Laminate manufacturing method

Abstract

Provided is a laminate manufacturing method that is able to efficiently manufacture a laminate which includes a plurality of light-emitting elements and in which the leakage of light from adjacent light-emitting elements is suppressed.　This laminate manufacturing method has: a step 1 in which a substrate equipped with light-emitting elements, which includes a substrate and a plurality of light-emitting elements arranged on the substrate, and a transfer film, which includes a temporary support body and a photosensitive layer, are bonded to each other such that the surface of the substrate on which the light-emitting elements are arranged faces the surface of the transfer film on the opposite side from the temporary support body, and the light-emitting elements are covered by the photosensitive layer; a step 2 in which the photosensitive layer undergoes pattern exposure; a step 3 in which the exposure photosensitive layer is developed, thereby forming a resin pattern having openings at positions corresponding to the light-emitting elements; and, between the step 1 and the step 2 or between the step 2 and the step 3, a step in which the temporary support body is peeled off.

Description

Manufacturing method of laminate

[0001] The present invention relates to a method for producing a laminate.

[0002] In recent years, micro LED display elements (e.g., micro LED displays) equipped with an array substrate on which a plurality of minute LED chips are mounted have been developed as next-generation display elements. For example, Patent Literature 1 discloses a micro LED mounting method using laser lift-off and a micro LED display.

[0003] Japanese Patent Application Laid-Open No. 2021-163945

[0004] The present inventors, referring to the micro LED display of Patent Document 1, fabricated a stack comprising multiple light-emitting elements (e.g., micro LED chips) arranged on a substrate and examined its performance. They found that light leakage from adjacent light-emitting elements can degrade display performance. For example, when a pixel is constructed with light-emitting elements each emitting red (R), green (G), and blue (B), light leakage from adjacent light-emitting elements can cause light mixing, preventing the desired display. Based on the above findings, the present inventors found that there is room for further investigation into a method for manufacturing a stack including multiple light-emitting elements that suppresses light leakage from adjacent light-emitting elements. It should be noted that a method for manufacturing a stack is typically also required to have a short manufacturing time (in other words, to be able to manufacture efficiently).

[0005] Therefore, an object of the present invention is to provide a method for manufacturing a stack that can efficiently manufacture a stack including multiple light-emitting elements in which light leakage from adjacent light-emitting elements is suppressed.

[0006] The present inventors have found that the above problems can be solved by the following configuration.

[0007] [1] A method for manufacturing a laminate, comprising: Step 1: bonding the substrate with light-emitting elements, the substrate including a substrate and a plurality of light-emitting elements arranged on the substrate, to a surface of the transfer film opposite to the temporary support, the surface of the transfer film including a temporary support and a photosensitive layer, the surface facing the light-emitting elements, and the light-emitting elements being covered by the photosensitive layer; Step 2: performing patternwise exposure on the photosensitive layer; and Step 3: developing the exposed photosensitive layer to form a resin pattern having openings in positions corresponding to the light-emitting elements, the method comprising: peeling off the temporary support between Steps 1 and 2, or between Steps 2 and 3. [2] The method for manufacturing the laminate according to [1], wherein the film thickness of the photosensitive layer in the transfer film is greater than the height of the light-emitting elements. [3] The method for manufacturing a laminate according to [1] or [2], wherein the photosensitive layer in the transfer film contains an alkali-soluble resin, a polymerizable compound, and a photopolymerization initiator. [4] The method for producing a laminate according to [1] or [2], wherein the photosensitive layer of the transfer film contains a polymer and a photoacid generator. [5] The method for producing a laminate according to any one of [1] to [4], wherein the photosensitive layer of the transfer film contains 5.0 mass% or less of water, relative to the total mass of the photosensitive layer. [6] The method for producing a laminate according to any one of [1] to [5], wherein the photosensitive layer of the transfer film contains 5.0 mass% or less of an organic solvent, relative to the total mass of the photosensitive layer. [7] The method for producing a laminate according to any one of [1] to [6], wherein the photosensitive layer of the transfer film contains 100 mass ppm or less of chloride ions, relative to the total mass of the photosensitive layer. [8] The method for producing a laminate according to any one of [1] to [7], wherein the photosensitive layer of the transfer film contains a white pigment. [9] The method for producing a laminate according to any one of [1] to [7], wherein the photosensitive layer in the transfer film has, in order from the temporary support side, a photosensitive light absorbing layer precursor layer and a photosensitive light reflecting layer precursor layer.

[10] The method for producing a laminate according to any one of [1] to [7], wherein the photosensitive layer in the transfer film is a photosensitive light absorbing layer precursor layer.

[11] The method for producing a laminate according to any one of [1] to [7], further comprising, after step 3, step 4 of arranging a light-reflecting film on the sidewall of the opening.

[0008] According to the present invention, it is possible to provide a method for manufacturing a stack that can efficiently manufacture a stack including a plurality of light-emitting elements in which light leakage from adjacent light-emitting elements is suppressed.

[0009] FIG. 1 is a schematic diagram for explaining step (1-1). FIG. 2 is a schematic diagram for explaining step (1-2). FIG. 3 is a schematic diagram for explaining step (1-3). FIG. 4 is a schematic diagram for explaining the structure of a transfer film. FIG. 5 is a schematic diagram for explaining the structure of a transfer film. FIG. 6 is a schematic diagram for explaining step (2-4).

[0010] The present invention will be described in detail below. In this specification, a numerical range expressed using "to" means a range that includes the numerical values ​​before and after "to" as the upper and lower limits. In this specification, in numerical ranges described in stages, the upper or lower limit value described in a certain numerical range may be replaced with the upper or lower limit value of another numerical range described in stages. Furthermore, in numerical ranges described in this specification, the upper or lower limit value described in a certain numerical range may be replaced with a value shown in the examples.

[0011] In this specification, the term "process" includes not only an independent process but also a process that cannot be clearly distinguished from other processes, as long as the intended purpose of the process is achieved.

[0012] In this specification, unless otherwise specified, the weight average molecular weight (Mw) and number average molecular weight (Mn) are values ​​converted using a gel permeation chromatography (GPC) analyzer using TSKgel GMHxL, TSKgel G4000HxL, or TSKgel G2000HxL (all trade names manufactured by Tosoh Corporation) as a column, THF (tetrahydrofuran) as an eluent, a differential refractometer as a detector, and polystyrene as a standard substance. Also, in this specification, unless otherwise specified, the molecular weight of a compound having a molecular weight distribution is the weight average molecular weight (Mw). In this specification, unless otherwise specified, the content of metal elements is a value measured using an inductively coupled plasma (ICP) spectrometer. In this specification, unless otherwise specified, the hue is a value measured using a color difference meter (CR-221, manufactured by Minolta Co., Ltd.).

[0013] In this specification, "(meth)acrylic" is a concept that includes both acrylic and methacrylic, "(meth)acryloyl" is a concept that includes both acryloyl and methacryloyl, and "(meth)acrylate" is a concept that includes both acrylate and methacrylate.

[0014] In this specification, "alkali-soluble" means that the solubility in 100 g of a 1 mass % aqueous sodium carbonate solution at a liquid temperature of 22° C. is 0.1 g or more. Therefore, for example, an alkali-soluble resin refers to a resin that satisfies the above-mentioned solubility conditions.

[0015] As used herein, "water-soluble" means that the solubility in 100 g of water having a pH of 7.0 and a liquid temperature of 22° C. is 0.1 g or more. Therefore, for example, a water-soluble resin refers to a resin that satisfies the above-mentioned solubility conditions.

[0016] In this specification, the "solid content" of a composition means components that form a composition layer formed using the composition, and when the composition contains a solvent (organic solvent, water, etc.), it means all components excluding the solvent. Furthermore, liquid components that form a composition layer are also considered to be solid content.

[0017] As used herein, "transparent" means that the average transmittance of visible light having a wavelength of 400 to 700 nm is 80% or more, preferably 90% or more. Therefore, a "transparent layer" refers to a layer having an average transmittance of visible light having a wavelength of 400 to 700 nm of 80% or more. The average transmittance is measured for rectilinear transmitted light at 1 nm intervals. As used herein, the average transmittance of visible light is a value measured at 25°C using a spectrophotometer, and can be measured using, for example, a spectrophotometer U-3310 manufactured by Hitachi, Ltd.

[0018] In this specification, unless otherwise specified, the thickness of each layer (for example, a photosensitive layer, a light-reflecting layer precursor layer, and a light-absorbing layer precursor layer) is a value obtained by observing a cross section cut with a microtome with a SEM (scanning electron microscope) or a TEM (transmission electron microscope) and measuring the thickness at 10 points, and using the average value of the thicknesses. However, thicknesses of 1 μm or more are measured with the SEM, and thicknesses of less than 1 μm are measured with the TEM.

[0019] In this specification, unless otherwise specified, the refractive index refers to the refractive index measured at 25° C. using a measuring device conforming to the ellipsometry method at a wavelength of 550 nm.

[0020] [Method for manufacturing laminate] The method for manufacturing a laminate of the present invention includes: step 1 of bonding the substrate with light-emitting elements and the transfer film so that a surface of the substrate with light-emitting elements, which includes a substrate and a plurality of light-emitting elements arranged on the substrate, faces the surface of the transfer film, which includes a temporary support and a photosensitive layer, opposite the temporary support, and the light-emitting elements are covered with the photosensitive layer; step 2 of exposing the photosensitive layer to patterned light; and step 3 of developing the exposed photosensitive layer to form a resin pattern having openings at positions corresponding to the light-emitting elements, and further includes a step of peeling off the temporary support between steps 1 and 2, or between steps 2 and 3.

[0021] According to the laminate manufacturing method of the present invention having the above-described configuration, a laminate comprising a substrate with light-emitting elements arranged thereon and a partition layer arranged around each light-emitting element on the substrate with light-emitting elements can be efficiently manufactured by lithography using a transfer film. The laminate obtained by the above manufacturing method has a partition layer around each light-emitting element, thereby suppressing light leakage from adjacent light-emitting elements. Furthermore, the laminate manufacturing method of the present invention can significantly reduce manufacturing time compared to a manufacturing method in which, for example, a partition layer is formed in advance at the intended position where the light-emitting element will be arranged on the substrate by lithography using a transfer film (i.e., a resin pattern having an opening at the intended position where the light-emitting element will be arranged), and then the light-emitting element is arranged in the predetermined position. Examples of uses of the laminate obtained by the laminate manufacturing method of the present invention include micro LED display elements, etc.

[0022] In the following, the term "better effect of the present invention" may also mean that the laminate obtained by the laminate manufacturing method of the present invention can better suppress light leakage from adjacent light-emitting elements and / or that the efficiency of the laminate manufacturing method of the present invention is better.

[0023] The method for producing a laminate of the present invention will be described below with reference to the drawings. [First Embodiment] The first embodiment of the method for producing a laminate of the present invention (hereinafter also simply referred to as "first embodiment of the present invention") has the following steps (1-1) to (1-3).

[0024] Step (1-1) (bonding step): a step of bonding the substrate with light-emitting elements to the transfer film so that a surface of the substrate with light-emitting elements, which includes a substrate and a plurality of light-emitting elements arranged on the substrate, facing the light-emitting element side of the substrate and a surface of the transfer film, which includes a temporary support and a photosensitive layer, facing away from the temporary support, and the light-emitting elements are covered with the photosensitive layer; Step (1-2) (exposure step): a step of performing pattern exposure on the photosensitive layer; Step (1-3) (development step): a step of developing the exposed photosensitive layer to form a resin pattern having openings at positions corresponding to the light-emitting elements; Furthermore, the first embodiment of the present invention has the following step (1-A) between step (1-1) and step (1-2), or between step (1-2) and step (1-3). Step (1-A) (temporary support peeling step): a step of peeling off the temporary support.

[0025] <<Step (1-1), Bonding Step>> Step (1-1) is a step of bonding the substrate with light-emitting elements, which includes a substrate and a plurality of light-emitting elements arranged on the substrate, to the transfer film, such that the surface of the substrate with light-emitting elements facing the light-emitting element faces the surface of the transfer film, which includes a temporary support and a photosensitive layer, opposite the temporary support, and the light-emitting elements are covered by the photosensitive layer. A specific procedure for step (1-1) will be described with reference to FIG. 1 . In step (1-1), the substrate with light-emitting elements 10 and the transfer film 20 are bonded together such that the surface of the substrate with light-emitting elements 10 opposite the substrate 12 (i.e., the surface having the light-emitting elements 14) faces the surface of the transfer film 20 opposite the temporary support 22 (i.e., the surface on the photosensitive layer 24 side). Note that FIG. 1 shows the state after bonding the substrate with light-emitting elements 10 and the transfer film 20.

[0026] In addition, the thickness of the photosensitive layer in the transfer film is preferably greater than the height of the light-emitting element, since this makes it easier to cover the light-emitting element with the photosensitive layer in the bonding process and makes the effects of the present invention more excellent. Here, the height of the light-emitting element refers to the thickness of the light-emitting element in the normal direction to the reference plane, where the substrate surface at a location where the light-emitting element is not arranged on the substrate with the light-emitting element is taken as the reference plane. In other words, in the case of the laminate shown in Figure 1, the height of the light-emitting element 14 refers to the thickness T1 of the light-emitting element 14 in the normal direction to the reference plane 12A, where the substrate surface 12A at a location where the light-emitting element 14 is not arranged on the substrate with the light-emitting element 10 is taken as the reference plane.

[0027] When the transfer film has a protective film, which will be described later, it is preferable to carry out the laminating step after peeling off the protective film.

[0028] In lamination, it is preferable to contact and press the surface of the transfer film opposite the temporary support side with the surface of the light-emitting element-equipped substrate on the light-emitting element side. Examples of the pressure-bonding method include known transfer methods and lamination methods. A preferred method involves placing the surface of the transfer film opposite the temporary support side on the surface of the light-emitting element side of the light-emitting element-equipped substrate, and applying pressure and heat with a roll or the like. Examples of the lamination method include a method using a known laminator such as a vacuum laminator or an auto-cut laminator. The lamination temperature is preferably 70 to 130°C.

[0029] <Substrate with Light-Emitting Elements> The substrate with light-emitting elements has a substrate and a plurality of light-emitting elements arranged on the substrate. Examples of the substrate include a resin substrate, a glass substrate, a ceramic substrate, and a semiconductor substrate. Examples of materials for the resin substrate include polyethylene terephthalate resins, polynaphthalene terephthalate resins, cycloolefin resins, polyimide resins, polycarbonate resins, polyacrylate resins, polyethersulfone resins, silicone resins, and epoxy resins. The thickness of the resin substrate is preferably 5 to 200 μm, and more preferably 10 to 100 μm. Considering the exposure step (step (1-2)), the substrate is preferably a transparent substrate. Examples of transparent substrates include a resin substrate (e.g., a resin film) and a glass substrate. The resin substrate is preferably a resin substrate that transmits visible light. Preferred components of the resin substrate that transmits visible light include, for example, polyamide resins, polyethylene terephthalate resins, polyethylene naphthalate resins, cycloolefin resins, polyimide resins, and polycarbonate resins. Among these, the transparent substrate is preferably a polyamide film, a polyethylene terephthalate film, a cycloolefin polymer, a polyethylene naphthalate film, a polyimide film, or a polycarbonate film, and more preferably a polyethylene terephthalate film. The thickness of the transparent substrate is not limited. The thickness of the transparent substrate is preferably 10 to 200 μm, more preferably 20 to 120 μm, and even more preferably 20 to 100 μm.

[0030] The substrate is preferably a substrate having at least one of an electrode and a lead wiring. The electrode is preferably composed of a metal oxide film such as ITO (indium tin oxide) or IZO (indium zinc oxide), or a thin metal wire such as a metal mesh or a metal nanowire. Examples of the thin metal wire include thin metal wires such as silver and copper, and conductive silver materials such as silver mesh and silver nanowire are preferred.

[0031] The material of the lead wire is preferably a metal, such as gold, silver, copper, molybdenum, aluminum, titanium, chromium, zinc, and manganese, and alloys of these metals, with copper, molybdenum, aluminum, and titanium being preferred, and copper being more preferred.

[0032] Examples of light-emitting elements include micro LED chips. The arrangement of the light-emitting elements on the substrate with light-emitting elements is not particularly limited. Examples of the arrangement of the light-emitting elements include providing multiple cells (e.g., corresponding to one pixel) on the substrate, and arranging N light-emitting elements (e.g., one, two, or three) emitting red (R), green (G), and blue (B) light-emitting elements in each cell. The shape of the cell is not particularly limited, and examples include a lattice-like shape. The arrangement of the light-emitting elements in the cell (e.g., a linear array) is also not particularly limited. While R, G, and B are given as examples of the light-emitting colors of the light-emitting elements, the light-emitting elements are not particularly limited as long as they emit light, and the light-emitting colors can be selected appropriately. The light-emitting elements typically have terminals for connection to external electrodes.

[0033] When the light-emitting element is a micro LED chip, the type of LED may be an LED having a peak wavelength in the visible light region (hereinafter also referred to as a "visible light LED"), or an LED having a peak wavelength in the ultraviolet light region (hereinafter also referred to as a "UV-LED").

[0034] <Transfer Film> The transfer film that can be used in the step (1-1) will be described later.

[0035] <<Step (1-2), Exposure Step>> The exposure step is a step of patternwise exposing the photosensitive layer. "Pattern exposure" refers to a form of patternwise exposure, in which exposed and non-exposed parts are present. The positional relationship between the exposed parts (exposed regions) and non-exposed parts (non-exposed regions) in the patternwise exposure can be adjusted as appropriate. The exposure direction may be from the photosensitive layer side or the side opposite to the photosensitive layer side (substrate side). The exposure step is typically a step of performing patternwise exposure via a photomask. In the exposure step, the photomask and the laminate, which is the photosensitive object, may or may not be in contact with each other.

[0036] When a temporary support peeling step described later is carried out between the laminating step and the exposure step, the exposure step is preferably an exposure step in which a photomask is brought into contact with the surface of the laminate from which the temporary support obtained in the temporary support peeling step is peeled, opposite to the substrate side, and pattern exposure is performed. In other words, an exposure step in which a photomask is brought into contact with the surface (such as the surface of the photosensitive layer) exposed by peeling the temporary support of the laminate from which the temporary support has been peeled, and pattern exposure is performed on the photosensitive layer is preferred.

[0037] When the photosensitive layer is a negative photosensitive layer, a curing reaction of components contained in the photosensitive layer can occur in the exposed regions (regions corresponding to the openings of the photomask) through an exposure process of pattern exposure. By performing a development process (step (1-3)) after exposure, the unexposed regions of the photosensitive layer are removed to form a pattern. In the exposure process, a photomask having a pattern in which the portions corresponding to the positions where the light-emitting elements are arranged are non-openings and the portions corresponding to the positions between adjacent light-emitting elements (in other words, the positions where the partition wall layer is formed) are open, so that a resin pattern having predetermined openings at positions corresponding to the light-emitting elements can be formed after the development process (step (1-3)). The exposure process allows the photosensitive layer to be exposed according to the pattern shape of the photomask. Note that FIG. 2 shows a pattern exposure process when the photosensitive layer is a negative photosensitive layer. In the laminate of FIG. 2, a curing reaction of components contained in the photosensitive layer 24 can occur in the openings (exposed regions) of the photomask 30. On the other hand, the photosensitive layer in the non-opening portions (non-exposed regions) of the photomask 30 is removed by carrying out a development step (step (1-3)) after exposure.

[0038] On the other hand, when the photosensitive layer is a positive photosensitive layer, structural changes may occur in the components contained in the photosensitive layer in the exposed regions (regions corresponding to the openings of the photomask), and the exposed regions of the photosensitive layer are removed by performing a development step (step (1-3)) after exposure to form a pattern. In other words, the structural changes in the components contained in the photosensitive layer in the exposed regions create a dissolution contrast in the developer between the exposed and unexposed regions, and as a result, the exposed regions of the photosensitive layer are removed by the development step (step (1-3)) after exposure to form a pattern. In the exposure step, a photomask having a pattern in which portions corresponding to the positions where the light-emitting elements are arranged are openings and portions corresponding to the positions between adjacent light-emitting elements (in other words, positions where the partition layer is formed) are non-openings can be used to form a resin pattern having predetermined openings at positions corresponding to the light-emitting elements after the development step (step (1-3)). The exposure step allows the photosensitive layer to be exposed according to the pattern shape of the photomask.

[0039] The method for producing a laminate of the present invention also preferably includes a photomask peeling step of peeling off the photomask used in the exposure step between the exposure step and the development treatment. Examples of the photomask peeling step include known peeling steps.

[0040] The light source for the pattern exposure can be appropriately selected and used as long as it can irradiate light in a wavelength range capable of curing the photosensitive layer (e.g., 365 nm and 405 nm). Among these, the dominant wavelength of the exposure light is preferably 365 nm. The dominant wavelength is the wavelength with the highest intensity.

[0041] Examples of light sources include various lasers, light-emitting diodes (LEDs), ultra-high pressure mercury lamps, high pressure mercury lamps, and metal halide lamps. The exposure dose is 5 to 200 mJ / cm. ２ is preferred, and 10 to 200 mJ / cm ２ Preferred embodiments of the light source, exposure dose, and exposure method used for exposure are described, for example, in paragraphs

[0146] to

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

[0042] It is also preferable that the cross section (cross section perpendicular to the substrate) of the resin pattern obtained through the development step (step (1-3)) is tapered. Specifically, the resin pattern preferably has openings formed therein, the opening area of ​​which increases from the substrate side toward the opposite side. When the photosensitive layer is a negative photosensitive layer, the cross section of the resin pattern can be tapered, for example, by introducing a light scattering plate into the exposure device and applying exposure light from an oblique direction. When the cross section of the resin pattern is tapered, the angle between the sidewall of the opening and the substrate surface on which the light-emitting element is not disposed in the light-emitting element-equipped substrate (the "taper angle"; specifically, this corresponds to the angle θ in FIG. 3) is preferably less than 90°, more preferably 10 to 80°, even more preferably 15 to 80°, particularly preferably 20 to 80°, and most preferably 40 to 60°.

[0043] <<Step (1-A), Temporary Support Peeling Step>> A temporary support peeling step is performed between the laminating step and the exposure step, or between the exposure step and the development step. It is particularly preferable to have a peeling step between the laminating step and the exposure step. The peeling step is a step of peeling the temporary support from the laminate of the transfer film and the substrate with the light-emitting element. Examples of methods for peeling the temporary support include known peeling methods. Specific examples include the cover film peeling mechanism described in paragraphs

[0161] to

[0162] of JP 2010-072589 A.

[0044] <<Step (1-3), Development Step>> The development step is a step in which the exposed photosensitive layer is developed using a developer to form a resin pattern. The developer is preferably an alkaline aqueous solution. Examples of alkaline compounds that can be contained in the alkaline aqueous solution include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, and choline (2-hydroxyethyltrimethylammonium hydroxide).

[0045] Examples of the development method include puddle development, shower development, spin development, and dip development.

[0046] In this specification, examples of developers that can be suitably used include the developers described in paragraph

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

[0195] of WO 2015 / 093271.

[0047] After development, it is also preferable to carry out a rinsing treatment before proceeding to the next step. Water or the like can be used for the rinsing treatment.

[0048] By undergoing the development process, a resin pattern can be formed on the substrate with light-emitting elements. The resin pattern is arranged in a position corresponding to the space between adjacent light-emitting elements, with openings at positions corresponding to the light-emitting elements. In other words, a partition layer can be formed around each light-emitting element to separate it from adjacent light-emitting elements and prevent light leakage. Figure 3 shows a schematic cross-sectional view of a laminate 40 after the development process has been performed. The laminate 40 is composed of a substrate with light-emitting elements 10 and a resin pattern 42. Specifically, the resin pattern 42 is arranged in a position corresponding to the space between adjacent light-emitting elements 14, with openings 44 at positions corresponding to the light-emitting elements 14. In the case of the laminate having the negative photosensitive layer shown in Figure 2, the resin pattern 42 corresponds to the cured film of the negative photosensitive layer.

[0049] <<Step (1-B) (Post-Exposure Step) and Step (1-C) (Post-Bake Step)>> The first embodiment of the present invention may further include a step of exposing the resin pattern obtained by the development step (step (1-3)) (hereinafter also referred to as "step (1-B)" or "post-exposure step") and / or a step of heating (hereinafter also referred to as "step (1-C)" or "post-bake step"). When the first embodiment of the present invention includes both the post-exposure step and the post-bake step, it is preferable to carry out the post-bake step after carrying out the post-exposure step. The exposure dose in the post-exposure step is 100 to 5000 mJ / cm ２ is preferred, and 200 to 3000 mJ / cm ２ The post-baking temperature in the post-baking step is preferably 80 to 250° C., more preferably 90 to 160° C. The post-baking time in the post-baking step is preferably 1 to 180 minutes, more preferably 10 to 60 minutes.

[0050] <<Transfer Film>> The transfer film that can be used in the first embodiment of the present invention will be described below. The configuration of the transfer film is not particularly limited as long as it has a temporary support and a photosensitive layer (a layer that exhibits photosensitivity). The photosensitive layer may be either a positive-type photosensitive layer or a negative-type photosensitive layer, but is preferably a negative-type photosensitive layer. The photosensitive layer may be a single layer or two or more layers. The transfer film may have a composition layer other than the photosensitive layer (for example, a water-soluble resin layer, etc.). The transfer film may have a protective film.

[0051] FIG. 4 shows a specific example of a transfer film. The transfer film 20A shown in FIG. 4 has a temporary support 22, a photosensitive layer 24, and a protective film 50, in this order. The photosensitive layer 24 is a layer that exhibits photosensitivity and may be either a positive-type photosensitive layer or a negative-type photosensitive layer, but a negative-type photosensitive layer is preferred. When the photosensitive layer 24 is a negative-type photosensitive layer, the components contained in the layer undergo a curing reaction upon exposure to light, resulting in a resin layer (cured layer). Note that the transfer film 20A shown in FIG. 4 has a protective film 50 disposed therein, but the protective film 50 does not necessarily have to be disposed. The transfer film 20A shown in FIG. 4 may also have a composition layer other than the photosensitive layer 24.

[0052] The transfer film preferably has the following configuration in the laminate formed according to the first embodiment of the present invention, in that the brightness of the light-emitting element is superior, external light reflection is more easily suppressed, and / or stray light that is unnecessarily generated when the light-emitting element is turned on can be absorbed: (N1) Temporary support / photosensitive light-absorbing layer precursor layer / protective film (N2) Temporary support / photosensitive light-reflecting layer precursor layer / protective film (N3) Temporary support / photosensitive light-absorbing layer precursor layer / photosensitive light-reflecting layer precursor layer / protective film

[0053] The transfer films shown in (N1) to (N3) above are in the form of a protective film, but the protective film need not be provided. The photosensitive light-absorbing layer precursor layer (hereinafter abbreviated as "light-absorbing layer precursor layer") and the photosensitive light-reflecting layer precursor layer (hereinafter abbreviated as "light-reflecting layer precursor layer") are layers that exhibit photosensitivity and are typically negative-type photosensitive layers.

[0054] The transfer films of the above (N1) and (N2) embodiments correspond to the transfer film 20A shown in FIG. 4 in which the photosensitive layer 24 is a photosensitive light-absorbing layer precursor layer, and the photosensitive layer 24 is a photosensitive light-reflecting layer precursor layer, respectively. In the first embodiment of the present invention, when the transfer film of the above (N1) embodiment is used, the light-absorbing layer precursor layer undergoes a curing reaction at the exposed locations in the patterned exposure in step (1-2), thereby forming a patterned light-absorbing layer. That is, the resin pattern can function as a light-absorbing partition wall layer. A laminate having such a resin pattern as a partition wall layer easily absorbs external light and stray light. As a result, the black density is better when the light-emitting element is not lit. Furthermore, in the first embodiment of the present invention, when the transfer film of the above (N2) embodiment is used, the light-reflecting layer precursor layer undergoes a curing reaction at the exposed locations in the patterned exposure in step (1-2), thereby forming a patterned light-reflecting layer. That is, the resin pattern can function as a light-reflective partition wall layer. In a laminate having such a resin pattern as a partition wall layer, light from the light emitting element is easily reflected by the partition wall when the light emitting element is turned on, resulting in high brightness.

[0055] The transfer film of the above-mentioned (N3) embodiment corresponds to the case where the photosensitive layer 24 in the transfer film 20A shown in Fig. 4 has a two-layer structure, one of which is a photosensitive light-absorbing layer precursor layer and the other is a photosensitive light-reflecting layer precursor layer. Fig. 5 shows a schematic cross-sectional view of the transfer film of the above-mentioned (N3) embodiment. The transfer film 20A shown in Fig. 5 has, in this order, a temporary support 22, a photosensitive layer 24, and a protective film 50. The photosensitive layer 24 has, from the temporary support 22 side toward the protective film 50, a light-absorbing layer precursor layer 26 and a light-reflecting layer precursor layer 28.

[0056] In the first embodiment of the present invention, when the transfer film of the above aspect (N3) is used, the light-absorbing layer precursor layer and the light-reflecting layer precursor layer undergo a curing reaction at the exposed locations in the patterned exposure in step (1-2), and a resin pattern having a light-reflecting layer and a light-absorbing layer in this order from the substrate side with light-emitting elements can be formed by the development step (step (1-3)). In a laminate having such a resin pattern as a partition layer, external light and stray light are absorbed by the light-absorbing layer, resulting in better black density when the light-emitting elements are not lit. Furthermore, the light-reflecting layer makes it easier for light from the light-emitting elements to be reflected by the partition when the light-emitting elements are lit, thereby increasing brightness.

[0057] As will be described later, the light absorbing layer precursor layer corresponds to a negative photosensitive layer containing a light absorbing substance, and the light reflecting layer precursor layer corresponds to a negative photosensitive layer containing a reflectivity adjusting agent.

[0058] The configuration of the transfer film is also preferably as follows, in that in the laminate formed by the first embodiment of the present invention, the brightness of the light-emitting element is superior, external light reflection is more easily suppressed, and / or stray light that is unnecessarily generated when the light-emitting element is turned on can be absorbed. (P1) Temporary support / photosensitive light-absorbing layer / protective film (P2) Temporary support / photosensitive light-reflecting layer / protective film (P3) Temporary support / photosensitive light-absorbing layer / photosensitive light-reflecting layer / protective film Note that the transfer films shown in (P1) to (P3) above are embodiments in which a protective film is disposed, but a protective film does not have to be disposed. Furthermore, the photosensitive light-absorbing layer and the photosensitive light-reflecting layer are layers that exhibit photosensitivity and are typically positive-type photosensitive layers.

[0059] The light absorbing layer corresponds to a positive photosensitive layer containing a light absorbing substance, and the light reflecting layer corresponds to a positive photosensitive layer containing a reflectivity adjusting agent.

[0060] Each element constituting the transfer film will be described below.

[0061] <Temporary Support> The transfer film has a temporary support, which is a member that supports the photosensitive layer and is ultimately removed by a peeling treatment.

[0062] The temporary support may have a single layer structure or a multi-layer structure. The temporary support is preferably a film, more preferably a resin film. The temporary support is preferably a film that is flexible and does not significantly deform, shrink, or stretch under pressure, or under pressure and heat. Examples of the film include polyethylene terephthalate film (e.g., biaxially oriented polyethylene terephthalate film), polymethyl methacrylate film, cellulose triacetate film, polystyrene film, polyimide film, and polycarbonate film. Among these, polyethylene terephthalate film is preferred as the temporary support. Furthermore, it is preferred that the film used as the temporary support be free of deformations such as wrinkles, scratches, etc.

[0063] The temporary support preferably has high transparency in order to enable pattern exposure through the temporary support, and the transmittance at 365 nm, 405 nm, and 436 nm is preferably 60% or more, more preferably 70% or more, even more preferably 80% or more, and particularly preferably 90% or more. Preferred values ​​of transmittance include, for example, 87%, 92%, and 98%. In terms of pattern formability during pattern exposure through the temporary support and transparency of the temporary support, it is preferable that the temporary support has a small haze. Specifically, the haze value of the temporary support is preferably 2% or less, more preferably 0.5% or less, and even more preferably 0.1% or less. In terms of pattern formability during pattern exposure through the temporary support and transparency of the temporary support, it is preferable that the number of fine particles, foreign matter, and defects contained in the temporary support is small. The number of fine particles, foreign matter, and defects with a diameter of 1 μm or more in the temporary support should be 50 / 10 mm. ２ Preferably, 10 pieces / 10 mm or less ２ More preferably, 3 pieces / 10 mm or less ２ More preferably, 0 pieces / 10 mm or less ２ is particularly preferred.

[0064] The thickness of the temporary support is not particularly limited, but is preferably 5 to 200 μm, and from the viewpoints of ease of handling and versatility, is more preferably 5 to 150 μm, still more preferably 5 to 50 μm, and particularly preferably 5 to 25 μm. The thickness of the temporary support can be calculated as the average value of any five points measured by cross-sectional observation using an SEM (Scanning Electron Microscope).

[0065] Furthermore, in order to improve the adhesion between the temporary support and the photosensitive layer formed on the temporary support, the surface of the temporary support that comes into contact with the photosensitive layer may be surface-modified by UV (ultraviolet) irradiation, corona discharge, plasma, or the like.

[0066] When the surface modification of the temporary support is carried out by UV irradiation, the exposure dose is 10 to 2000 mJ / cm ２ is preferably 50 to 1000 mJ / cm ２ Examples of light sources that emit light in the 150 to 450 nm wavelength band include low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, carbon arc lamps, metal halide lamps, xenon lamps, chemical lamps, electrodeless discharge lamps, and light-emitting diodes (LEDs). As long as the light irradiation amount is within this range, there are no particular limitations on the lamp output or illuminance.

[0067] Examples of the temporary support include a biaxially oriented polyethylene terephthalate film having a thickness of 16 μm, a biaxially oriented polyethylene terephthalate film having a thickness of 12 μm, and a biaxially oriented polyethylene terephthalate film having a thickness of 9 μm.

[0068] The temporary support may be a recycled product. Examples of recycled products include those obtained by cleaning used films, etc., and chipping them, and then using these as materials to form films. Specific examples of recycled products include the Ecouse series from Toray Industries, Inc. Preferred forms of the temporary support are described, for example, in paragraphs

[0017] to

[0018] of JP 2014-085643 A, paragraphs

[0019] to

[0026] of JP 2016-027363 A, paragraphs

[0041] to

[0057] of WO 2012 / 081680 A, and paragraphs

[0029] to

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

[0069] To improve handling properties, a layer containing fine particles (lubricant layer) may be provided on the surface of the temporary support. The lubricant layer may be provided on one or both sides of the temporary support. The diameter of the particles contained in the lubricant layer is preferably 0.05 to 0.8 μm. The thickness of the lubricant layer is preferably 0.05 to 1.0 μm. Commercially available temporary supports include Lumirror 16KS40, Lumirror 16FB40, Lumirror #38-U48, Lumirror #75-U34, and Lumirror #25T60 (all manufactured by Toray Industries, Inc.); and Cosmoshine A4100, Cosmoshine A4300, Cosmoshine A4160, Cosmoshine A4360, and Cosmoshine A8300 (all manufactured by Toyobo Co., Ltd.).

[0070] <Photosensitive Layer> (Components of Photosensitive Layer) The photosensitive layer may be either a positive-type photosensitive layer or a negative-type photosensitive layer, but a negative-type photosensitive layer is preferred. When the photosensitive layer is a negative-type photosensitive layer, the photosensitive layer preferably contains at least an alkali-soluble resin, a polymerizable compound, and a photopolymerization initiator, for example. Furthermore, as described above, the photosensitive layer may be a light-reflecting layer precursor layer and a light-absorbing layer precursor layer. When the photosensitive layer is a light-reflecting layer precursor layer, the photosensitive layer contains a reflectivity adjuster described later, and when the photosensitive layer is a light-absorbing layer precursor layer, the photosensitive layer contains a light-absorbing substance described later.

[0071] When the photosensitive layer is a positive photosensitive layer, it is preferable that the photosensitive layer contains at least a polymer and a photoacid generator. As described above, the photosensitive layer may be a photosensitive light-reflecting layer and a photosensitive light-absorbing layer. When the photosensitive layer is a photosensitive light-reflecting layer, the photosensitive layer contains a reflectivity adjusting agent described later, and when the photosensitive layer is a photosensitive light-absorbing layer, the photosensitive layer contains a light-absorbing substance described later.

[0072] (Impurities in the Photosensitive Layer) The photosensitive layer may contain an impurity (hereinafter also referred to as "impurity A") selected from the group consisting of metals and metal ions. Specific examples of impurity A include sodium, potassium, magnesium, calcium, iron, manganese, copper, aluminum, titanium, chromium, cobalt, nickel, zinc, tin, halogens, and ions thereof. Among these, halide ions, sodium ions, and potassium ions are easily mixed in as impurities, so the following contents are preferred. The upper limit of the content of impurity A is preferably 150 ppm by mass or less, more preferably 100 ppm by mass or less, still more preferably 10 ppm by mass or less, and particularly preferably 2 ppm by mass or less, relative to the total mass of the photosensitive layer. The lower limit of the content of impurity A can be 1 ppb by mass or more or 0.1 ppm by mass or more, relative to the total mass of the photosensitive layer. In particular, the upper limit of the chloride ion content is preferably 100 mass ppm or less, more preferably 50 mass ppm or less, even more preferably 10 mass ppm or less, and particularly preferably 2 mass ppm or less, relative to the total mass of the photosensitive layer. The lower limit of the chloride ion content can be 1 mass ppb or more, or 0.1 mass ppm or more, relative to the total mass of the photosensitive layer. Methods for controlling the impurity A within the above range include selecting raw materials for the photosensitive layer that have a low impurity content, preventing impurities from being mixed in during the formation of the photosensitive layer, and removing them by washing. By using such methods, the amount of impurities can be controlled within the above range.

[0073] The amount of impurity A can be determined by known methods such as ICP (Inductively Coupled Plasma) emission spectroscopy, atomic absorption spectroscopy, and ion chromatography.

[0074] Furthermore, the smaller the content of the organic solvent in the photosensitive layer, the better. The content of the organic solvent is preferably 100 ppm by mass or less, more preferably 20 ppm by mass or less, and even more preferably 4 ppm by mass or less, relative to the total mass of the photosensitive layer. The lower limit of the organic solvent content may be 10 ppb by mass or more, relative to the total mass of the photosensitive layer. The content of the organic solvent can be quantified by known methods such as ICP (Inductively Coupled Plasma) emission spectroscopy, atomic absorption spectroscopy, and ion chromatography. Specific examples of the organic solvent include those selected from the group consisting of benzene, formaldehyde, trichloroethylene, 1,3-butadiene, carbon tetrachloride, chloroform, N,N-dimethylformamide, N,N-dimethylacetamide, and hexane.

[0075] The water content in the photosensitive layer is preferably 5.0% by mass or less, more preferably 3.0% by mass or less, and even more preferably 1.0% by mass or less, based on the total mass of the photosensitive layer, from the viewpoint of improving reliability and lamination properties. The lower limit of the water content in the photosensitive layer is preferably as low as possible, but may be, for example, 0.01% by mass or more, based on the total mass of the layer.

[0076] The negative photosensitive layer and the positive photosensitive layer will be described below.

[0077] <<Negative Photosensitive Layer>> Components that can be contained in the negative photosensitive layer are described in detail below. -Alkali-Soluble Resin- The photosensitive layer preferably contains an alkali-soluble resin. Examples of alkali-soluble resins include (meth)acrylic resins, styrene resins, epoxy resins, amide resins, amide-epoxy resins, alkyd resins, phenolic resins, ester resins, urethane resins, epoxy acrylate resins obtained by reacting an epoxy resin with (meth)acrylic acid, and acid-modified epoxy acrylate resins obtained by reacting an epoxy acrylate resin with an acid anhydride.

[0078] (Preferred Aspect 1 of Alkali-Soluble Resin) One preferred aspect of the alkali-soluble resin is a (meth)acrylic resin, which has excellent alkali developability and film formability. In this specification, the term "(meth)acrylic resin" refers to a resin having structural units derived from (meth)acrylic compounds. The content of the structural units derived from (meth)acrylic compounds is preferably 50% by mass or more, more preferably 70% by mass or more, and even more preferably 90% by mass or more, based on the total structural units of the (meth)acrylic resin. The (meth)acrylic resin may be composed solely of structural units derived from (meth)acrylic compounds, or may also have structural units derived from polymerizable monomers other than (meth)acrylic compounds. In other words, the upper limit of the content of the structural units derived from (meth)acrylic compounds is 100% by mass or less, based on the total structural units of the (meth)acrylic resin. The content of the structural units derived from (meth)acrylic compounds is preferably 50 mol% or more, more preferably 70 mol% or more, and even more preferably 90 mol% or more, based on the total structural units of the (meth)acrylic resin. The (meth)acrylic resin may be composed solely of structural units derived from (meth)acrylic compounds, or may contain structural units derived from polymerizable monomers other than (meth)acrylic compounds. That is, the upper limit of the content of structural units derived from (meth)acrylic compounds is 100 mol% or less based on the total structural units of the (meth)acrylic resin. In this specification, when the content of "structural units" is specified by a molar ratio, the "structural units" are synonymous with "monomer units." In addition, in this specification, the "monomer units" may be modified after polymerization by a polymer reaction or the like. The same applies hereinafter.

[0079] Examples of (meth)acrylic compounds include (meth)acrylic acid, (meth)acrylic acid esters, (meth)acrylamide, and (meth)acrylonitrile. Examples of (meth)acrylic acid esters include (meth)acrylic acid alkyl esters, (meth)acrylic acid tetrahydrofurfuryl esters, (meth)acrylic acid dimethylaminoethyl esters, (meth)acrylic acid diethylaminoethyl esters, (meth)acrylic acid glycidyl esters, (meth)acrylic acid benzyl esters, 2,2,2-trifluoroethyl (meth)acrylate, and 2,2,3,3-tetrafluoropropyl (meth)acrylate, with (meth)acrylic acid alkyl esters being preferred. Examples of (meth)acrylamides include acrylamides such as diacetone acrylamide.

[0080] The alkyl group of the (meth)acrylic acid alkyl ester may be linear or branched. Specific examples include (meth)acrylic acid alkyl esters having an alkyl group having 1 to 12 carbon atoms, such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, and dodecyl (meth)acrylate. The alkyl group of the (meth)acrylic acid alkyl ester may be cyclic. The cyclic alkyl group may be monocyclic or polycyclic. Specific examples include cyclohexyl (meth)acrylate. As the (meth)acrylic acid ester, a (meth)acrylic acid alkyl ester having an alkyl group having 1 to 4 carbon atoms is preferred, with methyl (meth)acrylate or ethyl (meth)acrylate being more preferred.

[0081] The (meth)acrylic resin may have a structural unit other than the structural unit derived from the (meth)acrylic compound. The polymerizable monomer that forms the structural unit is not particularly limited as long as it is a compound other than the (meth)acrylic compound that is copolymerizable with the (meth)acrylic compound, and examples thereof include styrene compounds that may have a substituent at the α-position or on the aromatic ring, such as styrene, vinyltoluene, and α-methylstyrene, vinyl alcohol esters such as acrylonitrile and vinyl-n-butyl ether, maleic acid, maleic anhydride, maleic acid monoesters such as monomethyl maleate, monoethyl maleate, and monoisopropyl maleate, fumaric acid, cinnamic acid, α-cyanocinnamic acid, itaconic acid, and crotonic acid. These polymerizable monomers may be used alone or in combination of two or more.

[0082] In addition, the (meth)acrylic resin preferably has a structural unit having an acid group in order to improve alkaline developability. Examples of the acid group include a carboxy group, a sulfo group, a phosphate group, and a phosphonate group. Among these, the (meth)acrylic resin more preferably has a structural unit having a carboxy group, and even more preferably has a structural unit derived from the above-mentioned (meth)acrylic acid.

[0083] The content of structural units having an acid group in the (meth)acrylic resin (preferably structural units derived from (meth)acrylic acid) is preferably 10% by mass or more relative to all structural units of the (meth)acrylic resin, from the viewpoint of excellent developability. Furthermore, the upper limit is not particularly limited, but from the viewpoint of excellent alkali resistance, it is preferably 50% by mass or less, and more preferably 40% by mass or less. The content of structural units having an acid group in the (meth)acrylic resin (preferably structural units derived from (meth)acrylic acid) is preferably 10 mol% or more relative to all structural units of the (meth)acrylic resin, from the viewpoint of excellent developability. Furthermore, the upper limit is not particularly limited, but from the viewpoint of excellent alkali resistance, it is preferably 50 mol% or less, and more preferably 40 mol% or less.

[0084] Furthermore, the (meth)acrylic resin more preferably has structural units derived from the above-mentioned (meth)acrylic acid alkyl ester. The content of structural units derived from the (meth)acrylic acid alkyl ester in the (meth)acrylic resin is preferably 50 to 90 mass%, more preferably 60 to 90 mass%, and even more preferably 65 to 90 mass%, based on all structural units of the (meth)acrylic resin. Furthermore, the content of structural units derived from the (meth)acrylic acid alkyl ester in the (meth)acrylic resin is preferably 50 to 90 mol%, more preferably 60 to 90 mol%, and even more preferably 65 to 90 mol%, based on all structural units of the (meth)acrylic resin.

[0085] As the (meth)acrylic resin, a resin having both a structural unit derived from (meth)acrylic acid and a structural unit derived from a (meth)acrylic acid alkyl ester is preferred, and a resin composed only of a structural unit derived from (meth)acrylic acid and a structural unit derived from a (meth)acrylic acid alkyl ester is more preferred. Furthermore, as the (meth)acrylic resin, an acrylic resin having a structural unit derived from methacrylic acid, a structural unit derived from methyl methacrylate, and a structural unit derived from ethyl acrylate is also preferred.

[0086] Furthermore, the (meth)acrylic resin preferably has at least one selected from the group consisting of structural units derived from methacrylic acid and structural units derived from methacrylic acid alkyl esters, and preferably has both structural units derived from methacrylic acid and structural units derived from methacrylic acid alkyl esters. The total content of structural units derived from methacrylic acid and structural units derived from methacrylic acid alkyl esters in the (meth)acrylic resin is preferably 40% by mass or more, more preferably 60% by mass or more, based on the total structural units of the (meth)acrylic resin. The upper limit is not particularly limited, and may be 100% by mass or less, preferably 80% by mass or less. The total content of structural units derived from methacrylic acid and structural units derived from methacrylic acid alkyl esters in the (meth)acrylic resin is preferably 40 mol% or more, more preferably 60 mol% or more, based on the total structural units of the (meth)acrylic resin. The upper limit is not particularly limited, and may be 100 mol% or less, preferably 80 mol% or less.

[0087] The (meth)acrylic resin preferably contains at least one selected from the group consisting of structural units derived from methacrylic acid and structural units derived from methacrylic acid alkyl esters, and at least one selected from the group consisting of structural units derived from acrylic acid and structural units derived from acrylic acid alkyl esters. The total content of the structural units derived from methacrylic acid and the structural units derived from methacrylic acid alkyl esters is preferably in a mass ratio of 60 / 40 to 80 / 20 relative to the total content of the structural units derived from acrylic acid and the structural units derived from acrylic acid alkyl esters.

[0088] The (meth)acrylic resin preferably has an ester group at its terminal, since this provides excellent developability of the photosensitive layer after transfer. The terminal portion of the (meth)acrylic resin is composed of a moiety derived from the polymerization initiator used in the synthesis. The (meth)acrylic resin having an ester group at its terminal can be synthesized by using a polymerization initiator that generates a radical having an ester group.

[0089] (Preferred Aspect 2 of Alkali-Soluble Resin) Another preferred aspect of the alkali-soluble resin is an alkali-soluble resin having an acid value of 60 mgKOH / g or more, which has superior developability. Among such alkali-soluble resins, a resin having a carboxy group with an acid value of 60 mgKOH / g or more (hereinafter also referred to as a "carboxy group-containing resin") is more preferred, and a (meth)acrylic resin having a carboxy group with an acid value of 60 mgKOH / g or more (hereinafter also referred to as a "carboxy group-containing (meth)acrylic resin") is even more preferred, because they are easily thermally crosslinked with the crosslinking component by heating to form a strong film. When the alkali-soluble resin is a resin having a carboxy group, the three-dimensional crosslinking density can be increased by, for example, adding a thermally crosslinkable compound such as a blocked isocyanate compound to thermally crosslink the resin. Furthermore, when the carboxy group of the resin having a carboxy group is anhydrous and hydrophobicized, the wet heat resistance can be improved.

[0090] The carboxyl group-containing (meth)acrylic resin having an acid value of 60 mgKOH / g or more is not particularly limited as long as it satisfies the above-mentioned acid value requirement, and can be appropriately selected from known (meth)acrylic resins. For example, carboxyl group-containing acrylic resins having an acid value of 60 mgKOH / g or more among the polymers described in paragraph

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

[0033] to

[0052] of JP-A No. 2010-237589 can be preferably used.

[0091] (Preferred Aspect 3 of Alkali-Soluble Resin) Another preferred aspect of the alkali-soluble resin is an alkali-soluble resin having an aromatic ring structure, which has superior developability. As alkali-soluble resins having an aromatic ring structure, alkali-soluble resins having a structural unit with an aromatic ring structure are more preferred. Examples of monomers forming structural units with an aromatic ring structure include monomers having an aralkyl group, styrene, and polymerizable styrene derivatives (e.g., methylstyrene, vinyltoluene, tert-butoxystyrene, acetoxystyrene, 4-vinylbenzoic acid, styrene dimer, and styrene trimer). Of these, monomers having an aralkyl group or styrene are preferred. 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.

[0092] Examples of the monomer having a phenyl alkyl group include phenylethyl (meth)acrylate.

[0093] Examples of the monomer having a benzyl group include (meth)acrylates having a benzyl group, such as benzyl (meth)acrylate and chlorobenzyl (meth)acrylate, and vinyl monomers having a benzyl group, such as vinylbenzyl chloride and vinylbenzyl alcohol, with benzyl (meth)acrylate being preferred.

[0094] The alkali-soluble resin more preferably has a structural unit represented by the following formula (S) (a structural unit derived from styrene).

[0095]

[0096] When the alkali-soluble resin has a structural unit having an aromatic ring structure, the content of the structural unit having an aromatic ring structure is preferably 5 to 90 mass%, more preferably 10 to 80 mass%, even more preferably 10 to 70 mass%, and particularly preferably 20 to 60 mass%, based on the total structural units of the alkali-soluble resin. The content of the structural unit having an aromatic ring structure in the alkali-soluble resin is preferably 5 to 70 mol%, more preferably 10 to 60 mol%, and even more preferably 20 to 60 mol%, based on the total structural units of the alkali-soluble resin. Furthermore, the content of the structural unit represented by formula (S) in the alkali-soluble resin is preferably 5 to 70 mol%, more preferably 10 to 60 mol%, even more preferably 20 to 60 mol%, and particularly preferably 20 to 50 mol%, based on the total structural units of the alkali-soluble resin.

[0097] The alkali-soluble resin preferably has an aliphatic hydrocarbon ring structure. That is, the alkali-soluble resin preferably has a structural unit having an aliphatic hydrocarbon ring structure. The aliphatic hydrocarbon ring structure may be monocyclic or polycyclic. In particular, the alkali-soluble resin more preferably has a ring structure in which two or more aliphatic hydrocarbon rings are condensed.

[0098] Examples of the ring that constitutes the aliphatic hydrocarbon ring structure in the structural unit having an aliphatic hydrocarbon ring structure include a tricyclodecane ring, a cyclohexane ring, a cyclopentane ring, a norbornane ring, and an isoborone ring. Among these, a ring in which two or more aliphatic hydrocarbon rings are condensed is preferred, and a tetrahydrodicyclopentadiene ring (tricyclo[5.2.1.0] ２，６ ]decane ring) is more preferred. Examples of monomers that form a structural unit having an aliphatic hydrocarbon ring structure include dicyclopentanyl (meth)acrylate, cyclohexyl (meth)acrylate, and isobornyl (meth)acrylate. Furthermore, the alkali-soluble resin preferably has a structural unit represented by the following formula (Cy), and more preferably has a structural unit represented by the above formula (S) and a structural unit represented by the following formula (Cy).

[0099]

[0100] In formula (Cy), R Ｍ represents a hydrogen atom or a methyl group, R Ｃｙ represents a monovalent group having an aliphatic hydrocarbon ring structure.

[0101] R in formula (Cy) Ｍ is preferably a methyl group. Ｃｙ is preferably a monovalent group having an aliphatic hydrocarbon ring structure having 5 to 20 carbon atoms, more preferably a monovalent group having an aliphatic hydrocarbon ring structure having 6 to 16 carbon atoms, and even more preferably a monovalent group having an aliphatic hydrocarbon ring structure having 8 to 14 carbon atoms. Ｃｙ The aliphatic hydrocarbon ring structure in formula (Cy) is preferably a cyclopentane ring structure, a cyclohexane ring structure, a tetrahydrodicyclopentadiene ring structure, a norbornane ring structure, or an isoborone ring structure, more preferably a cyclohexane ring structure or a tetrahydrodicyclopentadiene ring structure, and even more preferably a tetrahydrodicyclopentadiene ring structure. Ｃｙ The aliphatic hydrocarbon ring structure in formula (Cy) is preferably a ring structure in which two or more aliphatic hydrocarbon rings are condensed, and more preferably a ring in which two to four aliphatic hydrocarbon rings are condensed. Ｃｙ is preferably a group in which the oxygen atom of —C(═O)O— in formula (Cy) is directly bonded to the aliphatic hydrocarbon ring structure, i.e., an aliphatic hydrocarbon ring group, more preferably a cyclohexyl group or a dicyclopentanyl group, and still more preferably a dicyclopentanyl group.

[0102] The alkali-soluble resin may have one or more types of structural units having an aliphatic hydrocarbon ring structure. When the alkali-soluble resin has a structural unit having an aliphatic hydrocarbon ring structure, the content of the structural unit having an aliphatic hydrocarbon ring structure is preferably 5 to 90 mass%, more preferably 10 to 80 mass%, and even more preferably 20 to 70 mass%, based on the total structural units of the alkali-soluble resin. The content of the structural unit having an aliphatic hydrocarbon ring structure in the alkali-soluble resin is preferably 5 to 70 mol%, more preferably 10 to 60 mol%, and even more preferably 20 to 50 mol%, based on the total structural units of the alkali-soluble resin. Furthermore, the content of the structural unit represented by the above formula (Cy) in the alkali-soluble resin is preferably 5 to 70 mol%, more preferably 10 to 60 mol%, and even more preferably 20 to 50 mol%, based on the total structural units of the alkali-soluble resin.

[0103] When the alkali-soluble resin has structural units having an aromatic ring structure and structural units having an aliphatic hydrocarbon ring structure, the total content of the structural units having an aromatic ring structure and the structural units having an aliphatic hydrocarbon ring structure is preferably 10 to 90 mass%, more preferably 20 to 80 mass%, and even more preferably 40 to 75 mass%, relative to all structural units of the alkali-soluble resin. Furthermore, the total content of the structural units having an aromatic ring structure and the structural units having an aliphatic hydrocarbon ring structure in the alkali-soluble resin is preferably 10 to 80 mol%, more preferably 20 to 70 mol%, and even more preferably 40 to 60 mol%, relative to all structural units of the alkali-soluble resin. Furthermore, the total content of the structural units represented by formula (S) and the structural units represented by formula (Cy) in the alkali-soluble resin is preferably 10 to 80 mol%, more preferably 20 to 70 mol%, and even more preferably 40 to 60 mol%, relative to all structural units of the alkali-soluble resin.

[0104] Furthermore, in order to achieve superior effects of the present invention, the molar amount nS of the structural unit represented by the formula (S) in the alkali-soluble resin and the molar amount nCy of the structural unit represented by the formula (Cy) preferably satisfy the relationship shown in the following formula (SCy), more preferably satisfy the following formula (SCy-1), and even more preferably satisfy the following formula (SCy-2): 0.2≦nS / (nS+nCy)≦0.8 formula (SCy) 0.30≦nS / (nS+nCy)≦0.75 formula (SCy-1) 0.40≦nS / (nS+nCy)≦0.70 formula (SCy-2)

[0105] The alkali-soluble resin preferably has a structural unit having an acid group. Examples of the acid group include a carboxy group, a sulfo group, a phosphonic acid group, and a phosphoric acid group, and the carboxy group is preferred. The structural unit having the acid group is preferably a structural unit derived from (meth)acrylic acid shown below, and more preferably a structural unit derived from methacrylic acid.

[0106]

[0107] The alkali-soluble resin may have one type of structural unit having an acid group alone, or two or more types. When the alkali-soluble resin has a structural unit having an acid group, the content of the structural unit having an acid group is preferably 5 to 50 mass%, more preferably 5 to 40 mass%, even more preferably 10 to 40 mass%, and particularly preferably 10 to 30 mass%, based on the total structural units of the alkali-soluble resin. Furthermore, the content of the structural unit having an acid group in the alkali-soluble resin is preferably 5 to 70 mol%, more preferably 10 to 50 mol%, and even more preferably 20 to 40 mol%, based on the total structural units of the alkali-soluble resin.

[0108] The alkali-soluble resin preferably has a reactive group, and more preferably has a structural unit having a reactive group. As the reactive group, a radically polymerizable group is preferred, and an ethylenically unsaturated group is more preferred. Furthermore, when the alkali-soluble resin has an ethylenically unsaturated group, the alkali-soluble resin preferably has a structural unit having an ethylenically unsaturated group in a side chain. In this specification, the term "main chain" refers to the relatively longest bond chain in the molecule of the polymer compound constituting the resin, and the term "side chain" refers to an atomic group branched from the main chain. As the ethylenically unsaturated group, an allyl group or a (meth)acryloyloxy group is more preferred. Examples of structural units having a reactive group include, but are not limited to, those shown below.

[0109]

[0110] The alkali-soluble resin may have one type of structural unit having a reactive group alone, or may have two or more types. When the alkali-soluble resin has a structural unit having a reactive group, the content of the structural unit having a reactive group is preferably 5 to 70 mass%, more preferably 10 to 50 mass%, and even more preferably 20 to 40 mass%, based on the total structural units of the alkali-soluble resin. Furthermore, the content of the structural unit having a reactive group in the alkali-soluble resin is preferably 5 to 70 mol%, more preferably 10 to 60 mol%, and even more preferably 10 to 50 mol%, based on the total structural units of the alkali-soluble resin.

[0111] Methods for introducing reactive groups into alkali-soluble resins include reacting functional groups such as hydroxy groups, carboxy groups, primary amino groups, secondary amino groups, acetoacetyl groups, and sulfo groups with compounds such as epoxy compounds, blocked isocyanate compounds, isocyanate compounds, vinyl sulfone compounds, aldehyde compounds, methylol compounds, and carboxylic acid anhydrides. A preferred example of a method for introducing reactive groups into alkali-soluble resins is to synthesize a polymer having carboxy groups by polymerization, and then react some of the carboxy groups of the resulting polymer with glycidyl (meth)acrylate through a polymer reaction to introduce (meth)acryloxy groups into the polymer. This method allows for the production of alkali-soluble resins having (meth)acryloyloxy groups in their side chains. The polymerization reaction is preferably carried out at a temperature of 70 to 100°C, more preferably at a temperature of 80 to 90°C. The polymerization initiator used in the polymerization reaction is preferably an azo-based initiator, and more preferably, for example, V-601 (trade name) or V-65 (trade name) manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. The polymerization reaction is preferably carried out at a temperature of 80 to 110° C. In the polymerization reaction, it is preferable to use a catalyst such as an ammonium salt.

[0112] The alkali-soluble resin also preferably has a structural unit derived from a (meth)acrylic acid alkyl ester. Examples of the structural unit derived from a (meth)acrylic acid alkyl ester include those described above, with methyl (meth)acrylate being particularly preferred. The alkali-soluble resin may have one structural unit derived from a (meth)acrylic acid alkyl ester, or two or more structural units derived from a (meth)acrylic acid alkyl ester. When the alkali-soluble resin has a structural unit derived from a (meth)acrylic acid alkyl ester, the content of the structural unit derived from the (meth)acrylic acid alkyl ester is preferably 1 to 10 mass%, more preferably 1 to 5 mass%, based on the total structural units of the alkali-soluble resin. The content of the structural unit derived from the (meth)acrylic acid alkyl ester in the alkali-soluble resin is preferably 1 to 10 mol%, more preferably 1 to 5 mol%, based on the total structural units of the alkali-soluble resin.

[0113] (Specific Examples of Alkali-Soluble Resins of Preferred Aspects 1 to 3) As the alkali-soluble resin, the following polymers X1 to X4 are preferred. Note that the content ratios (a to d) of each structural unit relative to all structural units and the weight-average molecular weight Mw shown below can be changed appropriately depending on the purpose, but the following structures are particularly preferred in terms of achieving better effects of the present invention. (Polymer X1) a: 20 to 60 mass%, b: 10 to 50 mass%, c: 5.0 to 25 mass%, d: 10 to 50 mass%. (Polymer X2) a: 20 to 60 mass%, b: 10 to 50 mass%, c: 5.0 to 25 mass%, d: 10 to 50 mass%. (Polymer X3) a: 30 to 65 mass%, b: 1.0 to 30 mass%, c: 0.5 to 15 mass%, d: 10 to 50 mass%. (Polymer X4) a: 1.0 to 20% by mass, b: 20 to 60% by mass, c: 5.0 to 230% by mass, d: 10 to 50% by mass.

[0114]

[0115] (Preferred embodiment 4 of alkali-soluble resin) As the alkali-soluble resin, a polymer having a structural unit with a carboxylic acid anhydride structure (hereinafter also referred to as "polymer X") is preferably used. The carboxylic acid anhydride structure may be either a linear carboxylic acid anhydride structure or a cyclic carboxylic acid anhydride structure, but is preferably a cyclic carboxylic acid anhydride structure. The ring of the cyclic carboxylic acid anhydride structure is preferably a 5- to 7-membered ring, more preferably a 5- or 6-membered ring, and even more preferably a 5-membered ring.

[0116] The structural unit having a carboxylic acid anhydride structure is preferably a structural unit containing, in its main chain, a divalent group obtained by removing two hydrogen atoms from a compound represented by the following formula P-1, or a structural unit in which a monovalent group obtained by removing one hydrogen atom from a compound represented by the following formula P-1 is bonded to the main chain directly or via a divalent linking group:

[0117]

[0118] In formula P-1, R Ａ１ａ represents a substituent, n １ａ R Ａ１ａ may be the same or different, Z １ａ represents a divalent group forming a ring containing —C(═O)—O—C(═O)—, n １ａ represents an integer of 0 or greater.

[0119] R Ａ１ａ Examples of the substituent represented by the formula: include an alkyl group. １ａ is preferably an alkylene group having 2 to 4 carbon atoms, more preferably an alkylene group having 2 or 3 carbon atoms, and even more preferably an alkylene group having 2 carbon atoms. １ａ represents an integer of 0 or more. １ａ represents an alkylene group having 2 to 4 carbon atoms, n １ａ is preferably an integer of 0 to 4, more preferably an integer of 0 to 2, and even more preferably 0. １ａ When R represents an integer of 2 or more, there are multiple R Ａ１ａ may be the same or different. Ａ１ａ may be bonded to each other to form a ring, but preferably do not bond to each other to form a ring.

[0120] As a structural unit having a carboxylic acid anhydride structure, a structural unit derived from an unsaturated carboxylic acid anhydride is preferred, a structural unit derived from an unsaturated cyclic carboxylic acid anhydride is more preferred, a structural unit derived from an unsaturated aliphatic cyclic carboxylic acid anhydride is even more preferred, a structural unit derived from maleic anhydride or itaconic anhydride is particularly preferred, and a structural unit derived from maleic anhydride is most preferred.

[0121] Specific examples of structural units having a carboxylic acid anhydride structure are listed below, but the structural units having a carboxylic acid anhydride structure are not limited to these specific examples. In the following structural units, Rx represents a hydrogen atom, a methyl group, a CH ２ OH group or CF ３ group, and Me represents a methyl group.

[0122]

[0123]

[0124] The structural unit having a carboxylic acid anhydride structure in polymer X may be of one type alone or may be of two or more types. The total content of the structural units having a carboxylic acid anhydride structure is preferably 0 to 60 mol %, more preferably 5 to 40 mol %, and even more preferably 10 to 35 mol %, based on all structural units of polymer X.

[0125] The polymer X is preferably used in combination with the alkali-soluble resin of any one of the above-mentioned preferred embodiments 1 to 3. When the photosensitive layer contains the polymer X, the content of the polymer X is preferably 0.1 to 30% by mass, more preferably 0.2 to 20% by mass, still more preferably 0.5 to 20% by mass, and particularly preferably 1 to 20% by mass, relative to the total mass of the photosensitive layer. The photosensitive layer may contain only one type of polymer X, or two or more types of polymer X.

[0126] The weight average molecular weight (Mw) of the alkali-soluble resin is preferably 3,500 or more, more preferably 5,000 or more, even more preferably 10,000 or more, and particularly preferably 20,000 or more, and the upper limit is preferably 50,000 or less, more preferably 30,000 or less.

[0127] The acid value of the alkali-soluble resin is preferably 10 to 200 mgKOH / g, more preferably 60 to 200 mgKOH / g, even more preferably 60 to 150 mgKOH / g, and particularly preferably 70 to 125 mgKOH / g. The acid value of the alkali-soluble resin is a value measured according to the method described in JIS K0070:1992. From the viewpoint of developability, the dispersity of the alkali-soluble resin is preferably 1.0 to 6.0, more preferably 1.0 to 5.0, even more preferably 1.0 to 4.0, and particularly preferably 1.0 to 3.0.

[0128] The photosensitive layer may contain only one type of alkali-soluble resin, or may contain two or more types. The lower limit of the content of the alkali-soluble resin is preferably 10.0 mass% or more, more preferably 15.0 mass% or more, even more preferably 20.0 mass% or more, and particularly preferably 30.0 mass% or more, based on the total mass of the photosensitive layer. The upper limit is preferably 90.0 mass% or less, more preferably 80.0 mass% or less, and even more preferably 70.0 mass% or less.

[0129] -Polymerizable Compound- The photosensitive layer preferably contains a polymerizable compound. The polymerizable compound is a compound having a polymerizable group. Examples of the polymerizable group include a radically polymerizable group and a cationic polymerizable group, and the radically polymerizable group is preferred.

[0130] The polymerizable compound preferably contains a radical polymerizable compound having an ethylenically unsaturated group (hereinafter also simply referred to as "ethylenically unsaturated compound"). The ethylenically unsaturated group is preferably a (meth)acryloyloxy group. The ethylenically unsaturated compound in this specification is a compound other than the alkali-soluble resin, and preferably has a molecular weight of less than 5,000.

[0131] One preferred embodiment of the polymerizable compound is a compound represented by the following formula (M) (also simply referred to as "compound M"). ２ -R １ -Q １ Formula (M) In formula (M), Q １ and Q ２each independently represents a (meth)acryloyloxy group, R １ represents a divalent linking group having a chain structure.

[0132] Q in formula (M) １ and Q ２ From the viewpoint of ease of synthesis, Q １ and Q ２ It is preferable that Q in formula (M) are the same group. １ and Q ２ In terms of reactivity, R in formula (M) is preferably an acryloyloxy group. １ Examples of the alkylene group include an alkyleneoxyalkylene group (-L １ -O-L １ -), or a polyalkyleneoxyalkylene group (-(L １ -O) ｐ -L １ -) is preferred, a hydrocarbon group having 2 to 20 carbon atoms or a polyalkyleneoxyalkylene group is more preferred, an alkylene group having 4 to 20 carbon atoms is even more preferred, and a straight-chain alkylene group having 6 to 18 carbon atoms is particularly preferred. The hydrocarbon group may have a chain structure at least in part, and the portion other than the chain structure is not particularly limited, and may be, for example, a branched, cyclic, or straight-chain alkylene group having 1 to 5 carbon atoms, an arylene group, an ether bond, or a combination thereof. An alkylene group or a group combining two or more alkylene groups and one or more arylene groups is preferred, an alkylene group is more preferred, and a straight-chain alkylene group is even more preferred. １ each independently represents an alkylene group, preferably an ethylene group, a propylene group, or a butylene group, and more preferably an ethylene group or a 1,2-propylene group. p represents an integer of 2 or more, preferably an integer of 2 to 10.

[0133] In addition, Q in compound M １ and Q ２ The number of atoms in the shortest linking chain connecting "Q" and "Q" is preferably 3 to 50, more preferably 4 to 40, still more preferably 6 to 20, and particularly preferably 8 to 12. １ and Q２ The number of atoms in the shortest chain connecting Q １ R connected to １ Q from atoms in ２ R connected to １ is the shortest number of atoms that connects to the atom in

[0134] Specific examples of compound M include 1,3-butanediol di(meth)acrylate, tetramethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,7-heptanediol di(meth)acrylate, 1,8-octanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, di(meth)acrylate of hydrogenated bisphenol A, di(meth)acrylate of hydrogenated bisphenol F, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, poly(ethylene glycol / propylene glycol) di(meth)acrylate, and polybutylene glycol di(meth)acrylate. The above ester monomers can also be used as a mixture. Among the above compounds, at least one compound selected from the group consisting of 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, and neopentyl glycol di(meth)acrylate is preferred, at least one compound selected from the group consisting of 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, and 1,10-decanediol di(meth)acrylate is more preferred, and at least one compound selected from the group consisting of 1,9-nonanediol di(meth)acrylate and 1,10-decanediol di(meth)acrylate is even more preferred.

[0135] Furthermore, one preferred embodiment of the polymerizable compound is a difunctional or higher ethylenically unsaturated compound. In this specification, "difunctional or higher ethylenically unsaturated compound" means a compound having two or more ethylenically unsaturated groups in one molecule. As the ethylenically unsaturated group in the ethylenically unsaturated compound, a (meth)acryloyl group is preferred. As the ethylenically unsaturated compound, a (meth)acrylate compound is preferred.

[0136] The difunctional ethylenically unsaturated compound can be appropriately selected from known compounds. Examples of the difunctional ethylenically unsaturated compound other than the compound M include tricyclodecane dimethanol di(meth)acrylate and 1,4-cyclohexanediol di(meth)acrylate.

[0137] Commercially available bifunctional ethylenically unsaturated compounds include tricyclodecane dimethanol diacrylate (trade name: NK Ester A-DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.), tricyclodecane dimenanol dimethacrylate (trade name: NK Ester DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.), 1,9-nonanediol diacrylate (trade name: NK Ester A-NOD-N, manufactured by Shin-Nakamura Chemical Co., Ltd.), and 1,6-hexanediol diacrylate (trade name: NK Ester A-HD-N, manufactured by Shin-Nakamura Chemical Co., Ltd.).

[0138] The tri- or higher functional ethylenically unsaturated compound can be appropriately selected from known compounds. Examples of the tri- or higher functional ethylenically unsaturated compound include dipentaerythritol (tri / tetra / penta / hexa)(meth)acrylate, pentaerythritol (tri / tetra)(meth)acrylate, trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, isocyanuric acid (meth)acrylate, and (meth)acrylate compounds having a glycerin tri(meth)acrylate skeleton.

[0139] 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.

[0140] One preferred embodiment of the polymerizable compound also includes a urethane (meth)acrylate compound. Examples of the urethane (meth)acrylate include urethane di(meth)acrylate, such as propylene oxide-modified urethane di(meth)acrylate and ethylene oxide and propylene oxide-modified urethane di(meth)acrylate. Examples of the urethane (meth)acrylate also include trifunctional or higher urethane (meth)acrylate. The lower limit of the number of functional groups is more preferably 6 or more, and even more preferably 8 or more. The upper limit of the number of functional groups is preferably 20 or less. Examples of tri- or higher functional urethane (meth)acrylates include 8UX-015A (manufactured by Taisei Fine Chemical Co., Ltd.), UA-32P (manufactured by Shin-Nakamura Chemical Co., Ltd.), U-15HA (manufactured by Shin-Nakamura Chemical Co., Ltd.), UA-1100H (manufactured by Shin-Nakamura Chemical Co., Ltd.), AH-600 (trade name) manufactured by Kyoeisha Chemical Co., Ltd., and UA-306H, UA-306T, UA-306I, UA-510H, and UX-5000 (all manufactured by Nippon Kayaku Co., Ltd.).

[0141] One preferred embodiment of the polymerizable compound is an ethylenically unsaturated compound having an acid group. Examples of the acid group include a phosphate group, a sulfo group, and a carboxy group. Of these, a carboxy group is preferred as the acid group. Examples of the ethylenically unsaturated compound having an acid group include a tri- or tetrafunctional ethylenically unsaturated compound having an acid group [a compound having a carboxy group introduced into a pentaerythritol tri- or tetraacrylate (PETA) skeleton (acid value: 80 to 120 mg KOH / g)], a penta- or hexafunctional ethylenically unsaturated compound having an acid group [a compound having a carboxy group introduced into a dipentaerythritol penta- or hexaacrylate (DPHA) skeleton (acid value: 25 to 70 mg KOH / g)], and the like. These tri- or higher functional ethylenically unsaturated compounds having an acid group may be used in combination with a difunctional ethylenically unsaturated compound having an acid group, if necessary.

[0142] The ethylenically unsaturated compound having an acid group is preferably at least one selected from the group consisting of difunctional or higher ethylenically unsaturated compounds having a carboxy group and carboxylic acid anhydrides thereof. When the ethylenically unsaturated compound having an acid group is at least one selected from the group consisting of difunctional or higher ethylenically unsaturated compounds having a carboxy group and carboxylic acid anhydrides thereof, developability and film strength are further improved. The difunctional or higher ethylenically unsaturated compound having a carboxy group is not particularly limited and can be appropriately selected from known compounds. Examples of difunctional or higher ethylenically unsaturated compounds having a carboxy group include ARONIX (registered trademark) TO-2349 (manufactured by Toagosei Co., Ltd.), ARONIX (registered trademark) M-520 (manufactured by Toagosei Co., Ltd.), and ARONIX (registered trademark) M-510 (manufactured by Toagosei Co., Ltd.).

[0143] As the ethylenically unsaturated compound having an acid group, the polymerizable compound having an acid group described in paragraphs

[0025] to

[0030] of JP-A No. 2004-239942 is preferred, and the contents of this publication are incorporated herein by reference.

[0144] Examples of polymerizable compounds include compounds obtained by reacting a polyhydric alcohol with an α,β-unsaturated carboxylic acid, compounds obtained by reacting a glycidyl group-containing compound with an α,β-unsaturated carboxylic acid, urethane monomers such as (meth)acrylate compounds having a urethane bond, phthalic acid compounds such as γ-chloro-β-hydroxypropyl-β'-(meth)acryloyloxyethyl-o-phthalate, β-hydroxyethyl-β'-(meth)acryloyloxyethyl-o-phthalate, and β-hydroxypropyl-β'-(meth)acryloyloxyethyl-o-phthalate, and (meth)acrylic acid alkyl esters. These may be used alone or in combination of two or more.

[0145] Examples of compounds obtained by reacting a polyhydric alcohol with an α,β-unsaturated carboxylic acid include bisphenol A-based (meth)acrylate compounds such as 2,2-bis(4-((meth)acryloxypolyethoxy)phenyl)propane, 2,2-bis(4-((meth)acryloxypolypropoxy)phenyl)propane, and 2,2-bis(4-((meth)acryloxypolyethoxypolypropoxy)phenyl)propane; polyethylene glycol di(meth)acrylate having 2 to 14 ethylene oxide groups; polypropylene glycol di(meth)acrylate having 2 to 14 propylene oxide groups; polyethylene polypropylene glycol di(meth)acrylate having 2 to 14 ethylene oxide groups and 2 to 14 propylene oxide groups; Examples of the acrylates include trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolpropane ethoxy tri(meth)acrylate, trimethylolpropane diethoxy tri(meth)acrylate, trimethylolpropane triethoxy tri(meth)acrylate, trimethylolpropane tetraethoxy tri(meth)acrylate, trimethylolpropane pentaethoxy tri(meth)acrylate, di(trimethylolpropane) tetraacrylate, tetramethylolmethane tri(meth)acrylate, tetramethylolmethane tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, and dipentaerythritol hexa(meth)acrylate. Among these, ethylenically unsaturated compounds having a tetramethylolmethane structure or a trimethylolpropane structure are preferred, and tetramethylolmethane tri(meth)acrylate, tetramethylolmethane tetra(meth)acrylate, trimethylolpropane tri(meth)acrylate, or di(trimethylolpropane)tetraacrylate is more preferred.

[0146] Examples of the polymerizable compound include caprolactone-modified ethylenically unsaturated compounds (e.g., KAYARAD (registered trademark) DPCA-20 manufactured by Nippon Kayaku Co., Ltd., A-9300-1CL manufactured by Shin-Nakamura Chemical Co., Ltd.), alkylene oxide-modified ethylenically unsaturated compounds (e.g., KAYARAD RP-1040 manufactured by Nippon Kayaku Co., Ltd., ATM-35E and A-9300 manufactured by Shin-Nakamura Chemical Co., Ltd., EBECRYL (registered trademark) 135 manufactured by Daicel-Allnex Corporation), and ethoxylated glycerin triacrylate (A-GLY-9E manufactured by Shin-Nakamura Chemical Co., Ltd.). Further, examples of the polymerizable compound include bis(2,2-dimethylethylene)(5-ethyl-1,3-dioxane-2,5-diyl)methylene acrylate (KAYARAD R-604, manufactured by Nippon Kayaku Co., Ltd.).

[0147] As the polymerizable compound (particularly, an ethylenically unsaturated compound), one containing an ester bond is particularly preferred in terms of excellent developability of the photosensitive layer after transfer. The ethylenically unsaturated compound containing an ester bond is not particularly limited as long as it contains an ester bond in the molecule, but in terms of excellent effects of the present invention, an ethylenically unsaturated compound having a tetramethylolmethane structure or a trimethylolpropane structure is preferred, and tetramethylolmethane tri(meth)acrylate, tetramethylolmethane tetra(meth)acrylate, trimethylolpropane tri(meth)acrylate, or di(trimethylolpropane)tetraacrylate is more preferred. In terms of imparting reliability, the ethylenically unsaturated compound preferably contains an ethylenically unsaturated compound having an aliphatic group having 6 to 20 carbon atoms and the above-mentioned ethylenically unsaturated compound having a tetramethylolmethane structure or a trimethylolpropane structure. Examples of ethylenically unsaturated compounds having an aliphatic structure with 6 or more carbon atoms include 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, and tricyclodecane dimethanol di(meth)acrylate.

[0148] One preferred embodiment of the polymerizable compound is a polymerizable compound having an aliphatic hydrocarbon ring structure (preferably a bifunctional ethylenically unsaturated compound).The polymerizable compound is preferably a polymerizable compound having a ring structure in which two or more aliphatic hydrocarbon rings are condensed (preferably a structure selected from the group consisting of a tricyclodecane structure and a tricyclodecene structure), more preferably a bifunctional ethylenically unsaturated compound having a ring structure in which two or more aliphatic hydrocarbon rings are condensed, and even more preferably tricyclodecane dimethanol di(meth)acrylate.The aliphatic hydrocarbon ring structure is preferably a cyclopentane structure, a cyclohexane structure, a tricyclodecane structure, a tricyclodecene structure, a norbornane structure, or an isoborone structure.

[0149] The molecular weight of the polymerizable compound is preferably from 200 to 3,000, more preferably from 250 to 2,600, still more preferably from 280 to 2,200, and particularly preferably from 300 to 2,200.

[0150] In addition, as one of the preferred embodiments of the photosensitive layer, the photosensitive layer preferably contains a compound represented by Formula (M) and an ethylenically unsaturated compound having an acid group, and more preferably contains 1,9-nonanediol diacrylate and a polyfunctional ethylenically unsaturated compound having a carboxylic acid group.

[0151] In addition, as one preferred embodiment of the photosensitive layer, from the viewpoints of suppressing development residues and rust prevention, the photosensitive layer preferably contains a bifunctional ethylenically unsaturated compound (preferably a bifunctional (meth)acrylate compound) and a trifunctional or higher ethylenically unsaturated compound (preferably a trifunctional or higher (meth)acrylate compound). The mass ratio of the bifunctional ethylenically unsaturated compound to the trifunctional or higher ethylenically unsaturated compound (mass of bifunctional ethylenically unsaturated compound / mass of trifunctional or higher ethylenically unsaturated compound) is preferably 10 / 90 to 90 / 10, more preferably 30 / 70 to 70 / 30. The content of the bifunctional ethylenically unsaturated compound relative to the total amount of all ethylenically unsaturated compounds is preferably 20.0% by mass or more, more preferably 30.0% by mass or more, and even more preferably 40.0% by mass or more. There is no particular upper limit, but it is, for example, 100% by mass or less, preferably 90.0% by mass or less, and more preferably 80.0% by mass or less. The content of the bifunctional ethylenically unsaturated compound in the photosensitive layer is preferably from 5.0 to 60.0% by mass, more preferably from 5.0 to 40.0% by mass, and even more preferably from 5.0 to 40.0% by mass.

[0152] The photosensitive layer may contain a monofunctional ethylenically unsaturated compound as the ethylenically unsaturated compound. The content of the difunctional or higher ethylenically unsaturated compound is preferably 50 to 100% by mass based on the total content of all ethylenically unsaturated compounds contained in the photosensitive layer.

[0153] The polymerizable compound (particularly, the ethylenically unsaturated compound) may be used alone or in combination of two or more. The lower limit of the content of the polymerizable compound (particularly, the ethylenically unsaturated compound) in the photosensitive layer is preferably 10.0 mass% or more, more preferably 15.0 mass% or more, based on the total mass of the photosensitive layer. The upper limit is preferably 70.0 mass% or less, more preferably 60.0 mass% or less, even more preferably 50.0 mass% or less, and particularly preferably 40.0 mass% or less.

[0154] Photopolymerization Initiator The photosensitive layer preferably contains a photopolymerization initiator. There are no particular limitations on the photopolymerization initiator, and known photopolymerization initiators can be used. Examples of the photopolymerization initiator include photopolymerization initiators having an oxime ester structure (hereinafter also referred to as "oxime-based photopolymerization initiators"), photopolymerization initiators having an α-aminoalkylphenone structure (hereinafter also referred to as "α-aminoalkylphenone-based photopolymerization initiators"), photopolymerization initiators having an α-hydroxyalkylphenone structure (hereinafter also referred to as "α-hydroxyalkylphenone-based polymerization initiators"), photopolymerization initiators having an acylphosphine oxide structure (hereinafter also referred to as "acylphosphine oxide-based photopolymerization initiators"), and photopolymerization initiators having an N-phenylglycine structure (hereinafter also referred to as "N-phenylglycine-based photopolymerization initiators").

[0155] The photopolymerization initiator preferably contains at least one selected from the group consisting of an oxime-based photopolymerization initiator, an α-aminoalkylphenone-based photopolymerization initiator, an α-hydroxyalkylphenone-based polymerization initiator, and an N-phenylglycine-based photopolymerization initiator, and more preferably contains at least one selected from the group consisting of an oxime-based photopolymerization initiator, an α-aminoalkylphenone-based photopolymerization initiator, and an N-phenylglycine-based photopolymerization initiator.

[0156] Furthermore, as the photopolymerization initiator, for example, the polymerization initiators described in paragraphs

[0031] to

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

[0064] to

[0081] of JP-A No. 2015-014783 may be used.

[0157] From the viewpoints of photosensitivity, visibility of exposed and unexposed areas, and resolution, the photopolymerization initiator preferably contains at least one selected from the group consisting of 2,4,5-triarylimidazole dimers and derivatives thereof, wherein the two 2,4,5-triarylimidazole structures in the 2,4,5-triarylimidazole dimers and derivatives thereof may be the same or different. Examples of derivatives of 2,4,5-triarylimidazole dimers include 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(o-chlorophenyl)-4,5-di(methoxyphenyl)imidazole dimer, 2-(o-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(o-methoxyphenyl)-4,5-diphenylimidazole dimer, and 2-(p-methoxyphenyl)-4,5-diphenylimidazole dimer. Examples of derivatives of 2,4,5-triarylimidazole dimers also include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole.

[0158] Examples of the photoradical polymerization initiator include ethyl dimethylaminobenzoate (DBE, CAS No. 10287-53-3), benzoin methyl ether, anisil (p,p'-dimethoxybenzyl), TAZ-110 (trade name: manufactured by Midori Chemical Industry Co., Ltd.), benzophenone, 4,4'-bis(diethylamino)benzophenone, TAZ-111 (trade name: manufactured by Midori Chemical Industry Co., Ltd.), Irgacure OXE01, OXE02, OXE03, OXE04 (manufactured by BASF), Omnirad 651 and 369 (trade name: manufactured by IGM Resins B.V.), and 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.).

[0159] Commercially available photoradical polymerization initiators include, for example, 1-[4-(phenylthio)]-1,2-octanedione-2-(O-benzoyloxime) (trade name: IRGACURE (registered trademark) OXE-01, manufactured by BASF), 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone-1-(O-acetyloxime) (trade name: IRGACURE OXE-02, manufactured by BASF), IRGACURE OXE-03 (manufactured by BASF), IRGACURE OXE-04 (manufactured by BASF), 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone (trade name: Omnirad 379EG, manufactured by IGM Resins), and B.V.), 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one (trade name: Omnirad 907, manufactured by IGM Resins B.V.), 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)benzyl]phenyl}-2-methylpropan-1-one (trade name: Omnirad 127, manufactured by IGM Resins B.V.), 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone-1 (trade name: Omnirad 369, manufactured by IGM Resins B.V.), 2-hydroxy-2-methyl-1-phenylpropan-1-one (trade name: Omnirad 1173, manufactured by IGM Resins B.V.), B.V.), 1-hydroxycyclohexyl phenyl ketone (trade name: Omnirad 184, manufactured by IGM Resins B.V.), 2,2-dimethoxy-1,2-diphenylethan-1-one (trade name: Omnirad 651, manufactured by IGM Resins B.V.), 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (trade name: Omnirad TPO H, manufactured by IGM Resins B.V.), bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (trade name: Omnirad 819, manufactured by IGM Resins B.V.), oxime ester photopolymerization initiator (trade name: Lunar 6, manufactured by DKSH Japan), 2,2'-bis(2-chlorophenyl)-4,4',5,5'-Tetraphenylbisimidazole (2-(2-chlorophenyl)-4,5-diphenylimidazole dimer) (trade name: B-CIM, manufactured by Hampford Chemical Industry Co., Ltd.), 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer (trade name: BCTB, manufactured by Tokyo Chemical Industry Co., Ltd.), 1-[4-(phenylthio)phenyl]-3-cyclopentylpropane-1,2-dione-2-(o-benzoyloxime) (trade name: TR-PBG-305, manufactured by Changzhou Strong Electronic New Materials Co., Ltd.), 1,2-propanedione 3-cyclohexyl-1-[9-ethyl-6-(2-furanylcarbonyl)-9H-carbazol-3-yl]-,2-(O-acetyloxime) (trade name: TR-PBG-326, Changzhou New Power Electronic Materials Co., Ltd.), and 3-cyclohexyl-1-(6-(2-(benzoyloxyimino)hexanoyl)-9-ethyl-9H-carbazol-3-yl)-propane-1,2-dione-2-(O-benzoyloxime) (trade name: TR-PBG-391, Changzhou New Power Electronic Materials Co., Ltd.). Commercially available photoradical polymerization initiators include alkylphenone compounds under the trade name "Omnirad 379" (IGM Resins B.V.).

[0160] The photopolymerization initiator may be used alone or in combination of two or more. When two or more types are used in combination, it is preferable to use an oxime-based photopolymerization initiator and at least one selected from an α-aminoalkylphenone-based photopolymerization initiator and an α-hydroxyalkylphenone-based polymerization initiator. When the photosensitive layer contains a photopolymerization initiator, the content of the photopolymerization initiator is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, and even more preferably 0.5% by mass or more, relative to the total mass of the photosensitive layer. The upper limit is preferably 10.0% by mass or less, more preferably 7.0% by mass or less, relative to the total mass of the photosensitive layer.

[0161] -Heterocyclic Compound- The photosensitive layer may contain a heterocyclic compound. The heterocycle contained in the heterocyclic compound may be either a monocyclic or polycyclic heterocycle. Examples of heteroatoms contained in the heterocyclic compound include a nitrogen atom, an oxygen atom, and a sulfur atom. The heterocyclic compound preferably contains at least one atom selected from the group consisting of a nitrogen atom, an oxygen atom, and a sulfur atom, and more preferably contains a nitrogen atom.

[0162] Examples of heterocyclic compounds include triazole compounds, benzotriazole compounds, tetrazole compounds, thiadiazole compounds, triazine compounds, rhodanine compounds, thiazole compounds, benzothiazole compounds, benzimidazole compounds, benzoxazole compounds, and pyrimidine compounds. Among these, the heterocyclic compound is preferably at least one compound selected from the group consisting of triazole compounds, benzotriazole compounds, tetrazole compounds, thiadiazole compounds, triazine compounds, rhodanine compounds, thiazole compounds, benzimidazole compounds, and benzoxazole compounds, and more preferably at least one compound selected from the group consisting of triazole compounds, benzotriazole compounds, tetrazole compounds, thiadiazole compounds, thiazole compounds, benzothiazole compounds, benzimidazole compounds, and benzoxazole compounds.

[0163] Preferred specific examples of the heterocyclic compound are shown below. Examples of the triazole compound and benzotriazole compound include the following compounds.

[0164]

[0165]

[0166] Examples of the tetrazole compound include the following compounds.

[0167]

[0168]

[0169] Examples of the thiadiazole compound include the following compounds:

[0170]

[0171] Examples of the triazine compound include the following compounds:

[0172]

[0173] Examples of rhodanine compounds include the following compounds:

[0174]

[0175] Examples of the thiazole compound include the following compounds:

[0176]

[0177] Examples of the benzothiazole compound include the following compounds:

[0178]

[0179] Examples of the benzimidazole compound include the following compounds:

[0180]

[0181]

[0182] Examples of the benzoxazole compound include the following compounds:

[0183]

[0184] The heterocyclic compound may be used alone or in combination of two or more. When the photosensitive layer contains a heterocyclic compound, the content of the heterocyclic compound is preferably 0.01 to 20.0 mass %, more preferably 0.10 to 10.0 mass %, still more preferably 0.30 to 8.0 mass %, and particularly preferably 0.50 to 5.0 mass %, relative to the total mass of the photosensitive layer.

[0185] Aliphatic Thiol Compound The photosensitive layer may contain an aliphatic thiol compound. When the photosensitive layer contains an aliphatic thiol compound, the aliphatic thiol compound undergoes an ene-thiol reaction with the radical polymerizable compound having an ethylenically unsaturated group, thereby suppressing cure shrinkage of the formed film and alleviating stress.

[0186] The aliphatic thiol compound is preferably a monofunctional aliphatic thiol compound or a polyfunctional aliphatic thiol compound (i.e., a di- or higher functional aliphatic thiol compound).

[0187] Among the above, polyfunctional aliphatic thiol compounds are preferred as the aliphatic thiol compounds from the viewpoint of the adhesion of the pattern to be formed (particularly the adhesion after exposure).

[0188] In this specification, the term "polyfunctional aliphatic thiol compound" refers to an aliphatic compound having two or more thiol groups (also called "mercapto groups") in the molecule.

[0189] The polyfunctional aliphatic thiol compound is preferably a low molecular weight compound having a molecular weight of at least 100. Specifically, the molecular weight of the polyfunctional aliphatic thiol compound is more preferably 100 to 1,500, and even more preferably 150 to 1,000.

[0190] The number of functional groups in the polyfunctional aliphatic thiol compound is preferably 2 to 10, more preferably 2 to 8, and even more preferably 2 to 6, from the viewpoint of the adhesion of the pattern to be formed.

[0191] Examples of polyfunctional aliphatic thiol compounds include trimethylolpropane tris(3-mercaptobutyrate), 1,4-bis(3-mercaptobutyryloxy)butane, pentaerythritol tetrakis(3-mercaptobutyrate), 1,3,5-tris(3-mercaptobutyryloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 1,3,5-tris(2-(3-sulfanylbutanoyloxy)ethyl)-1,3,5-triazinane-2,4,6-trione, trimethylolethane tris(3-mercaptobutyrate), and tris[(3-mercaptopropionyloxy)ethyl]isocyanurate. ester, trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptopropionate), tetraethylene glycol bis(3-mercaptopropionate), dipentaerythritol hexakis(3-mercaptopropionate), ethylene glycol bisthiopropionate, 1,4-bis(3-mercaptobutyryloxy)butane, 1,2-ethanedithiol, 1,3-propanedithiol, 1,6-hexamethylenedithiol, 2,2′-(ethylenedithio)diethanethiol, meso-2,3-dimercaptosuccinic acid, and di(mercaptoethyl)ether.

[0192] Among the above, the polyfunctional aliphatic thiol compound is preferably at least one compound selected from the group consisting of trimethylolpropane tris(3-mercaptobutyrate), 1,4-bis(3-mercaptobutyryloxy)butane, and 1,3,5-tris(3-mercaptobutyryloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione.

[0193] Examples of monofunctional aliphatic thiol compounds include 1-octanethiol, 1-dodecanethiol, β-mercaptopropionic acid, methyl-3-mercaptopropionate, 2-ethylhexyl-3-mercaptopropionate, n-octyl-3-mercaptopropionate, methoxybutyl-3-mercaptopropionate, and stearyl-3-mercaptopropionate.

[0194] The photosensitive layer may contain one kind of aliphatic thiol compound alone, or may contain two or more kinds of aliphatic thiol compounds.

[0195] When the photosensitive layer contains an aliphatic thiol compound, the content of the aliphatic thiol compound is preferably 5% by mass or more, more preferably 5 to 50% by mass, still more preferably 5 to 30% by mass, and particularly preferably 8 to 20% by mass, relative to the total mass of the photosensitive layer.

[0196] -Thermal Crosslinkable Compound- The photosensitive layer preferably contains a thermal crosslinkable compound from the viewpoints of the strength of the resulting cured film and the adhesiveness of the resulting uncured film. In this specification, the thermal crosslinkable compound having an ethylenically unsaturated group, described below, is not considered an ethylenically unsaturated compound but is considered a thermal crosslinkable compound. Examples of thermal crosslinkable compounds include epoxy compounds, oxetane compounds, methylol compounds, and blocked isocyanate compounds. Among these, blocked isocyanate compounds are preferred from the viewpoints of the strength of the resulting cured film and the adhesiveness of the resulting uncured film. Because blocked isocyanate compounds react with hydroxy groups and carboxy groups, for example, when at least one of an alkali-soluble resin and a radically polymerizable compound having an ethylenically unsaturated group contains at least one of a hydroxy group and a carboxy group, the hydrophilicity of the resulting film tends to decrease and its function as a protective film tends to be enhanced. The term "blocked isocyanate compound" refers to a compound having a structure in which the isocyanate group of an isocyanate is protected (i.e., masked) with a blocking agent.

[0197] The dissociation temperature of the blocked isocyanate compound is not particularly limited, but is preferably 100 to 160°C, and more preferably 130 to 150°C. The dissociation temperature of the blocked isocyanate means "the temperature of the endothermic peak accompanying the deprotection reaction of the blocked isocyanate when measured by DSC (Differential Scanning Calorimetry) analysis using a differential scanning calorimeter." As the differential scanning calorimeter, for example, a differential scanning calorimeter (Model: DSC6200) manufactured by Seiko Instruments Inc. can be suitably used. However, the differential scanning calorimeter is not limited to this.

[0198] Examples of blocking agents having a dissociation temperature of 100 to 160°C include active methylene compounds [malonic acid diesters (dimethyl malonate, diethyl malonate, di-n-butyl malonate, di-2-ethylhexyl malonate, etc.)] and oxime compounds (compounds having a structure represented by -C(=N-OH)- in the molecule, such as formaldoxime, acetaldoxime, acetoxime, methyl ethyl ketoxime, and cyclohexanone oxime). Among these, at least one oxime compound is preferred as the blocking agent having a dissociation temperature of 100 to 160°C, for example, from the viewpoint of storage stability.

[0199] The blocked isocyanate compound preferably has an isocyanurate structure, for example, from the viewpoint of improving the brittleness of the film and improving the adhesion to the transfer target. A blocked isocyanurate compound having an isocyanurate structure can be obtained, for example, by protecting hexamethylene diisocyanate through isocyanuration. Among blocked isocyanate compounds having an isocyanurate structure, a compound having an oxime structure in which an oxime compound is used as a blocking agent is preferred because it is easier to adjust the dissociation temperature to a preferred range and to reduce development residues than a compound not having an oxime structure.

[0200] The blocked isocyanate compound may have a polymerizable group. The polymerizable group is not particularly limited, and known polymerizable groups can be used, with a radical polymerizable group being preferred. Examples of the polymerizable group include ethylenically unsaturated groups such as (meth)acryloxy groups, (meth)acrylamide groups, and styryl groups, as well as groups having an epoxy group such as glycidyl groups. Among these, the polymerizable group is preferably an ethylenically unsaturated group, more preferably a (meth)acryloxy group, and even more preferably an acryloxy group.

[0201] Commercially available blocked isocyanate compounds can be used. Examples of commercially available blocked isocyanate compounds include Karenz (registered trademark) AOI-BM, Karenz (registered trademark) MOI-BM, Karenz (registered trademark) MOI-BP, etc. (all manufactured by Showa Denko K.K.), and the blocked Duranate series (e.g., Duranate (registered trademark) TPA-B80E, Duranate (registered trademark) WT32-B75P, etc., manufactured by Asahi Kasei Chemicals Corporation).

[0202] The thermally crosslinkable compound may be used alone or in combination of two or more. When the photosensitive layer contains a thermally crosslinkable compound, the content of the thermally crosslinkable compound is preferably 1.0 to 50.0 mass %, more preferably 5.0 to 30.0 mass %, and still more preferably 5.0 to 25.0 mass %, relative to the total mass of the photosensitive layer.

[0203] The photosensitive layer may contain a surfactant. Examples of the surfactant include those described in paragraph

[0017] of Japanese Patent No. 4502784 and paragraphs

[0060] to

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

[0204] The surfactant is preferably a fluorine-based surfactant or a silicone-based surfactant. Commercially available fluorine-based surfactants include, for example, Megafac F-171, F-172, F-173, F-176, F-177, F-141, F-142, F-143, F-144, F-437, F-475, F-477, F-479, F-482, F-551-A, F-552, F-554, F-555-A, F-556, F-557, F-558, F-559, and F-5 60, F-561, F-565, F-563, F-568, F-575, F-780, EXP, MFS-330, R-41, R-41-LM, R-01, R-40, R-40-LM, RS-43, TF-1956, RS-90, R-94, RS-72-K, DS-21 (all manufactured by DIC Corporation), Fluorad FC430, FC431, FC171 (all manufactured by Sumitomo 3M Limited), Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, KH-40 (all manufactured by AGC Inc.), PolyFox PF636, PF656, PF6320, PF6520, PF7002 (all manufactured by OMNOVA), Ftergent Examples of suitable fluorosurfactants include 710FM, 710FL, 610FM, 601AD, 601ADH2, 602A, 215M, 245F, 251, 212M, 250, 209F, 222F, 208G, 710LA, 710FS, 730LM, 650AC, and 681 (all manufactured by NEOS Corporation). Furthermore, acrylic compounds having a molecular structure with a functional group containing a fluorine atom, in which the fluorine atom-containing functional group is cleaved upon application of heat, causing the fluorine atom to volatilize, can also be suitably used. Examples of such fluorosurfactants include the Megafac DS series manufactured by DIC Corporation (The Chemical Daily (February 22, 2016), The Nikkei Business Daily (February 23, 2016)), such as Megafac DS-21. As the fluorosurfactant, it is also preferable to use a polymer of a fluorine atom-containing vinyl ether compound having a fluorinated alkyl group or a fluorinated alkylene ether group and a hydrophilic vinyl ether compound. Furthermore, as the fluorosurfactant, a block polymer can also be used.Furthermore, as the fluorosurfactant, a fluorine-containing polymer compound containing a structural unit derived from a (meth)acrylate compound having a fluorine atom and a structural unit derived from a (meth)acrylate compound having two or more (preferably five or more) alkyleneoxy groups (preferably ethyleneoxy groups or propyleneoxy groups) can also be preferably used. Furthermore, as the fluorosurfactant, a fluorine-containing polymer having an ethylenically unsaturated bond-containing group in the side chain can also be used. Examples include Megafac RS-101, RS-102, RS-718K, and RS-72-K (all manufactured by DIC Corporation). From the viewpoint of improving environmental compatibility, the fluorosurfactant is preferably a surfactant derived from a substitute material for a compound having a perfluoroalkyl group having seven or more carbon atoms, such as perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic acid (PFOS). Examples of nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane, and their ethoxylates and propoxylates (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 (registered trademark) L10, L31, L61, L62, 10R5, 17R2, 25R2 (all manufactured by BASF), Tetronic 304, 701, 704, 901, 904, 150R1 (all manufactured by BASF), and Solsperse 20000 (all manufactured by Lubrizol Nippon Corp.), NCW-101, NCW-1001, NCW-1002 (all manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), Paionin D-6112, D-6112-W, D-6315 (all manufactured by Takemoto Yushi Co., Ltd.), Olfine E1010, Surfynol 104, 400, 440 (all manufactured by Nissin Chemical Industry Co., Ltd.), and the like.

[0205] Examples of silicone surfactants include linear polymers consisting of siloxane bonds and modified siloxane polymers in which organic groups have been introduced into the side chains or terminals.

[0206] Specific examples of surfactants include DOWSIL 8032 ADDITIVE, Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, and Toray Silicone SH8400 (all manufactured by Dow Corning Toray Co., Ltd.), as well as X-22-4952, X-22-4272, X-22-6266, KF-351A, K354L, KF-355A, and KF- 945, KF-640, KF-642, KF-643, X-22-6191, X-22-4515, KF-6004, KP-341, KF-6001, KF-6002 (all manufactured by Shin-Etsu Silicones Co., Ltd.), F-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (all manufactured by Momentive Performance Materials), BYK307, BYK323, BYK330 (all manufactured by BYK-Chemie).

[0207] The surfactant may be used alone or in combination of two or more. When the photosensitive layer contains a surfactant, the content of the surfactant is preferably from 0.01 to 3.0% by mass, more preferably from 0.01 to 1.0% by mass, and still more preferably from 0.05 to 0.80% by mass, based on the total mass of the photosensitive layer.

[0208] -Polymerization inhibitor- The photosensitive layer may contain a polymerization inhibitor. A polymerization inhibitor refers to a compound that has the function of delaying or inhibiting a polymerization reaction. As the polymerization inhibitor, for example, a known compound used as a polymerization inhibitor can be used.

[0209] Examples of the polymerization inhibitor include phenothiazine compounds such as phenothiazine, bis-(1-dimethylbenzyl)phenothiazine, and 3,7-dioctylphenothiazine; bis[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionic acid][ethylenebis(oxyethylene)]2,4-bis[(laurylthio)methyl]-o-cresol, 1,3,5-tris(3,5-di-t-butyl-4-hydroxybenzyl), 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl), 2,4-bis-(n-octylthio)-6-(4-hydroxy-3,5-di-t-butylanilino)-1,3,5-triazine, and pentaerythritol tetrakis 3-(3,5-di-t nitroso compounds or salts thereof such as 4-nitrosophenol, N-nitrosodiphenylamine, N-nitrosocyclohexylhydroxylamine, and N-nitrosophenylhydroxylamine; quinone compounds such as methylhydroquinone, t-butylhydroquinone, 2,5-di-t-butylhydroquinone, and 4-benzoquinone; phenol compounds such as 4-methoxyphenol, 4-methoxy-1-naphthol, and t-butylcatechol; and metal salt compounds such as copper dibutyldithiocarbamate, copper diethyldithiocarbamate, manganese diethyldithiocarbamate, and manganese diphenyldithiocarbamate. Among these, in terms of more excellent effects of the present invention, the polymerization inhibitor is preferably at least one selected from the group consisting of a phenothiazine compound, a nitroso compound or a salt thereof, and a hindered phenol compound, and more preferably phenothiazine, bis[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionic acid][ethylenebis(oxyethylene)]2,4-bis[(laurylthio)methyl]-o-cresol, 1,3,5-tris(3,5-di-t-butyl-4-hydroxybenzyl), and N-nitrosophenylhydroxylamine aluminum salt.

[0210] The polymerization inhibitor may be used alone or in combination of two or more. When the photosensitive layer contains a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.001 to 5.0 mass%, more preferably 0.01 to 3.0 mass%, and even more preferably 0.02 to 2.0 mass%, relative to the total mass of the photosensitive layer. The content of the polymerization inhibitor is preferably 0.005 to 5.0 mass%, more preferably 0.01 to 3.0 mass%, and even more preferably 0.01 to 1.0 mass%, relative to the total mass of the polymerizable compounds.

[0211] -Hydrogen-donating compound- The photosensitive layer may contain a hydrogen-donating compound. The hydrogen-donating compound has the effects of further improving the sensitivity of the photopolymerization initiator to actinic rays and suppressing inhibition of polymerization of the polymerizable compound by oxygen.

[0212] Examples of hydrogen donor compounds include amines and amino acid compounds.

[0213] Examples of amines include compounds described in M. R. Sander et al., "Journal of Polymer Society," Vol. 10, p. 3173 (1972), JP-B No. 44-020189, JP-A No. 51-082102, JP-A No. 52-134692, JP-A No. 59-138205, JP-A No. 60-084305, JP-A No. 62-018537, JP-A No. 64-033104, and Research Disclosure No. 33825. More specific examples include 4,4'-bis(diethylamino)benzophenone, tris(4-dimethylaminophenyl)methane (also known as leuco crystal violet), triethanolamine, p-dimethylaminobenzoic acid ethyl ester, p-formyldimethylaniline, and p-methylthiodimethylaniline. Among these, at least one amine selected from the group consisting of 4,4'-bis(diethylamino)benzophenone and tris(4-dimethylaminophenyl)methane is preferred in terms of achieving superior effects of the present invention.

[0214] Examples of the amino acid compound include N-phenylglycine, N-methyl-N-phenylglycine, and N-ethyl-N-phenylglycine. Among these, N-phenylglycine is preferred as the amino acid compound in that it provides superior effects of the present invention.

[0215] Further, examples of the hydrogen donor compound include organometallic compounds (such as tributyltin acetate) described in JP-B-48-042965, hydrogen donors described in JP-B-55-034414, and sulfur compounds (such as trithiane) described in JP-A-6-308727.

[0216] The hydrogen donor compound may be used alone or in combination of two or more. When the photosensitive layer contains a hydrogen donor compound, the content of the hydrogen donor compound is preferably 0.01 to 10.0 mass %, more preferably 0.01 to 8.0 mass %, and still more preferably 0.03 to 5.0 mass %, relative to the total mass of the photosensitive layer, from the viewpoint of improving the curing rate by balancing the polymerization growth rate and chain transfer.

[0217] Residual Monomers The photosensitive layer may contain residual monomers of each structural unit of the alkali-soluble resin described above. From the viewpoints of patterning ability and reliability, the content of the residual monomers 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. The lower limit is not particularly limited, but is preferably 1 ppm by mass or more, and more preferably 10 ppm by mass or more. From the viewpoints of patterning ability and reliability, the content of the residual monomers of each structural unit of the alkali-soluble resin is preferably 3,000 ppm by mass or less, more preferably 600 ppm by mass or less, and even more preferably 100 ppm by mass or less, relative to the total mass of the photosensitive layer. The lower limit is not particularly limited, but is preferably 0.1 ppm by mass or more, and more preferably 1 ppm by mass or more.

[0218] The amount of residual monomers in the monomers used in synthesizing an alkali-soluble resin by a polymer reaction is also preferably within the above range. For example, when synthesizing an alkali-soluble resin by reacting glycidyl acrylate with a carboxylic acid side chain, the content of glycidyl acrylate is preferably within the above range. The amount of residual monomers can be measured by known methods such as liquid chromatography and gas chromatography.

[0219] -Other Components- The photosensitive layer may contain components other than those already described (hereinafter also referred to as "other components"). Examples of the other components include particles (e.g., metal oxide particles), colorants, antioxidants, reflectivity adjusters, light-absorbing materials, sensitizers, and chain transfer agents. Other components also include other additives described in paragraphs

[0058] to

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

[0220] --Particles-- Metal oxide particles are preferred as the particles. Metals in metal oxide particles also include semimetals such as B, Si, Ge, As, Sb, and Te. The average primary particle diameter of the particles is preferably 1 to 200 nm, more preferably 3 to 80 nm, from the viewpoint of the transparency of the cured film. The average primary particle diameter of the particles is calculated by measuring the particle diameters of 200 random particles using an electron microscope and arithmetically averaging the measurement results. Note that when the shape of the particles is not spherical, the particle diameter is determined as the longest side.

[0221] --Colorant-- The photosensitive layer may contain a small amount of a colorant (pigment, dye, etc.).

[0222] --Antioxidant-- Examples of antioxidants include 3-pyrazolidones such as 1-phenyl-3-pyrazolidone (also known as phenidone), 1-phenyl-4,4-dimethyl-3-pyrazolidone, and 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone; polyhydroxybenzenes such as hydroquinone, catechol, pyrogallol, methylhydroquinone, and chlorohydroquinone; para-methylaminophenol, para-aminophenol, para-hydroxyphenylglycine, and para-phenylenediamine. Among these, 3-pyrazolidones are preferred as the antioxidant, and 1-phenyl-3-pyrazolidone is more preferred, in terms of the superior effects of the present invention.

[0223] -Reflectivity Adjuster- The photosensitive layer preferably contains one or more reflectivity adjusters selected from the group consisting of white pigments, metal particles, hollow particles, and liquid crystal compounds (particularly pigment particles of cholesteric liquid crystal compounds). When the photosensitive layer contains a reflectivity adjuster, it can be used as a light-reflecting layer precursor layer. When the photosensitive layer contains a reflectivity adjuster, the resin pattern of the laminate formed by the first embodiment of the present invention has even better light reflectivity. Note that when the photosensitive layer contains white pigments or hollow particles, the photosensitive layer is likely to become a white layer, and a light-reflecting layer with characteristic X1 described below is likely to be obtained. On the other hand, when the photosensitive layer contains metal particles or liquid crystal compounds (particularly pigment particles of cholesteric liquid crystal compounds), a light-reflecting layer with characteristics X2 and X3 described below is likely to be obtained due to the reflectivity caused by the metal particles or liquid crystal compounds.

[0224] White Pigment Examples of white pigments include titanium oxide, zinc oxide, lithopone, precipitated calcium carbonate, white carbon, aluminum oxide, aluminum hydroxide, and barium sulfate. Furthermore, in terms of achieving the effects of the present invention more effectively, the white pigment is preferably a particle exhibiting a higher refractive index than the cured product of the polymerizable compound contained in the photosensitive layer. Among these, titanium oxide is more preferred, with rutile or anatase titanium oxide being even more preferred, and rutile titanium oxide being particularly preferred. The surface of the white pigment may be subjected to a treatment such as silica treatment, alumina treatment, titania treatment, zirconia treatment, or organic treatment. Furthermore, when the photosensitive layer contains a white pigment, the photosensitive layer may further contain a pigment dispersant.

[0225] The shape of the white pigment is not particularly limited, and examples thereof include spherical, irregular, plate-like, needle-like, and polyhedral. The average primary particle size of the white pigment is not particularly limited, and is preferably, for example, 50 to 1,000 nm, and more preferably 100 to 500 nm. The average primary particle size of the white pigment is a value obtained by measuring the diameters of 100 randomly selected particles observed with a transmission electron microscope (TEM) and calculating the arithmetic mean of the diameters of the 100 particles. The diameter of the white pigment refers to the diameter of a circle of the same area as the image observed with the transmission electron microscope (TEM).

[0226] --Metal Particles-- The type of metal contained in the metal particles is preferably silver, nickel, cobalt, iron, copper, palladium, gold, platinum, tin, zinc, aluminum, tungsten, or titanium, in terms of high reflectivity, and more preferably silver, gold, tin, nickel, aluminum, or cobalt, and even more preferably gold, silver, or aluminum, in terms of higher reflectivity in the visible light region, with silver being particularly preferred. The metal particles may be particles of a single metal or metal alloy particles. Note that when the metal particles are metal alloy particles, the metal alloy particles are preferably particles of an alloy of two or more of the above-mentioned metal species.

[0227] The shape of the metal particles is not particularly limited, and examples thereof include spherical, irregular, plate-like, acicular, and polyhedral. The average primary particle size of the metal particles is not particularly limited, and is preferably 1 to 5,000 nm, and more preferably 5 to 1,000 nm. The average primary particle size of the metal particles is determined by measuring the diameters of 100 randomly selected particles using a transmission electron microscope (TEM) and calculating the arithmetic mean of the diameters of the 100 particles. The diameter of the metal particles refers to the diameter of a circle of the same area as the image observed using a transmission electron microscope (TEM). Metal particles can be prepared, for example, by a method such as reduction of an organometallic compound, as disclosed in JP-A-10-183207.

[0228] --Hollow Particles-- The hollow particles are not particularly limited as long as they have an internal cavity, and examples thereof include hollow inorganic particles and hollow resin particles. Hollow inorganic particles are preferably hollow inorganic particles having a shell formed of a metal oxide selected from the group consisting of silica, alumina, zirconia, titanium oxide, and composite oxides thereof. Hollow resin particles include hollow resin particles having a shell formed of an organic material such as a polymer, such as a styrene-based resin, an acrylic-based resin, a silicone-based resin, an acrylic-styrene-based resin, a vinyl chloride-based resin, a vinylidene chloride-based resin, an amide-based resin, a urethane-based resin, a phenol-based resin, a styrene-conjugated diene-based resin, an acrylic-conjugated diene-based resin, or an olefin-based resin, as well as crosslinked products of these polymers. The hollow particles may be subjected to physical surface treatments, such as plasma discharge treatment and corona discharge treatment, or chemical surface treatments using surfactants, coupling agents, or the like.

[0229] The shape of the hollow particles is not particularly limited, and examples thereof include spherical, crushed, fibrous, acicular, and scale-like shapes. The average primary particle size of the hollow particles is not particularly limited, and is preferably 50 to 5,000 nm, and more preferably 100 to 1,000 nm. The average primary particle size of the hollow particles is determined by measuring the diameters of 100 randomly selected particles observed with a transmission electron microscope (TEM) and calculating the arithmetic mean of the diameters of the 100 particles. The diameter of the hollow particles refers to the diameter of a circle of the same area as the image observed with a transmission electron microscope (TEM).

[0230] Liquid Crystal Compounds Liquid crystal compounds include compounds with liquid crystallinity. The liquid crystal compound may be fixed in a predetermined orientation. That is, the photosensitive layer may contain a polymer obtained by polymerizing an aligned polymerizable liquid crystal compound. The orientation of the polymer is fixed. The liquid crystal compound is preferably a polymer obtained by polymerizing a polymerizable liquid crystal compound with cholesteric liquid crystal alignment (in other words, a polymer with fixed cholesteric liquid crystal alignment) because of its superior reflectivity. A polymer with fixed cholesteric liquid crystal alignment is obtained by using a cholesteric liquid crystal composition containing a nematic liquid crystal compound and a chiral agent and curing the liquid crystal composition in a cholesteric liquid crystal phase. A polymer with fixed cholesteric liquid crystal alignment has a circularly polarized light selective reflection function that selectively reflects normally circularly polarized light. Furthermore, the polymer with fixed cholesteric liquid crystal alignment in the photosensitive layer is preferably contained in the form of liquid crystal particles. In other words, the photosensitive layer preferably contains liquid crystal particles made of a polymer with fixed cholesteric liquid crystal alignment. The shape of the liquid crystal particles is not particularly limited, but flakes are preferred because they have better dispersibility. The average primary particle diameter of the flakes is, for example, preferably 1 to 120 μm, more preferably 1 to 100 μm. The average primary particle diameter of the liquid crystal particles is a value obtained by measuring the diameters of 100 random particles observed with a transmission electron microscope (TEM) and calculating the arithmetic mean of the diameters of the 100 particles. The diameter of the liquid crystal particles refers to the diameter of a circle of the same area as the image observed with a transmission electron microscope (TEM).

[0231] Commercially available liquid crystal particles include, for example, "HELICONE HC Sapphire," "HELICONE HC Aquarius," "HELICONE HC Scarabeus," "HELICONE HC Jade," and "HELICONE HC Maple" (all manufactured by Wacker Asahi Kasei Silicone Co., Ltd.).

[0232] When the photosensitive layer contains a reflectivity adjuster, the content of the reflectivity adjuster is preferably 10 to 90% by mass, more preferably 20 to 85% by mass, and even more preferably 30 to 80% by mass, relative to the total mass of the photosensitive layer. In particular, when the reflectivity adjuster contains a white pigment, the content of the white pigment is preferably 30 to 80% by mass, more preferably 40 to 70% by mass, relative to the total mass of the photosensitive layer. Furthermore, when the reflectivity adjuster contains metal particles, the content of the metal particles is preferably 20 to 95% by mass, more preferably 30 to 90% by mass, relative to the total mass of the photosensitive layer. Furthermore, when the reflectivity adjuster contains hollow particles, the content of the hollow particles is preferably 20 to 80% by mass, more preferably 30 to 70% by mass, relative to the total mass of the photosensitive layer. Furthermore, when the reflectivity adjusting agent contains a liquid crystal compound (preferably liquid crystal particles), the content of the liquid crystal compound (preferably liquid crystal particles) is preferably 10 to 90 mass %, more preferably 20 to 80 mass %, and even more preferably 30 to 70 mass %, relative to the total mass of the photosensitive layer.

[0233] -Light-absorbing substance- The photosensitive layer preferably contains a light-absorbing substance. When the photosensitive layer contains a light-absorbing substance, a light-absorbing layer precursor layer can be formed. When the photosensitive layer contains a light-absorbing substance, the external light reflectivity of the resin pattern of the laminate formed by the first embodiment of the present invention is reduced, and / or stray light that may be generated when the light-emitting element is turned on is easily absorbed, resulting in better black density when the light-emitting element is not turned on. Note that when the photosensitive layer contains a light-absorbing substance, a light-absorbing layer with characteristics Y1 and / or Y2, which will be described later, is easily obtained.

[0234] The light absorbing substance is not particularly limited, and examples thereof include black pigments, and specific examples thereof include carbon black, titanium black, titanium carbon, iron oxide, titanium oxide, and graphite, with carbon black being more preferred.

[0235] When the light-absorbing substance is a black pigment, its shape is not particularly limited, and examples thereof include spherical, amorphous, plate-like, acicular, and polyhedral shapes. The average primary particle size of the light-absorbing substance is not particularly limited, and is preferably 1 to 1,000 nm, and more preferably 2 to 500 nm. The average primary particle size of the light-absorbing substance is determined by measuring the diameters of 100 randomly selected particles observed with a transmission electron microscope (TEM) and calculating the arithmetic mean of the diameters of the 100 particles. The diameter of the light-absorbing substance refers to the diameter of a circle of the same area as the image observed with a transmission electron microscope (TEM). The light-absorbing substance may be subjected to physical surface treatments such as plasma discharge treatment and corona discharge treatment, or chemical surface treatments using surfactants, coupling agents, resins, and the like.

[0236] Furthermore, examples of the light-absorbing substance include black dyes as well as compounds that turn black upon exposure to light, heating, etc. Examples of compounds that turn black upon exposure to light, heating, etc. include the following compound (1):

[0237]

[0238] When the photosensitive layer contains a light-absorbing substance, the content of the light-absorbing substance is preferably 5 to 80 mass %, more preferably 10 to 70 mass %, still more preferably 10 to 60 mass %, and particularly preferably 10 to 50 mass %, relative to the total mass of the photosensitive layer.

[0239] The thickness of the photosensitive layer is, for example, preferably 1 μm or more, more preferably 2 μm or more, and the upper limit is not particularly limited, but is, for example, preferably 100 μm or less, more preferably 50 μm or less.

[0240] (Preferred embodiments of light-reflecting layer precursor layer and light-absorbing layer precursor layer) As described above, when the photosensitive layer contains a reflectivity adjusting agent, it can be a light-reflecting layer precursor layer, and when the photosensitive layer contains a light-absorbing substance, it can be a light-absorbing layer precursor layer. Preferred embodiments of the light-absorbing layer precursor layer and the light-absorbing layer precursor layer will be described below.

[0241] Light Reflecting Layer Precursor Layer Thickness of the Light Reflecting Layer Precursor Layer The thickness of the light reflecting layer precursor layer is preferably 3 μm or more, more preferably 5 μm or more, even more preferably 10 μm or more, and particularly preferably 16 μm or more. There is no particular upper limit, and for example, it is preferably 100 μm or less, more preferably 50 μm or less.

[0242] ...Characteristics of the light-reflecting layer formed from the light-reflecting layer precursor layer The light-reflecting layer formed from the light-reflecting layer precursor layer is preferably a layer that satisfies at least one of the following characteristics X1, X2, and X3. In particular, when the light-emitting element is a visible light LED, the light-reflecting layer is preferably a layer that satisfies at least one of characteristics X1 and X2, and when the LED in the light-emitting element is a UV-LED, the light-reflecting layer is preferably a layer that satisfies characteristic X3. {Characteristic X1} The total reflection of the light-reflecting layer (incident angle 8°, light source: D-65 (2° field of view)) is preferably 100% or more of the total reflection of the light-reflecting layer (incident angle 8°, light source: D-65 (2° field of view)) in accordance with CIE 1976 (L ＊ , a ＊ , b ＊ ) color space, L ＊ It is preferable that the value is 80 or more. ＊ , a ＊ , b ＊ ) L in color space ＊ The value is a value measured at 25° C. for a light-reflecting layer having a thickness of 30 μm using a spectrophotometer. As the spectrophotometer, for example, a spectrophotometer V-570 manufactured by JASCO Corporation can be used. ＊The value is preferably 90 or more. The upper limit is 100 or less. <Characteristic X2> The total reflectance of the light-reflective layer at a wavelength of 550 nm is preferably 60% or more, and more preferably 80% or more. The upper limit is 100% or less. The total reflectance at a wavelength of 550 nm is a value measured using a spectrophotometer on a light-reflective layer having a thickness of 30 μm at 25°C. As the spectrophotometer, for example, a V-570 spectrophotometer manufactured by JASCO Corporation can be used. <Characteristic X3> The total reflectance of the light-reflective layer at a wavelength of 385 nm is preferably 60% or more, and more preferably 80% or more. The upper limit is 100% or less. The total reflectance at a wavelength of 385 nm is a value measured using a spectrophotometer on a light-reflective layer having a thickness of 30 μm at 25°C. As the spectrophotometer, for example, a V-570 spectrophotometer manufactured by JASCO Corporation can be used.

[0243] Light-absorbing layer precursor layer Thickness of the light-absorbing layer precursor layer The thickness of the light-absorbing layer precursor layer is preferably 1 μm or more, more preferably 2 μm or more. There is no particular upper limit, and for example, 10 μm or less is preferred, and 5 μm or less is more preferred. Optical density of the light-absorbing layer precursor layer The optical density (OD) of the light-absorbing layer precursor layer at a wavelength of 550 nm is preferably 0.5 or more, more preferably 1.0 or more, even more preferably 2.0 or more, and particularly preferably 3.0 or more. There is no particular upper limit, and for example, 6.0 or less is preferred. The optical density of the light-absorbing layer precursor layer can be measured using a Macbeth densitometer (manufactured by Macbeth, TD-904, using a visual filter) or the like. The optical density (OD) of the light-absorbing layer precursor layer at a wavelength of 385 nm is preferably 0.5 or more, more preferably 1.0 or more, even more preferably 2.0 or more, and particularly preferably 3.0 or more. There is no particular upper limit, and for example, 6.0 or less is preferred. The optical density of the light absorbing layer precursor layer at a wavelength of 385 nm can be measured using an ultraviolet spectrophotometer U-3310 (manufactured by Hitachi, Ltd.) or the like.

[0244] ...Characteristics of the light absorbing layer formed from the light absorbing layer precursor layer The light absorbing layer formed from the light absorbing layer precursor layer preferably satisfies the characteristic Y1 and / or the characteristic Y2. In particular, when the light emitting element is a visible light LED, the light absorbing layer is preferably a layer that satisfies the characteristic Y1 in terms of having better anti-reflection properties for external light, and when the light emitting element is a UV-LED, the light absorbing layer is preferably a layer that satisfies the characteristic Y2 in terms of having better anti-reflection properties for external light and better suppression of stray light.

[0245] <<Characteristic Y1>> The optical density (OD) of the light-absorbing layer at a wavelength of 550 nm is preferably 0.5 or more, more preferably 1.0 or more, even more preferably 2.0 or more, and particularly preferably 3.0 or more. There is no particular upper limit, and for example, 6.0 or less is preferable. The optical density of the light-absorbing layer can be measured using a Macbeth densitometer (manufactured by Macbeth, TD-904, using a visual filter) or the like. <<Characteristic Y2>> The optical density (OD) of the light-absorbing layer at a wavelength of 385 nm is preferably 0.5 or more, more preferably 1.0 or more, even more preferably 2.0 or more, and particularly preferably 3.0 or more. There is no particular upper limit, and for example, 6.0 or less is preferable. The optical density of the light-absorbing layer at a wavelength of 385 nm can be measured using an ultraviolet spectrophotometer U-3310 (manufactured by Hitachi, Ltd.) or the like.

[0246] <<Positive Photosensitive Layer>> The positive photosensitive layer will be described in detail below. Examples of the photosensitive layer include a photosensitive layer containing at least a polymer and a photoacid generator. The polymer is preferably a polymer containing a repeating unit having a group whose hydrophilicity increases under the action of acid (for example, an acid-decomposable group in which a polar group is protected by a leaving group that leaves under the action of acid). Known positive photosensitive layers can be used as the photosensitive layer. The photosensitive layer may be a photosensitive light-reflecting layer or a photosensitive light-absorbing layer. When the photosensitive layer is a photosensitive light-reflecting layer, the photosensitive layer contains a reflectivity adjusting agent, and when the photosensitive layer is a photosensitive light-absorbing layer, the photosensitive layer contains a light-absorbing substance. The types of reflectivity adjuster and light absorbing substance, and the respective contents of the reflectivity adjuster and light absorbing substance relative to the total mass of the photosensitive layer, are similar to those of the negative-type photosensitive layer, and the preferred ranges are also similar.

[0247] The thickness of the photosensitive layer is, for example, preferably 1 μm or more, more preferably 2 μm or more, and the upper limit is not particularly limited, but is, for example, preferably 100 μm or less, more preferably 50 μm or less.

[0248] (Preferred Embodiments of Photosensitive Light Reflecting Layer and Photosensitive Light Absorbing Layer) Preferred embodiments of the photosensitive light reflecting layer and the photosensitive light absorbing layer will be described below.

[0249] Photosensitive Light Reflecting Layer: Thickness of the Photosensitive Light Reflecting Layer The thickness of the photosensitive light reflecting layer is preferably 3 μm or more, more preferably 5 μm or more, even more preferably 10 μm or more, and particularly preferably 16 μm or more. There is no particular upper limit, and for example, it is preferably 100 μm or less, more preferably 50 μm or less.

[0250] ...Characteristics of the Photosensitive Light Reflecting Layer The photosensitive light reflecting layer is preferably a layer that satisfies at least one of the above-mentioned characteristics X1, X2, and X3. In particular, when the light-emitting element is a visible light LED, the photosensitive light reflecting layer is preferably a layer that satisfies at least one of the characteristics X1 and X2, and when the LED in the light-emitting element is a UV-LED, the photosensitive light reflecting layer is preferably a layer that satisfies the characteristic X3.

[0251] Photosensitive Light-Absorbing Layer: Thickness of the Photosensitive Light-Absorbing Layer The thickness of the photosensitive light-absorbing layer is preferably 1 μm or more, more preferably 2 μm or more. There is no particular upper limit, and the thickness is, for example, preferably 10 μm or less, more preferably 5 μm or less.

[0252] ...Characteristics of Photosensitive Light Absorbing Layer The photosensitive light absorbing layer preferably satisfies the above-mentioned characteristic Y1 and / or characteristic Y2. In particular, when the light emitting element is a visible light LED, the photosensitive light absorbing layer is preferably a layer that satisfies characteristic Y1 in terms of superior anti-reflection properties for external light, and when the light emitting element is a UV-LED, the photosensitive light absorbing layer is preferably a layer that satisfies characteristic Y2 in terms of superior anti-reflection properties for external light and superior suppression of stray light.

[0253] <<Protective Film>> The transfer film may have a protective film. As the protective film, a resin film having heat resistance and solvent resistance can be used, and examples thereof include polyolefin films such as polypropylene film and polyethylene film, polyester films such as polyethylene terephthalate film, polycarbonate film, and polystyrene film. Alternatively, a resin film made of the same material as the temporary support may be used as the protective film. Among these, as the protective film, a polyolefin film is preferred, a polypropylene film or a polyethylene film is more preferred, and a polyethylene film is even more preferred.

[0254] The thickness of the protective film is preferably 1 to 100 μm, more preferably 5 to 50 μm, even more preferably 5 to 40 μm, and particularly preferably 15 to 30 μm. The thickness of the protective film can be calculated as the average value of any five points measured by cross-sectional observation using an SEM (scanning electron microscope). The thickness of the protective film is preferably 1 μm or more in terms of excellent mechanical strength, and is preferably 100 μm or less in terms of relatively low cost.

[0255] In addition, the number of fish eyes with a diameter of 80 μm or more contained in the protective film is 5 / m. ２ The term "fisheyes" refers to foreign matter, undissolved matter, oxidized degradation products, etc., that are trapped in a film when the material is thermally melted and then kneaded, extruded, biaxially stretched, cast, or other methods are used to produce the film.

[0256] The number of particles with a diameter of 3 μm or more contained in the protective film is 30 / mm ２ Preferably, 10 pieces / mm or less ２ More preferably, 5 or less pieces / mm ２ The following is more preferable: This can suppress defects caused by the transfer of irregularities due to particles contained in the protective film to the photosensitive layer.

[0257] From the viewpoint of providing winding properties, the arithmetic mean roughness Ra of the surface of the protective film opposite to the surface in contact with the photosensitive layer is preferably 0.01 μm or more, more preferably 0.02 μm or more, and even more preferably 0.03 μm or more. On the other hand, it is preferably less than 0.50 μm, more preferably 0.40 μm or less, and even more preferably 0.30 μm or less. From the viewpoint of suppressing defects during transfer, the surface roughness Ra of the protective film on the surface in contact with the photosensitive layer is preferably 0.01 μm or more, more preferably 0.02 μm or more, and even more preferably 0.03 μm or more. On the other hand, it is preferably less than 0.50 μm, more preferably 0.40 μm or less, and even more preferably 0.30 μm or less.

[0258] Second Embodiment A second embodiment of the method for producing a laminate of the present invention (hereinafter also simply referred to as "second embodiment of the present invention") includes the following steps (2-1) to (2-4).

[0259] Step (2-1) (bonding step): a step of bonding the substrate with light-emitting elements to the transfer film, the surface of the substrate with light-emitting elements including a substrate and a plurality of light-emitting elements arranged on the substrate facing the light-emitting elements and the surface of the transfer film including a temporary support and a photosensitive layer opposite the temporary support, so that the light-emitting elements are covered with the photosensitive layer; Step (2-2) (exposure step): a step of performing pattern exposure on the photosensitive layer; Step (2-3) (development step): a step of developing the exposed photosensitive layer to form a resin pattern having openings at positions corresponding to the light-emitting elements; Step (2-4) (light-reflecting film forming step): a step of arranging a light-reflecting film on the side walls of the openings; Furthermore, the second embodiment of the present invention has the following step (2-A) between step (2-1) and step (2-2), or between step (2-2) and step (2-3). Step (2-A) (temporary support peeling step): a step of peeling off the temporary support.

[0260] <Steps (2-1) to (2-3), (2-A) to (2-C)> Steps (2-1) to (2-3), and (2-A) in the second embodiment of the present invention are the same as those described as steps (1-1) to (1-3), and (1-A) in the first embodiment of the present invention, respectively. Furthermore, in the second embodiment of the present invention, after carrying out step (2-3) (development step), the formed resin pattern may further include a step of exposing the pattern to light (hereinafter also referred to as "step (2-B)" or "post-exposure step") and / or a step of heating the pattern (hereinafter also referred to as "step (2-C)" or "post-bake step"). Steps (2-B) and (2-C) in the second embodiment of the present invention are the same as those described as steps (1-B) and (1-C) in the first embodiment of the present invention, respectively.

[0261] <Step (2-4) Light Reflecting Film Forming Step> A second embodiment of the present invention is a step of forming a light reflecting film on the side walls of openings in a resin pattern formed on a substrate with light-emitting elements after a development step (step (2-3)) (note that, if the above-mentioned steps (2-B) and / or (2-C) are performed, this step is performed after this step). In a resin pattern that functions as a partition layer separating light-emitting elements from each other, when a light reflecting film is disposed on the side walls of the openings, light from the light-emitting elements is reflected by the light reflecting film, resulting in superior brightness. FIG. 6 shows a cross-sectional schematic diagram of a laminate formed through the light reflecting film forming step (step (2-4)). A laminate 60 is composed of a substrate with light-emitting elements 10, a resin pattern 42, and a light reflecting film 62 disposed on the side walls of openings 43 in the resin pattern 42.

[0262] The light-reflecting film preferably contains a metal. The type of metal is not particularly limited, but silver, nickel, cobalt, iron, copper, palladium, gold, platinum, tin, zinc, aluminum, tungsten, or titanium is preferred in terms of high reflectivity, silver, gold, tin, nickel, aluminum, or cobalt is more preferred, and gold, silver, or aluminum is even more preferred in terms of showing higher reflectivity in the visible light region, with silver being particularly preferred.

[0263] The light reflective film forming step (step (2-4)) can be performed by sputtering, vapor deposition, plating, printing with ink containing metal particles (screen printing, inkjet printing, etc.), etc. Alternatively, the light reflective film may be formed by patterning using a known method such as wet etching or dry etching so as to leave only necessary areas.

[0264] The thickness of the light-reflecting film is preferably 10 nm or more, more preferably 50 nm or more, and even more preferably 250 nm or more. There is no particular upper limit, and for example, it is preferably 100 μm or less, more preferably 50 μm or less, even more preferably 10 μm or less, particularly preferably 1 μm or less, and most preferably 800 nm or less.

[0265] The light-reflecting film is preferably a film that satisfies at least one of the following characteristics Z1 and Z2. When the light-emitting element is a visible light LED, the light-reflecting film preferably satisfies characteristic Z1. When the light-emitting element is a UV-LED, the light-reflecting film preferably satisfies characteristic Z2. (Characteristic Z1) The total reflectance of the light-reflecting film at a wavelength of 550 nm is preferably 60% or more, more preferably 80% or more. The upper limit is 100% or less. The total reflectance at a wavelength of 550 nm is a value measured using a spectrophotometer on a light-reflecting film having a thickness of 30 μm at 25°C. As the spectrophotometer, for example, the V-570 spectrophotometer manufactured by JASCO Corporation can be used. (Characteristic Z2) The total reflectance of the light-reflecting film at a wavelength of 385 nm is preferably 60% or more, more preferably 80% or more. The upper limit is 100% or less. The total reflectance of the light-reflecting film at a wavelength of 385 nm is a value measured using a spectrophotometer on a light-reflecting film having a thickness of 30 μm at 25°C. As the spectrophotometer, for example, a spectrophotometer V-570 manufactured by JASCO Corporation can be used.

[0266] As a transfer film that can be used in the second embodiment of the present invention, for example, various transfer films shown as transfer films that can be used in the first embodiment of the present invention can be used. Below, an example of a preferred embodiment of a transfer film that can be used in the second embodiment of the present invention is shown. Hereinafter, the light-reflecting layer precursor layer, light-absorbing layer precursor layer, protective film, and temporary support are synonymous with the light-reflecting layer precursor layer, light-absorbing layer precursor layer, protective film, and temporary support in the transfer film that can be used in the first embodiment of the present invention, and preferred embodiments are also the same. Another photosensitive layer means a photosensitive layer that does not fall into either the light-reflecting layer precursor layer or the light-absorbing layer precursor layer. - (N4) Temporary support / light-absorbing layer precursor layer / protective film - (N5) Temporary support / light-absorbing layer precursor layer / other photosensitive layer / protective film

[0267] In addition, when a transfer film (N5) is used in the second embodiment of the present invention, a light-reflecting film may be placed on the side wall of the opening of the resin pattern at least at a position corresponding to the resin layer derived from another photosensitive layer.

[0268] The present invention will be described in more detail below based on examples. The materials, amounts used, ratios, processing details, processing procedures, etc. shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be interpreted as being limited by the examples shown below. In the following, "parts" or "%" are based on mass unless otherwise specified.

[0269] [Preparation of Composition for Forming Light-Absorbing Layer Precursor Layer] Compositions for forming light-absorbing layer precursor layers (A-1 to A-2) were prepared based on the components and blending amounts shown in Table 1. The blending amount of each component shown in Table 1 is expressed in parts by mass.

[0270]

[0271] Other abbreviations and product names in Table 1 are detailed below. "Compound (1)": A compound having the following structure. Compound (1) is a compound that changes from transparent to black upon heat treatment.

[0272]

[0273] "Polymer P-1 solution": PGMEA solution (solid content: 40.5% by mass) of polymer P-1 [benzyl methacrylate / methacrylic acid copolymer, copolymer composition ratio (by mass) = 70 / 30, weight average molecular weight (Mw) = 5000]. "Aronix TO-2349": carboxyl group-containing monomer (manufactured by Toagosei Co., Ltd.). "SB-PI 701": 4,4'-bis(diethylamino)benzophenone (manufactured by Sanyo Trading Co., Ltd.). "TDP-G": phenothiazine (manufactured by Kawaguchi Chemical Industry Co., Ltd.). "Megafac F551A": fluorosurfactant (manufactured by DIC Corporation).

[0274] [Preparation of composition (B-1) for forming light-reflecting layer precursor layer and photosensitive composition (B-2)] A composition (B-1) for forming a light-reflecting layer precursor layer and a photosensitive composition (B-2) were prepared based on the components and blending amounts shown in Table 2. The blending amount of each component shown in Table 2 is expressed in parts by mass.

[0275]

[0276] [Method for Preparing P-2 Solution (Solution with 36.2% Solids by Mass of Polymer P-2)] P-2 solution (solution with 36.2% Solids by Mass of Polymer P-2) was prepared by the polymerization process and addition process described below. 113.5 g of propylene glycol monomethyl ether was charged into a flask and heated to 90°C under a nitrogen stream. To this liquid, a solution prepared by dissolving 172 g of styrene, 4.7 g of methyl methacrylate, and 112.1 g of methacrylic acid in 30 g of propylene glycol monomethyl ether, and a solution prepared by dissolving 27.6 g of polymerization initiator V-601 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) in 57.7 g of propylene glycol monomethyl ether were simultaneously added dropwise over 3 hours. After completion of the dropwise addition, 2.5 g of V-601 was added three times every hour. The mixture was then allowed to react for another 3 hours. The mixture was then diluted with 160.7 g of propylene glycol monomethyl ether acetate and 233.3 g of propylene glycol monomethyl ether. Under an air stream, the reaction solution was heated to 100°C, and 1.8 g of tetraethylammonium bromide and 0.86 g of p-methoxyphenol were added. To this was added dropwise 71.9 g of glycidyl methacrylate (Blemmer G, manufactured by NOF Corporation) over 20 minutes. After the dropwise addition, the reaction solution was reacted at 100°C for 7 hours to obtain a solution of resin P-2. The solids concentration of the resulting solution was 36.2% by mass. The weight average molecular weight, calculated in terms of standard polystyrene, measured by GPC was 18,000, the number average molecular weight was 7,800, the polydispersity was 2.3, and the acid value of the polymer was 124 mg KOH / g. The residual monomer amounts measured using gas chromatography were less than 0.1% by mass of the polymer solids for all monomers. The structure of polymer P-2 is shown below.

[0277] Polymer P-2: The composition of the structural units in the following structural formula represents the molar ratio. Polymer P-2 corresponds to an alkali-soluble resin.

[0278]

[0279] Details of the abbreviations and product names of the other ingredients in Table 2 are shown below. "A-NOD-N": 1,9-nonanediol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.) "A-DPH": dipentaerythritol hexaacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.) "Aronix TO-2349": carboxyl group-containing monomer (manufactured by Toagosei Co., Ltd.) "B-CIM": 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole (manufactured by Hampford Chemical Industry Co., Ltd.) "SB-PI 701": 4,4'-bis(diethylamino)benzophenone (manufactured by Sanyo Trading Co., Ltd.) "TDP-G": phenothiazine (manufactured by Kawaguchi Chemical Industry Co., Ltd.) "CBT-1": carboxybenzotriazole (manufactured by Johoku Chemical Industry Co., Ltd.) "Megafac F551A": fluorosurfactant (manufactured by DIC Corporation)

[0280] Example 1 Preparation of Transfer Film A polyethylene terephthalate film (Lumirror 16KS40, manufactured by Toray Industries, Inc., thickness: 16 μm) was prepared as a temporary support. A light-absorbing layer precursor layer-forming composition A-1 was applied onto the temporary support to a thickness of 3 μm after drying, and dried at 100°C for 1 minute to form a light-absorbing layer precursor layer. A light-reflecting layer precursor layer-forming composition B-1 was applied onto the light-absorbing layer precursor layer to a thickness of 30 μm after drying, and dried at 100°C for 3 minutes to form a light-reflecting layer precursor layer. A polyethylene terephthalate film (Lumirror 16KS40, manufactured by Toray Industries, Inc., thickness: 16 μm) was pressure-bonded onto the light-reflecting layer precursor layer. By the above procedure, a transfer film 1 was obtained, which included, in this order, a temporary support, a light-absorbing layer precursor layer, a light-reflecting layer precursor layer, and a protective film.

[0281] [Fabrication of Micro LED Display Element] A micro LED display element was fabricated using the transfer film 1 according to the following procedure. Specifically, an LED chip was bonded to a bonding member on an array substrate, and then a resin pattern (partition layer) was formed using the transfer film 1. The specific procedure is described below.

[0282] [[Mounting of LED Chips]] First, according to the method described in JP 2021-163945 A (particularly the claims, paragraphs 0013 to 0041), 200 LED chips on a sapphire substrate for peeling were bonded together onto an array substrate, and the sapphire substrate for peeling was peeled off.

[0283] [[Formation of Resin Pattern (Partition Wall Layer)]] Next, the protective film of transfer film 1 was peeled off, and transfer film 1 was attached to the array substrate to which the LED chips had been bonded under the lamination conditions shown below, to produce a substrate with precursor layers in which the light-reflecting layer precursor layer, the light-absorbing layer precursor layer, and the temporary support were laminated in this order on the substrate with light-emitting elements (substrate with chips). Heating temperature of substrate with chips: 40°C Temperature of rubber roller: 110°C Linear pressure: 3 N / cm Conveying speed: 2 m / min

[0284] The distance between the surface of the exposure mask (a mask having a pattern for forming openings) and the surface of the temporary support was set to 125 μm. Using a proximity exposure machine (Hitachi High-Tech Electronics Engineering Co., Ltd.) equipped with an ultra-high pressure mercury lamp, i-rays were irradiated at 100 mJ / cm2 onto the light-reflecting layer precursor layer and the light-absorbing layer precursor layer through the temporary support. ２ The pattern was irradiated with an exposure dose of 1000 mJ / cm. At that time, the pattern and position of the exposure mask were adjusted so that openings were formed in the portions where the LED chips were mounted, such that the taper angle of the partition layer (see taper angle θ in Figure 3) was the angle shown in Table 3. After the exposure treatment, the temporary support was peeled off, and then the exposed light-reflecting layer precursor layer and light-absorbing layer precursor layer were developed for 60 seconds using a 1 mass % aqueous solution of sodium carbonate at a temperature of 32°C. Next, the laminate obtained after the development treatment was sprayed with ultrapure water from an ultra-high pressure cleaning nozzle to remove residue, and then air was further sprayed to remove moisture. Next, the pattern in the obtained laminate was exposed to an exposure dose of 1000 mJ / cm using a post-exposure machine (manufactured by Ushio Inc.) equipped with a high-pressure mercury lamp. ２ The substrate was exposed to i-line light (post-exposure). After the exposure, the substrate was post-baked at 210° C. for 5 minutes. By the above procedure, a resin pattern (a partition layer in which a light-reflecting layer and a light-absorbing layer were laminated in this order) having openings at the positions of the LED chips was formed on the array substrate.

[0285] In this way, a micro LED display element was fabricated.

[0286] [Example 2] [Preparation of Transfer Film of Example] A polyethylene terephthalate film (Lumirror 16KS40, manufactured by Toray Industries, Inc., thickness: 16 μm) was prepared as a temporary support. A light-absorbing layer precursor layer-forming composition A-1 was applied onto the temporary support to a thickness of 3 μm after drying, and dried at 100°C for 1 minute to form a light-absorbing layer precursor layer. A photosensitive layer-forming composition B-2 was applied onto the light-absorbing layer precursor layer to a thickness of 30 μm after drying, and dried at 100°C for 3 minutes to form a photosensitive layer (another photosensitive layer). A polyethylene terephthalate film (Lumirror 16KS40, manufactured by Toray Industries, Inc., thickness: 16 μm) was pressure-bonded onto the photosensitive layer. By the above procedure, a transfer film 2 was obtained, which included, in this order, a temporary support, a light-absorbing layer precursor layer, a photosensitive layer, and a protective film.

[0287] [Fabrication of Micro LED Display Element of Example 2] First, LED chips were mounted on an array substrate in the same manner as in Example 1 ([Mounting of LED Chips]). Next, a resin pattern (a partition layer consisting of a resin layer and a light-absorbing layer stacked in this order) with openings was formed on the array substrate on which the LED chips were mounted, using the same procedure as in Example 1 ([Formation of Resin Pattern (Partition Layer)]), except that the process conditions were appropriately adjusted to obtain the taper angle of the partition layer shown in Table 3. After the partition walls were formed, a 300 nm silver layer was vapor-deposited in the openings of the partition walls using a known vapor deposition method. During this process, the positions on the chips and the surface of the partition wall layer opposite the substrate side were masked, so that a light-reflecting layer was formed only on the side surfaces of the openings in the partition layer. In this manner, the micro LED display element of Example 2 was fabricated.

[0288] Example 3 A-2 was used as the light-absorbing layer precursor layer composition, and was applied to a thickness of 30 μm after drying. A transfer film 3 was obtained in the same manner as in Example 1, except that no light-reflecting layer precursor layer was laminated.

[0289] [Fabrication of Micro LED Display Element of Example 3] First, LED chips were mounted on an array substrate in the same manner as in [[Mounting of LED Chips]] of Example 1. Next, a resin pattern (light absorbing layer) having openings was formed on the array substrate with the chips by the same procedure as in [[Formation of Resin Pattern (Partition Layer)]] of Example 1 described above, except that the process conditions were appropriately adjusted so that the taper angle of the partition layer was as shown in Table 3.

[0290] [Fabrication of Micro LED Display Element of Comparative Example 1] A micro LED display element of Comparative Example 1 was fabricated in the same manner as in Example 1, except that no partition wall layer was formed.

[0291] In each micro LED element fabricated as described above, the LED chip size was 20 μm square and 8 μm thick, the LED chips were arranged at a pitch of 400 μm, the through-hole size was 30 μm square, and the width of the partition wall between the LED chips was 370 μm.

[0292] (Evaluation of Light Bleeding to Adjacent Pixels) Using the micro LED display element fabricated as described above, evaluation of light bleeding to adjacent pixels was carried out. Using a micro ultraviolet-visible-near infrared spectrophotometer MSV-5500 (manufactured by JASCO Corporation), the light intensity at 530 nm was measured at the position of an adjacent pixel when a green pixel with a central emission wavelength of 530 nm was made to emit light. At this time, the light intensity at 530 nm of the adjacent pixel was evaluated according to the following criteria when the light intensity at 530 nm of the emitting pixel was taken as 100%. (Evaluation criteria) "A": The light intensity at the adjacent pixel was less than 0.1% "B": The light intensity at the adjacent pixel was 0.1% or more but less than 1% "C": The light intensity at the adjacent pixel was 1% or more

[0293] The evaluation results for each example are shown in Table 3.

[0294]

[0295] From the results in Table 3, it is clear that the laminate including a plurality of light-emitting elements obtained by the laminate manufacturing method of the Example suppresses light leakage from adjacent light-emitting elements. On the other hand, it is clear that the laminate including a plurality of light-emitting elements obtained by the laminate manufacturing method of Comparative Example 1 does not achieve the above effect. Furthermore, it was confirmed that the laminates obtained by the laminate manufacturing methods of Examples 1 and 2 are capable of displaying higher brightness when the light-emitting elements are lit, compared to Example 1 and Comparative Example 1.

[0296] [Fabrication of Micro LED Display Element of Comparative Example 2] A partition structure was formed in advance on an array substrate before connecting LED chips using transfer film 1, and then LED chips were mounted on the substrate to fabricate a micro LED display element. Because the array substrate had a 33 μm-thick partition structure, it was difficult to mount multiple micro LED chips on the array substrate all at once, as in Example 1 [[Mounting of LED Chips]]. Therefore, the LED chips were bonded to the connecting portions one by one and peeled off from the peeling sapphire substrate repeatedly to fabricate the micro LED display element. As a result, it took more than 100 times longer to fabricate the micro LED display element in Comparative Example 2 than in Examples 1 to 3.

[0297] REFERENCE SIGNS LIST 10 Substrate with light-emitting element 12 Substrate 12A Substrate surface T1 Height of light-emitting element 14 Light-emitting element 20, 20A, 20B Transfer film 22 Temporary support 24 Photosensitive layer 26 Light-absorbing layer precursor layer 28 Light-reflecting layer precursor layer 30 Mask 40, 60 Laminate 42 Resin pattern 44 Opening 50 Protective film 62 Light-reflecting film θ Taper angle

Claims

1. A step 1 of bonding a substrate with light-emitting elements and a transfer film such that a surface of the substrate with light-emitting elements, the substrate including a substrate and a plurality of light-emitting elements arranged on the substrate, faces a surface of the transfer film opposite to the temporary support, the transfer film including a temporary support and a photosensitive layer, and the light-emitting elements are covered with the photosensitive layer; A step 2 of subjecting the photosensitive layer to pattern exposure; and a step 3 of developing the exposed photosensitive layer to form a resin pattern having openings at positions corresponding to the light-emitting elements. The method for producing a laminate, comprising a step of peeling off the temporary support between the step 1 and the step 2, or between the step 2 and the step 3.

2. The method for producing a laminate according to claim 1 , wherein the thickness of the photosensitive layer on the transfer film is greater than the height of the light emitting element.

3. The method for producing a laminate according to claim 1 or 2, wherein the photosensitive layer in the transfer film contains an alkali-soluble resin, a polymerizable compound, and a photopolymerization initiator.

4. The method for producing a laminate according to claim 1 or 2, wherein the photosensitive layer in the transfer film contains a polymer and a photoacid generator.

5. The method for producing a laminate according to claim 1 or 2, wherein the photosensitive layer in the transfer film has a water content of 5.0 mass % or less with respect to a total mass of the photosensitive layer.

6. The method for producing a laminate according to claim 1 or 2, wherein the content of the organic solvent in the photosensitive layer of the transfer film is 5.0 mass % or less with respect to the total mass of the photosensitive layer.

7. 3. The method for producing a laminate according to claim 1, wherein the photosensitive layer in the transfer film has a chloride ion content of 100 ppm by mass or less with respect to the total mass of the photosensitive layer.

8. The method for producing a laminate according to claim 1 or 2, wherein the photosensitive layer in the transfer film contains a white pigment.

9. The method for producing a laminate according to claim 1 or 2, wherein the photosensitive layer in the transfer film has, in this order from the temporary support side, a photosensitive light absorbing layer precursor layer and a photosensitive light reflecting layer precursor layer.

10. The method for producing a laminate according to claim 1 or 2, wherein the photosensitive layer in the transfer film is a photosensitive light absorbing layer precursor layer.

11. The method for producing a laminate according to claim 1 or 2, further comprising, after step 3, step 4 of arranging a light reflecting film on a side wall of the opening.