.

[0309] -Resolution- The prepared photosensitive transfer material was laminated onto the above-mentioned copper-layered PET substrate under lamination conditions of a roll temperature of 100°C, a linear pressure of 1.0 MPa, and a linear speed of 4.0 m / min. The temporary support was peeled off from the substrate having the temporary support and photosensitive layer, and the substrate was placed on the substrate set stage of a projection exposure machine (UX-2023SM manufactured by Ushio Inc.). A glass chrome photomask having a line and space pattern (duty ratio 1:1, line width varying in 1 μm increments from 1 μm to 10 μm) was set in the mask holder of the exposure machine, and an exposure dose of 100 mJ / cm was applied through a projection lens. 2 The temporary support was peeled off, and 10 minutes later, the film was exposed to light and then developed. Development was carried out using a 1.0% aqueous sodium carbonate solution at 25°C by shower development for 30 seconds. When a 10 μm line and space pattern was formed using the above method, the residue in the space area was observed using a scanning electron microscope (SEM). When exposed to an exposure dose that resulted in a resist line width of exactly 10 μm, the minimum line width at which the resist pattern could be resolved without peeling or residue was evaluated as the resolution. A: Resolution is 2 μm or less B: Resolution is between 3 μm and 4 μm C: Resolution is 5 μm or more and 6 μm or less D: Resolution is 7 μm or more A to C are preferred.

[0310] -Pattern shape (pattern formability)- The cross section of the minimum line width pattern for which the resolution was evaluated was observed with a scanning electron microscope (SEM) to evaluate the pattern shape. A: The pattern shape is rectangular B: The pattern shape is slightly constricted C: The top of the pattern is rounded and narrow. D: The pattern is broken and the hem is wide. A to C are preferred.

[0311] (Examples 2 to 7 and Comparative Example 1) Photosensitive transfer materials of Examples 2 to 7 and Comparative Example 1 were prepared in the same manner as in Example 1, except that the intermediate layer and photosensitive layer were changed as shown in Table 1. Furthermore, performance evaluation was carried out in the same manner as in Example 1. The evaluation results are summarized in Table 1.

[0312] [Table 1]

[0313] As shown in Table 1 above, the photosensitive transfer materials of Examples 1 to 7 have superior resolution compared to the photosensitive transfer material of Comparative Example 1, even when the photosensitive layer is directly exposed without a temporary support. Furthermore, as shown in Table 1 above, the photosensitive transfer materials of Examples 1 to 7 also have excellent pattern formability.

[0314] (Example 101: Contact Exposure) The photosensitive transfer material prepared in Example 1 was laminated onto the above-mentioned copper-layered PET substrate under lamination conditions of a roll temperature of 100°C, a linear pressure of 1.0 MPa, and a linear speed of 4.0 m / min. The temporary support was peeled off, and the substrate was exposed to an ultra-high pressure mercury lamp through a line and space pattern mask (duty ratio 1:1, line width varying stepwise from 1 μm to 10 μm in 1 μm increments), followed by development. Development was carried out using a 1.0% aqueous sodium carbonate solution at 25°C by shower development for 30 seconds. When the obtained patterned substrate was observed under a microscope, it was found that the pattern had good resolution and pattern shape.

[0315] (Example 102: Laser direct writing) The photosensitive transfer material prepared in Example 1 was laminated onto the above-mentioned copper-layered PET substrate under lamination conditions of a roll temperature of 100°C, a linear pressure of 1.0 MPa, and a linear speed of 4.0 m / min. Using a direct imaging exposure machine (Hitachi Via Mechanics, DE-1DH, light source: GaN blue-violet diode (dominant wavelength 405 nm ± 5 nm)), a Stouffer 21-step tablet or a predetermined DI exposure mask pattern was used, and the illuminance was 80 mW / cm. 2 The exposure was carried out under the following conditions: This exposure was carried out at an exposure dose such that when the above-mentioned Stouffer 21-step tablet was used as a mask and development was carried out, the maximum number of remaining film steps would be 6. Development was carried out using a 1.0% aqueous sodium carbonate solution at 25°C for 30 seconds by shower development. When the obtained patterned substrate was observed under a microscope, it was found that the pattern had good resolution and pattern shape.

[0316] (Example 103) A 150 nm thick ITO film was formed by sputtering on a 100 μm thick PET substrate as the second conductive layer, and a 200 nm thick copper film was formed on top of that by vacuum deposition as the first conductive layer to create a circuit formation substrate. The photosensitive transfer material obtained in Example 1 was placed on the copper layer, and the cover film was peeled off and the substrate was attached (laminating roll temperature 100°C, linear pressure 0.8 MPa, linear speed 3.0 m / min) to form a laminate. The temporary support was peeled off from the resulting laminate, and the laminate was exposed to contact patterns using a photomask with pattern A shown in Figure 2, which has a structure in which the conductive layer pads are connected in one direction. A high-pressure mercury lamp with i-line (365 nm) as the dominant exposure wavelength was used for exposure. Thereafter, development and washing with water were carried out to obtain pattern A. Next, the copper layer was etched using a copper etching solution (Cu-02 manufactured by Kanto Chemical Co., Ltd.), and then the ITO layer was etched using an ITO etching solution (ITO-02 manufactured by Kanto Chemical Co., Ltd.), thereby obtaining a substrate on which pattern A was drawn on both copper and ITO. Next, the photosensitive transfer material obtained in Example 1 was again laminated on the remaining resist (cured negative photosensitive layer) under the same conditions as in Example 101, after peeling off the cover film. With alignment adjusted, the temporary support was peeled off and pattern exposure was performed using a photomask with pattern B shown in FIG. 3, followed by development and washing with water to obtain pattern B. Next, the copper wiring was etched using Cu-02, and the remaining cured negative photosensitive layer was peeled off using a stripping solution (KP-301, manufactured by Kanto Chemical Co., Inc.) to obtain a circuit wiring board. When the obtained circuit wiring board was observed under a microscope, it was found that there was no peeling or chipping and the pattern was clean.

[0317] The disclosure of Japanese Patent Application No. 2020-217790, filed on December 25, 2020, is incorporated herein by reference in its entirety. 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 temporary support; a photosensitive layer; the photosensitive layer contains a polymerization initiator and a polymerizable compound, the polymerization initiator includes a radical polymerization initiator and a cationic polymerization initiator, or includes a polymerization initiator that generates radicals and an acid; the polymerizable compound includes a radical polymerizable compound and a cation polymerizable compound, The radical polymerizable compound includes a radical polymerizable compound having a polyethylene oxide structure. Photosensitive transfer material.

2. 2. The photosensitive transfer material according to claim 1, wherein the pKa of the acid generated from the cationic polymerization initiator or the polymerization initiator that generates radicals and an acid is −5 or less.

3. 3. The photosensitive transfer material according to claim 1, wherein the polymerization initiator comprises a radical polymerization initiator and a cationic polymerization initiator.

4. 4. The photosensitive transfer material according to claim 1, wherein the molecular weight or weight average molecular weight of the radical polymerizable compound is 2,000 or less.

5. 5. The photosensitive transfer material according to claim 1, wherein the molecular weight or weight average molecular weight of the cationically polymerizable compound is 2,000 or less.

6. 6. The photosensitive transfer material according to claim 1, wherein the radical polymerizable compound comprises a radical polymerizable compound having two or more functionalities.

7. 7. The photosensitive transfer material according to claim 1, wherein the radical polymerizable compound comprises a radical polymerizable compound having three or more functionalities.

8. 8. The photosensitive transfer material according to claim 1, further comprising an intermediate layer between the temporary support and the photosensitive layer.

9. a step of laminating the photosensitive transfer material according to any one of claims 1 to 8 to the substrate so that the photosensitive layer side of the photosensitive transfer material is in contact with the substrate; peeling off the temporary support; and a step of subjecting the exposed photosensitive layer to an exposure treatment and a development treatment, in this order, to form a pattern. A method for manufacturing a resin pattern.

10. a step of laminating the photosensitive transfer material according to any one of claims 1 to 8 to the substrate so that the photosensitive layer side of the photosensitive transfer material is in contact with the substrate; peeling off the temporary support; and a step of subjecting the exposed photosensitive layer to an exposure treatment and a development treatment, in this order, to form a pattern. A method for manufacturing a laminate.

11. a step of laminating the photosensitive transfer material to a substrate having a conductive layer such that the photosensitive layer side of the photosensitive transfer material according to any one of claims 1 to 8 is in contact with the conductive layer of the substrate; peeling off the temporary support; performing an exposure process and a development process on the exposed photosensitive layer to form a pattern; and etching the conductive layer in the region where the pattern is not arranged. A method for manufacturing circuit wiring.

12. a step of laminating the photosensitive transfer material to a substrate having a conductive layer such that the photosensitive layer side of the photosensitive transfer material according to any one of claims 1 to 8 is in contact with the conductive layer of the substrate; peeling off the temporary support; performing an exposure process and a development process on the exposed photosensitive layer to form a pattern; and etching the conductive layer in the region where the pattern is not arranged. A method for manufacturing electronic devices.

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