Method for manufacturing laminate, method for manufacturing circuit wiring, method for manufacturing electronic device, and photosensitive transfer material

Abstract

The present invention provides a method for manufacturing a laminate, a method for manufacturing an electronic device and a method for manufacturing circuit wiring in which the laminate obtained by the above-described method for manufacturing a laminate is used, and a photosensitive transfer material. Said method for manufacturing a laminate comprises a bonding step in which a photosensitive transfer material having a temporary support and a transfer layer including a photosensitive layer is bonded with a substrate such that the transfer-layer side of the photosensitive transfer material is in contact with the substrate, an exposure step in which the photosensitive layer is exposed, and a developing step in which the photosensitive layer is developed to form a resin pattern. The number of particles and voids having a diameter of at least Y μm on the surface and interior of the photosensitive layer in the exposure step does not exceed 15 / cm2, where X (μm) is the limiting resolution of the photosensitive layer in the exposure step and Y (μm) is the reference diameter of the particles and voids (Y=0.5×X).

Description

[Technical Field]

[0001] The present disclosure relates to a method for manufacturing a laminate, a method for manufacturing circuit wiring, a method for manufacturing an electronic device, and a photosensitive transfer material. [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 roll, the one described in Patent Document 1 is known. Patent Document 1 describes a photosensitive resin laminate roll formed by rolling up a photosensitive resin laminate comprising a support film and a photosensitive resin composition layer containing a photosensitive resin composition formed on the support film, wherein the support film has regions in which, when small pieces of 0.75 mm × 11 mm are cut out from the support film at any 10 different locations, the number of fine particles having a diameter of 2 μm or more contained in each small piece is 200 or less, calculated as a number average at the 10 locations, and the back surface of the support film includes a region in which the arithmetic mean roughness is 0.01 μm or more.

[0004] Patent Document 1: JP 2019-101405 A Summary of the Invention [Problem to be solved by the invention]

[0005] An object of one embodiment of the present invention is to provide a method for producing a laminate having a resin pattern with few pinhole defects. Another problem to be solved by another embodiment of the present invention is to provide a method for manufacturing circuit wiring and a method for manufacturing an electronic device using a laminate obtained by the above-mentioned method for manufacturing a laminate. A further problem to be solved by a further embodiment of the present invention is to provide a photosensitive transfer material that can provide a resin pattern with fewer pinhole defects. [Means for solving the problem]

[0006] The means for solving the above problems include the following aspects. <1> The method includes a lamination step of laminating a photosensitive transfer material having a temporary support and a transfer layer including a photosensitive layer to a substrate so that the transfer layer side of the photosensitive transfer material is in contact with the substrate, an exposure step of exposing the photosensitive layer to light, and a development step of developing the photosensitive layer to form a resin pattern, wherein, when the limit resolution of the photosensitive layer in the exposure step is defined as X μm and the reference diameter of particles and voids is defined as Y μm expressed by Y = 0.5 × X, the number of particles and voids having a diameter of Y μm or more on the surface and inside of the photosensitive layer in the exposure step is 15 particles / cm 2 A method for producing a laminate, which is as follows: <2> The thickness of the photosensitive layer is 5.0 μm or less. <1> A method for producing the laminate described in 1. <3> The thickness of the temporary support is 16 μm or less. <1> or <2> A method for producing the laminate described in 1. <4> The resin pattern has a line width of 10 μm or less. <1> ~ <3> 10. A method for producing the laminate according to any one of the preceding items. <5> A peeling step of peeling off the temporary support is included between the laminating step and the exposure step. <1> ~ <4> 10. A method for producing the laminate according to any one of the preceding items. <6> In the exposure step, the transfer layer is brought into contact with a mask and an exposure process is performed. <1> ~ <5> 10. A method for producing the laminate according to any one of the preceding items. <7> The transfer layer further includes a thermoplastic resin layer and a water-soluble resin layer. <1> ~ <6> 10. A method for producing the laminate according to any one of the preceding items. <8> The photosensitive layer contains a polyfunctional polymerizable compound. <1> ~ <7> 10. A method for producing the laminate according to any one of the preceding items. <9> The photosensitive layer contains a trifunctional or higher functional polymerizable compound. <1> ~ <8> 10. A method for producing the laminate according to any one of the preceding items. <10> The photosensitive layer contains a polymerizable compound having a polyethylene oxide structure. <1> ~ <9> 10. A method for producing the laminate according to any one of the preceding items. <11> <1> ~ <10> and an etching step of etching the substrate in an area where the resin pattern is not arranged. <12> <1> ~ <10> and an etching step of etching the substrate in an area where the resin pattern is not arranged. <13> A transfer layer including a temporary support and a photosensitive layer, and the limit resolution of the photosensitive layer is X T The reference diameter of the particle is defined as Y μm. T =0.5×X T Y represented by T When defined as Y μm on the surface and inside of the photosensitive layer, T The number of particles with a diameter of 1 μm or more is 15 / cm 2 A photosensitive transfer material that is: <14> The thickness of the photosensitive layer is 5.0 μm or less. <13> The photosensitive transfer material according to claim 1. <15> The thickness of the temporary support is 16 μm or less. <13> or <14> The photosensitive transfer material according to claim 1. [Effects of the Invention]

[0007] According to one embodiment of the present invention, it is possible to provide a method for producing a laminate having a resin pattern with few pinhole defects. According to another embodiment of the present invention, it is possible to provide a method for manufacturing a circuit wiring and a method for manufacturing an electronic device using a laminate obtained by the above-described method for manufacturing a laminate. According to another embodiment of the present invention, a photosensitive transfer material can be provided that allows a resin pattern with few pinhole defects to be obtained. [Brief explanation of the drawings]

[0008] [Figure 1] FIG. 1 is a schematic diagram illustrating an example of the configuration of a photosensitive transfer material. [Figure 2] FIG. 1 is a schematic plan view showing pattern A. [Figure 3] FIG. 10 is a schematic plan view showing pattern B. DETAILED DESCRIPTION OF THE INVENTION

[0009] 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.

[0010] (Method of manufacturing laminate) The method for producing a laminate according to the present disclosure includes a lamination step of laminating a photosensitive transfer material having a temporary support and a transfer layer including a photosensitive layer to a substrate so that the transfer layer side of the photosensitive transfer material is in contact with the substrate, an exposure step of exposing the photosensitive layer to light, and a development step of developing the photosensitive layer to form a resin pattern, wherein when the limiting resolution of the photosensitive layer in the exposure step is defined as X μm and the reference diameter of particles and voids is defined as Y μm expressed by Y=0.5×X, the number of particles and voids having a diameter of Y μm or more on the surface and inside of the photosensitive layer in the exposure step is 15 particles / cm. 2 The following is the result.

[0011] As conductive patterns become finer, in other words, as the required resolution improves, defects in the conductive patterns (especially pinholes) caused by foreign matter and voids (e.g., coarse particles, bubbles, etc.) on the surface and inside of the photosensitive layer become more apparent. The particles and voids on the surface and inside of the photosensitive layer inhibit the photosensitive layer from curing upon exposure to light, causing defects in the resin pattern (e.g., pinholes). For example, if a resin pattern containing pinholes is used as a protective film during etching to form a conductive pattern, pinholes will occur in the conductive pattern. Therefore, there is a need to reduce the occurrence of pinholes in the resin pattern.

[0012] The reason why the above-mentioned effects are exhibited is presumably explained below. For example, the technology disclosed in Patent Document 1 limits the number of particles with a diameter of 2 μm or more to avoid a decrease in resolution due to foreign matter contained in the temporary support. However, the size of particles and voids that cause exposure failure varies depending on the required resolution. As the required resolution decreases, even small particles and voids that were tolerated in conventional technologies also hinder the exposure of the photosensitive layer. Therefore, the present inventors focused on the relationship between the resolution of the photosensitive layer and the size and number of particles and voids on the surface and inside of the photosensitive layer. By examining the relationship between the resolution of the photosensitive layer and the size of particles and voids that cause exposure failure, the present inventors found that particles and voids with a diameter of Y (Y = 0.5 × X) μm or more increase the incidence of exposure failure relative to the limit resolution of the photosensitive layer (X μm). According to the reference diameter (Y μm) of particles and voids derived from the limit resolution of the photosensitive layer (X μm), the number of particles and voids with a diameter of Y μm or more on the surface and inside of the photosensitive layer is limited to 15 particles / cm. 2 The incidence of exposure damage can be reduced by adjusting the following: Therefore, the method for producing a laminate according to the present disclosure provides a method for producing a laminate having a resin pattern with few pinhole defects.

[0013] <Number of particles and voids with a diameter of Y μm or more on the surface and inside of the photosensitive layer> In the method for producing a laminate according to the present disclosure, when the limit resolution of the photosensitive layer in the exposure step is defined as X μm and the reference diameter of particles and voids is defined as Y μm, where Y=0.5×X, the number of particles and voids having a diameter of Y μm or more on the surface and inside of the photosensitive layer in the exposure step is 15 particles / cm. 2 From the viewpoint of pinhole defect prevention, the number of pinholes per cm is 10 or less. 2 Preferably, it is 7 or less per cm 2 More preferably, it is 5 or less per cm 2 It is particularly preferable that the lower limit is 0 particles / cm or less. 2 is.

[0014] The method for measuring the limiting resolution of the photosensitive layer in the present disclosure is described below. The photosensitive layer of the laminate is exposed to light using an ultra-high pressure mercury lamp through a line and space pattern mask (duty ratio 1:1, line width varying in steps of 1 μm from 1 μm to 20 μm). If necessary, the temporary support is peeled off and then the film is developed by shower development using a 1.0% by mass aqueous solution of sodium carbonate at 25°C for 30 seconds. The photosensitive layer is developed to form a resin pattern. The exposure dose (unit: mJ / cm ) is increased until a resin pattern (hereinafter referred to as a "reference pattern" in this paragraph) having the minimum line width corresponding to the mask pattern is obtained. 2 The above series of steps are carried out while adjusting the minimum line width of the reference pattern each time. The minimum line width of the reference pattern is adopted as the limiting resolution of the photosensitive layer, X μm.

[0015] When measuring from a photosensitive transfer material, the photosensitive transfer material and PET substrate are laminated onto a 100 μm thick polyethylene terephthalate (PET) film using a roll-to-roll method using a vacuum laminator (manufactured by MCK Corporation, roll temperature: 100°C, linear pressure: 1.0 MPa, linear speed: 0.5 m / min) to produce a laminate, which is then pressure-degassed for 30 minutes using an autoclave under conditions of 0.6 MPa and 60°C, and the limiting resolution of the photosensitive layer is then measured.

[0016] The method for measuring the number of particles and voids having a diameter of Y μm or more on the surface and inside of the photosensitive layer in the present disclosure is described below. After peeling off the temporary support as necessary, the laminate was subjected to 10 arbitrary areas on the surface of the photosensitive layer (size of each area: 10 mm × 10 mm, total area: 1,000 mm). 2 ) is visually observed using an optical microscope. The number of foreign particles and voids with a diameter of Y μm or more contained in each area is counted. Based on the total number of particles and voids with a diameter of Y μm or more measured in 10 areas, the number of particles and voids per 1 cm of the measurement area is calculated. 2 Number of particles and voids of Y μm or more per unit area (number / cm2 ) is calculated. The particles and voids may be measured together or separately.

[0017] The method for manufacturing a laminate according to the present disclosure includes a lamination step of laminating a photosensitive transfer material having a temporary support and a transfer layer including a photosensitive layer to a substrate so that the transfer layer side of the photosensitive transfer material is in contact with the substrate, an exposure step of exposing the photosensitive layer to light, and a development step of developing the photosensitive layer to form a resin pattern. Furthermore, the method for producing a laminate according to the present disclosure preferably includes a peeling step of peeling off the temporary support between the laminating step and the exposing step. Furthermore, the method for producing a laminate according to the present disclosure preferably includes a protective film peeling step of peeling off the protective film, as necessary, before the laminating step.

[0018] <Protective film peeling process> The method for producing a laminate according to the present disclosure preferably includes a step of peeling the protective film from the photosensitive transfer material. The method for peeling the protective film is not limited, and any known method can be applied.

[0019] <Lamination process> The method for producing a laminate according to the present disclosure includes a lamination step. In the lamination step, it is preferable to bring the transfer layer of the photosensitive transfer material into contact with a substrate (or the conductive layer if the conductive layer is provided on the surface of the substrate) and press-bond the photosensitive transfer material and the substrate together. In this embodiment, the adhesion between the transfer layer of the photosensitive transfer material and the substrate is improved, and the patterned photosensitive layer after exposure and development can be suitably used as an etching resist when etching the conductive layer. Preferable embodiments of the photosensitive transfer material used in the method for producing a laminate according to the present disclosure will be described below.

[0020] Furthermore, in the lamination process, if 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 surface of the photosensitive layer that does not have the temporary support and the substrate are laminated via that layer.

[0021] 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.

[0022] The method for producing a laminate according to the present disclosure is preferably carried out by a roll-to-roll method. 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 manufacturing method of a laminate according to the present disclosure, 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 other than 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.

[0023] <Substrate> As the substrate used in the method for producing a laminate 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.

[0024] 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.

[0025] 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.

[0026] 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.

[0027] 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.

[0028] 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.

[0029] 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.

[0030] 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.

[0031] 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.

[0032] 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.

[0033] The touch panel electrode protective film formed using the photosensitive transfer material used in the present disclosure is preferably provided to cover the electrodes, etc. directly or via another layer, for the purpose of protecting the electrodes, etc. (i.e., at least one of the touch panel electrodes and the touch panel wiring).

[0034] <Temporary support peeling process> The method for producing a laminate according to the present disclosure preferably includes a temporary support peeling step of peeling off the temporary support between the laminating step and the exposing 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.

[0035] <Exposure process> The method for producing a laminate according to the present disclosure includes an exposure step. The exposure treatment in the exposure step is a patterned exposure treatment (also called "pattern exposure"), that is, an exposure treatment in a form in which exposed areas and non-exposed areas exist. The positional relationship between the exposed and unexposed regions in the pattern exposure is not particularly limited and may be adjusted as appropriate.

[0036] 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. Furthermore, from the viewpoint of further exerting the effects of the present disclosure, the obtained resin pattern preferably has a line width of 20 μm or less, more preferably has a line width of 10 μm or less, even more preferably has a line width of 8 μm or less, and particularly preferably has a line width of 5 μm or less.

[0037] 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.

[0038] In the exposure step, pattern exposure may be performed after peeling the temporary support from the transfer 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 transfer 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 transfer 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. Note that 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 non-contact 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 transfer layer. In the exposure step, from the viewpoint of resolution, it is preferable to carry out the exposure treatment while bringing the transfer layer into contact with a mask.

[0039] <Developing process> The method for producing a laminate according to the present disclosure includes a development step. The development of the exposed photosensitive layer in the development step can be carried out 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.

[0040] 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 development step, it is preferable to remove development residues by spraying a cleaning agent by showering and scrubbing with a brush. The temperature of the developer is not particularly limited, but is preferably 20°C to 40°C.

[0041] <Surface adhesion particle removal process> The method for producing a laminate according to the present disclosure preferably includes a surface-adhered particle removal step of removing particles adhering to the surface of the transfer layer or the temporary support before the exposure step, preferably after the temporary support peeling step and before the exposure step. A suitable method for removing particles in the surface-adhering particle removal step is to bring an adhesive roll or a cleaning roll into contact with the surface of the transfer layer or the temporary support to remove the particles. The material, size, contact pressure, etc. of the adhesive roll or cleaning roll can be appropriately selected as desired.

[0042] <Other processes> The method for producing a laminate according to the present disclosure may include any steps (other steps) other than the steps described above, including, but not limited to, the following steps. Furthermore, examples of the exposure step, development step, and other steps that can be applied to the method for producing a laminate according to the present disclosure include the steps described in paragraphs 0035 to 0051 of JP-A No. 2006-23696.

[0043] <Application> The laminate manufactured by the laminate manufacturing method according to the present disclosure can be applied to various devices. Examples of devices including the laminate include input devices, preferably touch panels, and more preferably capacitive touch panels. Furthermore, the input devices can be applied to display devices such as organic electroluminescence 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 the electrodes or wiring for the touch panel.

[0044] <Photosensitive transfer material> The photosensitive transfer material used in the method for producing a laminate according to the present disclosure has a temporary support and a transfer layer including a photosensitive layer, and preferably has a temporary support, a transfer layer including a photosensitive layer, and a protective film in this order. The photosensitive transfer material used in 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 used in the present disclosure preferably further has a thermoplastic resin layer and a water-soluble resin layer between the temporary support and the photosensitive layer. Furthermore, the transfer layer preferably further includes a thermoplastic resin layer and a water-soluble resin layer. The photosensitive transfer material used in the present disclosure is preferably a roll-shaped photosensitive transfer material from the viewpoint of better demonstrating the effects of the present disclosure.

[0045] An example of the embodiment of the photosensitive transfer material used in the present disclosure is shown below, but the present disclosure is not limited to this. (1) "Temporary support / photosensitive layer / refractive index adjusting layer / protective film" (2) "Temporary support / photosensitive layer / protective film" (3) "Temporary support / water-soluble resin layer / photosensitive layer / protective film" (4) "Temporary support / thermoplastic resin layer / water-soluble resin layer / photosensitive layer / protective film" In each of the above-described 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 used in 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.

[0046] 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%.

[0047] Hereinafter, a specific example of an embodiment will be given to explain the photosensitive transfer material used in the present disclosure.

[0048] An example of the photosensitive transfer material will be described below. The photosensitive transfer material 20 shown in FIG. 1 has, in this order, a temporary support 11, a transfer layer 12 including a thermoplastic resin layer 13, a water-soluble resin layer 15, and a photosensitive layer 17, and a protective film 19. Furthermore, the photosensitive transfer material 20 shown in FIG. 1 has a thermoplastic resin layer 13 and a water-soluble resin layer 15 arranged therein, but the thermoplastic resin layer 13 and the water-soluble resin layer 15 do not necessarily have to be arranged. Each element constituting the photosensitive transfer material will be described below.

[0049] [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.

[0050] 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.

[0051] 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.

[0052] 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. Furthermore, from the viewpoint of defect suppression, resolution, and linearity of the resin pattern, the thickness of the temporary support is preferably 50 μm or less, more preferably 25 μm or less, even more preferably 20 μm or less, and particularly preferably 16 μm or less.

[0053] 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. 2 It is more preferable that the number of pieces is 3 pieces / 10 mm or less. 2 More preferably, it is 0 pieces / 10 mm or less. 2 It is particularly preferred that:

[0054] 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.

[0055] 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.

[0056] 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.

[0057] 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.

[0058] 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.

[0059] 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 having 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 stage. 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.

[0060] 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.

[0061] [Photosensitive layer] The photosensitive transfer material used in the present disclosure has a photosensitive layer. The photosensitive layer is preferably a negative photosensitive layer. The photosensitive layer preferably contains an alkali-soluble resin, a polymerizable compound, and a photopolymerization 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 ethylenically unsaturated compound; and 0.01% by mass to 20% by mass of the photopolymerization initiator. Each component will be explained in turn below.

[0062] <<Polymerizable compounds>> The photosensitive layer preferably contains a polymerizable compound. In this specification, the term "polymerizable compound" refers to a compound that undergoes polymerization under the action of a photopolymerization initiator, which will be described later, and is different from the alkali-soluble resin described above.

[0063] The polymerizable group contained in the polymerizable compound is not particularly limited as long as it is a group that participates in a polymerization reaction, and examples thereof include groups having an ethylenically unsaturated group such as a vinyl group, an acryloyl group, a methacryloyl group, a styryl group, and a maleimide group; and groups having a cationically polymerizable group such as an epoxy group and an oxetane group. The polymerizable group is preferably a group having an ethylenically unsaturated group, more preferably an acryloyl group or a methacryloyl group. The polymerizable compound preferably contains an ethylenically unsaturated compound, and more preferably contains a (meth)acrylate compound.

[0064] From the viewpoint of resolution and pattern formability, the photosensitive layer preferably contains a difunctional or higher polymerizable compound (a polyfunctional polymerizable compound), and more preferably contains a trifunctional or higher polymerizable compound. Here, the bifunctional or higher functional polymerizable compound means a compound having two or more polymerizable groups in one molecule. In terms of excellent resolution and releasability, the number of polymerizable groups that the polymerizable compound has in one molecule is preferably 6 or less.

[0065] The photosensitive layer preferably contains a difunctional or trifunctional ethylenically unsaturated compound, and more preferably contains a difunctional ethylenically unsaturated compound, in order to achieve a better balance between the photosensitivity, resolution, and peelability of the photosensitive layer. The content of the difunctional or trifunctional ethylenically unsaturated compound in the photosensitive layer relative to the total content of ethylenically unsaturated compounds 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 difunctional ethylenically unsaturated compounds.

[0066] From the viewpoints of resolution and pattern formability, the photosensitive layer preferably contains a polymerizable compound having a polyalkylene oxide structure, and more preferably contains a polymerizable compound having a polyethylene oxide structure. Preferred examples of the polymerizable compound having a polyalkylene oxide structure include polyalkylene glycol di(meth)acrylate, which will be described later.

[0067] -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.

[0068] 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.

[0069] 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.

[0070] 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.

[0071] 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.

[0072] 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.).

[0073] As the ethylenically unsaturated compound B1, a compound represented by the following formula (Bis) can be used.

[0074] [ka]

[0075] 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.

[0076] 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.

[0077] 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.

[0078] 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.

[0079] 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.).

[0080] 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.

[0081] 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.).

[0082] 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.

[0083] 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.

[0084] The molecular weight (weight average molecular weight (Mw) when the molecular weight has a distribution) of the ethylenically unsaturated compound including the ethylenically unsaturated compound B1 is preferably from 200 to 3,000, more preferably from 280 to 2,200, and even more preferably from 300 to 2,200.

[0085] The ethylenically unsaturated compounds may be used alone or in combination of two or more. The content of the ethylenically unsaturated compound in the photosensitive layer is preferably 10 to 70% by mass, more preferably 20 to 60% by mass, and even more preferably 20 to 50% by mass, based on the total mass of the photosensitive layer.

[0086] <<Photopolymerization initiator>> The photosensitive layer preferably contains a photopolymerization initiator. A photopolymerization initiator is a compound that initiates polymerization of an ethylenically unsaturated 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. Among these, the photosensitive layer preferably contains a photoradical polymerization initiator from the viewpoints of resolution and pattern formability.

[0087] 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.

[0088] 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.

[0089] 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.).

[0090] 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.).

[0091] 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. The cationic photopolymerization initiator is preferably a cationic photopolymerization initiator that generates an acid with a pKa of 4 or less, more preferably a cationic photopolymerization initiator that generates an acid with a pKa of 3 or less, and particularly preferably a cationic photopolymerization initiator that generates an acid with a pKa of 2 or less. There is no particular restriction on the lower limit of the pKa, but it is preferably, for example, −10.0 or more.

[0092] 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.

[0093] 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.

[0094] The photosensitive layer may contain one type of photopolymerization initiator alone or two or more types of photopolymerization initiators. The content of the photopolymerization initiator in the photosensitive layer is not particularly limited, but is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and even more preferably 1.0% by mass or more, relative to the total mass of the photosensitive layer. The upper limit is not particularly limited, but is preferably 10% by mass or less, more preferably 5% by mass or less, relative to the total mass of the photosensitive layer.

[0095] <<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.

[0096] -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.

[0097] 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.

[0098] 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).

[0099] 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.

[0100] 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.

[0101] 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.

[0102] Examples of the monomer having a phenyl alkyl group include phenylethyl (meth)acrylate.

[0103] 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.

[0104] 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.

[0105] 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.

[0106] 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.

[0107] 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.

[0108] 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.

[0109] 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.

[0110] The polymer A may have a linear structure, a branched structure, or an alicyclic structure in the side chain. By using a monomer containing a group having a branched structure in the side chain or a monomer containing a group having an alicyclic structure in the side chain, a branched structure or an alicyclic structure can be introduced into the side chain of the polymer A. The group having an alicyclic structure may be monocyclic or polycyclic. 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.

[0111] 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.

[0112] 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.

[0113] 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.

[0114] 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.

[0115] 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.

[0116] <<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.

[0117] 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.

[0118] 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 N whose maximum absorption wavelength changes in response to radicals and a photoradical polymerization initiator. From the viewpoint of visibility of exposed and unexposed areas, dye N is preferably a dye that develops color in response to an acid, a base, or a radical.

[0119] 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.

[0120] 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.

[0121] 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).

[0122] 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.

[0123] 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.

[0124] 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.

[0125] 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.

[0126] 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.

[0127] 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.

[0128] 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.

[0129] 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.

[0130] <<Thermal crosslinkable compounds>> 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.

[0131] 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.

[0132] 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.

[0133] 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.

[0134] 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.

[0135] 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.

[0136] [ka]

[0137] 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.

[0138] <<Other ingredients>> The photosensitive layer may contain components other than the above-mentioned alkali-soluble resin, ethylenically unsaturated compound, photopolymerization initiator, dye, and thermally crosslinkable compound.

[0139] -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.

[0140] 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, and F-5 55-A, F-556, F-557, F-558, F-559, F-560, F-561, F-565, F-563, F-568, F-575, F-780, EX P.MFS-578-2, EXP.MFS-579, EXP.MFS-586, EXP.MFS-587, EXP.MFS-628, EXP.MFS-631, E XP.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, PF6320, PF6520, PF7002 (all manufactured by OMNOVA), Ftergent Examples include 710FL, 710FM, 610FM, 601AD, 601ADH2, 602A, 215M, 245F, 251, 212M, 250, 209F, 222F, 208G, 710LA, 710FS, 730LM, 650AC, 681, 683 (all manufactured by NEOS Co., Ltd.), and U-120E (manufactured by 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.

[0141] 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).

[0142] Examples of nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane, and their ethoxylates and propoxylates (for example, glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid esters, Pluronic (trade names) L10, L31, L61, L62, 10R5, 17R2, 25R2 (all manufactured by BASF), Tetronic (trade names) 304, 701, 704, 901, 904, 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).

[0143] 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-22-626. 6, KF-351A, K354L, KF-355A, KF-945, KF-640, KF-642, KF-643, X-22-6191, X-22-4515, KF-6004, KP-341, K F-6001, KF-6002, KP-101, KP-103, KP-104, KP-105, KP-106, KP-109, 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 Momentive Polymers Co., Ltd.) Examples include BYK300, BYK306, BYK307, BYK310, BYK320, BYK323, BYK325, BYK330, BYK313, BYK315N, BYK331, BYK333, BYK345, BYK347, BYK348, BYK349, BYK370, BYK377, BYK378, and BYK323 (all manufactured by BYK-Chemie).

[0144] 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.

[0145] -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.

[0146] 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.

[0147] 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.

[0148] 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.).

[0149] 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.

[0150] 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.

[0151] 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.

[0152] 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.

[0153] 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.

[0154] 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.

[0155] <<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.

[0156] 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.

[0157] 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.

[0158] The amount of impurities can be determined by known methods such as ICP (Inductively Coupled Plasma) emission spectroscopy, atomic absorption spectroscopy, and ion chromatography.

[0159] 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.

[0160] 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.

[0161] <<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.

[0162] 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.

[0163] <<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. Furthermore, from the viewpoint of achieving high resolution and the effects of the present disclosure, the thickness of the photosensitive layer is preferably 10 μm or less, more preferably 5.0 μm or less, even more preferably 0.5 μm to 4.0 μm, and particularly preferably 0.5 μm to 3.0 μm. The thickness of each layer in the photosensitive transfer material or laminate 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.

[0164] 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.

[0165] <<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, a polymerizable 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.

[0166] The photosensitive resin composition used to form the photosensitive layer may be, for example, a composition containing an alkali-soluble resin, a polymerizable 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.

[0167] -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, polymerizable compound, 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, a water-soluble resin 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.

[0168] 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.

[0169] 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.

[0170] 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. From the viewpoint of the ability to remove particles of Y μm or larger, the photosensitive resin composition is preferably filtered using a filter before forming the photosensitive layer, more preferably using a filter with a pore size of 0.2 μm to 10 μm, even more preferably using a filter with a pore size of 0.2 μm to 7 μm, and particularly preferably using a filter with a pore size of 0.2 μm to 5 μm. The material and shape of the filter are not particularly limited, and known materials can be used. The filtration is preferably carried out at least once, and is also preferably carried out multiple times.

[0171] 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.

[0172] 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 a water-soluble resin layer, a thermoplastic resin layer, and a protective film. In particular, the transfer layer preferably has a water-soluble resin layer, and more preferably has a thermoplastic resin layer and a water-soluble resin layer.

[0173] [Water-soluble resin layer] The photosensitive transfer material preferably has a water-soluble resin layer between the temporary support and the photosensitive layer, or, if a thermoplastic resin layer (described later) is present, between the thermoplastic resin layer and the photosensitive layer. The water-soluble resin layer can prevent components from mixing when forming multiple layers and during storage.

[0174] The water-soluble resin 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.

[0175] An example of the water-soluble resin layer is an oxygen-blocking layer having an oxygen-blocking function, which is described as a "separation layer" in JP-A-5-72724. When the water-soluble resin layer is an oxygen-blocking layer, the sensitivity during exposure is improved, reducing the time load on the exposure machine, thereby improving productivity. The oxygen-blocking layer used as the water-soluble resin layer may be appropriately selected from known layers. The oxygen-blocking layer used as the water-soluble resin 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). In addition, the water-soluble resin layer preferably contains an inorganic layered compound from the viewpoints of oxygen blocking properties, resolution, and pattern formability. The inorganic layered compounds are thin, tabular particles, and examples thereof include mica compounds such as natural mica and synthetic mica, talc represented by the formula 3MgO 4SiO HO, taeniolite, montmorillonite, saponite, hectorite, and zirconium phosphate. Examples of mica compounds include those represented by the formula: A(B,C) 2-5 D4O 10 Examples of micas include natural mica and synthetic mica represented by the formula (OH,F,O)2 (wherein A is K, Na, or Ca; B and C are Fe(II), Fe(III), Mn, Al, Mg, or V; and D is Si or Al).

[0176] In the mica group, natural micas include muscovite, sodalite, phlogopite, biotite, and lepidolite. Synthetic micas include fluorphlogopite KMg3(AlSiO 10 )F2, potassium tetrasilicic mica KMg 2.5 SiO 10 )F2 and other non-swelling micas, and Na tetrasilicic mica NaMg 2.5 (SiO 10 )F2, Na or Li taeniolite (Na,Li)Mg2Li(SiO 10 ) F2, Na or Li hectorite of the montmorillonite series (Na, Li) 1 / 8 Mg 2 / 5 Li 1 / 8 (SiO 10 Examples include swelling mica such as )F2. Synthetic smectite is also useful.

[0177] Regarding the shape of the inorganic layered compound, from the viewpoint of diffusion control, the thinner the thickness, the better, and the larger the planar size, the better, as long as it does not impair the smoothness of the coated surface or the transmittance of actinic rays. Therefore, the aspect ratio is preferably 20 or more, more preferably 100 or more, and particularly preferably 200 or more. The aspect ratio is the ratio of the major axis to the thickness of the particle, and can be measured, for example, from a projection view of the particle in a micrograph. The larger the aspect ratio, the greater the effect obtained.

[0178] The particle size of the inorganic layered compound is preferably 0.3 μm to 20 μm, more preferably 0.5 μm to 10 μm, and particularly preferably 1 μm to 5 μm in terms of average major axis. The average particle thickness is preferably 0.1 μm or less, more preferably 0.05 μm or less, and particularly preferably 0.01 μm or less. Specifically, for example, in the case of swellable synthetic mica, a representative compound, a preferred embodiment is that the thickness is about 1 nm to 50 nm, and the face size (major axis) is about 1 μm to 20 μm.

[0179] The content of the inorganic layered compound is preferably 0.1% by mass to 50% by mass, more preferably 1% by mass to 20% by mass, based on the total mass of the water-soluble resin layer, from the viewpoints of oxygen blocking property, resolution, and pattern formability.

[0180] The water-soluble resin layer preferably contains a resin. Examples of the resin contained in the water-soluble resin 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 water-soluble resin layer is preferably a water-soluble resin.

[0181] From the viewpoint of suppressing mixing of components between multiple layers, it is preferable that the resin contained in the water-soluble resin 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.

[0182] Furthermore, from the viewpoints of oxygen blocking properties, developability, resolution, and pattern formability, the water-soluble resin 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, and more preferably at least one water-soluble resin selected from the group consisting of polyvinyl alcohol, polyvinylpyrrolidone, hydroxypropyl cellulose, and hydroxypropylmethyl cellulose. 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.

[0183] The water-soluble resin layer preferably contains polyvinyl alcohol, more preferably polyvinyl alcohol and polyvinylpyrrolidone, from the viewpoints of oxygen barrier properties and suppressing mixing of components when applying multiple layers and during storage after application.

[0184] The water-soluble resin layer may contain one type of resin alone, or two or more types of resins.

[0185] The content of the water-soluble compound in the water-soluble resin 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 water-soluble resin layer, from the viewpoints of oxygen blocking properties and suppressing mixing of components when multiple layers are applied and during storage after application.

[0186] The water-soluble resin layer may contain additives, such as surfactants, if necessary.

[0187] The thickness of the water-soluble resin layer is not limited. The average thickness of the water-soluble resin layer is preferably 0.1 μm to 5 μm, and more preferably 0.5 μm to 3 μm. When the thickness of the water-soluble resin layer is within the above range, the oxygen barrier properties are not reduced, mixing of components can be suppressed when forming multiple layers and during storage, and an increase in the time required to remove the water-soluble resin layer during development can be suppressed.

[0188] The method for forming the water-soluble 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 water-soluble resin layer include a method in which a water-soluble resin layer composition is applied to the surface of a thermoplastic resin layer or a photosensitive layer, and then the coating film of the water-soluble resin layer composition is dried.

[0189] Examples of water-soluble resin layer compositions include compositions containing a resin and optional additives. The water-soluble resin layer composition preferably contains a solvent to adjust the viscosity of the water-soluble resin layer composition and facilitate the formation of the water-soluble resin 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.

[0190] 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.

[0191] [Thermoplastic resin layer] The photosensitive transfer material used in 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. When the photosensitive transfer material has a thermoplastic resin layer between the temporary support and the photosensitive layer, the conformability to the adherend is improved, and the inclusion of air bubbles between the adherend and the photosensitive transfer material is suppressed, resulting in improved adhesion between the layers.

[0192] The thermoplastic resin layer preferably contains an alkali-soluble resin as the thermoplastic resin.

[0193] 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.

[0194] 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.

[0195] 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.

[0196] 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.

[0197] 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.

[0198] 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.

[0199] 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.

[0200] 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.

[0201] 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).

[0202] 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.

[0203] The thermoplastic resin layer may contain one kind of alkali-soluble resin alone, or two or more kinds of alkali-soluble resins.

[0204] 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.

[0205] 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.

[0206] 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.

[0207] 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.

[0208] The thermoplastic resin layer may contain one type of dye B alone, or two or more types of dye B.

[0209] 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.

[0210] 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.

[0211] 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.

[0212] From the viewpoint of resolution, the thermoplastic resin layer preferably contains a photoacid generator. Examples of the photoacid generator include the cationic photopolymerization initiators that may be contained in the photosensitive layer described above, and preferred embodiments are the same as those described below except for the points mentioned below.

[0213] 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.

[0214] The photoacid generator is also preferably a photoacid generator having the following structure:

[0215] [ka]

[0216] 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.

[0217] The thermoplastic resin layer may contain a photoradical polymerization initiator. Examples of the photoradical polymerization initiator include the photoradical polymerization initiators that may be contained in the photosensitive layer described above, and preferred embodiments are also the same.

[0218] The thermoplastic resin layer may contain one or more types of compound C.

[0219] 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.

[0220] The thermoplastic resin layer preferably contains a plasticizer from the viewpoints of resolution, adhesion to layers adjacent to the thermoplastic resin layer, and developability.

[0221] 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.

[0222] 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.

[0223] 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.

[0224] 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 photosensitive layer are disposed in direct contact with each other, it is preferable that the thermoplastic resin layer and the photosensitive layer each contain the same (meth)acrylate compound. This is because the thermoplastic resin layer and the photosensitive layer each contain the same (meth)acrylate compound, which suppresses component diffusion between the layers and improves storage stability.

[0225] 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.

[0226] 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.

[0227] 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.

[0228] The thermoplastic resin layer may contain one kind of plasticizer alone or two or more kinds of plasticizers.

[0229] 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.

[0230] 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 photosensitive layer described above, and preferred embodiments are also the same.

[0231] The thermoplastic resin layer may contain one or more types of surfactants.

[0232] 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.

[0233] The thermoplastic resin layer may contain a sensitizer, such as the sensitizers that may be contained in the negative-type photosensitive layer.

[0234] The thermoplastic resin layer may contain one or more types of sensitizers.

[0235] 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.

[0236] The thermoplastic resin layer may contain known additives in addition to the above components, if necessary.

[0237] 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.

[0238] 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.

[0239] 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.

[0240] 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.

[0241] 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.

[0242] The thermoplastic resin composition may contain one solvent alone or two or more solvents.

[0243] 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.

[0244] 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.

[0245] [Protective film] The photosensitive transfer material has a protective film. The protective film is not included in the transfer layer. It is preferable that the photosensitive layer and the protective film are in direct contact with each other.

[0246] 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.

[0247] 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.

[0248] 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.

[0249] 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, water-soluble resin 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.

[0250] [Method for producing photosensitive transfer material] The method for producing the photosensitive transfer material used in 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 used in the present disclosure will be described with reference to Fig. 1. However, the photosensitive transfer material used in the present disclosure is not limited to one having 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 used in 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, a water-soluble resin layer 15, a photosensitive layer 17, and a protective film 19 are laminated in this order. The transfer layer 12 in Fig. 1 is the thermoplastic resin layer 13, the water-soluble resin layer 15, and the photosensitive layer 17.

[0251] 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 13; applying a water-soluble resin layer composition to the surface of the thermoplastic resin layer 13, and then drying the coating of the water-soluble resin layer composition to form a water-soluble resin layer 15; and applying a photosensitive resin composition containing an ethylenically unsaturated compound to the surface of the water-soluble resin layer 15, and then drying the coating of the photosensitive resin composition to form a photosensitive layer 16. In the above manufacturing method, it is preferable to use a thermoplastic resin composition containing at least one selected from the group consisting of alkylene glycol ether solvents and alkylene glycol ether acetate solvents, a water-soluble resin layer composition containing at least one 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 selected from the group consisting of alkylene glycol ether solvents and alkylene glycol ether acetate solvents. This can suppress mixing of the components contained in the thermoplastic resin layer 13 and the water-soluble resin layer 15 during the application of the water-soluble resin layer composition to the surface of the thermoplastic resin layer 13 and / or the storage period of a laminate having a coating film of the water-soluble resin layer composition. Furthermore, it can suppress mixing of the components contained in the water-soluble resin layer 15 and the photosensitive layer 16 during the application of the photosensitive resin composition to the surface of the water-soluble resin layer 15 and / or the storage period of a laminate having a coating film of the photosensitive resin composition.

[0252] 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, a water-soluble resin 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.

[0253] The photosensitive transfer material used in 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 used in 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.

[0254] In addition, the photosensitive transfer material used in 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.

[0255] <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.

[0256] 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.

[0257] 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.

[0258] 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.

[0259] 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.

[0260] 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.

[0261] 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.

[0262] 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.

[0263] 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).

[0264] (Circuit Wiring Manufacturing Method) The method for manufacturing circuit wiring according to the present disclosure is not particularly limited, as long as it is a method that uses a laminate manufactured by the method for manufacturing a laminate according to the present disclosure or a photosensitive transfer material according to the present disclosure described below. In addition, the method for manufacturing circuit wiring according to the present disclosure is preferably a method including, in this order, a preparation step of preparing a laminate obtained by the method for manufacturing a laminate according to the present disclosure, and an etching step of etching the substrate in areas where the resin pattern is not arranged. Below, we will explain each step included in the method for manufacturing circuit wiring, but unless otherwise specified, the contents explained for each step included in the method for manufacturing a laminate will also apply to each step included in the method for manufacturing circuit wiring.

[0265] <Preparation process> The method for producing circuit wiring according to the present disclosure preferably includes a preparation step of preparing a laminate obtained by the method for producing a laminate according to the present disclosure. A preferred aspect of the laminate in the preparation step is the same as a preferred aspect in the laminate manufacturing method according to the present disclosure.

[0266] <Etching process> The method for manufacturing circuit wiring preferably includes a step of etching the substrate in the region where the resin pattern is not disposed (etching step).

[0267] 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.

[0268] 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.

[0269] <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.

[0270] 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.

[0271] <Other processes> The method for manufacturing a circuit wiring may include any other steps (other steps) in addition to the steps described above, such as, but not limited to, the following steps. Furthermore, examples of the exposure step, development step, 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.

[0272] -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.

[0273] - 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.

[0274] 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.

[0275] <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.

[0276] (Electronic device manufacturing method) The method for manufacturing an electronic device according to the present disclosure is not particularly limited as long as it is a method that uses a laminate manufactured by the method for manufacturing a laminate according to the present disclosure or a photosensitive transfer material according to the present disclosure described below. In addition, the method for manufacturing an electronic device according to the present disclosure is preferably a method including, in this order, a preparation step of preparing a laminate obtained by the method for manufacturing a laminate according to the present disclosure, and an etching step of etching the substrate in areas where the resin pattern is not arranged. An electronic device manufactured by the method for manufacturing an electronic device according to the present disclosure preferably has the resin pattern as a permanent film.

[0277] 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 laminate" and "Method for manufacturing a circuit wiring," 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.

[0278] 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.

[0279] 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.

[0280] 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.

[0281] 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.

[0282] (Photosensitive transfer material) The photosensitive transfer material according to the present disclosure has a temporary support and a transfer layer including a photosensitive layer, and the limiting resolution of the photosensitive layer is X T The reference diameter of the particle is defined as Y μm. T =0.5×X T Y represented by T When defined as Y μm on the surface and inside of the photosensitive layer, T The number of particles with a diameter of 1 μm or more is 15 / cm 2 The following is the result. Furthermore, preferred aspects of the photosensitive transfer material according to the present disclosure are the same as the preferred aspects of the photosensitive transfer material used in the method for producing a laminate according to the present disclosure described above, except as described below.

[0283] <Limit resolution of the photosensitive layer X T μm, and Y on the surface and inside of the photosensitive layer T Number of particles with a diameter of 1 μm or more The photosensitive transfer material according to the present disclosure has a limiting resolution of the photosensitive layer of X T The reference diameter of the particle is defined as Y μm. T =0.5×X T Y represented by T When defined as Y μm on the surface and inside of the photosensitive layer, T The number of particles with a diameter of 1 μm or more is 15 / cm 2 From the viewpoint of pinhole defect prevention, the number of pinholes per cm is 10 or less. 2 Preferably, it is 7 or less per cm 2 More preferably, it is 5 or less per cm 2 It is particularly preferable that the lower limit is 0 particles / cm or less. 2 is.

[0284] Limiting resolution X of the photosensitive layer in the photosensitive transfer material according to the present disclosure T and Y on the surface and inside of the photosensitive layer.T The number of particles having a diameter of 1 μm or more can be measured in the same manner as the method for measuring the limit resolution of X μm and the number of particles having a diameter of 1 μm or more in the laminate manufacturing method according to the present disclosure described above. [Example]

[0285] 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.

[0286] <Preparation of temporary support A> Temporary support A was produced by the following method.

[0287] [Preparation of particle-containing layer-forming composition 1] The components were mixed according to the formulation shown below to obtain particle-containing layer-forming composition 1. After preparing particle-containing layer-forming composition 1, it was filtered through a 6 μm filter (F20, manufactured by Mahle Filter Systems Co., Ltd.) and then subjected to membrane degassing using a 2x6 Radial Flow Superphobic (manufactured by Polypore Co., Ltd.). 167 parts of acrylic polymer (AS-563A, manufactured by Daicel FineChem Co., Ltd., solid content 27.5% by mass) 0.7 parts of nonionic surfactant (Naroacty CL95, manufactured by Sanyo Chemical Industries, Ltd., solid content 100% by mass) 114.4 parts of anionic surfactant (Rapisol A-90, manufactured by NOF Corporation, diluted with water to a solids content of 1% by mass) 7 parts of carnauba wax dispersion (Cellosol 524, manufactured by Chukyo Yushi Co., Ltd., solid content 30% by mass) 20.9 parts of carbodiimide compound (Carbodilite V-02-L2, manufactured by Nisshinbo, Inc., diluted with water to a solid content of 10% by mass) 2.8 parts of matting agent (Snowtex XL, manufactured by Nissan Chemical Industries, Ltd., solid content 40% by mass, average particle size 50 nm) ·Wednesday 690.2 parts

[0288] [Extrusion molding] Pellets of polyethylene terephthalate (PET) produced using the citric acid chelate organic titanium complex described in Japanese Patent Publication No. 5575671 as a polymerization catalyst were dried to reduce the moisture content of the pellets to 50 ppm or less. The dried pellets were placed in the hopper of a single-screw kneading extruder with a diameter of 30 mm and melted at 280°C. The melt was passed through a filter (pore size 2 μm) and then extruded from a die onto a cooling roll at 25°C to obtain an unstretched film. In this method, the melt was brought into close contact with the cooling roll using an electrostatic application method.

[0289] [Stretching and Coating] The solidified unstretched film was subjected to sequential biaxial stretching by the following method to form a particle-containing layer with a thickness of 40 nm on a polyethylene terephthalate film with a thickness of 16 μm.

[0290] (a) Longitudinal stretching The unstretched film was passed between two pairs of nip rolls with different peripheral speeds and stretched in the machine direction (transport direction). The machine stretching conditions are as follows: Preheat temperature: 75℃ ·Stretching temperature: 90℃ ·Stretching ratio: 3.4 times ·Stretching speed: 1,300% / sec

[0291] (b) Application Composition 1 for forming a particle-containing layer was applied to one surface of the longitudinally stretched film using a bar coater so that the thickness of the film after formation would be 40 nm.

[0292] (c) Lateral stretching The film coated with the particle-containing layer-forming composition 1 was stretched transversely using a tenter under the following conditions. Preheat temperature: 110℃ ·Stretching temperature: 120℃ ·Stretching ratio: 4.2x ·Stretching speed: 50% / sec

[0293] [Heat Fixation and Heat Relaxation] The biaxially stretched film that had been stretched longitudinally and transversely was heat-set under the following conditions. ·Heat fixing temperature: 227℃ ·Heat setting time: 6 seconds

[0294] After heat setting, the tenter width was reduced and the biaxially stretched film was heat-relaxed under the following conditions. ·Thermal relaxation temperature: 190℃ ·Thermal relaxation rate: 4%

[0295] [Winding] After heat setting and heat relaxation, both ends of the film were trimmed, and the ends of the film were knurled to a width of 10 mm. The film was then wound up under a tension of 40 kg / m. The film width was 1.5 m and the wound length was 6,300 m. The resulting film roll was used as temporary support A.

[0296] The temporary support A has a polyethylene terephthalate film (base material) and a particle-containing layer in this order. The haze of temporary support A was 0.2%. The haze was measured as total light haze using a haze meter (NDH2000 manufactured by Nippon Denshoku Industries Co., Ltd.). The thickness of the particle-containing layer measured from a cross-sectional TEM photograph of temporary support A was 40 nm. The average particle diameter of the particles contained in the particle-containing layer measured by the above-mentioned method using a HT-7700 transmission electron microscope (TEM) manufactured by Hitachi High-Technologies Corporation was 50 nm.

[0297] <Preparation of temporary support B> Temporary support B was obtained in the same manner as temporary support A, except that the thickness was adjusted to 25 μm by adjusting the melt flow rate and stretching conditions.

[0298] <Preparation of Photosensitive Compositions 1 to 4> A mixed solution was obtained by adding each component listed in Table 1 to a mixed solvent of methyl ethyl ketone (manufactured by Sankyo Chemical Co., Ltd.) (60 parts) and propylene glycol monomethyl ether acetate (manufactured by Showa Denko K.K.) (40 parts) so that the solid content concentration of the photosensitive composition would be 13 mass %. Thereafter, the obtained mixed solution was filtered using a polytetrafluoroethylene filter having a pore size listed in Table 4 described below for the number of times listed in Table 4, thereby preparing Photosensitive Compositions 1 to 4, respectively.

[0299] [Table 1]

[0300] The details of the compounds listed in Table 1 are shown below. BPE-500: 2,2-bis(4-(methacryloxypentaethoxy)phenyl)propane, manufactured by Shin-Nakamura Chemical Co., Ltd. M-270: Polypropylene glycol diacrylate, manufactured by Toagosei Co., Ltd. A-TMPT: Trimethylolpropane triacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd. SR-454: Ethoxylated (3) trimethylolpropane triacrylate, manufactured by Sartomer A-9300-CL1: ε-caprolactone-modified tris(2-acryloxyethyl) isocyanurate, manufactured by Shin-Nakamura Chemical Co., Ltd. B-CIM: Photoradical generator (photopolymerization initiator), manufactured by Hampford, 2-(2-chlorophenyl)-4,5-diphenylimidazole dimer SB-PI 701: Sensitizer, 4,4'-bis(diethylamino)benzophenone, obtained from Sanyo Trading Co., Ltd. CBT-1: Rust inhibitor, carboxybenzotriazole, manufactured by Johoku Chemical Industry Co., Ltd. TDP-G: Polymerization inhibitor, phenothiazine, manufactured by Kawaguchi Chemical Industry Co., Ltd. Irganox 245: Hindered phenolic polymerization inhibitor, manufactured by BASF F-552: Fluorine-based surfactant, Megafac F552, manufactured by DIC Corporation

[0301] <Preparation of Thermoplastic Resin Composition> The components listed in Table 2 were mixed to prepare a thermoplastic resin composition.

[0302] [Table 2]

[0303] The numerical values ​​of each component listed in Table 2 are in parts by mass. The meanings of the abbreviations listed in Table 2 above are as follows: A-2: Benzyl methacrylate / methacrylic acid / acrylic acid copolymer (75% by mass / 10% by mass / 15% by mass, weight average molecular weight: 30,000, Tg: 75°C, acid value: 186 mgKOH / g) B-1: Compound with the structure shown below (a dye that develops color when exposed to acid)

[0304] [ka]

[0305] C-1: Compound with the structure shown below (photoacid generator, compound described in paragraph 0227 of JP-A 2013-47765, synthesized according to the method described in paragraph 0227)

[0306] [ka]

[0307] D-3: NK Ester A-DCP (tricyclodecane dimethanol diacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.) D-4: 8UX-015A (multifunctional urethane acrylate compound, Taisei Fine Chemical Co., Ltd.) D-5: Aronix TO-2349 (a polyfunctional acrylate compound with a carboxy group, manufactured by Toagosei Co., Ltd.) E-1: Megafac F552 (DIC Corporation) F-1: Phenothiazine (Fujifilm Wako Pure Chemical Industries, Ltd.) ·F-2:CBT-1 (manufactured by Johoku Chemical Industry Co., Ltd.) MEK: Methyl ethyl ketone PGME: Propylene glycol monomethyl ether PGMEA: Propylene glycol monomethyl ether acetate

[0308] <Preparation of Water-Soluble Resin Composition> The following components were mixed to prepare a water-soluble resin composition, where the amount of each component is expressed in parts by mass. Ion-exchanged water: 38.12 parts Methanol (Mitsubishi Gas Chemical Co., Ltd.): 57.17 parts Kuraray Poval 4-88LA (polyvinyl alcohol, manufactured by Kuraray Co., Ltd.): 3.22 parts Polyvinylpyrrolidone K-30 (manufactured by Nippon Shokubai Co., Ltd.): 1.49 parts Megafac F-444 (fluorine-based surfactant, manufactured by DIC Corporation): 0.0035 parts

[0309] Examples 1 to 5 The thermoplastic resin composition was applied onto a temporary support substrate (polyethylene terephthalate film) using a slit nozzle. The applied thermoplastic resin composition was dried at 100°C for 120 seconds to form a thermoplastic resin layer having the thickness shown in Table 3.

[0310] A water-soluble resin composition was applied onto the thermoplastic resin layer using a slit nozzle, and the applied water-soluble resin composition was dried at 120°C for 120 seconds to form a water-soluble resin layer having the thickness shown in Table 3.

[0311] A photosensitive composition shown in Table 3 was applied onto the water-soluble resin layer using a slit nozzle. The applied photosensitive composition was dried at 100°C for 120 seconds to form a photosensitive layer having the thickness shown in Table 3 (layer structure: coated layer 1 shown in Table 3), thereby obtaining a photosensitive transfer material.

[0312] The photosensitive transfer material obtained by the above procedure contains a temporary support, a thermoplastic resin layer, a water-soluble resin layer, and a photosensitive layer in this order. The layer configurations (coating layers 1 to 5) of the thermoplastic resin layer, the water-soluble resin layer, and the photosensitive layer are shown in Table 3.

[0313] (Examples 6 to 18 and Comparative Example 1) A photosensitive transfer material was obtained in the same manner as in Example 1, except that appropriate changes were made according to the descriptions in Tables 3 and 4.

[0314] <Resolution> (1) A 200 nm thick copper layer was formed on a 100 μm thick polyethylene terephthalate (PET) film by sputtering to prepare a copper-layered PET substrate. The photosensitive transfer material and the copper-layered PET substrate were bonded together using a roll-to-roll process with a vacuum laminator (manufactured by MCK Corporation, roll temperature: 100°C, linear pressure: 1.0 MPa, linear speed: 0.5 m / min) to obtain a laminate. The resulting laminate contained at least a PET film, a copper layer, a photosensitive layer, and a temporary support, in this order. (2) The obtained laminate was degassed under pressure at 0.6 MPa and 60° C. for 30 minutes using an autoclave. Thereafter, the surface of the temporary support was manually rubbed 10 times with a cleaning roll (DCH-12H2LS, manufactured by Osada Corporation) to remove foreign matter from the temporary support. (3) Using an ultra-high pressure mercury lamp, the photosensitive layer was exposed through a line and space pattern mask (the duty ratio was 1:1, and the line width changed in steps of 1 μm from 1 μm to 20 μm) without peeling off the temporary support. (4) After peeling off the temporary support, the film was developed by shower development using a 1.0% by mass aqueous solution of sodium carbonate at 25° C. for 30 seconds. The photosensitive layer was developed to form a resin pattern. The exposure dose (unit: mJ / cm ) is increased until a resin pattern (hereinafter referred to as a "reference pattern" in this paragraph) having the minimum line width corresponding to the mask pattern is obtained. 2The above-mentioned series of steps (1) to (4) were carried out while adjusting the value of the reference pattern as needed. The minimum line width of the reference pattern was adopted as the limiting resolution of the photosensitive layer, X μm. The measurement results are shown in Table 4.

[0315] <Total number of foreign particles and voids on the surface and inside of the photosensitive layer> (1) A photosensitive transfer material and a PET substrate were laminated onto a 100 μm-thick polyethylene terephthalate (PET) film by a roll-to-roll method using a vacuum laminator (manufactured by MCK Corporation, roll temperature: 100°C, linear pressure: 1.0 MPa, linear speed: 0.5 m / min). The resulting laminate contained at least the PET film, the photosensitive layer, and the temporary support, in this order. (2) The resulting laminate was defoamed under pressure at 0.6 MPa and 60° C. for 30 minutes using an autoclave. After peeling off the temporary support, 10 randomly selected areas on the surface (size of each area: 10 mm × 10 mm, total area: 1,000 mm) were measured. 2 ) was visually observed using an optical microscope. The number of foreign matter and voids with a diameter of Y μm or more contained in each area was counted. Based on the total number of foreign matter and voids with a diameter of Y μm or more measured in the 10 areas, the number of foreign matter and voids per 1 cm of the measurement area was calculated. 2 Number of foreign objects and voids of Y μm or more per square centimeter (pieces / cm 2 The measurement results are shown in Table 4.

[0316] <Pinholes in wiring patterns> A wiring pattern (i.e., a resin pattern) was formed using the same method as described in the "Resolution" section above (i.e., a method of exposing a photosensitive layer to a standard exposure dose to form a resin pattern), except that a wiring formation mask (duty ratio 1:1, line width varying in 1-μm increments from 1 μm to 20 μm, wiring pattern length 50 mm, and number of wiring lines 10) was used. The wiring pattern was visually observed using an optical microscope, and pinholes in the wiring pattern were evaluated according to the following criteria based on the maximum size and number of pinholes. The evaluation results are shown in Table 4. A: No pinholes were found, or pinholes smaller than 1 / 4 of the wiring width were found. B: Pinholes larger than 1 / 4 and smaller than 1 / 2 of the wiring width were observed. C: A pinhole larger than 1 / 2 and smaller than 3 / 4 of the wiring width was observed. D: A pinhole larger than 3 / 4 of the wiring width was observed.

[0317] <Wiring pattern defects> The samples used for pinhole evaluation of the wiring pattern were visually observed using an optical microscope to check for defects (so-called bites) in the pattern, and were evaluated according to the following criteria. A: No pattern defects were observed, or pattern defects with a maximum diameter of less than 1 μm were observed. B: Defects in the pattern with a maximum diameter of 1 μm or more and 2 μm or less were observed. C: Pattern defects with a maximum diameter exceeding 2 μm were observed.

[0318] <Linearity of wiring pattern> The 10 μm pattern of the pattern for which resolution was evaluated was observed with a scanning electron microscope (SEM), and the linearity of the resin pattern was evaluated according to the following criteria by evaluating the maximum-minimum value of the line width (also called the "variation value of the line width") within a length range of 100 μm. A: The line width fluctuation value is less than 0.4 μm. B: The line width fluctuation value is 0.4 μm or more and less than 0.7 μm. C: The line width fluctuation value is 0.7 μm or more and less than 1.0 μm. D: The line width fluctuation value is 1.0 μm or more and less than 1.5 μm. E: The line width fluctuation value is 1.5 μm or more.

[0319] [Table 3]

[0320] [Table 4]

[0321] In the laminates obtained in Examples 1 to 18, the number of voids having a diameter of Y μm or more was 0 / cm 2 It is estimated that the generation of voids was suppressed by the pressurized degassing treatment using an autoclave.

[0322] As shown in Table 4 above, the photosensitive transfer materials and laminate manufacturing methods of Examples 1 to 18 produced wiring patterns with fewer pinhole defects compared to the photosensitive transfer material and laminate manufacturing method of Comparative Example 1, and also produced resin patterns with fewer pinhole defects corresponding to the above wiring patterns.

[0323] (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.

[0324] (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 mask pattern for DI exposure was used, and the illuminance was 80 mW / cm. 2The 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.

[0325] (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.

[0326] The disclosure of Japanese Patent Application No. 2021-011932, filed on January 28, 2021, is incorporated herein by reference in its entirety. All publications, patent applications, and technical standards mentioned in this specification are herein incorporated by reference to the same extent as if each individual publication, patent application, or technical standard was specifically and individually indicated to be incorporated by reference. [Explanation of symbols]

[0327] 11: temporary support, 12: transfer layer, 13: thermoplastic resin layer, 15: water-soluble resin layer, 17: photosensitive layer, 19: protective film, 20: photosensitive transfer material, GR: light-shielding area (non-image area), EX: exposed area (image area), DL: alignment frame

Claims

1. a lamination step of laminating a photosensitive transfer material having a temporary support and a transfer layer including a photosensitive layer to a substrate so that a transfer layer side of the photosensitive transfer material is in contact with the substrate; an exposure step of exposing the photosensitive layer to light; and a developing step of developing the photosensitive layer to form a resin pattern, The method further comprises a surface-adhered particle removing step of removing particles adhering to the surface of the transfer layer or the temporary support before the exposure step, When the limit resolution of the photosensitive layer in the exposure step is defined as X μm and the reference diameter of particles and voids is defined as Y μm, which is expressed as Y=0.5×X, the number of particles and voids having a diameter of Y μm or more on the surface and inside of the photosensitive layer in the exposure step is 15 particles / cm ２ is A method for manufacturing a laminate.

2. The method for producing a laminate according to claim 1, wherein the photosensitive layer has a thickness of 5.0 μm or less.

3. The method for producing a laminate according to claim 1 or 2, wherein the temporary support has a thickness of 16 μm or less.

4. The method for producing a laminate according to any one of claims 1 to 3, wherein the resin pattern has a line width of 10 µm or less.

5. The method for producing a laminate according to any one of claims 1 to 4, further comprising a peeling step of peeling off the temporary support between the laminating step and the exposing step.

6. 6. The method for producing a laminate according to claim 1, wherein the exposure step involves contacting the transfer layer with a mask to perform the exposure treatment.

7. 7. The method for producing a laminate according to claim 1, wherein the transfer layer further comprises a thermoplastic resin layer and a water-soluble resin layer.

8. The method for producing a laminate according to any one of claims 1 to 7, wherein the photosensitive layer contains a polyfunctional polymerizable compound.

9. The method for producing a laminate according to any one of claims 1 to 8, wherein the photosensitive layer contains a tri- or higher functional polymerizable compound.

10. The method for producing a laminate according to any one of claims 1 to 9, wherein the photosensitive layer contains a polymerizable compound having a polyethylene oxide structure.

11. The method further includes a temporary support peeling step of peeling off a temporary support between the laminating step and the exposing step, The method for producing a laminate according to any one of claims 1 to 10, further comprising the step of removing particles adhering to the surface after the step of peeling off the temporary support and before the step of exposing.

12. A preparation step of preparing a laminate obtained by the laminate manufacturing method according to any one of claims 1 to 11; and an etching step of etching the substrate in an area where the resin pattern is not disposed, in this order. A method for manufacturing circuit wiring.

13. A preparation step of preparing a laminate obtained by the laminate manufacturing method according to any one of claims 1 to 11; and an etching step of etching the substrate in an area where the resin pattern is not disposed, in this order. A method for manufacturing electronic devices.

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