Photosensitive transfer material

Abstract

To provide a method for manufacturing a laminate having a resin pattern with few pinhole defects.SOLUTION: A bonding step of bonding a photosensitive transfer material and a substrate to each other such that a transfer layer side of the photosensitive transfer material including a temporary support and a transfer layer including a photosensitive layer comes into contact with the substrate, an exposure step of exposing the photosensitive layer, and a development step of developing the photosensitive layer to form a resin pattern, in which a limiting resolution of the photosensitive layer in the exposure step is defined as X μ m, in a case where reference diameters of the particles and the voids are defined as Y μm represented by Y = 0.5 * X, the number of the particles and the voids having diameters equal to or greater than Y μm on and in the photosensitive layer in the exposure step is 15 pieces / cm2 or less.SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] The present disclosure relates to a method for producing a layered product, a method for producing a circuit wiring, a method for producing an electronic device, and a photosensitive transfer material.

Background Art

[0002] In a display device including a touch panel such as a capacitive input device (such as an organic electroluminescence (EL) display device and a liquid crystal display device), conductive layer patterns such as an electrode pattern corresponding to a sensor in a visible portion, wirings in a peripheral wiring portion and an extraction wiring portion are provided inside the touch panel. In general, for forming a patterned layer, since the number of steps required to obtain a required pattern shape is small, a method is widely used in which a layer of a photosensitive resin composition provided on an arbitrary substrate using a photosensitive transfer material is exposed through a mask having a desired pattern and then developed.

[0003] In addition, as a conventional photosensitive resin layered product roll, one described in Patent Document 1 is known. Patent Document 1 discloses a photosensitive resin layered product roll obtained by rolling a photosensitive resin layered product including 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 where, when 0.75 mm × 11 mm small pieces are cut out at any 10 mutually different locations of the support film, the average number of particles having a diameter of 2 µm or more contained in each small piece at the 10 locations is 200 or less on average, and a photosensitive resin layered product roll in which the back surface of the support film includes a region having an arithmetic average roughness of 0.01 µm or more is described.

[0004] Patent Document 1: Japanese Patent Application Laid-Open No. 2019-101405

Summary of Invention

Problem to be Solved by the Invention

[0005] < / think_never_used_51bce0c785ca2f68081bfa7d91973934>An object to be solved by one embodiment of the present invention is to provide a method for producing a laminate having a resin pattern with few pinhole defects. An object to be solved by another embodiment of the present invention is to provide a method for producing a circuit wiring using a laminate obtained by the method for producing a laminate, and a method for producing an electronic device. Furthermore, an object to be solved by still another embodiment of the present invention is to provide a photosensitive transfer material capable of obtaining a resin pattern with few pinhole defects. [Means for Solving the Problems]

[0006] Means for solving the above problems include the following aspects. <1> A bonding step of bonding the photosensitive transfer material and a substrate such that the transfer layer side of the photosensitive transfer material having a temporary support and a transfer layer including a photosensitive layer is in contact with the substrate; an exposure step of exposing the photosensitive layer; and a developing 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 represented 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 or less in the method for producing a laminate. <2> The method for producing a laminate according to <1>, wherein the thickness of the photosensitive layer is 5.0 μm or less. <3> The method for producing a laminate according to <1> or <2>, wherein the thickness of the temporary support is 16 μm or less. <4> The method for producing a laminate according to any one of <1> to <3>, wherein the resin pattern has a resin pattern with a line width of 10 μm or less. <5> The method for producing a laminate according to any one of <1> to <4>, comprising a peeling step of peeling off the temporary support between the bonding step and the exposure step. <6> The method for producing a laminate according to any one of <1> to <5>, wherein in the exposure step, exposure treatment is performed by bringing the transfer layer into contact with a mask. <7> The above transfer layer further comprises a thermoplastic resin layer and a water-soluble resin layer. <1> ~ <6> A method for manufacturing a laminate as described in any one of the following. <8> The above photosensitive layer contains a polyfunctional polymerizable compound. <1> ~ <7> A method for manufacturing a laminate as described in any one of the following. <9> The above photosensitive layer contains a polymerizable compound with three or more functions. <1> ~ <8> A method for manufacturing a laminate as described in any one of the following. <10> The above photosensitive layer contains a polymerizable compound having a polyethylene oxide structure. <1> ~ <9> A method for manufacturing a laminate as described in any one of the following. <11> <1> ~ <10> A method for manufacturing circuit wiring, comprising, in this order, a preparation step of preparing a laminate obtained by a method for manufacturing a laminate described in any one of the above, and an etching step of etching the substrate in areas where the resin pattern is not arranged. <12> <1> ~ <10> A method for manufacturing an electronic device, comprising, in this order, a preparation step of preparing a laminate obtained by a method for manufacturing a laminate described in any one of the above, and an etching step of etching the substrate in areas where the resin pattern is not arranged. <13> It has a temporary support and a transfer layer including a photosensitive layer, and the limiting resolution of the photosensitive layer is X T Defined as μm, the reference diameter of the particle is Y T = 0.5 × X T Y represented by T When defined as μm, Y in the surface and interior of the above photosensitive layer T The number of particles with a diameter of μm or more is 15 particles / cm². 2 The following are photosensitive transfer materials. <14> The thickness of the above photosensitive layer is 5.0 μm or less. <13> The photosensitive transfer material described in [reference]. <15> The thickness of the above-mentioned temporary support is 16 μm or less. <13> or <14> The photosensitive transfer material described in [reference]. [Effects of the Invention]

[0007] According to one embodiment of the present invention, a method for manufacturing a laminate having a resin pattern with few pinhole defects can be provided. According to another embodiment of the present invention, a method for manufacturing circuit wiring using a laminate obtained by the above-described method for manufacturing a laminate, and a method for manufacturing an electronic device can be provided. Furthermore, according to another embodiment of the present invention, a photosensitive transfer material can be provided that yields a resin pattern with fewer pinhole defects. [Brief explanation of the drawing]

[0008] [Figure 1] This is a schematic diagram showing an example of the composition of a photosensitive transfer material. [Figure 2] This is a schematic plan view showing pattern A. [Figure 3] This is a schematic plan view showing Pattern B. [Modes for carrying out the invention]

[0009] The contents of this disclosure are described below. While the explanation will be given with reference to the attached drawings, reference numerals may be omitted. Furthermore, in this specification, numerical ranges represented using "~" mean a range that includes the numbers written before and after "~" as the lower and upper limits, respectively. Furthermore, in this specification, "(meth)acrylic" refers to both acrylic and methacrylic, or either of them; "(meth)acrylate" refers to both acrylate and methacrylate, or either of them; and "(meth)acryloyl" refers to both acryloyl and methacryloyl, or either of them. Furthermore, in this specification, the amount of each component in a composition means the total amount of multiple substances corresponding to each component present in the composition, unless otherwise specified. In this specification, the term "process" includes not only independent processes but also processes that cannot be clearly distinguished from other processes, provided that the intended purpose of the process is achieved. In this specification, when groups (atomic groups) are not explicitly labeled as substituted or unsubstituted, the term includes both substituted and unsubstituted groups. For example, "alkyl group" includes not only unsubstituted alkyl groups but also substituted alkyl groups. In this specification, "exposure" includes not only exposure using light but also drawing using particle beams such as electron beams and ion beams, unless otherwise specified. Generally, the light used for exposure includes the emission spectrum of mercury lamps, far ultraviolet light represented by excimer lasers, extreme ultraviolet (EUV) light, X-rays, electron beams, and other active light rays (active energy rays). Furthermore, chemical structural formulas in this specification may sometimes be described as simplified structural formulas in which hydrogen atoms are omitted. In this disclosure, "mass%" and "weight%" are synonymous, and "parts by mass" and "parts by weight" are synonymous. Furthermore, in this 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 this disclosure are molecular weights obtained by detecting the solvent THF (tetrahydrofuran) using a differential refractometer with a gel permeation chromatography (GPC) analyzer using TSKgel GMHxL, TSKgel G4000HxL, or TSKgel G2000HxL (all product names of Tosoh Corporation) columns, and then converting them using polystyrene as a standard substance. In this specification, "total solids" refers to the total mass of the components of the composition excluding the solvent. Furthermore, "solids" refers to the components excluding the solvent, and may be solid or liquid at 25°C, for example.

[0010] (Method of manufacturing a laminate) A method for manufacturing a laminate according to this disclosure includes a bonding step of bonding a photosensitive transfer material to a substrate such that the transfer layer side of the photosensitive transfer material, which has a temporary support and a transfer layer including a photosensitive layer, is in contact with the substrate; an exposure step of exposing the photosensitive layer; and a developing step of developing the photosensitive layer to form a resin pattern. If 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, represented by Y = 0.5 × X, then the number of particles and voids having a diameter of Y μm or more on the surface and inside the photosensitive layer in the exposure step is 15 particles / cm². 2 The following applies:

[0011] As conductive patterns become more detailed, or in other words, as the required resolution increases, defects in conductive patterns (e.g., pinholes) caused by foreign matter and voids (e.g., coarse particles, air bubbles, etc.) on the surface and within the photosensitive layer are becoming more apparent. Particles and voids on the surface and within the photosensitive layer inhibit the curing of the photosensitive layer by exposure, 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 number of pinholes that occur in the resin pattern.

[0012] The estimated reasons for the above-mentioned effects are explained below. For example, in the technology disclosed in Patent Document 1, by limiting the number of particles having a diameter of 2 µm or more, a decrease in resolution caused by foreign substances contained in the temporary support is avoided. However, the size of particles and voids that cause exposure failure varies depending on the required resolution. As the required resolution becomes finer, fine particles and voids that have been tolerated in conventional techniques also inhibit the exposure of the photosensitive layer. Accordingly, the present inventors focused on the relationship between the size and number of particles and voids on the surface and inside of the photosensitive layer with respect to the resolution of the photosensitive layer. Through verification on the relationship between the resolution of the photosensitive layer and the size of particles and voids that cause exposure failure, the present inventors have clarified that, with respect to the limiting resolution (X µm) of the photosensitive layer, particles and voids having a diameter of Y (Y=0.5×X) µm or more cause an increase in the incidence of exposure failure. According to the reference diameter (Y µm) of particles and voids derived from the limiting resolution (X µm) of the photosensitive layer, the number of particles and voids having a diameter of Y µm or more on the surface and inside of the photosensitive layer is adjusted to 15 particles / cm 2 or less, thereby reducing the incidence of exposure failure. Therefore, according to the method for producing a laminate of the present disclosure, there is provided a method for producing a laminate having a resin pattern with fewer pinhole defects.

[0013] <Number of particles and voids having 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 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 represented 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 or less, and from the viewpoint of suppressing pinhole defects, it is 10 particles / cm 2 or less, which is preferable, more preferably 7 particles / cm 2 or less, even more preferably 5 particles / cm 2 or less, which is particularly preferable. The lower limit is 0 particles / cm 2 .

[0014] The method for measuring the limiting resolution of the photosensitive layer in this disclosure is described below. The laminate is exposed to light using an ultra-high pressure mercury lamp, via a line-and-space pattern mask (with a duty cycle of 1:1 and line widths that gradually change in 1 μm increments from 1 μm to 20 μm). If necessary, remove the temporary support and then develop the film. Development is performed using a 1.0% by mass sodium carbonate aqueous solution at 25°C and shower development for 30 seconds. A resin pattern is formed by developing the photosensitive layer. The exposure dose (unit: mJ / cm²) is increased until a resin pattern with the minimum line width corresponding to the mask pattern (hereinafter referred to as the "reference pattern" in this paragraph) is obtained. 2 Perform the above series of steps while adjusting the settings 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, a laminate is prepared by laminating the photosensitive transfer material and a PET substrate onto a 100 μm thick polyethylene terephthalate (PET) film using a roll-to-roll method with a vacuum laminator (manufactured by MCK Co., Ltd., roll temperature: 100°C, linear pressure: 1.0 MPa, linear speed: 0.5 m / min). After that, the laminate is degassed under pressure for 30 minutes under conditions of 0.6 MPa and 60°C using an autoclave, and then the limiting resolution of the photosensitive layer is 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 the photosensitive layer in this disclosure is described below. If necessary, remove the temporary support and select any 10 locations on the surface of the photosensitive layer in the laminate (each location: 10mm x 10mm, total area: 1,000mm²). 2 The area is observed visually using an optical microscope. The number of foreign matter and voids with a diameter of Y μm or more in each region is measured. Based on the total number of particles and voids with a diameter of Y μm or more measured in 10 regions, the measurement area is measured in 1 cm². 2 Number of particles and voids larger than Yμm per unit area (particles / cm²)2 Calculate ). Note that particles and voids can be measured together or separately.

[0017] A method for manufacturing a laminate according to this disclosure includes a bonding step of bonding a photosensitive transfer material and a substrate such that the transfer layer side of the photosensitive transfer material, which has a temporary support and a transfer layer including a photosensitive layer, is in contact with the substrate; an exposure step of exposing the photosensitive layer; and a developing step of developing the photosensitive layer to form a resin pattern. Furthermore, the method for manufacturing the laminate according to this disclosure preferably includes a peeling step for peeling off the temporary support between the bonding step and the exposure step. Furthermore, the method for manufacturing a laminate according to this disclosure preferably includes a protective film peeling step of peeling off a protective film before the bonding step, if necessary.

[0018] <Protective film removal process> The method for manufacturing the laminate according to this 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 known methods can be applied.

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

[0020] Furthermore, in the bonding process, if the photosensitive transfer material further includes layers other than the protective film (e.g., 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 bonded together via these layers.

[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 bonding of the photosensitive transfer material to the substrate is preferably performed by overlapping the outermost layer of the photosensitive transfer material, which has a photosensitive layer on the temporary support, with the substrate, and then applying pressure and heat using means such as a roll. Known laminators such as laminators, vacuum laminators, and auto-cut laminators, which can increase productivity, can be used for bonding. The lamination temperature is not particularly limited, but it is preferably, for example, 70°C to 130°C.

[0022] The method for manufacturing the laminate according to this disclosure is preferably carried out by a roll-to-roll method. The following explains the roll-to-roll method. The roll-to-roll method refers to a method in which a substrate capable of being wound and unwound is used as the substrate, and the method includes a step of unwinding the substrate or a structure containing the substrate (also referred to as the "unwinding step") before any of the steps included in the method of manufacturing a laminate according to this disclosure, and a step of winding the substrate or a structure containing the substrate (also referred to as the "winding step") after any of the steps, wherein at least one of the steps (preferably all of the steps, or all of the steps except the heating step) is performed while transporting the substrate or a structure containing the substrate. The unwinding method in the unwinding process and the winding method in the winding process are not particularly limited, and any known method in a manufacturing method that applies a roll-to-roll system may be used.

[0023] <Circuit board> Any known substrate can be used as the substrate in the manufacturing method of the laminate according to this disclosure, but a substrate having a conductive layer is preferred, and a substrate having a conductive layer on its surface is more preferred. The substrate may have any layers other than the conductive layer, as needed. Examples of substrates include resin substrates, glass substrates, and semiconductor substrates. A preferred embodiment of the substrate is, for example, the one described in paragraph 0140 of International Publication No. 2018 / 155193, which is incorporated herein by reference.

[0024] Examples of substrates that make up the substrate include glass, silicon, and film. The substrate constituting the base material 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. Furthermore, 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 Corning's Gorilla Glass. Additionally, materials described in Japanese Patent Publication Nos. 2010-86684, 2010-152809, and 2010-257492 can be used as transparent glass substrates.

[0026] When using a film substrate, it is preferable to use a film substrate that has low optical distortion and / or high transparency. Examples of such film substrates include polyethylene terephthalate (PET), polyethylene naphthalate, polycarbonate, triacetylcellulose, and cycloolefin polymers.

[0027] When manufacturing using a roll-to-roll method, a film substrate is preferred as the substrate. Furthermore, when manufacturing circuit wiring for a touch panel using a roll-to-roll method, the substrate is preferably a sheet-like resin composition.

[0028] Examples of conductive layers on a substrate include those commonly used in circuit wiring or touch panel wiring. As the conductive layer, from the viewpoint of conductivity and fine wire formation, 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 is preferred, a metal layer is more preferred, and a copper layer or a silver layer is even more preferred. The substrate may have a single conductive layer or two or more conductive layers. If there are two or more conductive layers, it is preferable that the conductive layers be made of different materials.

[0029] Examples of materials for the conductive layer include metals and conductive metal oxides. Examples of 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, "conductivity" means a volume resistivity of 1 × 10⁻⁶. 6 This means that the resistivity is less than Ωcm. The volume resistivity of a conductive metal oxide is 1 × 10⁻⁶. 4 A value less than Ωcm is preferable.

[0030] When manufacturing a resin pattern using a substrate having multiple conductive layers, it is preferable that at least one of the conductive layers contains a conductive metal oxide. The conductive layer is preferably an electrode pattern corresponding to the sensor in the viewing area used in a capacitive touch panel, or wiring for the peripheral extraction area. A preferred embodiment of the conductive layer is described, for example, in paragraph 0141 of International Publication No. 2018 / 155193, which is incorporated herein by reference.

[0031] A substrate having a conductive layer is preferably one having at least one of transparent electrodes and routing wiring. Such a substrate can be suitably used as a substrate for a touch panel. Transparent electrodes can function suitably as electrodes for touch panels. Preferably, transparent electrodes are composed of metal oxide films such as ITO (indium tin oxide) and IZO (indium zinc oxide), as well as metal meshes and metal nanowires such as silver nanowires. Examples of metal wires include those made of silver and copper. Among these, silver conductive materials such as silver mesh and silver nanowires are preferred.

[0032] Metal is preferred as the material for routing the wiring. Examples of metals used for wiring include gold, silver, copper, molybdenum, aluminum, titanium, chromium, zinc, and manganese, as well as alloys composed of two or more of these metallic elements. Copper, molybdenum, aluminum, or titanium are preferred materials for wiring, with copper being particularly preferred.

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

[0034] <Temporary support removal process> The method for manufacturing a laminate according to this disclosure preferably includes a temporary support peeling step for peeling off a temporary support between the bonding step and the exposure step. The method for peeling off the temporary support is not particularly limited, and a mechanism similar to the cover film peeling mechanism described in paragraphs 0161 to 0162 of Japanese Patent Application Publication No. 2010-072589 can be used.

[0035] <Exposure process> The method for manufacturing a laminate according to this disclosure includes an exposure step. The exposure process in the exposure stage is a patterned exposure process (also called "pattern exposure"), that is, an exposure process in which exposed and unexposed areas exist. The positional relationship between the exposed and unexposed areas in pattern exposure is not particularly restricted and can be adjusted as appropriate.

[0036] The detailed arrangement and specific size of the pattern in pattern exposure are not particularly limited. For example, 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 extraction wiring, it is preferable that at least a portion of the pattern (preferably the electrode pattern and / or extraction wiring portion of the touch panel) includes fine lines with a width of 20 μm or less, and more preferably fine lines with a width of 10 μm or less. Furthermore, from the viewpoint of better demonstrating the effects of this disclosure, the resulting resin pattern is preferably a resin pattern with a line width of 20 μm or less, more preferably a resin pattern with a line width of 10 μm or less, even more preferably a resin pattern with a line width of 8 μm or less, and particularly preferably a resin pattern with 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 emits light of a wavelength that can expose the photosensitive layer (for example, 365 nm or 405 nm). Specifically, 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 / cm². 2 ~200 mJ / cm 2 Preferably, 10 mJ / cm 2 ~100 mJ / cm 2 This is preferable. Preferred embodiments of the light source, exposure amount, and exposure method used for exposure are described, for example, in paragraphs 0146-0147 of International Publication No. 2018 / 155193, which are incorporated herein by reference.

[0038] In the exposure process, pattern exposure may be performed after peeling the temporary support from the transfer layer, or pattern exposure may be performed through the temporary support before peeling it off, 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 it may be exposed in close proximity without contact. If exposure is performed without peeling off the temporary support, the mask may be exposed in contact with the temporary support, or it may be exposed 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 adhering to the mask on exposure, it is preferable to perform pattern exposure without peeling off the temporary support. The exposure method can be appropriately selected and used from the contact exposure method in the case of contact exposure, and from the proximity exposure method, the lens system or mirror system projection exposure method, or the direct exposure method using an exposure laser, etc. in the case of non-contact exposure. In the case of lens system or mirror system projection exposure, an exposure machine with an appropriate numerical aperture (NA) of the lens can be used according to the required resolution and depth of field. In the direct exposure method, the image may be drawn directly onto the photosensitive layer, or reduced projection exposure may be performed onto the photosensitive layer via a lens. Furthermore, exposure may be performed not only in the atmosphere, but also under reduced pressure or vacuum, or with a liquid such as water interposed between the light source and the transfer layer. Furthermore, in the exposure process, from the viewpoint of resolution, it is preferable to bring the transfer layer and the mask into contact and perform the exposure treatment.

[0039] <Developing process> The method for manufacturing a laminate according to this disclosure includes a developing step. The development of the exposed photosensitive layer in the development process can be carried out using a developer solution. The developer is not particularly limited as long as it can remove the non-image portion of the photosensitive layer. For example, known developers such as the developer described in Japanese Patent Publication No. 5-72724 can be used. As the developer, an alkaline aqueous solution containing a compound with a pKa of 7 to 13 at a concentration of 0.05 mol / L to 5 mol / L (liter) is preferred. The developer may also contain a water-soluble organic solvent and / or a surfactant. Examples of alkaline compounds that may be contained in an alkaline aqueous solution include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, and choline (2-hydroxyethyltrimethylammonium hydroxide). As a developer, the developer described in paragraph 0194 of International Publication No. 2015 / 093271 is also preferred. A preferred developing method is, for example, the developing method described in paragraph 0195 of International Publication No. 2015 / 093271.

[0040] The development method is not particularly limited and may include paddle development, shower development, shower and spin development, and dip development. Shower development is a development process in which non-image areas are removed by spraying a developer solution onto the photosensitive layer after exposure using a shower. After the developing process, it is preferable to spray a cleaning agent with a shower and remove the developing residue by scrubbing with a brush. The temperature of the developer solution is not particularly restricted, but 20°C to 40°C is preferred.

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

[0042] <Other processes> The method for manufacturing a laminate according to this disclosure may include any steps other than those described above (other steps). For example, the following steps are listed, but are not limited to these steps. Furthermore, examples of exposure steps, development steps, and other steps applicable to the method for manufacturing a laminate according to this disclosure include the steps described in paragraphs 0035 to 0051 of Japanese Patent Application Publication No. 2006-23696.

[0043] <Application> The laminate manufactured by the manufacturing method of the laminate according to this disclosure can be applied to various devices. Examples of devices equipped with the laminate include input devices, which are preferably touch panels, and more preferably capacitive touch panels. Furthermore, the input device can be applied to display devices such as organic electroluminescent display devices and liquid crystal display devices. When the laminate is applied to a touch panel, it is preferable that the formed resin pattern be used as a protective film for touch panel electrodes or touch panel wiring.

[0044] <Photosensitive transfer material> The photosensitive transfer material used in the method for manufacturing a laminate according to this disclosure comprises a temporary support and a transfer layer including a photosensitive layer, and preferably comprises a temporary support, a transfer layer including a photosensitive layer, and a protective film in this order. Furthermore, the photosensitive transfer material used in this disclosure may have other layers, such as between the temporary support and the photosensitive layer, or between the photosensitive layer and the protective film. Furthermore, the photosensitive transfer material used in this disclosure preferably further comprises a thermoplastic resin layer and a water-soluble resin layer between the temporary support and the photosensitive layer. Furthermore, it is preferable that the transfer layer further comprises a thermoplastic resin layer and a water-soluble resin layer. The photosensitive transfer material used in this disclosure is preferably a roll-type photosensitive transfer material from the viewpoint of better exhibiting the effects of this disclosure.

[0045] Examples of the photosensitive transfer material used in this disclosure are shown below, but are not limited thereto. (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 configurations, the photosensitive layer is preferably a negative-type photosensitive layer. It is also preferable that the photosensitive layer is a colored resin layer. The photosensitive transfer material used in this disclosure is preferably used as a photosensitive transfer material for etching resists. When used as a photosensitive transfer material for etching resist, the configuration of the photosensitive transfer material is preferably one of the configurations described in (2) to (4) above.

[0046] In a photosensitive transfer material, if the photosensitive layer has an additional layer on the side opposite to the temporary support, the total thickness of the additional layer located on the side opposite to the temporary support is preferably 0.1% to 30%, and more preferably 0.1% to 20%, of the thickness of the photosensitive layer.

[0047] In the following, a photosensitive transfer material used in this disclosure will be described with reference to a specific embodiment.

[0048] Below, we will explain a photosensitive transfer material with an example. The photosensitive transfer material 20 shown in Figure 1 comprises, 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, although the photosensitive transfer material 20 shown in Figure 1 has a thermoplastic resin layer 13 and a water-soluble resin layer 15 arranged therein, the thermoplastic resin layer 13 and the water-soluble resin layer 15 do not necessarily have to be arranged. The following describes each element that constitutes the photosensitive transfer material.

[0049] [Temporary support] The photosensitive transfer material used in this disclosure has a temporary support. The temporary support is a peelable support that supports a photosensitive layer or a laminate containing a photosensitive layer.

[0050] The temporary support preferably has light transmittance, from the viewpoint of enabling exposure of the photosensitive layer through the temporary support when pattern exposure of the photosensitive layer. In this specification, "having light transmittance" means that the transmittance of light of the wavelength used for pattern 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, and more preferably 70% or more, of light at the wavelength used for pattern exposure (more preferably 365 nm). The transmittance of a photosensitive transfer material layer is the ratio of the intensity of the emitted light that passes through the layer to the intensity of the incident light when light is incident in a direction perpendicular to the main surface of the layer (thickness direction), and is measured using the MCPD Series manufactured by Otsuka Electronics Co., Ltd.

[0051] Examples of materials that make up the temporary support include glass substrates, resin films, and paper, with resin films being preferred from the viewpoint of strength, flexibility, and light transmittance. Examples of resin films include polyethylene terephthalate (PET) film, cellulose triacetate film, polystyrene film, and polycarbonate film. Among these, PET film is preferred, and biaxially oriented PET film is more preferred.

[0052] The thickness (layer thickness) of the temporary support is not particularly limited and should be selected according to the material, taking into account the strength as a support, the flexibility required for bonding with the circuit wiring substrate, and the light transmittance required in the initial exposure process. The thickness of the temporary support is preferably in the range of 5 μm to 100 μm, more preferably in the range of 10 μm to 50 μm, even more preferably in the range of 10 μm to 20 μm, and particularly preferably in the range of 10 μm to 16 μm, from the viewpoint of ease of handling and versatility. Furthermore, 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, from the viewpoint of defect suppression, resolution, and linearity of the resin pattern.

[0053] Furthermore, it is preferable that the film used as a temporary support is free from deformation such as wrinkles, scratches, or defects. From the viewpoint of pattern formation during pattern exposure via a temporary support and the transparency of the temporary support, it is preferable to have a small number of fine particles, foreign matter, defects, precipitates, etc., contained in the temporary support. The number of fine particles, foreign matter, or defects with a diameter of 1 μm or more is 50 per 10 mm. 2 The following is preferable: 10 pieces / 10mm 2 The following is more preferable: 3 pieces / 10mm 2 More preferably, the following is true: 0 pieces / 10mm 2 It is particularly preferable that this be the case.

[0054] From the viewpoint of defect suppression, resolution, and transparency of the temporary support in the resin pattern, it is preferable that the haze of the temporary support be 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 values ​​in this disclosure are measured using a haze meter (NDH-2000, manufactured by Nippon Denshoku Industries Co., Ltd.) in accordance with the method specified in JIS K 7105:1981.

[0055] A layer containing fine particles (a lubricant layer) may be provided on the surface of the temporary support to improve handling. The lubricant layer may be provided on one side of the temporary support or on both sides. The diameter of the particles in the lubricant layer can be, for example, 0.05 μm to 0.8 μm. The thickness of the lubricant layer can be, for example, 0.05 μm to 1.0 μm.

[0056] From the viewpoints of transportability, resin pattern defect suppression, and resolution, it is preferable that the arithmetic mean roughness Ra of the surface of the temporary support opposite to the photosensitive layer side be greater than or equal to the arithmetic mean roughness Ra of the surface of the temporary support on the photosensitive layer side. The arithmetic mean roughness Ra of the temporary support on the side opposite to 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 viewpoint of transportability, resin pattern defect suppression, and resolution. The arithmetic mean roughness Ra of the photosensitive layer side of the temporary support 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 viewpoint of peelability of the temporary support, defect suppression of the resin pattern, and resolution. Furthermore, the arithmetic mean roughness Ra of the side of the temporary support opposite to the photosensitive layer side is preferably 0 nm to 10 nm, and more preferably 0 nm to 5 nm, from the viewpoints of transportability, resin pattern defect suppression, and resolution.

[0057] The arithmetic mean roughness Ra of the surface of the temporary support or protective film in this disclosure shall be measured by the following method. Using a 3D optical profiler (New View7300, Zygo), the surface of the temporary support or protective film is measured under the following conditions to obtain the film's surface profile. For measurement and analysis, we use the Microscope Application of MetroPro ver8.3.2. Next, we display the Surface Map screen in the analysis software and obtain histogram data from the Surface Map screen. From the obtained histogram data, we calculate the arithmetic mean roughness and obtain the Ra value of the surface of the temporary support or protective film. If a temporary support or protective film is attached to a photosensitive layer, the temporary support or protective film should be peeled off from the photosensitive layer, and the Ra value of the peeled surface should be measured.

[0058] The peeling force of the temporary support, specifically the peeling force between the temporary support and the photosensitive layer or 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 the peeling of the temporary support caused by adhesion between stacked laminates when the wound laminate is transported again in a roll-to-roll manner.

[0059] The peeling force of the temporary support in this disclosure shall be measured as follows: A 200 nm thick copper layer is fabricated on a 100 μm thick polyethylene terephthalate (PET) film using the sputtering method to create a PET substrate with a copper layer. The protective film is peeled off the prepared photosensitive transfer material, and it is laminated onto the copper-layered PET substrate under the lamination conditions of a lamination 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) is attached to the surface of the temporary support, and then the laminate having at least the temporary support and the photosensitive layer on the copper-layered PET substrate is cut to 70 mm x 10 mm to prepare a sample. The PET substrate side of the above sample is fixed onto the sample stage. Using a tensile and compression testing machine (SV-55, manufactured by Imada Seisakusho Co., Ltd.), the tape is pulled at 5.5 mm / second in a 180-degree direction to delaminate the photosensitive layer or thermoplastic resin layer from the temporary support, and the force required for delamination (peel force) and adhesion force are measured.

[0060] Preferred embodiments of the temporary support are described, for example, in paragraphs 0017-0018 of Japanese Patent Publication No. 2014-85643, paragraphs 0019-0026 of Japanese Patent Publication No. 2016-27363, paragraphs 0041-0057 of International Publication No. 2012 / 081680, paragraphs 0029-0040 of International Publication No. 2018 / 179370, and paragraphs 0012-0032 of Japanese Patent Publication No. 2019-101405, the contents of which are incorporated herein by reference.

[0061] [Photosensitive layer] The photosensitive transfer material used in this disclosure has a photosensitive layer. The photosensitive layer is preferably a negative-type 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% to 90% by mass of the alkali-soluble resin; 5% to 70% by mass of the ethylenically unsaturated compound; and 0.01% to 20% by mass of the photopolymerization initiator. The following explains each component in order.

[0062] <<Polymerizable compounds>> The photosensitive layer preferably contains a polymerizable compound. In this specification, "polymerizable compound" means a compound that polymerizes upon the action of a photopolymerization initiator described later, and is different from the alkali-soluble resin described above.

[0063] The polymerizable groups in polymerizable compounds are not particularly limited as long as they are groups that participate in polymerization reactions. Examples include groups having ethylenically unsaturated groups such as vinyl groups, acryloyl groups, methacryloyl groups, styryl groups, and maleimide groups; and groups having cationic polymerizable groups such as epoxy groups and oxetane groups. The polymerizable group is preferably a group having an ethylenically unsaturated group, and more preferably an acryloyl group or a methacryloyl group. Furthermore, the polymerizable compound preferably contains an ethylenically unsaturated compound, and more preferably contains a (meth)acrylate compound.

[0064] The photosensitive layer preferably contains a bifunctional or higher polymerizable compound (polyfunctional polymerizable compound) and more preferably a trifunctional or higher polymerizable compound, from the viewpoint of resolution and pattern formation. Here, a bifunctional or more polymerizable compound refers to a compound that has two or more polymerizable groups in a single molecule. Furthermore, in terms of excellent resolution and exfoliation properties, it is preferable that the number of polymerizable groups in a single molecule of the polymerizable compound be six or less.

[0065] The photosensitive layer preferably contains a bifunctional or trifunctional ethylenically unsaturated compound, and more preferably a bifunctional ethylenically unsaturated compound, in that it provides a better balance of photosensitivity, resolution, and peelability of the photosensitive layer. In the photosensitive layer, the content of difunctional or trifunctional ethylenically unsaturated compounds relative to the total content of ethylenically unsaturated compounds is preferably 60% by mass or more, more preferably over 70% by mass, and even more preferably 90% by mass or more, from the viewpoint of excellent peelability. There is no particular upper limit, and it 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] 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, from the viewpoint of resolution and pattern formation. Preferred polymerizable compounds having a polyalkylene oxide structure include polyalkylene glycol di(meth)acrylates, which will be discussed later.

[0067] -Ethylene-unsaturated compound B1- The photosensitive layer preferably contains an ethylenically unsaturated compound B1 having an aromatic ring and two ethylenically unsaturated groups. Ethylenelycolonized compound B1 is a difunctional ethylenically unsaturated compound having one or more aromatic rings in one molecule, among the ethylenically unsaturated compounds described above.

[0068] In the photosensitive layer, the mass ratio of the ethylenically unsaturated compound B1 content to the ethylenically unsaturated compound content 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. There is no particular upper limit, 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] Examples of aromatic rings in ethylenically unsaturated compound B1 include aromatic hydrocarbon rings such as benzene, naphthalene, and anthracene rings, aromatic heterocycles such as thiophene, furan, pyrrole, imidazole, triazole, and pyridine rings, and fused rings thereof. Aromatic hydrocarbon rings are preferred, and benzene rings are more preferred. The above aromatic rings may have substituents. The ethylenically unsaturated compound B1 may have only one aromatic ring or may have two or more aromatic rings.

[0070] Ethylene-unsaturated compound B1 is preferably a bisphenol structure because it improves resolution by suppressing swelling of the photosensitive layer due to the developer. Examples of bisphenol structures include the bisphenol A structure derived from bisphenol A (2,2-bis(4-hydroxyphenyl)propane), the bisphenol F structure derived from bisphenol F (2,2-bis(4-hydroxyphenyl)methane), and the bisphenol B structure derived from bisphenol B (2,2-bis(4-hydroxyphenyl)butane), with the bisphenol A structure being preferred.

[0071] Examples of ethylenically unsaturated compounds B1 having a bisphenol structure include compounds having a bisphenol structure and two polymerizable groups (preferably (meth)acryloyl groups) bonded to both ends of the bisphenol structure. The two polymerizable groups at both ends of the bisphenol structure may be directly bonded, or they may be bonded via one or more alkylene oxy groups. The alkylene oxy groups added to both ends of the bisphenol structure are preferably ethylene oxy groups or propylene oxy groups, with ethylene oxy groups being more preferred. The number of alkylene oxy groups added to the bisphenol structure is not particularly limited, but 4 to 16 per molecule is preferred, and 6 to 14 are more preferred. The ethylenically unsaturated compound B1 having a bisphenol structure is described in paragraphs 0072 to 0080 of Japanese Patent Publication No. 2016-224162, and the contents described in this publication 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 Industry Co., Ltd.), and 2,2-bis(4-(methacryloxydodecaethoxy Examples include tetrapropoxy)phenyl)propane (FA-3200MY, manufactured by Hitachi Chemical Co., Ltd.), 2,2-bis(4-(methacryloxypentadecaethoxy)phenyl)propane (BPE-1300, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), 2,2-bis(4-(methacryloxydiethoxy)phenyl)propane (BPE-200, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), and ethoxylated (10)bisphenol A diacrylate (NK ester A-BPE-10, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.).

[0073] As the ethylenically unsaturated compound B1, the 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 are integers from 1 to 39, and n1+n3 is an integer from 2 to 40, and n2 and n4 each independently are integers from 0 to 29, and n2+n4 is an integer from 0 to 30, and the sequence of repeating units -(AO)- and -(BO)- may be random or in a block. In the case of a block, either -(AO)- or -(BO)- may be on the bisphenol structure side. In one embodiment, n1+n2+n3+n4 is preferably an integer between 2 and 20, more preferably an integer between 2 and 16, and even more preferably an integer between 4 and 12. Also, n2+n4 is preferably an integer between 0 and 10, more preferably an integer between 0 and 4, even more preferably an integer between 0 and 2, and particularly preferably 0.

[0076] Ethylene-unsaturated compound B1 may be used alone or in combination of two or more types. In the photosensitive layer, the content of ethylenically unsaturated compound B1 is preferably 10% by mass or more, and more preferably 20% by mass or more, relative to the total mass of the photosensitive layer, from the viewpoint of superior resolution. There is no particular upper limit, but from the viewpoint of transferability and edge fusion (the phenomenon in which components in the photosensitive layer seep out from the edges of the photosensitive transfer material), it is preferably 70% by mass or less, and more preferably 60% by mass or less.

[0077] The photosensitive layer may contain ethylenically unsaturated compounds other than the ethylenically unsaturated compound B1 described above. Other ethylenically unsaturated compounds besides ethylenically unsaturated compound B1 are not particularly limited and can be appropriately selected from known compounds. Examples include compounds having one ethylenically unsaturated group in one molecule (monofunctional ethylenically unsaturated compounds), difunctional ethylenically unsaturated compounds without aromatic rings, and trifunctional or more ethylenically unsaturated compounds.

[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 that do not have an 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 Industry Co., Ltd.), tricyclodecane dimethanol dimethacrylate (DCP, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), 1,9-nonanediol diacrylate (A-NOD-N, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), 1,6-hexanediol diacrylate (A-HD-N, manufactured by Shin-Nakamura Chemical Industry 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. Examples of commercially available products include 8UX-015A (manufactured by Taisei Fine Chemical Co., Ltd.), UA-32P (manufactured by Shin Nakamura Chemical Industry Co., Ltd.), and UA-1100H (manufactured by Shin Nakamura Chemical Industry Co., Ltd.).

[0080] Examples of ethylenically unsaturated compounds with three or more functions include dipentaerythritol (tri / tetra / penta / hexa)(meth)acrylate, pentaerythritol (tri / tetra)(meth)acrylate, trimethylolpropane tri(meth)acrylate, ditrimethylolpropanetetra(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-mentioned ethylenically unsaturated compound B1 and a trifunctional or higher ethylenically unsaturated compound, and more preferably contains the above-mentioned ethylenically unsaturated compound B1 and two or more trifunctional or higher ethylenically unsaturated compounds. In this case, the mass ratio of the ethylenically unsaturated compound B1 to the trifunctional or higher ethylenically unsaturated compounds is preferably (total mass of ethylenically unsaturated compound B1):(total mass of trifunctional or higher ethylenically unsaturated compounds) = 1:1 to 5:1, more preferably 1.2:1 to 4:1, and even more preferably 1.5:1 to 3:1. In one embodiment, the photosensitive layer preferably contains the ethylenically unsaturated compound B1 described above and two or more trifunctional ethylenically unsaturated compounds.

[0081] Examples of alkylene oxide modified products of ethylenically unsaturated compounds with three or more functions include caprolactone-modified (meth)acrylate compounds (such as KAYARAD® DPCA-20 manufactured by Nippon Kayaku Co., Ltd., and A-9300-1CL manufactured by Shin Nakamura Chemical Industry Co., Ltd.), and alkylene oxide-modified (meth)acrylate compounds (such as KAYARAD RP-1040 manufactured by Nippon Kayaku Co., Ltd., ATM-35E and A-9300 manufactured by Shin Nakamura Chemical Industry Co., Ltd., and EBECRYL® manufactured by Daicel Ornex). Examples include 135, ethoxylated glycerin triacrylate (A-GLY-9E, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), Arronix (registered trademark) TO-2349 (manufactured by Toagosei Co., Ltd.), Arronix M-520 (manufactured by Toagosei Co., Ltd.), and Arronix M-510 (manufactured by Toagosei Co., Ltd.).

[0082] Furthermore, as an ethylenically unsaturated compound other than ethylenically unsaturated compound B1, an ethylenically unsaturated compound having an acid group as described in paragraphs 0025 to 0030 of Japanese Patent Application Publication No. 2004-239942 may be used.

[0083] From the viewpoint of resolution and linearity, the ratio Mm / Mb of the content of ethylenically unsaturated compounds in the photosensitive layer to the content of alkali-soluble resin is preferably 1.0 or less, more preferably 0.9 or less, and particularly preferably 0.5 to 0.9. Furthermore, the ethylenically unsaturated compound in the photosensitive layer preferably contains a (meth)acrylic compound from the viewpoint of curability and resolution. Furthermore, from the viewpoint of curability, resolution, and linearity, the ethylenically unsaturated compound in the photosensitive layer preferably contains a (meth)acrylic compound, and the content of the acrylic compound relative to the total mass of the (meth)acrylic compound contained in the photosensitive layer is 60% by mass or less.

[0084] The molecular weight (or weight-average molecular weight (Mw) if there is a distribution) of the ethylenically unsaturated compound containing ethylenically unsaturated compound B1 is preferably 200 to 3,000, more preferably 280 to 2,200, and even more preferably 300 to 2,200.

[0085] Ethylene-unsaturated compounds may be used individually or in combination of two or more. The content of ethylenically unsaturated compounds 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 upon exposure to active light 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 photopolymerization initiators include photoradical polymerization initiators and photocationic polymerization initiators. In particular, for the photosensitive layer, a photoradical polymerization initiator is preferred from the viewpoint of resolution and pattern formation.

[0087] Examples of photoradical polymerization initiators include photopolymerization initiators having an oxime ester structure, photopolymerization initiators having an α-aminoalkylphenone structure, photopolymerization initiators having an α-hydroxyalkylphenone structure, photopolymerization initiators having an acylphosphine oxide structure, photopolymerization initiators having an N-phenylglycine structure, and biimidazole compounds.

[0088] As photoradical polymerization initiators, for example, polymerization initiators described in paragraphs 0031 to 0042 of Japanese Patent Publication No. 2011-95716 and paragraphs 0064 to 0081 of Japanese Patent Publication No. 2015-14783 may be used.

[0089] Examples of photoradical polymerization initiators include ethyl dimethylaminobenzoate (DBE, CAS No. 10287-53-3), benzoin methyl ether, anisyl (p,p'-dimethoxybenzyl), TAZ-110 (trade name: manufactured by Midori Chemical Co., Ltd.), benzophenone, TAZ-111 (trade name: manufactured by Midori Chemical Co., Ltd.), Irgacure OXE01, OXE02, OXE03, OXE04 (manufactured by BASF), Omnirad 651 and 369 (trade name: manufactured by IGM Resins BV), and 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.).

[0090] Examples of commercially available photoradical polymerization initiators include 1-[4-(phenylthio)phenyl]-1,2-octanedione-2-(O-benzoyl oxime) (trade name: IRGACURE® OXE-01, manufactured by BASF), 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]ethanone-1-(O-acetyl oxime) (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 (manufactured by IGM Resins BV), 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)benzyl]phenyl}-2-methylpropan-1-one (product name: Omnirad 127, manufactured by IGM Resins BV), 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone-1 (product name: Omnirad 369, manufactured by IGM Resins BV), 2-hydroxy-2-methyl-1-phenylpropan-1-one (product name: Omnirad 1173, manufactured by IGM Resins BV), 1-hydroxycyclohexylphenyl ketone (product name: Omnirad 184, manufactured by IGM Resins BV), 2,2-dimethoxy-1,2-diphenylethane-1-one (product name: Omnirad 651, manufactured by IGM Resins (Manufactured by BV), 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (Trade name: Omnirad TPO H, manufactured by IGM Resins BV), bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (Trade name: Omnirad 819, manufactured by IGM Resins BV)Examples include oxime ester-based photopolymerization initiators (product 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) (product name: B-CIM, manufactured by Hampford), and 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer (product name: BCTB, manufactured by Tokyo Chemical Industry Co., Ltd.).

[0091] A photocationic polymerization initiator (photoacid generator) is a compound that generates acid upon receiving active light. While compounds that are sensitive to active light with a wavelength of 300 nm or higher, preferably 300-450 nm, and generate acid are preferred as photocationic polymerization initiators, their chemical structure is not limited. Furthermore, photocationic polymerization initiators that are not directly sensitive to active light with a wavelength of 300 nm or higher can also be preferably used in combination with a sensitizer, provided they become sensitive to active light with a wavelength of 300 nm or higher and generate acid. As the photocationic polymerization initiator, a photocationic polymerization initiator that generates an acid with a pKa of 4 or less is preferred, a photocationic polymerization initiator that generates an acid with a pKa of 3 or less is more preferred, and a photocationic polymerization initiator that generates an acid with a pKa of 2 or less is particularly preferred. There is no specific lower limit for the pKa, but for example, -10.0 or higher is preferred.

[0092] Examples of photocationic polymerization initiators include ionic photocationic polymerization initiators and nonionic photocationic polymerization initiators. Examples of ionic photocationic polymerization initiators include onium salt compounds such as diaryliodonium salts and triarylsulfonium salts, as well as quaternary ammonium salts. As the ionic photocationic polymerization initiator, the ionic photocationic polymerization initiator described in paragraphs 0114 to 0133 of Japanese Patent Application Publication No. 2014-85643 may be used.

[0093] Examples of nonionic photocationic polymerization initiators include trichloromethyl-s-triazines, diazomethane compounds, imidosulfonate compounds, and oximesulfonate compounds. For trichloromethyl-s-triazines, diazomethane compounds, and imidosulfonate compounds, compounds described in paragraphs 0083 to 0088 of Japanese Patent Publication No. 2011-221494 may be used. For oximesulfonate compounds, compounds described in paragraphs 0084 to 0088 of International Publication No. 2018 / 179640 may be used.

[0094] The photosensitive layer may contain one type of photopolymerization initiator alone, or it may contain two or more types. 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, based on the total mass of the photosensitive layer. There is no particular upper limit, but is preferably 10% by mass or less, and more preferably 5% by mass or less, based on the total mass of the photosensitive layer.

[0095] <<Alkali-soluble resin>> The photosensitive layer preferably contains an alkali-soluble resin. In this specification, "alkaline soluble" means that the solubility of sodium carbonate in 100 g of a 1% by mass aqueous solution at a liquid temperature of 22°C is 0.1 g or more. There are no particular restrictions on the alkali-soluble resin; for example, known alkali-soluble resins used in etching resists are preferred. Furthermore, the alkali-soluble resin is preferably a binder polymer. The alkali-soluble resin is preferably an alkali-soluble resin having an acidic group. Among these, polymer A, described later, is preferred as the alkali-soluble resin.

[0096] -polymerizationA- The alkali-soluble resin preferably contains polymer A. The acid value of polymer A is preferably 220 mg KOH / g or less, more preferably less than 200 mg KOH / g, and even more preferably less than 190 mg KOH / g, in order to suppress swelling of the photosensitive layer by the developer and thereby improve resolution. The lower limit of the acid value of polymer A is not particularly limited, but from the standpoint of superior developability, it is preferably 60 mg KOH / g or higher, more preferably 120 mg KOH / g or higher, even more preferably 150 mg KOH / g or higher, and particularly preferably 170 mg KOH / g or higher.

[0097] The acid value is the mass [mg] of potassium hydroxide required to neutralize 1g of the 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 can be adjusted by the types of constituent units that make up polymer A and the content of constituent units that contain acid groups.

[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 preferable from the viewpoint of improving resolution and developability. A weight-average molecular weight of 100,000 or less is more preferable, 60,000 or less is even more preferable, and 50,000 or less is particularly preferable. On the other hand, a weight-average molecular weight of 5,000 or more is preferable from the viewpoint of controlling the properties of the developed aggregates and the properties of the unexposed film, such as edge fusing and cut-tip properties, when used as a photosensitive resin laminate. A weight-average molecular weight of 10,000 or more is more preferable, 20,000 or more is even more preferable, and 30,000 or more is particularly preferable. Edge fusing refers to the degree to which the photosensitive layer tends to protrude from the end face of a roll when the photosensitive transfer material is wound into a roll. Cut-tip properties refer to the degree to which chips tend to fly off when the unexposed film is cut with a cutter. If this chip adheres to the upper surface of a photosensitive resin laminate, it will be transferred to the mask during subsequent exposure processes, causing defective products. The degree of dispersion 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 still more preferably 1.0 to 3.0. In this disclosure, the molecular weight is a value measured using gel permeation chromatography. The degree of dispersion is the ratio of the weight-average molecular weight to the number-average molecular weight (weight-average molecular weight / number-average molecular weight).

[0099] The photosensitive layer preferably contains monomer components having aromatic hydrocarbon groups as polymer A, from the viewpoint of suppressing line width thickening and deterioration of resolution when the focal position shifts during exposure. Examples of such aromatic hydrocarbon groups include substituted or unsubstituted phenyl groups and substituted or unsubstituted aralkyl groups. The content of monomer components having aromatic hydrocarbon groups 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. There is no particular upper limit, but it is preferably 95% by mass or less, more preferably 85% by mass or less. When polymer A contains multiple types, the content of monomer components having aromatic hydrocarbon groups was determined as the weight average.

[0100] Examples of monomers having the aromatic hydrocarbon group include monomers 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, monomers having an aralkyl group or styrene are 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% to 50% by mass, more preferably 25% to 45% by mass, even more preferably 30% to 40% by mass, and particularly preferably 30% to 35% by mass, based on the total mass of all monomer components.

[0101] Examples of aralkyl groups include substituted or unsubstituted phenylalkyl groups (excluding benzyl groups) and substituted or unsubstituted benzyl groups, with substituted or unsubstituted benzyl groups being preferred.

[0102] Examples of monomers having a phenylalkyl group include phenylethyl (meth)acrylate.

[0103] Examples of monomers having a benzyl group include (meth)acrylates having a benzyl group, such as benzyl (meth)acrylate and chlorobenzyl (meth)acrylate; and vinyl monomers having a benzyl group, such as vinylbenzyl chloride and vinylbenzyl alcohol. Among these, benzyl (meth)acrylate is preferred. In one embodiment, when the monomer component having an aromatic hydrocarbon group in polymer A is benzyl (meth)acrylate, the content of the benzyl (meth)acrylate monomer component is preferably 50% to 95% by mass, more preferably 60% to 90% by mass, even more preferably 70% to 90% by mass, and particularly preferably 75% to 90% by mass, based on the total mass of all monomer components.

[0104] Polymer A containing a monomer component having an aromatic hydrocarbon group is preferably obtained by polymerizing the monomer having an aromatic hydrocarbon group with at least one of the first monomers described later and / or at least one of the second monomers described later.

[0105] Polymer A, which does not contain monomer components having aromatic hydrocarbon groups, is preferably obtained by polymerizing at least one of the first monomers described later, and more preferably by copolymerizing at least one of the first monomers with at least one of the second monomers described later.

[0106] The first monomer is a monomer having a carboxyl group in its 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 semi-ester. Among these, (meth)acrylic acid is preferred. The content of the first monomer in polymer A is preferably 5% to 50% by mass, more preferably 10% to 40% by mass, and even more preferably 15% to 30% by mass, based on the total mass of all monomer components.

[0107] The copolymerization ratio of the first monomer is preferably 10% to 50% by mass, based on the total mass of all monomer components. A copolymerization ratio of 10% by mass or more is preferable from the viewpoint of exhibiting good developability and controlling edge fusing, 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 preferable from the viewpoint of high resolution and tail shape of the resist pattern, and further from the viewpoint of chemical resistance of the resist pattern, and from these viewpoints, more preferably 35% by mass or less, even more preferably 30% by mass or less, and particularly preferably 27% by mass or less.

[0108] The second monomer is non-acidic and has at least one polymerizable unsaturated group in its molecule. Examples of the second monomer include (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, cyclohexyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate; esters of vinyl alcohols such as vinyl acetate; and (meth)acrylonitrile. Among these, methyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and n-butyl (meth)acrylate are preferred, and methyl (meth)acrylate is particularly preferred. The content of the second monomer in polymer A is preferably 5% to 60% by mass, more preferably 15% to 50% by mass, and even more preferably 20% to 45% by mass, based on the total mass of all monomer components.

[0109] It is preferable to include monomers having aralkyl groups and / or styrene as monomers from the viewpoint of suppressing line width thickening and deterioration of resolution when the focal position shifts during exposure. For example, copolymers containing methacrylic acid, benzyl methacrylate and styrene, and copolymers containing methacrylic acid, methyl methacrylate and benzyl methacrylate and styrene are preferred. In one embodiment, polymer A is preferably a polymer containing 25% to 40% by mass of monomer components having aromatic hydrocarbon groups, 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 monomer components having aromatic hydrocarbon groups and 10% to 25% by mass of a first monomer component.

[0110] Polymer A may have a linear, branched, or alicyclic structure in its side chains. Branched or alicyclic structures can be introduced into the side chains of polymer A by using monomers containing groups with branched or alicyclic structures in their side chains. The groups with alicyclic structures may be monocyclic or polycyclic. Specific examples of monomers containing a group having a branched structure in its side chain include, for example, i-propyl (meth)acrylate, i-butyl (meth)acrylate, s-butyl (meth)acrylate, t-butyl (meth)acrylate, i-amyl (meth)acrylate, t-amyl (meth)acrylate, sec-iso-amyl (meth)acrylate, 2-octyl (meth)acrylate, 3-octyl (meth)acrylate, and t-octyl (meth)acrylate. Among these, i-propyl (meth)acrylate, i-butyl (meth)acrylate, or t-butyl methacrylate are preferred, and i-propyl methacrylate or t-butyl methacrylate are more preferred. Monomers containing a group with an alicyclic structure in its side chain include monomers having a monocyclic aliphatic hydrocarbon group, monomers having a polycyclic aliphatic hydrocarbon group, and (meth)acrylates having an alicyclic hydrocarbon group with 5 to 20 carbon atoms. More specific examples include (meth)acrylic acid (bicyclo[2.2.1]heptyl-2), (meth)acrylic acid-1-adamantyl, (meth)acrylic acid-2-adamantyl, (meth)acrylic acid-3-methyl-1-adamantyl, (meth)acrylic acid-3,5-dimethyl-1-adamantyl, (meth)acrylic acid-3-ethyladamantyl, (meth)acrylic acid-3-methyl-5-ethyl-1-adamantyl, (meth)acrylic acid-3,5,8-triethyl-1-adamantyl, (meth)acrylic acid-3,5-dimethyl-8-ethyl-1-adamantyl, (meth)acrylic acid-2-methyl-2-adamantyl, (meth)acrylic acid-2-ethyl-2-adamantyl, (meth)acrylic acid-3-Hy- Examples include droxy-1-adamantyl, 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, fentyl (meth)acrylate, 2,2,5-trimethylcyclohexyl (meth)acrylate, and cyclohexyl (meth)acrylate.Among these (meth)acrylic acid esters, cyclohexyl (meth)acrylate, (nor)bornyl (meth)acrylate, isobornyl (meth)acrylate, 1-adamantyl (meth)acrylate, 2-adamantyl (meth)acrylate, phenthyl (meth)acrylate, 1-menthyl (meth)acrylate, or tricyclodecane (meth)acrylate are preferred, and cyclohexyl (meth)acrylate, (nor)bornyl (meth)acrylate, isobornyl (meth)acrylate, 2-adamantyl (meth)acrylate, or tricyclodecane (meth)acrylate are particularly preferred.

[0111] Polymer A can be used alone or in a mixture of two or more types. When using a mixture of two or more types, it is preferable to use a mixture of two types of polymer A containing monomer components having aromatic hydrocarbon groups, or to use a mixture of polymer A containing monomer components having aromatic hydrocarbon groups and polymer A not containing monomer components having aromatic hydrocarbon groups. In the latter case, the proportion of polymer A containing monomer components having aromatic hydrocarbon groups is preferably 50% by mass or more, more preferably 70% by mass or more, more preferably 80% by mass or more, and more preferably 90% by mass or more, relative to the total amount of polymer A.

[0112] The synthesis of polymer A is preferably carried out by diluting one or more monomers described above with a solvent such as acetone, methyl ethyl ketone, or isopropanol, adding an appropriate amount of a radical polymerization initiator such as benzoyl peroxide or azoisobutyronitrile to the solution, and then heating and stirring. In some cases, the synthesis may be carried out by adding a portion of the mixture dropwise to the reaction solution. After the reaction is complete, the solvent may be further added to adjust the concentration to the desired level. In addition to solution polymerization, bulk polymerization, suspension polymerization, or emulsion polymerization may also be used as synthesis methods.

[0113] The glass transition temperature (Tg) of polymer A is preferably 30°C or higher and 135°C or lower. By using polymer A having a Tg of 135°C or lower in the photosensitive layer, line width thickening and deterioration of resolution when the focal position shifts during exposure can be suppressed. From this viewpoint, the Tg of 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 polymer A having a Tg of 30°C or higher is preferable from the viewpoint of improving edge fusing resistance. From this viewpoint, the Tg of 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 resins other than alkali-soluble resins. Examples of resins other than alkali-soluble resins include acrylic resins, styrene-acrylic copolymers (provided that the styrene content is 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] Alkali-soluble resins can be used individually or in mixtures of two or more types. The ratio of alkali-soluble resin to the total mass of the photosensitive layer is preferably in the range of 10% to 90% by mass, more preferably 30% to 70% by mass, and even more preferably 40% to 60% by mass. Setting the ratio of alkali-soluble resin to the photosensitive layer to 90% by mass or less is preferable from the viewpoint of controlling the development time. On the other hand, setting the ratio of alkali-soluble resin to the photosensitive layer to 10% by mass or more is preferable from the viewpoint of improving edge fusing resistance.

[0116] <<Dye>> The photosensitive layer preferably contains a dye, from the viewpoint of visibility of exposed and unexposed areas, pattern visibility after development, and resolution. More preferably, it contains a dye (also simply called "dye N") whose maximum absorption wavelength in the wavelength range of 400 nm to 780 nm during color development is 450 nm or higher, and whose maximum absorption wavelength changes with acid, base, or radical. Although the detailed mechanism is unknown, the presence of dye N improves adhesion with adjacent layers (e.g., temporary support and first resin layer) and results in superior resolution.

[0117] In this specification, the phrase "the maximum absorption wavelength of a dye changes due to an acid, base, or radical" may mean any of the following: a dye in a colored state becomes decolorized due to an acid, base, or radical; a dye in a decolorized state becomes colored due to an acid, base, or radical; or a dye in a colored state changes to a colored state of another hue. Specifically, the dye N may be a compound that changes from a decolorized state to a colored state upon exposure, or a compound that changes from a colored state to a decolorized state upon exposure. In this case, the dye may change its colored or decolorized state due to the generation and action of acids, bases, or radicals within the photosensitive layer upon exposure, or it may change its colored or decolorized state due to a change in the state within the photosensitive layer (e.g., pH) caused by acids, bases, or radicals. Furthermore, the dye may change its colored or decolorized state upon direct stimulation by acids, bases, or radicals without exposure.

[0118] In particular, from the viewpoint of visibility and resolution of the exposed and unexposed areas, the dye N is preferably a dye whose maximum absorption wavelength changes with acid or radicals, and more preferably a dye whose maximum absorption wavelength changes with radicals. From the viewpoint of visibility and resolution of the exposed and unexposed areas, the photosensitive layer preferably contains both a dye N whose maximum absorption wavelength changes due to radicals, and a photoradical polymerization initiator. Furthermore, from the viewpoint of visibility between the exposed and unexposed areas, it is preferable that the dye N is a dye that develops color in response to an acid, base, or radical.

[0119] An example of the color development mechanism of dye N in this disclosure is a configuration in which a photoradical polymerization initiator, a photocationic polymerization initiator (photoacid generator), or a photobase generator is added to a photosensitive layer, and after exposure, radicals, acids, or bases generated from the photoradical polymerization initiator, photocationic polymerization initiator, or photobase generator cause a radical-reactive dye, an acid-reactive dye, or a base-reactive dye (e.g., a leuco dye) to develop color.

[0120] From the viewpoint of visibility of the exposed and unexposed areas, the maximum absorption wavelength of dye N in the wavelength range of 400 nm to 780 nm during color development is preferably 550 nm or higher, more preferably 550 nm to 700 nm, and even more preferably 550 nm to 650 nm. Furthermore, the dye N may have only one maximum absorption wavelength in the wavelength range of 400 nm to 780 nm during color development, or it may have two or more. If the dye N has two or more maximum absorption wavelengths in the wavelength range of 400 nm to 780 nm during color development, the maximum absorption wavelength with the highest absorbance among the two or more maximum absorption wavelengths should be 450 nm or higher.

[0121] The maximum absorption wavelength of dye N is obtained by measuring the transmission spectrum of a solution containing dye N (at a temperature of 25°C) in the range of 400 nm to 780 nm using a spectrophotometer: UV3100 (manufactured by Shimadzu Corporation) in an atmospheric environment, and detecting the wavelength at which the light intensity is minimum (maximum absorption wavelength).

[0122] Examples of dyes that develop or decolorize upon exposure include leuco compounds. Examples of dyes that decolorize upon exposure include leuco compounds, diarylmethane dyes, oxazine dyes, xanthene dyes, iminonaphthoquinone dyes, azomethine dyes, and anthraquinone dyes. As for the dye N, a leuco compound is preferred from the viewpoint of visibility between the exposed and unexposed areas.

[0123] Examples of leuco compounds include leuco compounds having a triarylmethane skeleton (triarylmethane dyes), leuco compounds having a spiropyran skeleton (spiropyran dyes), leuco compounds having a fluorane skeleton (fluorane dyes), leuco compounds having a diarylmethane skeleton (diarylmethane dyes), leuco compounds having a rhodamine lactam skeleton (rhodamine lactam dyes), leuco compounds having an indolylphthalide skeleton (indolylphthalide dyes), and leuco compounds having a leucoauramine skeleton (leucoauramine dyes). Among these, triarylmethane-based dyes or fluorane-based dyes are preferred, and leuco compounds having a triphenylmethane skeleton (triphenylmethane-based dyes) or fluorane-based dyes are more preferred.

[0124] As a leuco compound, it is preferable to have a lactone ring, sultine ring, or sultone ring from the viewpoint of visibility between the exposed and unexposed areas. This allows the lactone ring, sultine ring, or sultone ring of the leuco compound to react with radicals generated from a photoradical polymerization initiator or acids generated from a photocationic polymerization initiator, thereby changing the leuco compound to a closed state and decolorizing it, or changing the leuco compound to an open state and developing color. As a leuco compound, it is preferable to have a lactone ring, sultine ring, or sultone ring, and the lactone ring, sultine ring, or sultone ring opens and develops color in response to radicals or acids, and more preferably a lactone ring, and the lactone ring opens and develops color in response to radicals or acids.

[0125] Examples of pigment N include the following dyes and leuco compounds. Specific examples of dyes among pigment N include Brilliant Green, Ethyl Violet, Methyl Green, Crystal Violet, Basic Fuchsine, Methyl Violet 2B, Quinaldine Red, Rose Bengal, Methanyl Yellow, Thymol Sulfophthalein, Xylenol Blue, Methyl Orange, Paramethyl Red, Congofred, Benzopurine 4B, α-Naphthyl Red, Nile Blue 2B, Nile Blue A, Methyl Violet, Malachite Green, Parafuchsine, Victoria Pure Blue-Naphthalene Sulfonate, Victoria Pure Blue BOH (manufactured by Hodogaya Chemical Co., Ltd.), Oil Blue #603 (manufactured by Orient Chemical Co., Ltd.), Oil Pink #312 (manufactured by Orient Chemical Co., Ltd.), Oil Red 5B (manufactured by Orient Chemical Co., Ltd.), Oil Scarlet #308 (Orient Examples include: Oil Red OG (manufactured by Orient Chemical Industry Co., Ltd.), Oil Red RR (manufactured by Orient Chemical Industry Co., Ltd.), Oil Green #502 (manufactured by Orient Chemical Industry Co., Ltd.), Spiron Red BEH Special (manufactured by Hodogaya Chemical Industry Co., Ltd.), m-Cresol Purple, Cresol Red, Rhodamine B, Rhodamine 6G, Sulforhodamine B, Auramine, 4-p-diethylaminophenyliminonaphthoquinone, 2-carboxyanilino-4-p-diethylaminophenyliminonaphthoquinone, 2-carboxystearylamino-4-pN,N-bis(hydroxyethyl)aminophenyliminonaphthoquinone, 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 pigment N include p,p',p''-hexamethyltriaminotriphenylmethane (leucocrystal violet), Pergascript Blue SRB (Ciba-Geigy), crystal violet lactone, malachite green lactone, benzoylleucomethylene blue, 2-(N-phenyl-N-methylamino)-6-(Np-tolyl-N-ethyl)aminofluorane, 2-anilino-3-methyl-6-(N-ethyl-p-toluidino)fluorane, 3,6-dimethoxyfluorane, 3-(N,N-diethylamino)-5-methyl-7-(N,N-dibenzylamino)fluorane, and 3-(N-cyclohexyl-N-methylamino)-6 -Methyl-7-anilinofluorane, 3-(N,N-diethylamino)-6-methyl-7-anilinofluorane, 3-(N,N-diethylamino)-6-methyl-7-xylidinofluorane, 3-(N,N-diethylamino)-6-methyl-7-chlorofluorane, 3-(N,N-diethylamino)-6-methoxy-7-aminofluorane, 3-(N,N-diethylamino)-7-(4-chloroanilino)fluorane, 3-(N,N-diethylamino)-7-chlorofluorane, 3-(N,N-diethylamino) (Tylamino)-7-benzylaminofluorane, 3-(N,N-diethylamino)-7,8-benzofluorane, 3-(N,N-dibutylamino)-6-methyl-7-anilinofluorane, 3-(N,N-dibutylamino)-6-methyl-7-xylidinofluorane, 3-piperidino-6-methyl-7-anilinofluorane, 3-pyrrolidino-6-methyl-7-anilinofluorane, 3,3-bis(1-ethyl-2-methylindole-3-yl)phthalide, 3,3-bis(1-n-butyl-2-methylindole-3-yl)phthalide Examples include cylindole-3-yl)phthalide, 3,3-bis(p-dimethylaminophenyl)-6-dimethylaminophthalide, 3-(4-diethylamino-2-ethoxyphenyl)-3-(1-ethyl-2-methylindole-3-yl)-4-zaphthalide, 3-(4-diethylaminophenyl)-3-(1-ethyl-2-methylindole-3-yl)phthalide, and 3',6'-bis(diphenylamino)spiroisobenzofuran-1(3H),9'-[9H]xanthene-3-one.

[0127] From the viewpoint of visibility of exposed and unexposed areas, pattern visibility after development, and resolution, dye N is preferably a dye whose maximum absorption wavelength changes due to radicals, and more preferably a dye that develops color due to radicals. As the dye N, leucocrystal violet, crystal violet lactone, brilliant green, or Victoria pure blue naphthalene sulfonate are preferred.

[0128] The pigments may be used individually or in combination of two or more types. From the viewpoint of visibility of exposed and unexposed areas, pattern visibility after development, and resolution, the dye content is preferably 0.1% by mass or more, more preferably 0.1% to 10% by mass, even more preferably 0.1% to 5% by mass, and particularly preferably 0.1% to 1% by mass, relative to the total mass of the photosensitive layer. Furthermore, from the viewpoint of visibility of exposed and unexposed areas, pattern visibility after development, and resolution, the content of dye N is preferably 0.1% by mass or more, more preferably 0.1% to 10% by mass, even more preferably 0.1% to 5% by mass, and particularly preferably 0.1% to 1% by mass, relative to the total mass of the photosensitive layer.

[0129] The pigment N content refers to the amount of pigment N present in the photosensitive layer when all of it is in a color-developed state. Below, we will explain how to quantify the pigment N content using a radical-activated pigment as an example. Two solutions are prepared by dissolving 0.001 g or 0.01 g of dye in 100 mL of methyl ethyl ketone. To each solution, the photoradical polymerization initiator Irgacure OXE01 (trade name, BASF Japan Ltd.) is added, and radicals are generated by irradiating with 365 nm light, causing all dyes to develop color. Subsequently, under an atmospheric environment, the absorbance of each solution at a liquid temperature of 25°C is measured using a spectrophotometer (UV3100, Shimadzu Corporation), and a calibration curve is created. Next, the absorbance of the solution in which all of the dye has developed is measured, using the same method as above, except that 3 g of the photosensitive layer is dissolved in methyl ethyl ketone instead of the dye. The amount of dye contained in the photosensitive layer is calculated from the absorbance of the obtained solution containing the photosensitive layer, based on the calibration curve.

[0130] <<Thermal crosslinkable compounds>> The photosensitive layer preferably contains a thermally crosslinkable compound, from the viewpoint of the strength of the resulting cured film and the tackiness of the resulting uncured film. In this specification, thermally crosslinkable compounds having ethylenically unsaturated groups, as described later, will not be treated as polymerizable compounds, but as thermally crosslinkable compounds. Examples of thermally crosslinkable compounds include methylol compounds and blocked isocyanate compounds. Among these, blocked isocyanate compounds are preferred from the viewpoint of the strength of the resulting cured film and the tackiness of the resulting uncured film. Since blocked isocyanate compounds react with hydroxyl and carboxyl groups, for example, if the resin and / or polymerizable compound has at least one of a hydroxyl and a carboxyl group, the hydrophilicity of the formed film tends to decrease, and the function of the film when the cured photosensitive layer is used as a protective film is enhanced. Blocked isocyanate compounds refer to "compounds 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 blocked isocyanates refers to "the temperature of the endothermic peak associated with the deprotection reaction of blocked isocyanates, as measured by differential scanning calorimetry (DSC) analysis using a differential scanning calorimeter." As a 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 with 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 formaldehyde oxime, acetaldehyde oxime, acetoxime, methyl ethyl ketoxime, and cyclohexanone oxime). Among these, for blocking agents with a dissociation temperature of 100°C to 160°C, it is preferable, for example, that they contain oxime compounds from the viewpoint of storage stability.

[0133] Blocked isocyanate compounds are preferably configured to have an isocyanurate structure, for example, from the viewpoint of improving the brittleness of the film and enhancing adhesion to the transfer target. Blocked isocyanate compounds having an isocyanurate structure can be obtained, for example, by isocyanurating and protecting hexamethylene diisocyanate. Among blocked isocyanate compounds having an isocyanurate structure, compounds having an oxime structure using an oxime compound as a blocking agent are preferred from the viewpoint of making it easier to set the dissociation temperature within a favorable range and reducing development residue compared to compounds without an oxime structure.

[0134] The blocked isocyanate compound may have polymerizable groups. There are no particular restrictions on the polymerizable group; known polymerizable groups can be used, and radical polymerizable groups are preferred. Polymerizable groups include ethylenically unsaturated groups such as (meth)acryloxy groups, (meth)acrylamide groups, and styryl groups, as well as epoxy groups such as glycidyl groups. Among the polymerizable groups, ethylenically unsaturated groups are preferred, (meth)acryloxy groups are more preferred, and acryloxy groups are even more preferred.

[0135] Commercially available blocked isocyanate compounds can be used. Examples of commercially available blocked isocyanate compounds include Karenz® AOI-BM, Karenz® MOI-BM, Karenz® MOI-BP, etc. (all manufactured by Showa Denko K.K.), and the block-type Duranate series (for example, Duranate® TPA-B80E, Duranate® WT32-B75P, etc., manufactured by Asahi Kasei Chemicals Corporation). Furthermore, a compound with the following structure can also be used as a blocked isocyanate compound.

[0136] [ka]

[0137] The thermally crosslinkable compound may be used alone or in combination of two or more types. If the photosensitive layer contains a thermally crosslinkable compound, the content of the thermally crosslinkable compound is preferably 1% to 50% by mass, and more preferably 5% to 30% by mass, relative to the total mass of the photosensitive layer.

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

[0139] - Surfactants - From the viewpoint of uniform thickness, 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 Publication No. 4502784 and paragraphs 0060 to 0071 of Japanese Unexamined Patent Publication No. 2009-237362.

[0140] As the surfactant, fluorine-based surfactants or silicone-based surfactants are preferred. Examples of commercially available fluorine-based surfactants include Megafac (product name) F-171, F-172, F-173, F-176, F-177, F-141, F-142, F-143, F-144, F-437, F-444, F-475, F-477, F-479, F-482, F-551-A, F-552, F-554, F-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), Florard (product name) FC430, FC431, FC171 (all manufactured by Sumitomo 3M Co., Ltd.), Surflon (product 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 Inc.), PolyFox (product name) PF636, PF656, PF6320, PF6520, PF7002 (all manufactured by OMNOVA Corporation), Futtergent 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 Corporation), U-120E (manufactured by Unichem Corporation), etc. Furthermore, fluorinated surfactants can also suitably include acrylic compounds that have a molecular structure with a functional group containing a fluorine atom, and when heated, the fluorine atom-containing functional group is cleaved, causing the fluorine atom to volatilize. Examples of such fluorinated surfactants include the Megafac (product name) DS series manufactured by DIC Corporation (Chemical Daily (February 22, 2016), Nikkei Sangyo Shimbun (February 23, 2016)), for example, Megafac (product name) DS-21.

[0141] Furthermore, it is also preferable to use a polymer of a fluorine-containing vinyl ether compound having a fluorinated alkyl group or a fluorinated alkylene ether group and a hydrophilic vinyl ether compound as the fluorine-based surfactant. Fluorine-based surfactants can also be made using block polymers. Fluorine-based surfactants can also preferably be fluorine-containing polymer compounds that include 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) alkylene oxy groups (preferably ethylene oxy groups, propylene oxy groups). Fluorine-based surfactants can also be fluorine-containing polymers having ethylenically unsaturated groups in their side chains. Examples include Megafac (trade name) RS-101, RS-102, RS-718K, RS-72-K (all manufactured by DIC Corporation).

[0142] Nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane and their ethoxylates and propoxylates (e.g., glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid esters, Pluronic (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 Examples include 3323 (manufactured by BASF), Solspers (trade name) 20000 (manufactured by Lubrizol Nippon Co., Ltd.), NCW-101, NCW-1001, NCW-1002 (manufactured by Fujifilm Wako Pure Chemical Industries Ltd.), Paionin (trade name) D-1105, D-6112, D-6112-W, D-6315 (manufactured by Takemoto Oil & Fat Co., Ltd.), Orfin E1010, Surfinol 104, 400, 440 (manufactured by Nisshin Chemical Industry Co., Ltd.). Furthermore, in recent years, compounds having linear perfluoroalkyl groups with 7 or more carbon atoms have raised concerns regarding their environmental suitability. Therefore, it is preferable to use surfactants that utilize alternative materials for perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic acid (PFOS).

[0143] Examples of silicone-based surfactants include linear polymers composed of siloxane bonds, and modified siloxane polymers in which organic groups are introduced into the side chains or terminals. Specific examples of silicone-based surfactants include EXP.S-309-2, EXP.S-315, EXP.S-503-2, EXP.S-505-2 (all manufactured by DIC Corporation), DOWSIL (product name) 8032 ADDITIVE, Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, Toray Silicone SH8400 (all manufactured by Toray Dow Corning Co., Ltd.), as well as X-22-4952, X-22-4272, 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 Pa 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 Bic Chemie).

[0144] The photosensitive layer may contain one surfactant alone or two or more surfactants. The surfactant content is preferably 0.001% to 10% by mass, and more preferably 0.01% to 3% by mass, relative to the total mass of the photosensitive layer.

[0145] - Additives - The photosensitive layer may contain known additives in addition to the above components, as needed. 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 of these additives alone or two or more.

[0146] The photosensitive layer may contain a polymerization inhibitor. A radical polymerization inhibitor is preferred as the polymerization inhibitor. Examples of polymerization inhibitors include the thermal polymerization inhibitors described in paragraph 0018 of Japanese Patent No. 4502784. Among these, phenothiazine, phenoxazine, or 4-methoxyphenol are preferred. Other polymerization inhibitors include naphthylamine, cuprous chloride, nitrosophenylhydroxyamine aluminum salt, and diphenylnitrosamine. In order not to impair the sensitivity of the photosensitive resin composition, it is preferable to use nitrosophenylhydroxyamine aluminum salt as a 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, and N-(N,N-di-2-ethylhexyl)aminoethylenecarboxybenzotriazole. Commercially available carboxybenzotriazoles such as CBT-1 (manufactured by Johoku Chemical Industry Co., Ltd., trade name) can be used.

[0149] The total content of polymerization inhibitors, benzotriazoles, and carboxybenzotriazoles is preferably 0.01% to 3% by mass, and more preferably 0.05% to 1% by mass, based on the total mass of the photosensitive layer. A content of 0.01% by mass or more is preferable 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 preferable from the viewpoint of maintaining sensitivity and suppressing dye decolorization.

[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 sensitizers 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 it may contain two or more types of sensitizers. When the photosensitive layer contains a sensitizer, the amount of sensitizer can be appropriately selected depending on the purpose, but from the viewpoint of improving sensitivity to light sources and improving curing speed by balancing polymerization rate and chain transfer, 0.01% to 5% by mass and more preferably 0.05% to 1% by mass are preferred based on 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 plasticizers and heterocyclic compounds include those described in paragraphs 0097-0103 and 0111-0118 of International Publication No. 2018 / 179640.

[0153] The photosensitive layer may contain a solvent. When a photosensitive layer is formed using a photosensitive resin composition containing a solvent, the solvent may remain in the photosensitive layer.

[0154] Furthermore, the photosensitive layer may further contain known additives such as metal oxide particles, antioxidants, dispersants, acid growth agents, development accelerators, conductive fibers, thermal radical polymerization initiators, thermal acid generators, ultraviolet absorbers, thickeners, crosslinking agents, and organic or inorganic precipitation inhibitors. The additives contained in the photosensitive layer are described in paragraphs 0165 to 0184 of Japanese Patent Publication No. 2014-85643, and the contents of this publication are incorporated herein by reference.

[0155] <<Impurities etc.>> The photosensitive layer may contain a predetermined amount of impurities. Specific examples of impurities include sodium, potassium, magnesium, calcium, iron, manganese, copper, aluminum, titanium, chromium, cobalt, nickel, zinc, tin, halogens, and their ions. Among these, halide ions, sodium ions, and potassium ions are particularly prone to contamination as impurities, so it is preferable to have the following content levels.

[0156] The impurity content in the photosensitive layer is preferably 80 ppm or less by mass, more preferably 10 ppm or less, and even more preferably 2 ppm or less. The impurity content can be 1 ppb or more by mass, and may also be 0.1 ppm or more.

[0157] Methods to keep impurities within the above range include selecting raw materials for the composition that have a low impurity content, preventing the inclusion of impurities during the preparation of the photosensitive layer, and removing them by washing. By such methods, the amount of impurities can be kept within the above range.

[0158] Impurities can be quantified using known methods such as ICP (Inductively Coupled Plasma) emission spectroscopy, atomic absorption spectroscopy, and ion chromatography.

[0159] The photosensitive layer preferably contains low amounts of compounds such as benzene, formaldehyde, trichloroethylene, 1,3-butadiene, carbon tetrachloride, chloroform, N,N-dimethylformamide, N,N-dimethylacetamide, and hexane. 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, based on mass. The lower limit, based on mass, can be 10 ppb or more, or 100 ppb or more, relative to the total mass of the photosensitive layer. The content of these compounds can be suppressed in the same way as the impurities of the metals mentioned above. Furthermore, they can be quantified using known measurement methods.

[0160] From the viewpoint of improving reliability and lamination, the water content in the photosensitive layer is preferably 0.01% to 1.0% by mass, and more preferably 0.05% to 0.5% by mass.

[0161] <<Residual monomers>> The photosensitive layer may contain residual monomers corresponding to each constituent unit of the alkali-soluble resin described above. From the viewpoint of patternability and reliability, the residual monomer content 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. There is no particular lower limit, but it is preferably 1 ppm by mass or more, and more preferably 10 ppm by mass or more. The residual monomers of each constituent unit of the alkali-soluble resin are 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, from the viewpoint of patternability and reliability. There is no particular lower limit, but it is preferably 0.1 ppm by mass or more, and more preferably 1 ppm by mass or more.

[0162] It is preferable that the amount of residual monomers when synthesizing alkali-soluble resins by polymer reactions be within the above range. For example, when synthesizing alkali-soluble resins by reacting glycidyl acrylate with a carboxylic acid side chain, it is preferable that the content of glycidyl acrylate be 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, even more preferably 0.5 μm to 15 μm, particularly preferably 0.5 μm to 10 μm, and most preferably 0.5 μm to 8 μm. This improves the developability of the photosensitive layer and enhances resolution. Furthermore, 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, from the viewpoint of resolution and better demonstrating the effects of this disclosure. The thickness of each layer in a photosensitive transfer material or laminate is measured by observing a cross-section perpendicular to the main surface of the photosensitive transfer material using a scanning electron microscope (SEM), measuring the thickness of each layer at 10 or more points based on the obtained observation image, and calculating the average value.

[0164] Furthermore, for superior adhesion, the transmittance of light at a wavelength of 365 nm in the photosensitive layer is preferably 10% or more, preferably 30% or more, and more preferably 50% or more. There is no particular upper limit, but 99.9% or less is preferred.

[0165] <<Formation method>> The method for forming the photosensitive layer is not particularly limited as long as it is a method capable of forming a layer containing the above-mentioned components. One method for forming a photosensitive layer is to prepare a photosensitive resin composition containing an alkali-soluble resin, a polymerizable compound, a photopolymerization initiator, and a solvent, apply the photosensitive resin composition to the surface of a temporary support or the like, and then dry the coating film of the photosensitive resin composition.

[0166] Examples of photosensitive resin compositions used for forming the photosensitive layer include compositions 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 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 any of the above-mentioned optional components; known solvents can be used. Examples of solvents include alkylene glycol ether solvents, alkylene glycol ether acetate solvents, alcohol solvents (methanol and ethanol, etc.), ketone solvents (acetone and 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 comprising 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 selected from the group consisting of alkylene glycol ether solvents and alkylene glycol ether acetate solvents. More preferably, a mixed solvent containing at least one selected from the group consisting of alkylene glycol ether solvents and alkylene glycol ether acetate solvents and at least one selected from the group consisting of ketone solvents and cyclic ether solvents is preferred, and even more preferably, a mixed solvent containing at least three types: at least one selected from the group consisting of alkylene glycol ether solvents and alkylene glycol ether acetate solvents, a ketone solvent, and a cyclic ether solvent.

[0168] Examples of alkylene glycol ether solvents include ethylene glycol monoalkyl ether, ethylene glycol dialkyl ether, propylene glycol monoalkyl ether, propylene glycol dialkyl ether, diethylene glycol dialkyl ether, dipropylene glycol monoalkyl ether, and dipropylene glycol dialkyl ether. 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 solvents, those described in paragraphs 0092-0094 of International Publication No. 2018 / 179640 and those described in paragraph 0014 of Japanese Patent Application Publication No. 2018-177889 may be used, and these contents are incorporated herein by reference.

[0169] The photosensitive resin composition may contain one solvent alone or two or more solvents. The solvent content when applying the photosensitive resin composition is preferably 50 to 1,900 parts by mass, and more preferably 100 to 900 parts by mass, per 100 parts by mass of total solids in the photosensitive resin composition.

[0170] The method for preparing the photosensitive resin composition is not particularly limited. For example, one method involves preparing a solution in which each component is dissolved in the solvent, and then mixing the resulting solution in a predetermined ratio to prepare the photosensitive resin composition. From the viewpoint of removing particles larger than Y μm, it is preferable to filter the photosensitive resin composition 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. There are no particular restrictions on the material and shape of the filter; known materials can be used. Furthermore, it is preferable to perform the above filtration once or more times, and it is also preferable to perform it multiple times.

[0171] The method of coating the photosensitive resin composition is not particularly limited and can be done by known methods. Examples of coating methods include slit coating, spin coating, curtain coating, and inkjet coating. Alternatively, the photosensitive layer may be formed by applying a photosensitive resin composition onto a protective film (described later) and drying it.

[0172] Furthermore, in the photosensitive transfer material of this disclosure, it is preferable to have another layer between the temporary support and the photosensitive layer, from the viewpoint of resolution and the peelability of the temporary support. Other preferred layers include water-soluble resin layers, thermoplastic resin layers, and protective films. 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] In photosensitive transfer materials, it is preferable to have a water-soluble resin layer between the temporary support and the photosensitive layer, and, if a thermoplastic resin layer (described later) is present, between the thermoplastic resin layer and the photosensitive layer. The water-soluble resin layer helps to suppress the mixing of components when forming multiple layers and during storage.

[0174] The water-soluble resin layer is preferably a water-soluble layer from the viewpoint of developability and suppression of component mixing when applying multiple layers and during storage after application. In this disclosure, "water-soluble" means that the solubility in 100g of water at a pH of 7.0 at a liquid temperature of 22°C is 0.1g or more.

[0175] Examples of water-soluble resin layers include oxygen-blocking layers with oxygen-blocking properties, as described as "separation layers" in Japanese Patent Publication No. 5-72724. The presence of an oxygen-blocking layer in the water-soluble resin layer improves sensitivity during exposure, reduces the time load on the exposure machine, and consequently improves productivity. The oxygen-blocking layer used as the water-soluble resin layer can be appropriately selected from known layers. Preferably, the oxygen-blocking layer used as the water-soluble resin layer exhibits low oxygen permeability and is dispersed or dissolved in water or an alkaline aqueous solution (a 1% by mass aqueous solution of sodium carbonate at 22°C). Furthermore, the water-soluble resin layer preferably contains an inorganic layered compound from the viewpoint of oxygen barrier properties, resolution, and pattern formation properties. Inorganic layered compounds include particles having a thin, flat shape, such as mica compounds including natural mica and synthetic mica, talc represented by the formula 3MgO·4SiO·H2O, teniolite, montmorillonite, saponite, hectorite, and zirconium phosphate. Examples of mica compounds include those with formula A(B,C) 2-5 D4O 10 Examples of mica groups include natural mica and synthetic mica represented by (OH,F,O)2 [where A is one of K, Na, or Ca; B and C are one of Fe(II), Fe(III), Mn, Al, Mg, or V; and D is Si or Al].

[0176] In the mica group, natural micas include muscovite, soda mica, phlogopite, biotite, and scallop mica. Synthetic micas include fluorinated phlogopite (KMg3(AlSi3O)). 10 ) F2, Potassium tetrasilicon mica KMg 2.5 Si4O 10 ) Non-swelling mica such as F2, and Na tetrasilyl mica NaMg 2.5 (Si4O 10 )F2, Na or Li teniolite (Na,Li)Mg2Li(Si4O 10 )F2, montmorillonite-based Na or Li hectorite (Na,Li) 1 / 8 Mg 2 / 5 Li 1 / 8 (Si4O 10 Examples include swelling mica such as F2. Furthermore, synthetic smectite is also useful.

[0177] From the viewpoint of diffusion control, the shape of the inorganic layered compound is such that the thinner the layer, the better, and the larger the plane size, as long as it does not hinder the smoothness of the coated surface or the transmittance of active light. 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 image of a microscopic photograph of the particle. 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 average major axis. The average thickness of the particles 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 swelling synthetic mica, a representative compound, a preferred embodiment is a thickness of about 1 nm to 50 nm and a surface size (major axis) of about 1 μm to 20 μm.

[0179] From the viewpoint of oxygen barrier properties, resolution, and pattern formation properties, the content of the inorganic layered compound is preferably 0.1% to 50% by mass, and more preferably 1% to 20% by mass, relative to the total mass of the water-soluble resin layer.

[0180] The water-soluble resin layer preferably contains a resin. Examples of resins that can be included 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 included in the water-soluble resin layer is preferably a water-soluble resin.

[0181] From the viewpoint of suppressing the mixing of components between multiple layers, it is preferable that the resin contained in the water-soluble resin layer is different from both polymer A contained in the negative-type photosensitive layer and the thermoplastic resin (alkali-soluble resin) contained in the thermoplastic resin layer.

[0182] Furthermore, the water-soluble resin layer preferably contains a water-soluble compound, and more preferably contains a water-soluble resin, from the viewpoint of oxygen barrier properties, developability, resolution, and pattern formation properties. The water-soluble compound is not particularly limited, but is preferably at least one compound selected from the group consisting of water-soluble cellulose derivatives, polyhydric alcohols, oxide adducts of polyhydric alcohols, polyethers, phenol derivatives, and amide compounds, from the viewpoints of oxygen barrier properties, developability, resolution, and pattern forming properties, and is more preferably at least one water-soluble resin selected from the group consisting of polyvinyl alcohol, polyvinylpyrrolidone, hydroxypropyl cellulose, and hydroxypropyl methyl cellulose. Examples of the water-soluble resin include resins such as 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, from the viewpoints of oxygen barrier properties, developability, resolution, and pattern forming properties, the water-soluble compound preferably contains polyvinyl alcohol, and is more preferably polyvinyl alcohol. The degree of hydrolysis of polyvinyl alcohol is not particularly limited, but is preferably from 73 mol% to 99 mol% from the viewpoints of oxygen barrier properties, developability, resolution, and pattern forming properties. Further, from the viewpoints of oxygen barrier properties, developability, resolution, and pattern forming properties, polyvinyl alcohol preferably contains ethylene as a monomer unit.

[0183] From the viewpoints of oxygen barrier properties and suppression of component mixing during application of multiple layers and during storage after application, the water-soluble resin layer preferably contains polyvinyl alcohol, and more preferably contains polyvinyl alcohol and polyvinylpyrrolidone.

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

[0185] The content ratio of water-soluble compounds in the water-soluble resin layer is preferably 50% to 100% by mass, more preferably 70% to 100% by mass, even more preferably 80% to 100% by mass, and particularly preferably 90% to 100% by mass, based on the total mass of the water-soluble resin layer, from the viewpoint of oxygen barrier properties and suppressing the mixing of components when applying multiple layers and during storage after application.

[0186] Furthermore, the water-soluble resin layer may contain additives as needed. Examples of additives include surfactants.

[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. By having the thickness of the water-soluble resin layer within the above range, the oxygen barrier properties are not reduced, mixing of components is suppressed when forming multiple layers and during storage, and the increase in the removal time of the water-soluble resin layer during development is 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. For example, a method for forming the water-soluble resin layer may be one 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 comprising 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, and more preferably methanol or ethanol.

[0191] [Thermoplastic resin layer] The photosensitive transfer material used in this disclosure may have a thermoplastic resin layer. Preferably, the photosensitive transfer material has a thermoplastic resin layer between the temporary support and the photosensitive layer. This is because having a thermoplastic resin layer between the temporary support and the photosensitive layer of the photosensitive transfer material improves its conformability to the substrate, suppresses the incorporation of air bubbles between the substrate and the photosensitive transfer material, and as a result improves the 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 viewpoint of developability and adhesion to layers adjacent to the thermoplastic resin layer. Here, "acrylic resin" means a resin having at least one selected from the group consisting of constituent units derived from (meth)acrylic acid, constituent units derived from (meth)acrylic acid esters, and constituent units derived from (meth)acrylamide.

[0195] In acrylic resins, the total content of constituent units derived from (meth)acrylic acid, constituent units derived from (meth)acrylic acid esters, and constituent units derived from (meth)acrylamide is preferably 50% by mass or more of the total mass of the acrylic resin. In acrylic resins, the total content of constituent units derived from (meth)acrylic acid and constituent units derived from (meth)acrylic acid esters is preferably 30% to 100% by mass, and more preferably 50% to 100% by mass, of the total mass of the acrylic resin.

[0196] Furthermore, the alkali-soluble resin is preferably a polymer having an acidic group. Examples of acidic groups include carboxyl groups, sulfol groups, phosphate groups, and phosphonic acid groups, with carboxyl groups being preferred.

[0197] From the viewpoint of developability, the alkali-soluble resin is preferably an alkali-soluble resin with an acid value of 60 mgKOH / g or more, and more preferably a carboxyl group-containing acrylic resin with 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 carboxyl group-containing acrylic resins 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 from the polymer described in paragraph 0025 of Japanese Patent Application Publication No. 2011-95716, the carboxyl group-containing acrylic resin having an acid value of 60 mgKOH / g or more from the polymer described in paragraphs 0033 to 0052 of Japanese Patent Application Publication No. 2010-237589, and the carboxyl group-containing acrylic resin having an acid value of 60 mgKOH / g or more from the binder polymer described in paragraphs 0053 to 0068 of Japanese Patent Application Publication No. 2016-224162.

[0199] The content ratio 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 only needs to be, for example, an addition-polymerizable group. 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 10,000 to 100,000, and particularly preferably 20,000 to 50,000.

[0203] The thermoplastic resin layer may contain one type of alkali-soluble resin alone, or two or more types thereof.

[0204] From the viewpoints of developability and adhesion to a layer adjacent to the thermoplastic resin layer, the content ratio of the alkali-soluble resin is preferably 10% by mass to 99% by mass, more preferably 20% by mass to 90% by mass, still 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 higher, and whose maximum absorption wavelength changes with the presence of an acid, base, or radical. The preferred embodiment of dye B is the same as the preferred embodiment of dye N described above, except for the points described later.

[0206] From the viewpoint of visibility of exposed areas, visibility of unexposed areas, and resolution, dye B is preferably a dye whose maximum absorption wavelength changes with acid or radicals, and more preferably a dye whose maximum absorption wavelength changes with acid.

[0207] From the viewpoint of visibility of exposed areas, visibility of unexposed areas, and resolution, the thermoplastic layer preferably contains, as dye B, a dye whose maximum absorption wavelength changes with acid, and a compound that generates acid with light, as described later.

[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 the exposed and unexposed areas, the content of dye B is preferably 0.2% by mass or more, more preferably 0.2% to 6% by mass, even more preferably 0.2% to 5% by mass, and particularly preferably 0.25% to 3.0% by mass, relative to the total mass of the thermoplastic resin layer.

[0210] Here, the content of dye B refers to the content of the dye when all of the dye B contained in the thermoplastic resin layer is brought into a colored state. Below, the method for quantifying the content of dye B is explained using a dye that develops color via radicals as an example. Two solutions are prepared by dissolving dye (0.001 g) and dye (0.01 g) in methyl ethyl ketone (100 mL), respectively. After adding IRGACURE OXE-01 (BASF) as a photoradical polymerization initiator to each of the obtained solutions, radicals are generated by irradiating with 365 nm light, and all of the dye is brought into a colored state. Next, under an atmospheric atmosphere, the absorbance of each solution at a liquid temperature of 25°C is measured using a spectrophotometer (UV3100, Shimadzu Corporation) and a calibration curve is created. Next, the absorbance of the solution in which all of the dye has developed color is measured in the same manner as above, except that a thermoplastic resin layer (0.1 g) is dissolved in methyl ethyl ketone instead of the dye. The amount of dye contained in the thermoplastic resin layer is calculated based on the calibration curve, using the absorbance of the solution containing the obtained thermoplastic resin layer.

[0211] The thermoplastic resin layer may contain a compound that generates an acid, base, or radical upon exposure to light (hereinafter sometimes referred to as "compound C"). Compound C is preferably a compound that generates an acid, base, or radical upon exposure to active light (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 photoacid generators include photocationic polymerization initiators that may be included in the photosensitive layer described above, and the preferred embodiments are the same except for the points described later.

[0213] From the viewpoint of sensitivity and resolution, the photoacid generator preferably contains at least one selected from the group consisting of onium salt compounds and oxime sulfonate compounds, and from the viewpoint of sensitivity, resolution and adhesion, it is more preferable to contain an oxime sulfonate compound.

[0214] Furthermore, it is also preferable that the photoacid generator has the following structure.

[0215] [ka]

[0216] The thermoplastic resin layer may contain a photobase generator. Examples of photobase generators include 2-nitrobenzylcyclohexylcarbamate, triphenylmethanol, O-carbamoylhydroxylamide, O-carbamoyloxime, [[(2,6-dinitrobenzyl)oxy]carbonyl]cyclohexylamine, bis[[(2,6-nitrobenzyl)oxy]carbonyl]hexane1,6-diamine, 4-(methylthiobenzoyl)-1-methyl-1-morpholinoethane, (4-morpholinobenzoyl)-1-benzyl-1-di Examples include 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 photoradical polymerization initiators include those that may be included in the photosensitive layer described above, and the preferred embodiment is the same.

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

[0219] From the viewpoint of visibility of the exposed area, visibility of the unexposed area, and resolution, the content of compound C is preferably 0.1% to 10% by mass, and more preferably 0.5% 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 viewpoint of resolution, adhesion to adjacent layers, and developability.

[0221] The molecular weight of the plasticizer (for oligomers or polymers, 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 between 200 and 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 alkylene oxy group in its molecule, and more preferably a polyalkylene glycol compound. The alkylene oxy group contained in the plasticizer preferably has a polyethylene oxy structure or a polypropylene oxy structure.

[0223] From the viewpoint of resolution and storage stability, the plasticizer preferably contains a (meth)acrylate compound. From the viewpoint of compatibility, resolution, and adhesion to layers 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 photosensitive transfer materials, when a thermoplastic resin layer and a photosensitive layer are arranged in direct contact, it is preferable that the thermoplastic resin layer and the photosensitive layer each contain the same (meth)acrylate compound. This is because the inclusion of the same (meth)acrylate compound in both the thermoplastic resin layer and the photosensitive layer suppresses the diffusion of components between layers, thereby improving storage stability.

[0225] When a thermoplastic resin layer contains a (meth)acrylate compound as a plasticizer, it is preferable that the (meth)acrylate compound does not polymerize in the exposed area after exposure, from the viewpoint of adhesion with the layer 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 viewpoint of resolution, adhesion to the thermoplastic resin layer and adjacent layers, and developability.

[0227] In one embodiment, the (meth)acrylate compound used as a 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 type of plasticizer alone, or two or more types of plasticizers.

[0229] From the viewpoint of resolution, adhesion to adjacent layers of the thermoplastic resin layer, and developability, the plasticizer content is preferably 1% to 70% by mass, more preferably 10% to 60% by mass, and particularly preferably 20% to 50% by mass, relative to the total mass of the thermoplastic resin layer.

[0230] The thermoplastic resin layer preferably contains a surfactant from the viewpoint of uniform thickness. Examples of surfactants include those that may be included in the photosensitive layer described above, and the preferred embodiments are the same.

[0231] The thermoplastic resin layer may contain one type of surfactant alone, or two or more types of surfactants.

[0232] The surfactant content is preferably 0.001% to 10% by mass, and more preferably 0.01% to 3% by mass, relative to the total mass of the thermoplastic resin layer.

[0233] The thermoplastic resin layer may contain a sensitizer. Examples of sensitizers include those that may be included in the negative-type photosensitive layer described above.

[0234] The thermoplastic resin layer may contain one type of sensitizer alone, or two or more types of sensitizers.

[0235] The sensitizer content is preferably 0.01% to 5% by mass, and more preferably 0.05% to 1% by mass, relative to the total mass of the thermoplastic resin layer, from the viewpoint of improving sensitivity to the light source, visibility of the exposed area, and visibility of the unexposed area.

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

[0237] Furthermore, the thermoplastic resin layer is described in paragraphs 0189 to 0193 of Japanese Patent Publication No. 2014-85643. The contents of the above publication are incorporated herein by reference.

[0238] The thickness of the thermoplastic resin layer is not limited. The average thickness of the thermoplastic resin layer is preferably 1 μm or more, and more preferably 2 μm or more, from the viewpoint of adhesion to the layer adjacent to the thermoplastic resin layer. The upper limit of the average thickness of the thermoplastic resin layer is not limited. 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, from the viewpoint of developability and resolution.

[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 components. An example of a method for forming a thermoplastic resin layer is to apply a thermoplastic resin composition to the surface of a temporary support and dry the coating film of the thermoplastic resin composition.

[0240] Examples of thermoplastic resin compositions include compositions 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 included in the thermoplastic resin composition is not limited as long as it is capable of dissolving or dispersing the components contained in the thermoplastic resin layer. Examples of solvents include those that may be included in the photosensitive resin composition described above, and the preferred embodiments are the same.

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

[0243] The solvent content in the thermoplastic resin composition is preferably 50 to 1,900 parts by mass, and more preferably 100 to 900 parts by mass, per 100 parts by mass of total solids 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 method for preparing the photosensitive resin composition and the method for forming the negative-type photosensitive layer described above. For example, a thermoplastic resin composition can be prepared by first preparing solutions in which each component contained in the thermoplastic resin layer is dissolved in a solvent, and then mixing the obtained solutions in predetermined proportions. After that, the obtained thermoplastic resin composition can be applied to the surface of a temporary support, and the thermoplastic resin layer can be formed by drying the coating film of the thermoplastic resin composition. Alternatively, a negative-type photosensitive layer may be formed on a protective film, and then a thermoplastic resin layer may be formed on the surface of the negative-type photosensitive layer.

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

[0246] Materials that make up the protective film include resin film and paper, and from the viewpoint of strength and flexibility, resin film is preferred. Examples of resin films include polyethylene film, polypropylene film, polyethylene terephthalate film, cellulose triacetate film, polystyrene film, and polycarbonate film. Among these, polyethylene film, polypropylene film, or 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, and more preferably 10 μm to 50 μm. The arithmetic mean roughness Ra of the protective film on the side opposite to the photosensitive layer is preferably less than or equal to the arithmetic mean roughness Ra of the side with the photosensitive layer, and more preferably less than the arithmetic mean roughness Ra of the side with the photosensitive layer, from the viewpoints of transportability, defect suppression of the resin pattern, and resolution. The arithmetic mean roughness Ra of the protective film on the side opposite to 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 transportability and windingability. Furthermore, the arithmetic mean roughness Ra of the photosensitive layer side of the protective film 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 standpoint of superior resolution. This is because having the Ra value of the surface of the protective film within the above range improves the uniformity of the layer thickness of the photosensitive layer and the formed resin pattern. The lower limit of the Ra value on the surface of the protective film is not particularly limited, but it is preferably 1 nm or more, more preferably 10 nm or more, and particularly preferably 20 nm or more on both sides. Furthermore, it is preferable that the peeling force of the protective film is less than the peeling force of the temporary support.

[0248] The photosensitive transfer material may include layers other than those described above (hereinafter also referred to as "other layers"). Examples of other layers include a contrast enhancement layer. The contrast enhancement layer is described in paragraph 0134 of International Publication No. 2018 / 179640. Other layers are described in paragraphs 0194-0196 of Japanese Patent Publication No. 2014-85643. 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. From the viewpoint of better demonstrating the effects of this disclosure, the total thickness of each layer in the photosensitive transfer material, excluding the temporary support and 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, 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, from the viewpoint of better exhibiting the effects of this disclosure.

[0250] [Method for manufacturing photosensitive transfer material] The method for producing the photosensitive transfer material used in this disclosure is not particularly limited, and known production methods, such as known methods for forming each layer, can be used. The method for manufacturing the photosensitive transfer material used in this disclosure will be described below with reference to Figure 1. However, the photosensitive transfer material used in this disclosure is not limited to having the configuration shown in Figure 1. Figure 1 is a schematic cross-sectional view showing an example of the layer structure in one embodiment of the photosensitive transfer material used in this disclosure. The photosensitive transfer material 20 shown in Figure 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 Figure 1 consists of the thermoplastic resin layer 13, the water-soluble resin layer 15, and the photosensitive layer 17.

[0251] Examples of methods for producing the above-mentioned photosensitive transfer material 20 include the steps of: applying a thermoplastic resin composition to the surface of a 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 solvent and alkylene glycol ether acetate solvent, a water-soluble resin layer composition containing at least one selected from the group consisting of water and water-miscible organic solvent, 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 solvent and alkylene glycol ether acetate solvent. This makes it possible to suppress the mixing of components contained in the thermoplastic resin layer 13 and components contained in 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 during the storage period of the laminate having a coating of the water-soluble resin layer composition, and also makes it possible to suppress the mixing of components contained in the water-soluble resin layer 15 and components contained in the photosensitive layer 16 during the application of the photosensitive resin composition to the surface of the water-soluble resin layer 15 and / or during the storage period of the laminate having a coating of the photosensitive resin composition.

[0252] A photosensitive transfer material 20 is manufactured by pressing a protective film 19 onto the photosensitive layer 17 of the laminate manufactured by the above manufacturing method. In the method for producing the photosensitive transfer material used in this disclosure, it is preferable to produce 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 by including a step of providing a protective film 19 so as to be in contact with the second surface of the photosensitive layer 17. After manufacturing the photosensitive transfer material 20 using the above manufacturing method, the photosensitive transfer material 20 may be wound up to produce and store a roll of photosensitive transfer material. The roll of photosensitive transfer material can be provided in its original form for the substrate bonding process using the roll-to-roll method described later.

[0253] The photosensitive transfer material used in this disclosure can be suitably used in various applications requiring precise microfabrication by photolithography. After patterning the photosensitive layer, the photosensitive layer may be etched as a coating, or electroforming, mainly by electroplating, may be performed. The cured film obtained by patterning may 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. Furthermore, the photosensitive transfer material used in this disclosure can be suitably used in applications such as various wiring formation applications for semiconductor packages, printed circuit boards, and sensor substrates, as well as conductive films such as touch panels, electromagnetic shielding materials, and film heaters, liquid crystal sealing materials, and the formation of structures in the fields of micromachines or microelectronics.

[0254] Furthermore, a preferred embodiment of the photosensitive transfer material used in this disclosure is one in which the photosensitive layer is a colored resin layer containing a pigment. In addition to the applications mentioned above, the colored resin layer is also suitable for forming colored pixels or black matrices in color filters used in liquid crystal display devices (LCDs) and solid-state image sensors (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 recent electronic devices, liquid crystal display windows may have a cover glass attached to the back edge of a transparent glass substrate or similar material to protect the liquid crystal display window. This cover glass has a black, frame-shaped light-shielding layer formed on the back edge. A colored resin layer can be used to form such a light-shielding layer. The pigment can be selected appropriately according to the desired hue, and can be chosen from black pigment, white pigment, or chromatic pigments other than black and white. Among these, black pigment is preferably selected when forming black patterns.

[0256] As the black pigment, any known black pigment (organic pigment or inorganic pigment, etc.) can be appropriately selected, as long as it does not impair the effects described herein. Among these, 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 for carbon black, from the viewpoint of surface resistance, carbon black in which at least a portion of the surface is coated with 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 in number average particle size, and more preferably 0.01 μm to 0.08 μm. Here, particle size refers to the diameter of a circle with the same area as the pigment particle, calculated from the area of ​​the pigment particle taken with an electron microscope. Number-average particle size is the average value obtained by calculating the above particle size for any 100 particles and averaging the calculated particle sizes of those 100 particles.

[0258] As for pigments other than black pigments, white pigments can be used, specifically those described in paragraphs 0015 and 0114 of Japanese Patent Publication No. 2005-007765. Specifically, among the white pigments, titanium dioxide, zinc oxide, lithopone, light calcium carbonate, white carbon, aluminum oxide, aluminum hydroxide, or barium sulfate are preferred as inorganic pigments, titanium dioxide or zinc oxide are more preferred, and titanium dioxide is even more preferred. Among the inorganic pigments, rutile-type or anatase-type titanium dioxide is even more preferred, and rutile-type titanium dioxide is particularly preferred. Furthermore, the surface of titanium dioxide may be treated with silica, alumina, titania, zirconia, or organic substances, and may be treated with two or more of these treatments. This suppresses the catalytic activity of titanium dioxide and improves its heat resistance and fading properties. From the viewpoint of reducing the thickness of the photosensitive layer after heating, at least one of alumina treatment and zirconia treatment is preferred as the surface treatment for the titanium oxide surface, and both alumina treatment and zirconia treatment are particularly preferred.

[0259] Furthermore, if the photosensitive layer is a colored resin layer, from the viewpoint of transferability, it is also preferable that the photosensitive layer further contains chromatic pigments other than black and white pigments. When chromatic pigments are included, the particle size of the chromatic pigments is preferably 0.1 μm or less, and more preferably 0.08 μm or less, in terms of superior 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), and Monastral First Blue (CI Pigment Examples include CI Pigment Blue 15), Monolight First Black B (CI Pigment Black 1), 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. Among these, CI Pigment Red 177 is preferred.

[0260] If the photosensitive layer contains a pigment, the pigment content is preferably more than 3% by mass and 40% by mass or less, more preferably more than 3% by mass and 35% by mass or less, even more preferably more than 5% by mass and 35% by mass or less, and particularly preferably 10% by mass or more and 35% by mass or less, based on the total mass of the photosensitive layer.

[0261] When the photosensitive layer contains pigments other than black pigment (white pigment and chromatic pigment), the content of pigments other than black pigment is preferably 30% by mass or less, more preferably 1% to 20% by mass, and even more preferably 3% to 15% by mass, relative to the black pigment.

[0262] Furthermore, when the photosensitive layer contains a black pigment and is formed from a photosensitive resin composition, it is preferable that the black pigment (preferably carbon black) is introduced into the photosensitive resin composition in the form of a pigment dispersion. The dispersion may also be prepared by pre-mixing a mixture of black pigment and a pigment dispersant, adding the mixture to an organic solvent (or vehicle), and dispersing it in a disperser. The pigment dispersant can be selected according to the pigment and solvent; for example, commercially available dispersants can be used. The vehicle refers to the medium that disperses the pigment in the pigment dispersion, and is liquid in form, containing a binder component that holds the black pigment in a dispersed state, and a solvent component (organic solvent) that dissolves and dilutes the binder component.

[0263] There are no particular restrictions on the disperser, and examples of known dispersers include kneaders, roll mills, attritors, super mills, dissolvers, homomixers, and sand mills. Furthermore, fine grinding may be performed using frictional force through mechanical grinding. For information on dispersers and fine grinding, refer to the "Dictionary of Pigments" (by Kunizo Asakura, 1st edition, Asakura Shoten, 2000, pp. 438, 310).

[0264] (Method of manufacturing circuit wiring) The method for manufacturing circuit wiring relating to this disclosure is not particularly limited, as long as it uses a laminate manufactured by the method for manufacturing a laminate relating to this disclosure or a photosensitive transfer material relating to this disclosure described later. Furthermore, the method for manufacturing circuit wiring according to the present disclosure preferably includes, 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. The following describes each step of the circuit wiring manufacturing method. Unless otherwise specified, the descriptions of each step included in the laminate manufacturing method also apply to each step included in the circuit wiring manufacturing method.

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

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

[0267] In the etching process, a resin pattern formed from the photosensitive layer is used as an etching resist to perform etching on the conductive layer. As for the etching process, known methods can be applied, for example, the method described in paragraphs 0209 to 0210 of Japanese Patent Publication No. 2017-120435, the method described in paragraphs 0048 to 0054 of Japanese Patent Publication No. 2010-152155, wet etching by immersion in an etching solution, and dry etching methods such as plasma etching.

[0268] For wet etching, the etching solution used should be appropriately selected from either acidic or alkaline solutions depending on the object being etched. Examples of acidic etching solutions include aqueous solutions of a single acidic component selected from hydrochloric acid, sulfuric acid, nitric acid, acetic acid, hydrofluoric acid, oxalic acid, and phosphoric acid, as well as aqueous mixed solutions 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 a single alkaline component selected from sodium hydroxide, potassium hydroxide, ammonia, organic amines, and salts of organic amines (such as tetramethylammonium hydroxide), as well as aqueous solutions of mixed alkaline components and salts (such as 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 perform a step to remove any remaining resin patterns (removal step). The removal process is not particularly limited and can be performed as needed, but it is preferable to perform it after the etching process. There are no particular limitations on the method for removing the remaining resin pattern, but one method is to remove it by chemical treatment, and a method using a removal solution is preferred. A method for removing the photosensitive layer is to immerse a substrate having the remaining resin pattern in a stirring removal solution, preferably at a liquid temperature of 30°C to 80°C, more preferably 50°C to 80°C, for 1 to 30 minutes.

[0270] Examples of removal solutions include those obtained by dissolving an inorganic or organic alkaline component in water, dimethyl sulfoxide, N-methylpyrrolidone, or a mixture thereof. Examples of inorganic alkaline components include sodium hydroxide and potassium hydroxide. Examples of organic alkaline components include primary amine compounds, secondary amine compounds, tertiary amine compounds, and quaternary ammonium salt compounds. Alternatively, the substance may be removed using a removal solution by known methods such as the spray method, shower method, and paddle method.

[0271] <Other processes> The method for manufacturing circuit wiring may include any other steps (other steps) besides those described above. For example, the following steps are possible, but are not limited to these steps. Furthermore, examples of exposure steps, development steps, and other steps applicable to the method of manufacturing circuit wiring include the steps described in paragraphs 0035 to 0051 of Japanese Patent Application Publication No. 2006-23696. Furthermore, other steps include, but are not limited to, the steps of reducing the visible light reflectance as described in paragraph 0172 of International Publication No. 2019 / 022089, and the steps of forming a new conductive layer on the insulating film as described in paragraph 0172 of International Publication No. 2019 / 022089.

[0272] -A process to reduce visible light reflectance- A method for manufacturing circuit wiring may include a step of performing a process to reduce the visible light reflectance of some or all of the multiple conductive layers on the substrate. One treatment that reduces visible light reflectivity is oxidation. If the substrate has a conductive layer containing copper, the copper can be oxidized to copper oxide, which blackens the conductive layer and reduces its visible light reflectivity. Treatments for reducing visible light reflectance are described in paragraphs 0017 to 0025 of Japanese Patent Publication No. 2014-150118 and in paragraphs 0041, 0042, 0048, and 0058 of Japanese Patent Publication No. 2013-206315, and the contents described in these publications are incorporated herein by reference.

[0273] -Steps to form an insulating film, and steps to form a new conductive layer on the surface of the insulating film- The method for manufacturing circuit wiring may also preferably include 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. Through the above process, a second electrode pattern insulated from the first electrode pattern can be formed. The process for forming the insulating film is not particularly limited and includes known methods for forming permanent films. Alternatively, an insulating film with a desired pattern may be formed by photolithography using an insulating photosensitive material. The process of forming a new conductive layer on an insulating film is not particularly limited, and for example, a new conductive layer with a desired pattern may be formed by photolithography using a conductive photosensitive material.

[0274] In the method for manufacturing circuit wiring, it is preferable to use a substrate having multiple conductive layers on both surfaces of the substrate, and to form circuits sequentially or simultaneously on the conductive layers formed on both surfaces of the substrate. With such a configuration, it is possible to form 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 preferable to form such touch panel circuit wiring from both sides of the substrate using a roll-to-roll method.

[0275] <Application> The resin patterns produced by the resin pattern manufacturing method according to this disclosure, the laminates produced by the laminate manufacturing method according to this disclosure, and the circuit wiring produced by the circuit wiring manufacturing method according to this disclosure can be applied to various devices. Examples of devices equipped with the laminates include input devices, which are preferably touch panels, and more preferably capacitive touch panels. Furthermore, the input devices can be applied to display devices such as organic electroluminescent 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 touch panel electrodes or touch panel wiring. In other words, the photosensitive transfer material according to this disclosure is preferably used to form a protective film for touch panel electrodes or touch panel wiring.

[0276] (Method of manufacturing electronic devices) The method for manufacturing the electronic device relating to this disclosure is not particularly limited, as long as it uses a laminate manufactured by the method for manufacturing a laminate relating to this disclosure or a photosensitive transfer material relating to this disclosure described later. Furthermore, a preferred method for manufacturing an electronic device according to this disclosure includes, in this order, a preparation step of preparing a laminate obtained by the method for manufacturing a laminate according to this disclosure, and an etching step of etching the substrate in areas where the resin pattern is not arranged. The electronic device manufactured by the method for manufacturing an electronic device according to this disclosure preferably has the above-mentioned resin pattern as a permanent film.

[0277] The specific details of each step in the method for manufacturing electronic devices, as well as the sequence in which each step is performed, are as described in the sections on "Method for Manufacturing Laminates" and "Method for Manufacturing Circuit Wirings" above, and the preferred embodiments are also as described. The method for manufacturing electronic devices can be based on known methods for manufacturing electronic devices, except for forming the wiring for the electronic device using the method described above. Furthermore, the method for manufacturing electronic devices may include any other steps (other steps) not mentioned above.

[0278] While there are no particular limitations on the electronic devices, suitable examples include semiconductor packages, printed circuit boards, various wiring applications for sensor boards, touch panels, electromagnetic shielding materials, conductive films such as film heaters, liquid crystal sealing materials, and structures in the fields of micromachines or microelectronics. The above resin pattern is preferably used in the above electronic device as a permanent film, such as an interlayer insulating film, a wiring protective film, or a wiring protective film having an index matching layer. Among these, touch panels are particularly suitable as electronic devices.

[0279] Examples of mask patterns used in the manufacture of touch panels are shown in Figures 2 and 3. In pattern A shown in Figure 2 and pattern B shown in Figure 3, GR is the non-image area (light-shielding area), EX is the image area (exposure area), and DL is a hypothetical alignment frame. In a method for manufacturing a touch panel, for example, by exposing the photosensitive layer through a mask having pattern A shown in Figure 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 Figure 1 of International Publication No. 2016 / 190405. In an example of a manufactured touch panel, the central part of the exposure area EX (the patterned part where the lines are connected) is the part where transparent electrodes (electrodes for the touch panel) are formed, and the peripheral part of the exposure area EX (the part with thin lines) is the part where wiring for the peripheral extraction area is formed.

[0280] The above-described method for manufacturing an electronic device produces an electronic device having at least wiring for the electronic device, preferably, for example, a touch panel having at least wiring for the touch panel. The touch panel preferably comprises a transparent substrate, electrodes, and an insulating or protective layer. Known methods for touch panel detection include resistive, capacitive, ultrasonic, electromagnetic induction, and optical methods. Among these, the capacitive method is preferred.

[0281] Examples of touch panel types include the so-called in-cell type (for example, those described in Figures 5, 6, 7, and 8 of Japanese Patent Publication No. 2012-517051), the so-called on-cell type (for example, those described in Figure 19 of Japanese Patent Application Publication No. 2013-168125, and those described in Figures 1 and 5 of Japanese Patent Application Publication No. 2012-89102), the OGS (One Glass Solution) type, the TOL (Touch-on-Lens) type (for example, those described in Figure 2 of Japanese Patent Application Publication No. 2013-54727), various out-cell types (so-called GG, G1·G2, GFF, GF2, GF1, and G1F, etc.), and other configurations (for example, those described in Figure 6 of Japanese Patent Application Publication No. 2013-164871). Examples of touch panels include those described in paragraph 0229 of Japanese Patent Publication No. 2017-120435.

[0282] (Photosensitive transfer material) The photosensitive transfer material according to this disclosure comprises a temporary support and a transfer layer including a photosensitive layer, wherein the limiting resolution of the photosensitive layer is X T Defined as μm, the reference diameter of the particle is Y T = 0.5 × X T Y represented by T When defined as μm, Y in the surface and interior of the above photosensitive layer T The number of particles with a diameter of μm or more is 15 particles / cm². 2 The following applies: Furthermore, preferred embodiments of the photosensitive transfer material relating to this disclosure are the same as preferred embodiments of the photosensitive transfer material used in the method for manufacturing the laminate relating to this disclosure described above, except as described later.

[0283] <The limiting resolution of the photosensitive layer is X T μm, and Y on the surface and inside the photosensitive layer T Number of particles with a diameter of μm or more > The photosensitive transfer material relating to this disclosure has a limiting resolution of X for the photosensitive layer. T Defined as μm, the reference diameter of the particle is Y T = 0.5 × X T Y represented by T When defined as μm, Y in the surface and interior of the above photosensitive layer T The number of particles with a diameter of μm or more is 15 particles / cm². 2 The following is the result, and from the perspective of suppressing pinhole defects, 10 defects / cm 2 Preferably, the following: 7 pieces / cm 2 More preferably, it is 5 pieces / cm 2 The following is particularly preferable. The lower limit is 0 pieces / cm². 2 That is the case.

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

[0285] The embodiments of the present invention will be described in more detail below with reference to examples. The materials, amounts used, proportions, processing content, and processing procedures shown in the following examples can be modified as appropriate, as long as they do not depart 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 manufactured 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 FILM Systems, Inc.), and then degassed using a 2x6 radial flow superphobic filter (manufactured by Polypore, Inc.). • Acrylic polymer (AS-563A, manufactured by Daicel Finechem Co., Ltd., solids content 27.5% by mass) 167 parts • Nonionic surfactant (Naroacty CL95, manufactured by Sanyo Chemical Industries, Ltd., solid content 100% by mass) 0.7 parts • Anionic surfactant (Rapizol A-90, manufactured by NOF Corporation, diluted with water to 1% solids by mass) 114.4 parts • Carnauba wax dispersion (Cellosol 524, manufactured by Chukyo Oil & Fat Co., Ltd., solids content 30% by mass) 7 parts • Carbodiimide compound (Carbodilite V-02-L2, manufactured by Nisshinbo Inc., diluted with water to 10% solids by mass) 20.9 parts • Matting agent (Snowtex XL, manufactured by Nissan Chemical Corporation, solid content 40% by mass, average particle size 50 nm) 2.8 parts ·Wednesday 690.2 parts

[0288] [Extrusion molding] Pellets of polyethylene terephthalate (PET) produced using a citrate chelate organotitanium 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 compounding extruder with a diameter of 30 mm and melted at 280°C. After passing this molten material through a filter (pore size 2 μm), it was extruded from the die onto a cooling roll at 25°C to obtain an unstretched film. In the above method, the molten material was brought into close contact with the cooling roll using an electrostatic application method.

[0289] [Stretching and coating] A particle-containing layer with a thickness of 40 nm was formed on a 16 μm thick polyethylene terephthalate film by sequentially biaxial stretching of a solidified, unstretched film using the following method.

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

[0291] (b) Application On one side of a longitudinally stretched film, particle-containing layer-forming composition 1 was applied using a bar coater to a film thickness of 40 nm after film formation.

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

[0293] [Thermal fixation and thermal relaxation] Biaxially oriented films, which had undergone longitudinal and transverse stretching, were heat-fixed 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 oriented film was heat-relaxed under the following conditions. ·Thermal relaxation temperature: 190℃ ·Thermal relaxation rate: 4%

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

[0296] The temporary support A comprises a polyethylene terephthalate film (substrate) and a particle-containing layer in that order. The haze of temporary support A was 0.2%. The haze was measured as total optical 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 image of temporary support A, was 40 nm. The average particle diameter of the particles contained in the particle-containing layer, measured using the method described above with a Hitachi High-Technologies Corporation HT-7700 transmission electron microscope (TEM), was 50 nm.

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

[0298] <Preparation of photosensitive compositions 1-4> Each component listed in Table 1 was mixed with 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) to obtain a mixed solution, with the mixed solvent added so that the solid content concentration of the photosensitive composition was 13% by mass. Subsequently, the obtained mixed solution was filtered using a polytetrafluoroethylene filter with the pore size described in Table 4 the number of times shown in Table 4 to prepare photosensitive compositions 1 to 4, respectively.

[0299] [Table 1]

[0300] Furthermore, 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 Industry Co., Ltd. M-270: Polypropylene glycol diacrylate, manufactured by Toagosei Co., Ltd. A-TMPT: Trimethylolpropane triacrylate, manufactured by Shin-Nakamura Chemical Industry 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 Industry 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 phenol polymerization inhibitor, manufactured by BASF. F-552: Fluorine-based surfactant, Megafac F552, manufactured by DIC Corporation.

[0301] <Preparation of thermoplastic resin composition> A thermoplastic resin composition was prepared by mixing the components listed in Table 2.

[0302] [Table 2]

[0303] Note that the units of the numerical values ​​for each component listed in Table 2 are parts by mass. The meanings of the abbreviations listed in Table 2 above are explained below. 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℃, acid value: 186 mgKOH / g) • B-1: Compounds with the structure shown below (pigments that develop color when exposed to acid)

[0304] [ka]

[0305] • C-1: Compound having the structure shown below (photoacid generator, compound described in paragraph 0227 of Japanese Patent Publication No. 2013-47765, synthesized according to the method described in paragraph 0227).

[0306] [ka]

[0307] • D-3: NK Ester A-DCP (Tricyclodecanedimethanol diacrylate, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) • D-4: 8UX-015A (Polyfunctional urethane acrylate compound, Taisei Fine Chemical Co., Ltd.) • D-5: Arronix TO-2349 (a polyfunctional acrylate compound containing a carboxyl group, manufactured by Toagosei Co., Ltd.) • E-1: Megafuck F552 (manufactured by DIC Corporation) • F-1: Phenothiazine (manufactured by Fujifilm Wako Pure Chemical Corporation) ·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> A water-soluble resin composition was prepared by mixing the following components. The unit of measurement for each component is parts by mass. Deionized water: 38.12 parts Methanol (manufactured by Mitsubishi Gas Chemical Company, Inc.): 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 1-5) A thermoplastic resin composition was applied to a temporary support substrate (polyethylene terephthalate film) using a slit-shaped nozzle. The applied thermoplastic resin composition was dried at 100°C for 120 seconds to form a thermoplastic resin layer having the thickness described in Table 3.

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

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

[0312] The photosensitive transfer material obtained by the above procedure comprises a temporary support, a thermoplastic resin layer, a water-soluble resin layer, and a photosensitive layer in that order. The layer configuration (coated layers 1 to 5) for the thermoplastic resin layer, water-soluble resin layer, and photosensitive layer is shown in Table 3.

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

[0314] <Resolution> (1) A copper-layered PET substrate was fabricated by sputtering a 200 nm thick copper layer onto a 100 μm thick polyethylene terephthalate (PET) film. A photosensitive transfer material and the copper-layered PET substrate were bonded together using a roll-to-roll method with a vacuum laminator (manufactured by MCK Co., Ltd., roll temperature: 100°C, linear pressure: 1.0 MPa, linear speed: 0.5 m / min) to obtain a laminate. The resulting laminate contained, in this order, at least a PET film, a copper layer, a photosensitive layer, and a temporary support. (2) The obtained laminate was degassed under pressure for 30 minutes using an autoclave under conditions of 0.6 MPa and 60°C. Then, foreign matter on the temporary support was removed by manually rubbing the surface of the temporary support 10 times using a cleaning roll (DCH-12H2LS, manufactured by Osada Corporation). (3) Using an ultra-high pressure mercury lamp, the photosensitive layer was exposed via a line-and-space pattern mask (with a duty cycle of 1:1 and line widths that gradually changed in 1 μm increments from 1 μm to 20 μm) without removing the temporary support. (4) After removing the temporary support, the film was developed. Development was performed using a 1.0% by mass aqueous sodium carbonate solution at 25°C and shower development for 30 seconds. A resin pattern was formed by developing the photosensitive layer. The exposure dose (unit: mJ / cm²) is increased until a resin pattern with the minimum line width corresponding to the mask pattern (hereinafter referred to as the "reference pattern" in this paragraph) is obtained. 2The above series of steps (1) to (4) were performed while adjusting the settings each time. 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 matter and voids on the surface and inside the photosensitive layer> (1) A photosensitive transfer material and a PET substrate were bonded onto a polyethylene terephthalate (PET) film with a thickness of 100 μm using a roll-to-roll method with a vacuum laminator (manufactured by MCK Co., Ltd., roll temperature: 100°C, linear pressure: 1.0 MPa, linear speed: 0.5 m / min). The resulting laminate contained, in this order, at least a PET film, a photosensitive layer, and a temporary support. (2) The resulting laminate was degassed under pressure for 30 minutes using an autoclave under conditions of 0.6 MPa and 60°C. Ten arbitrary areas on the surface after the temporary support has been removed (each area: 10mm x 10mm, total area: 1,000mm²) 2 The area was observed visually using an optical microscope. The number of foreign matter and voids with a diameter of Y μm or more in each region was measured. Based on the total number of foreign matter and voids with a diameter of Y μm or more measured in 10 regions, the measurement area was measured in 1 cm². 2 Number of foreign matter and voids larger than Y μm per unit area (number of particles / cm²) 2 The value was calculated. The measurement results are shown in Table 4.

[0316] <Pinholes in wiring patterns> Except for using a wiring mask (with a duty cycle of 1:1 and line widths that gradually change in 1 μm increments from 1 μm to 20 μm; the length of the wiring pattern is 50 mm; and there are 10 wirings), the wiring pattern (i.e., the resin pattern) was formed using the same method as described in the "Resolution" section above (i.e., the method of forming a resin pattern by exposing the photosensitive layer with a standard exposure dose). The wiring pattern was visually observed using an optical microscope, and the 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 were found that were more than 1 / 4 but less than 1 / 2 the width of the wiring. C: Pinholes were found that were larger than 1 / 2 but less than 3 / 4 of the wiring width. D: A pinhole larger than 3 / 4 of the wiring width was found.

[0317] <Missing wiring pattern> For samples used to evaluate pinholes in wiring patterns, the condition of pattern defects (so-called bites) was visually observed using an optical microscope and evaluated according to the following criteria. A: No pattern defects were found, or pattern defects with a maximum diameter of less than 1 μm were found. B: Defects were observed in patterns with a maximum diameter of 1 μm to 2 μm. C: Defects in the pattern with a maximum diameter exceeding 2 μm were observed.

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

[0319] [Table 3]

[0320] [Table 4]

[0321] In addition, in the laminates obtained in Examples 1 to 18 above, the number of voids with a diameter of Y μm or more is 0 voids / cm². 2 It is presumed that the generation of voids was suppressed by pressurized degassing treatment using an autoclave.

[0322] As shown in Table 4 above, the methods for manufacturing the photosensitive transfer material and laminate in Examples 1 to 18 yielded wiring patterns with fewer pinhole defects compared to the method for manufacturing the photosensitive transfer material and laminate in Comparative Example 1, and also yielded 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 copper-layered PET substrate under the lamination conditions of roll temperature 100°C, linear pressure 1.0 MPa, and linear speed 4.0 m / min. After peeling off the temporary support, the material was exposed to ultra-high pressure mercury lamp through a line-and-space pattern mask (duty cycle 1:1, line width gradually changing from 1 μm to 10 μm in 1 μm increments) and then developed. Development was performed using a 1.0% sodium carbonate aqueous solution at 25°C, using a shower development method for 30 seconds. When the resulting patterned substrate was observed under a microscope, it was found to have a pattern with good resolution and pattern shape.

[0324] (Example 102: Laser direct writing) The photosensitive transfer material prepared in Example 1 was laminated onto the copper-layered PET substrate under the lamination conditions of roll temperature 100°C, linear pressure 1.0 MPa, and linear speed 4.0 m / min. Direct writing exposure was performed using a direct writing exposure machine (Hitachi Via Mechanics Co., Ltd., DE-1DH, light source: GaN blue-violet diode (main wavelength 405 nm ± 5 nm)) with a 21-step stoffer tablet or a predetermined mask pattern for DI exposure, at an illuminance of 80 mW / cm². 2The exposure was performed under the following conditions. This exposure was carried out using the above-mentioned Stofer 21-step step tablet as a mask, with an exposure amount that resulted in a maximum of 6 remaining film steps when exposed and developed. Development was performed using a 1.0% sodium carbonate aqueous solution at 25°C with shower development for 30 seconds. When the resulting patterned substrate was observed under a microscope, it was found to have a pattern with good resolution and pattern shape.

[0325] (Example 103) A circuit formation substrate was prepared by sputtering a 150 nm thick ITO film as a second conductive layer on a 100 μm thick PET substrate, and then depositing a 200 nm thick copper film as a first conductive layer on top of that using vacuum deposition. The photosensitive transfer material obtained in Example 1 was placed on a copper layer, and after peeling off the cover film, it was bonded to the substrate (laminate roll temperature 100°C, linear pressure 0.8 MPa, linear speed 3.0 m / min.) to form a laminate. The resulting laminate was then subjected to contact pattern exposure using a photomask with pattern A shown in Figure 2, in which conductive layer pads were connected in one direction after peeling off the temporary support. A high-pressure mercury lamp with the i-line (365 nm) as the main exposure wavelength was used for exposure. Subsequently, development and washing were performed 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 in which both copper and ITO were patterned with pattern A. Next, the photosensitive transfer material obtained in Example 1 was reattached to the remaining resist (cured negative-type photosensitive layer) under the same conditions as in Example 101, after peeling off the cover film. With the alignment correct, the temporary support was peeled off and the pattern was exposed using a photomask with pattern B shown in Figure 3. After that, development and washing were performed to obtain pattern B. Next, the copper wiring was etched using Cu-02, and the remaining cured negative-type photosensitive layer was peeled off using a stripping solution (KP-301 manufactured by Kanto Chemical Co., Ltd.) to obtain a circuit wiring board. When the obtained circuit wiring board was examined under a microscope, it was found to have a clean pattern with no peeling or chipping.

[0326] The disclosure of Japanese Patent Application No. 2021-011932, filed on 28 January 2021, is incorporated herein by reference in its entirety. All documents, patent applications, and technical standards described herein are incorporated by reference to the same extent as if each individual document, patent application, and technical standard were specifically and individually noted 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: Exposure area (image area), DL: Alignment frame

Claims

1. It has a temporary support and a transfer layer including a photosensitive layer, The limiting resolution of the photosensitive layer is X Ｔ Defined as μm, the reference diameter of the particle is Y Ｔ = 0.5 × X Ｔ Y represented by Ｔ When defined as μm, Y in the surface and interior of the photosensitive layer Ｔ The number of particles with a diameter of μm or more is 15 particles / cm². ２ The following is A photosensitive transfer material used to form patterns through exposure and development. Note: Limit resolution X Ｔ This shall be determined by the following method. A photosensitive transfer material is transferred onto a substrate to create a laminate. The resulting laminate is exposed to light through a line-and-space pattern mask, which has a duty cycle of 1:1 and a line width that changes gradually from 1 μm to 20 μm in 1 μm increments. After removing the temporary support, the resin pattern is formed by developing the resin. The above series of procedures are performed while adjusting the exposure amount (unit: mJ / cm²) each time until a resin pattern with the minimum line width corresponding to the mask pattern (hereinafter referred to as the "reference pattern") is obtained. The minimum line width of the reference pattern is set to the limiting resolution X of the photosensitive layer. Ｔ We will use μm as the unit.

2. The photosensitive transfer material according to claim 1, wherein the thickness of the photosensitive layer is 5.0 μm or less.

3. The photosensitive transfer material according to claim 1 or claim 2, wherein the thickness of the temporary support is 16 μm or less.

4. The photosensitive transfer material according to any one of claims 1 to 3, further comprising a protective film on the transfer layer.

5. The photosensitive transfer material according to any one of claims 1 to 4, further comprising a water-soluble resin layer between the temporary support and the photosensitive layer.

6. The photosensitive transfer material according to any one of claims 1 to 4, further comprising a thermoplastic resin layer and a water-soluble resin layer between the temporary support and the photosensitive layer.

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