WO2024024842A1 - 積層体の製造方法 - Google Patents

積層体の製造方法 Download PDF

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Publication number
WO2024024842A1
WO2024024842A1 PCT/JP2023/027400 JP2023027400W WO2024024842A1 WO 2024024842 A1 WO2024024842 A1 WO 2024024842A1 JP 2023027400 W JP2023027400 W JP 2023027400W WO 2024024842 A1 WO2024024842 A1 WO 2024024842A1
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WO
WIPO (PCT)
Prior art keywords
light
photosensitive layer
layer
meth
mass
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2023/027400
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English (en)
French (fr)
Japanese (ja)
Inventor
健太郎 豊岡
正弥 鈴木
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Fujifilm Corp
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Fujifilm Corp
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Priority to JP2024537190A priority Critical patent/JPWO2024024842A1/ja
Priority to CN202380046195.0A priority patent/CN119365830A/zh
Priority to KR1020247040700A priority patent/KR20250008523A/ko
Publication of WO2024024842A1 publication Critical patent/WO2024024842A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10H—INORGANIC LIGHT-EMITTING SEMICONDUCTOR DEVICES HAVING POTENTIAL BARRIERS
    • H10H29/00—Integrated devices, or assemblies of multiple devices, comprising at least one light-emitting semiconductor element covered by group H10H20/00
    • H10H29/01—Manufacture or treatment
    • H10H29/02—Manufacture or treatment using pick-and-place processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/023—Optical properties
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/095—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having more than one photosensitive layer
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/38—Treatment before imagewise removal, e.g. prebaking

Definitions

  • the present invention relates to a method for manufacturing a laminate.
  • Patent Document 1 discloses a micro LED mounting method and a micro LED display using laser lift-off.
  • the present inventors made a laminate in which a plurality of light emitting elements (e.g., micro LED chips) are arranged on a substrate, with reference to the micro LED display of Patent Document 1, and examined its performance. It has been revealed that display performance may deteriorate due to light leakage from light emitting elements. For example, when a pixel is configured with light emitting elements that emit red (R), green (G), and blue (B), color mixing of light may occur due to light leakage from adjacent light emitting elements. This may cause the desired display to fail. Based on the above findings, the present inventors have clarified that there is room to study a method for manufacturing a laminate including a plurality of light emitting elements in which light leakage from adjacent light emitting elements is suppressed. In addition, in the method for manufacturing a laminate, it is usually required that the manufacturing time is short (in other words, it can be manufactured efficiently).
  • the manufacturing time is short (in other words, it can be manufactured efficiently).
  • an object of the present invention is to provide a method for manufacturing a laminate, which can efficiently manufacture a laminate including a plurality of light emitting elements in which light leakage from adjacent light emitting elements is suppressed.
  • a method for manufacturing 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.
  • 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, [1] to [ 7]
  • 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.
  • the present invention it is possible to provide a method for manufacturing a laminate, which can efficiently manufacture a laminate including a plurality of light emitting elements in which light leakage from adjacent light emitting elements is suppressed.
  • FIG. 2 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). It is a schematic diagram for explaining the structure of a transfer film. It is a schematic diagram for explaining the structure of a transfer film.
  • FIG. 3 is a schematic diagram for explaining step (2-4).
  • a numerical range expressed using " ⁇ " means a range that includes the numerical values written before and after " ⁇ " as lower and upper limits.
  • the upper limit or lower limit of a certain numerical range may be replaced with the upper or lower limit of another numerical range described in stages.
  • the upper limit or lower limit value described in a certain numerical range may be replaced with the value shown in the Examples.
  • process is used not only to refer to an independent process, but also to include it in the term even if the process cannot be clearly distinguished from other processes, as long as the intended purpose of the process is achieved. .
  • the weight average molecular weight (Mw) and number average molecular weight (Mn) refer to columns such as TSKgel GMHxL, TSKgel G4000HxL, or TSKgel G2000HxL (all products manufactured by Tosoh Corporation). (name), THF (tetrahydrofuran) as the eluent, a differential refractometer as the detector, and polystyrene as the standard substance. Values converted using polystyrene as the standard substance, measured with a gel permeation chromatography (GPC) analyzer. It is.
  • GPC gel permeation chromatography
  • the molecular weight of a compound having a molecular weight distribution is a weight average molecular weight (Mw).
  • Mw weight average molecular weight
  • the content of metal elements is a value measured using an inductively coupled plasma (ICP) spectrometer.
  • hue is a value measured using a color difference meter (CR-221, manufactured by Minolta Corporation).
  • (meth)acrylic is a concept that includes both acrylic and methacrylic
  • (meth)acryloyl is a concept that includes both acryloyl and methacryloyl
  • (meth)acrylate is a concept that includes both acryloyl and methacryloyl.
  • ” is a concept that includes both acrylates and methacrylates.
  • alkali-soluble means that the solubility in 100 g of a 1% by mass sodium carbonate aqueous solution at a liquid temperature of 22° C. is 0.1 g or more. Therefore, for example, an alkali-soluble resin is intended to be a resin that satisfies the above-mentioned solubility conditions.
  • water-soluble means that the solubility in 100 g of water at pH 7.0 and a liquid temperature of 22° C. is 0.1 g or more. Therefore, for example, water-soluble resin is intended to be a resin that satisfies the above-mentioned solubility conditions.
  • solid content of a composition refers to components that form a composition layer formed using the composition, and when the composition contains a solvent (organic solvent, water, etc.), the means all ingredients except.
  • liquid components are also considered solid components as long as they form a composition layer.
  • transparent means that the average transmittance of visible light with a wavelength of 400 to 700 nm is 80% or more, preferably 90% or more. Therefore, the term “transparent layer” means a layer having an average transmittance of 80% or more for visible light with a wavelength of 400 to 700 nm.
  • the average transmittance is measured by measuring straight transmitted light every 1 nm. In this specification, 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.
  • the thickness of each layer is determined by measuring a cross section cut with a microtome using an SEM (scanning method). This value is the average value of the thicknesses measured at 10 points when observed with an electron microscope) or a TEM (transmission electron microscope). However, those with a thickness of 1 ⁇ m or more were measured using SEM, and those with a thickness of less than 1 ⁇ m were measured using TEM.
  • the refractive index is intended to be the refractive index at a wavelength of 550 nm, measured at 25° C. based on a measuring device based on the ellipsometry method.
  • the method for manufacturing a laminate of the present invention includes: A surface on the light emitting element side of a substrate with a light emitting element that includes a substrate and a plurality of light emitting elements arranged on the substrate, and a side opposite to the temporary support of a transfer film that includes a temporary support and a photosensitive layer.
  • the method includes 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.
  • a substrate with a light emitting element on which a plurality of light emitting elements are arranged is formed by lithography using a transfer film, and a periphery of each light emitting element on the substrate with a light emitting element. It is possible to efficiently manufacture a laminate including a partition wall layer disposed in the laminate. Since the laminate obtained by the above manufacturing method includes a partition layer around each light emitting element, light leakage from adjacent light emitting elements is suppressed.
  • the method for producing a laminate of the present invention includes forming a partition layer in advance at a position where a light emitting element is to be placed on a substrate (that is, an opening is formed at a position where a light emitting element is to be placed on a substrate), for example, by lithography using a transfer film.
  • a resin pattern is formed (with a resin pattern) and a light emitting element is then placed at a predetermined position
  • the manufacturing time can be significantly shortened.
  • Applications of the laminate obtained by the laminate manufacturing method of the present invention include, for example, micro LED display elements.
  • the laminate obtained by the laminate manufacturing method of the present invention in the laminate obtained by the laminate manufacturing method of the present invention, light leakage from adjacent light emitting elements can be further suppressed, and/or the efficiency of the laminate manufacturing method of the present invention is better. is sometimes referred to as "the effect of the present invention is better".
  • first embodiment of the method for manufacturing a laminate of the present invention includes the following steps (1-1) to (1-3).
  • Step (1-1) (bonding step): The surface of the light emitting element side of the light emitting element-equipped substrate, which includes a substrate and a plurality of light emitting elements arranged on the substrate, the temporary support and the photosensitive layer. A step of laminating the light emitting element-equipped substrate and the transfer film so that the surface of the transfer film opposite to the temporary support faces each other and the light emitting element is covered with the photosensitive layer.
  • Step (1-2) exposure step: Step of exposing the photosensitive layer to pattern light
  • Step (1-3) developing step: Developing the exposed photosensitive layer to form the light emitting element
  • the first embodiment of the present invention includes step (1-1) and step (1-2), or step (1-2) and step The following step (1-A) is included between (1-3).
  • Step (1-A) temporary support peeling step: Step of peeling off the temporary support.
  • Step (1-1) is to transfer the surface of the light-emitting element-equipped substrate, which includes a substrate and a plurality of light-emitting elements arranged on the substrate, on the light-emitting element side, and the transfer film, which includes a temporary support and a photosensitive layer.
  • This is a step of laminating the light-emitting element-equipped substrate and the transfer film so that the surfaces opposite to the temporary support face each other and the light-emitting element is covered with the photosensitive layer.
  • the specific procedure of step (1-1) will be explained with reference to FIG.
  • step (1-1) the light-emitting element-equipped substrate 10 and the transfer film 20 are transferred to the surface of the light-emitting element-equipped substrate 10 opposite to the substrate 12 side (that is, the surface on the side having the light-emitting element 14).
  • the film 20 is laminated so that the surface of the film 20 on the opposite side to the temporary support 22 (that is, the surface on the photosensitive layer 24 side) faces each other.
  • FIG. 1 shows the state after the light emitting element-attached substrate 10 and the transfer film 20 are pasted together.
  • the thickness of the photosensitive layer in the transfer film is greater than the height of the light emitting element in order to make it easier for the light emitting element to be covered with the photosensitive layer in the bonding process and to improve the effects of the present invention. It is preferable.
  • the height of the light-emitting element means the thickness of the light-emitting element in the normal direction of the reference plane, which is the surface of the substrate with the light-emitting element where the light-emitting element is not arranged. . In other words, in the case of the laminate shown in FIG.
  • the height of the light emitting element 14 is the reference plane 12A when the substrate surface 12A at a location where the light emitting element 14 is not arranged on the substrate 10 with a light emitting element is used as a reference plane. means the thickness T1 of the light emitting element 14 in the normal direction.
  • the transfer film has a protective film described below, it is preferable to carry out the bonding step after peeling off the protective film.
  • the surface of the transfer film on the opposite side to the temporary support side and the surface of the light emitting element-attached substrate on the light emitting element side are brought into contact and pressure bonded.
  • pressure bonding methods include known transfer methods and lamination methods, in which the surface of the transfer film on the side opposite to the temporary support side is placed on the surface of the light emitting element side of the substrate with a light emitting element, and pressure is applied using a roll or the like.
  • a heating method is preferred.
  • the bonding method include a method using a known laminator such as a vacuum laminator and an auto-cut laminator.
  • the lamination temperature is preferably 70 to 130°C.
  • a substrate with a light emitting element includes a substrate and a plurality of light emitting elements arranged on the substrate.
  • the substrate include a resin substrate, a glass substrate, a ceramic substrate, and a semiconductor substrate.
  • Materials for the resin substrate include polyethylene terephthalate resin, polynaphthalene terephthalate resin, cycloolefin resin, polyimide resin, polycarbonate resin, polyacrylate resin, polyether sulfone resin, silicone resin, and epoxy resin. etc.
  • the thickness of the resin substrate is preferably 5 to 200 ⁇ m, more preferably 10 to 100 ⁇ m.
  • the substrate is preferably a transparent substrate in consideration of the exposure step (step (1-2)).
  • the transparent substrate examples include a resin substrate (for example, 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 transmit visible light include, for example, polyamide resins, polyethylene terephthalate resins, polyethylene naphthalate resins, cycloolefin resins, polyimide resins, and polycarbonate resins.
  • polyamide films, polyethylene terephthalate films, cycloolefin polymers, polyethylene naphthalate films, polyimide films, and polycarbonate films are preferred, and polyethylene terephthalate films are more preferred.
  • the thickness of the transparent substrate is not limited.
  • the thickness of the transparent substrate is preferably 10 to 200 ⁇ m, more preferably 20 to 120 ⁇ m, and even more preferably 20 to 100 ⁇ m.
  • the electrode is preferably composed of a metal oxide film such as ITO (indium tin oxide) and IZO (indium zinc oxide), and a metal thin wire such as a metal mesh or metal nanowire.
  • a metal oxide film such as ITO (indium tin oxide) and IZO (indium zinc oxide)
  • a metal thin wire such as a metal mesh or metal nanowire.
  • the thin metal wire include thin metal wires made of silver and copper, and silver conductive materials such as silver mesh and silver nanowires are preferred.
  • Metal is preferable as the material for the lead wiring.
  • the metal include gold, silver, copper, molybdenum, aluminum, titanium, chromium, zinc, and manganese, and alloys of combinations thereof, with copper, molybdenum, aluminum, or titanium being preferred; Copper is more preferred.
  • the light emitting element a micro LED chip can be mentioned.
  • the substrate with light emitting elements there are no particular restrictions on the arrangement of the plurality of light emitting elements.
  • a plurality of cells for example, one pixel or equivalent to one pixel
  • red (R), green (G), and blue colors are provided in the cell.
  • An example is a configuration in which N light emitting elements each having the emission color of (B) are arranged (eg, one, two, three, etc.).
  • the shape of the cell is not particularly limited, and examples thereof include a lattice shape and the like.
  • each light emitting element within the cell is not particularly limited.
  • R, G, and B are cited as examples of the emitted light color of the light emitting element, the light emitting element is not particularly limited as long as it emits light, and the emitted light color can be selected as appropriate.
  • the light emitting element usually has a terminal for connecting to an external electrode.
  • the type of LED may be an LED with a peak wavelength in the visible light region (hereinafter also referred to as “visible light LED”), or an LED with a peak wavelength in the ultraviolet light region. (hereinafter also referred to as "UV-LED").
  • the exposure step is a step of exposing the photosensitive layer to light in a pattern.
  • Pattern exposure refers to exposure in a pattern, in which there are exposed areas and non-exposed areas. The positional relationship between the exposed part (exposed area) and the unexposed part (unexposed area) in pattern 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 process is typically a process of performing pattern exposure through a photomask. In the exposure step, the photomask and the laminate that is the photosensitive object may or may not be in contact with each other.
  • the temporary support obtained in the temporary support peeling process is removed from the substrate side of the laminate. It is preferable to perform an exposure process in which the opposite surface is brought into contact with a photomask and pattern exposure is performed. In other words, the surface of the laminate from which the temporary support has been peeled off is brought into contact with the surface exposed by peeling off the temporary support (such as the surface of the photosensitive layer), and the photosensitive layer is exposed to pattern light. The process is preferred.
  • a curing reaction of components contained in the photosensitive layer may occur in the exposed area (area corresponding to the opening of the photomask) through the exposure process of pattern exposure. .
  • a developing step (step (1-3)) is performed to remove the non-exposed area of the photosensitive layer and form a pattern.
  • a portion corresponding to the position where the light emitting element is placed is left with no opening so that a resin pattern having a predetermined opening at the position corresponding to the light emitting element can be formed after the development process (step (1-3)).
  • the exposure process may be carried out using a photomask having a pattern in which openings are located at positions corresponding to the positions between adjacent light emitting elements (in other words, positions where the partition layer is formed). .
  • the photosensitive layer can be exposed according to the pattern shape of the photomask.
  • FIG. 2 shows a pattern exposure process when the photosensitive layer is a negative type photosensitive layer.
  • a curing reaction of components contained in the photosensitive layer 24 may occur in the opening (exposure region) of the photomask 30.
  • the photosensitive layer in the non-opening portion (non-exposed region) of the photomask 30 is removed by performing a development step (step (1-3)) after exposure.
  • the photosensitive layer is a positive photosensitive layer
  • structural changes of components contained in the photosensitive layer may occur in the exposed region (region corresponding to the opening of the photomask), and the development step ( By performing step (1-3)), the exposed area of the photosensitive layer is removed and a pattern is formed.
  • structural changes in the components contained in the photosensitive layer in the exposed area create a solubility contrast in the developing solution between the exposed area and the non-exposed area, and as a result, the development process after exposure (step (1) -3))
  • the exposed areas of the photosensitive layer are removed to form a pattern.
  • openings are formed in the areas corresponding to the positions where the light emitting elements are arranged 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 may be carried out using a photomask having a pattern in which portions corresponding to the positions between adjacent light emitting elements (in other words, the positions where the partition layer is formed) are non-openings. .
  • the photosensitive layer can be exposed according to the pattern shape of the photomask.
  • the method for manufacturing a laminate of the present invention includes a photomask peeling process of peeling off the photomask used in the exposure process between the exposure process and the development process.
  • Examples of the photomask peeling process include a known peeling process.
  • any light source that can irradiate light in a wavelength range that can harden the photosensitive layer for example, 365 nm and 405 nm
  • the main wavelength of the exposure light for exposure is preferably 365 nm.
  • the dominant wavelength is the wavelength with the highest intensity.
  • the light source examples include various lasers, light emitting diodes (LEDs), ultra-high pressure mercury lamps, high pressure mercury lamps, and metal halide lamps.
  • the exposure amount is preferably 5 to 200 mJ/cm 2 , more preferably 10 to 200 mJ/cm 2 .
  • Preferred aspects of the light source, exposure amount, and exposure method used for exposure are described, for example, in paragraphs [0146] to [0147] of International Publication No. 2018/155193, the contents of which are incorporated herein. It will be done.
  • the resin pattern obtained through the development step (step (1-3)) has a tapered cross section (a cross section perpendicular to the substrate). Moreover, specifically, it is preferable that the resin pattern is formed with an opening whose opening area increases from the substrate side toward the opposite side.
  • the cross-sectional shape of the resin pattern may be made tapered by, for example, introducing a light scattering plate into the exposure machine and applying exposure light from an oblique direction. Can be done.
  • the cross section of the resin pattern is tapered, the angle between the side wall of the opening and the surface of the substrate with a light emitting element on which the light emitting element is not placed (the "taper angle"; specifically, the angle in FIG. 3 (corresponds to ⁇ ) 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°.
  • a temporary support peeling process is performed between the bonding process and the exposure process, or between the exposure process and the development process. Among these, it is more preferable to include a peeling step between the bonding step and the exposure step.
  • the peeling process is a process of peeling the temporary support from the laminate of the transfer film and the light emitting element-attached substrate. Examples of the method for peeling off the temporary support include known peeling methods. Specifically, the cover film peeling mechanism described in paragraphs [0161] to [0162] of JP-A-2010-072589 can be mentioned.
  • the developing step is a step of developing the exposed photosensitive layer using a developer to form a resin pattern.
  • a developer an alkaline aqueous solution is preferred.
  • 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, and tetrapropylammonium hydroxy. and choline (2-hydroxyethyltrimethylammonium hydroxide).
  • development methods include paddle development, shower development, spin development, and dip development.
  • Examples of the developer suitably used herein include the developer described in paragraph [0194] of International Publication No. 2015/093271, and examples of the development method suitably used include, for example, the developer described in International Publication No. 2015/093271, paragraph [0194].
  • the development method described in paragraph [0195] of No. 2015/093271 can be mentioned.
  • FIG. 3 shows a schematic cross-sectional view of the laminate 40 after the development step.
  • the laminate 40 is composed of a substrate 10 with a light emitting element and a resin pattern 42.
  • the resin pattern 42 is disposed at a location corresponding to between adjacent light emitting elements 14, and the opening 44 is located at a position corresponding to the light emitting element 14.
  • the resin pattern 42 corresponds to a cured film of the negative photosensitive layer.
  • the first embodiment of the present invention is a step of further exposing the resin pattern obtained by the developing step (step (1-3)) (hereinafter also referred to as “step (1-B)” or “post-exposure step”). ) and/or a heating step (hereinafter also referred to as “step (1-C)" or "post-bake step”).
  • step (1-B) or “post-exposure step”
  • step (1-C) or "post-bake step”
  • the first embodiment of the present invention includes both a post-exposure step and a post-bake step, it is preferable to perform the post-bake step after the post-exposure step.
  • the exposure amount in the post-exposure step is preferably 100 to 5000 mJ/cm 2 , more preferably 200 to 3000 mJ/cm 2 .
  • the post-bake temperature in the post-bake step is preferably 80 to 250°C, more preferably 90 to 160°C.
  • the post-bake time in the post-bake step is preferably 1 to 180 minutes, more preferably 10 to 60 minutes.
  • the structure of the transfer film is not particularly limited as long as it has a temporary support and a photosensitive layer (a layer exhibiting photosensitivity).
  • the photosensitive layer may be either a positive photosensitive layer or a negative photosensitive layer, it is preferably a negative photosensitive layer.
  • the photosensitive layer may be a single layer or may have two or more layers.
  • the transfer film may include a composition layer other than the photosensitive layer (for example, a water-soluble resin layer, etc.).
  • the transfer film may have a protective film.
  • FIG. 4 shows a specific example of the transfer film.
  • the transfer film 20A shown in FIG. 4 includes a temporary support 22, a photosensitive layer 24, and a protective film 50 in this order.
  • the photosensitive layer 24 is a layer exhibiting photosensitivity, and may be either a positive photosensitive layer or a negative photosensitive layer, but a negative photosensitive layer is preferable.
  • the photosensitive layer 24 is a negative type photosensitive layer, the components contained in the layer undergo a curing reaction upon exposure to become a resin layer (cured layer).
  • the transfer film 20A shown in FIG. 4 has a protective film 50 disposed therein, the protective film 50 does not need to be disposed. Further, the transfer film 20A shown in FIG. 4 may have a composition layer other than the photosensitive layer 24.
  • the structure of the transfer film is that in the laminate formed according to the first embodiment of the present invention, the brightness of the light emitting element is better, reflection of external light is more easily suppressed, and/or when the light emitting element is turned on.
  • the following embodiments are also preferable in that they can absorb stray light that occurs unnecessarily during the process.
  • 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 Layer precursor layer/photosensitive light reflective layer precursor layer/protective film
  • the transfer films shown in (N1) to (N3) above have a protective film disposed thereon, but the protective film may not be disposed.
  • a photosensitive light-absorbing layer precursor layer hereinafter abbreviated as "light-absorbing layer precursor layer”
  • a photosensitive light-reflecting layer precursor layer hereinafter abbreviated as “light-reflecting layer precursor layer”
  • light-reflecting layer precursor layer is a layer exhibiting photosensitivity, and is typically a negative photosensitive layer.
  • the transfer film of the embodiments (N1) and (N2) above is a transfer film 20A shown in FIG. 4, when the photosensitive layer 24 is a photosensitive light absorption layer precursor layer.
  • the photosensitive layer 24 is a photosensitive light absorption layer precursor layer.
  • the light absorption layer precursor layer causes a curing reaction at the exposed location in the pattern exposure of step (1-2)
  • a patterned light absorption layer can be formed. That is, the resin pattern can function as a light-absorbing partition layer.
  • a laminate having such a resin pattern as a partition layer easily absorbs external light and stray light.
  • the black density is better when the light emitting element is not lit.
  • the transfer film of the above aspect (N2) when the transfer film of the above aspect (N2) is used, the light reflective layer precursor layer causes a curing reaction at the exposed portion in the pattern exposure of step (1-2), A patterned light reflecting layer can be formed. That is, the resin pattern can function as a light-reflective partition layer.
  • a laminate having such a resin pattern as a partition wall layer has high brightness because light from the light emitting element is easily reflected by the partition wall when the light emitting element is turned on.
  • the transfer film of the embodiment (N3) above has a transfer film 20A shown in FIG. 4, in which the photosensitive layer 24 has a two-layer structure, one of which is a photosensitive light-absorbing layer precursor layer, and the other is a photosensitive light-absorbing layer precursor layer. This applies when it is used as a reflective layer precursor layer.
  • FIG. 5 shows a schematic cross-sectional view of the transfer film of the above embodiment (N3).
  • the transfer film 20A shown in FIG. 5 includes a temporary support 22, a photosensitive layer 24, and a protective film 50 in this order.
  • the photosensitive layer 24 includes a light-absorbing layer precursor layer 26 and a light-reflecting layer precursor layer 28 from the temporary support 22 side toward the protective film 50.
  • the light-absorbing layer precursor layer and the light-reflecting layer precursor are A curing reaction occurs in the layer, and a resin pattern having a light-reflecting layer and a light-absorbing layer can be formed in order from the light-emitting element-equipped substrate side through a developing step (step (1-3)).
  • a resin pattern having a light-reflecting layer and a light-absorbing layer can be formed in order from the light-emitting element-equipped substrate side through a developing step (step (1-3)).
  • a laminate having such a resin pattern as a partition layer external light and stray light are absorbed by the light absorption layer, and as a result, black density is better when the light emitting element is not lit.
  • the light-reflecting layer allows light from the light-emitting element to be easily reflected by the partition walls when the light-emitting element is turned on, increasing brightness.
  • the light-absorbing layer precursor layer corresponds to a negative-type photosensitive layer containing a light-absorbing substance
  • the light-reflecting layer precursor layer corresponds to a negative-type photosensitive layer containing a reflectance modifier.
  • the structure of the transfer film is that in the laminate formed according to the first embodiment of the present invention, the brightness of the light emitting element is better, reflection of external light is more easily suppressed, and/or when the light emitting element is turned on.
  • the following embodiments are also preferable in that they can absorb stray light that occurs unnecessarily during the process.
  • P1 Temporary support/photosensitive light absorption layer/protective film
  • P2 Temporary support/photosensitive light reflection layer/protective film
  • P3 Temporary support/photosensitive light absorption layer/photosensitive light Reflective Layer/Protective Film
  • the transfer films shown in (P1) to (P3) above are embodiments in which a protective film is disposed, but the protective film may not be disposed.
  • the photosensitive light absorption layer and the photosensitive light reflection layer are layers that exhibit photosensitivity, and are typically positive photosensitive layers.
  • the light-absorbing layer corresponds to a positive-type photosensitive layer containing a light-absorbing substance
  • the light-reflecting layer corresponds to a positive-type photosensitive layer containing a reflectance modifier
  • the transfer film has a temporary support.
  • the temporary support is a member that supports the photosensitive layer, and is finally removed by a peeling process.
  • the temporary support may have a single layer structure or a multilayer 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 undergo significant deformation, shrinkage, or elongation under pressure or under pressure and heat.
  • the film include polyethylene terephthalate film (for example, biaxially oriented polyethylene terephthalate film), polymethyl methacrylate film, cellulose triacetate film, polystyrene film, polyimide film, and polycarbonate film.
  • polyethylene terephthalate film is preferred as the temporary support.
  • the film used as the temporary support is preferably free from deformation such as wrinkles and scratches.
  • the temporary support preferably has high transparency because pattern exposure can be performed 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, More preferably 80% or more, particularly preferably 90% or more. Preferred values of transmittance include, for example, 87%, 92%, and 98%. From the viewpoints of pattern formation properties during pattern exposure through the temporary support and transparency of the temporary support, it is preferable that the haze of the temporary support is small. Specifically, the haze value of the temporary support is preferably 2% or less, more preferably 0.5% or less, and even more preferably 0.1% or less.
  • the number of fine particles, foreign matter, and defects contained in the temporary support be small.
  • the number of fine particles, foreign matter, and defects with a diameter of 1 ⁇ m or more in the temporary support is preferably 50 pieces/10 mm 2 or less, more preferably 10 pieces/10 mm 2 or less, even more preferably 3 pieces/10 mm 2 or less, and 0. pieces/10 mm 2 is particularly preferred.
  • the thickness of the temporary support is not particularly limited, but is preferably 5 to 200 ⁇ m, more preferably 5 to 150 ⁇ m, even more preferably 5 to 50 ⁇ m, and particularly preferably 5 to 25 ⁇ m from the viewpoint of ease of handling and versatility.
  • the thickness of the temporary support can be calculated as the average value of five arbitrary points measured by cross-sectional observation using a SEM (Scanning Electron Microscope).
  • the surface of the temporary support in contact with the photosensitive layer is exposed to UV (ultraviolet) irradiation.
  • the surface may be modified by corona discharge, plasma, or the like.
  • the exposure amount is preferably 10 to 2000 mJ/cm 2 , more preferably 50 to 1000 mJ/cm 2 .
  • the light sources 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 (which emit light in the wavelength band of 150 to 450 nm). LED), etc. As long as the amount of light irradiation can be within this range, there are no particular restrictions on the lamp output or illuminance.
  • Examples of the temporary support include a 16 ⁇ m thick biaxially stretched polyethylene terephthalate film, a 12 ⁇ m thick biaxially stretched polyethylene terephthalate film, and a 9 ⁇ m thick biaxially stretched polyethylene terephthalate film.
  • the temporary support may be a recycled product.
  • recycled products include those that have been washed and made into chips from used films, etc., and made into films using these as materials.
  • a specific example of a recycled product is Toray's Ecouse series.
  • Preferred forms of the temporary support include, for example, paragraphs [0017] to [0018] of JP2014-085643A, paragraphs [0019] to [0026] of JP2016-027363A, and International Publication No. 2012/ The descriptions are given in paragraphs [0041] to [0057] of No. 081680 and paragraphs [0029] to [0040] of International Publication No. 2018/179370, and the contents of these publications are incorporated herein.
  • a layer containing fine particles may be provided on the surface of the temporary support in order to impart handling properties.
  • the lubricant layer may be provided on one side or both sides of the temporary support.
  • the diameter of the particles contained in the lubricant layer is preferably 0.05 to 0.8 ⁇ m. Further, the thickness of the lubricant layer is preferably 0.05 to 1.0 ⁇ m.
  • Commercially available temporary supports include Lumirror 16KS40, Lumirror 16FB40, Lumirror #38-U48, Lumirror #75-U34, and Lumirror #25T60 (manufactured by Toray Industries, Inc.); Cosmoshine A4100, Cosmoshine A4300, and Cosmoshine. Examples include Cosmoshine A4160, Cosmoshine A4360, and Cosmoshine A8300 (all manufactured by Toyobo Co., Ltd.).
  • the photosensitive layer may be either a positive photosensitive layer or a negative photosensitive layer, but a negative photosensitive layer is preferred.
  • the photosensitive layer preferably contains, for example, at least an alkali-soluble resin, a polymerizable compound, and a photopolymerization initiator.
  • the photosensitive layer may be a light-reflecting layer precursor layer or a light-absorbing layer precursor layer.
  • the photosensitive layer When the photosensitive layer is a light-reflecting layer precursor layer, the photosensitive layer contains the below-mentioned reflectivity modifier, and when the photosensitive layer is a light-absorbing layer precursor layer, the photosensitive layer contains the below-mentioned light-adjusting agent. Contains absorbent materials.
  • the photosensitive layer when the photosensitive layer is a positive photosensitive layer, the photosensitive layer preferably contains, for example, at least a polymer and a photoacid generator. Furthermore, as described above, the photosensitive layer may be a photosensitive light reflecting layer or a photosensitive light absorbing layer. When the photosensitive layer is a photosensitive light reflection layer, the photosensitive layer contains a reflection modifier described below, and when the photosensitive layer is a photosensitive light absorption layer, the photosensitive layer contains a reflection modifier described below. Contains absorbent materials.
  • the photosensitive layer may contain an impurity (hereinafter also referred to as "impurity A") selected from the group consisting of metals and metal ions.
  • impurity A include sodium, potassium, magnesium, calcium, iron, manganese, copper, aluminum, titanium, chromium, cobalt, nickel, zinc, tin, halogen, and ions thereof.
  • halide ions, sodium ions, and potassium ions are likely to be mixed in as impurities, so it is preferable to have the following content.
  • the upper limit of the content of impurity A is preferably 150 mass ppm or less, more preferably 100 mass ppm or less, even more preferably 10 mass ppm or less, particularly 2 mass ppm or less, based on the total mass of the photosensitive layer.
  • the lower limit of the content of impurity A can be 1 mass ppb or more or 0.1 mass ppm or more with respect to the total mass of the photosensitive layer.
  • the upper limit of the content of chloride ions is preferably 100 mass ppm or less, more preferably 50 mass ppm or less, even more preferably 10 mass ppm or less, and 2 mass ppm or less, based on the total mass of the photosensitive layer. Particularly preferred is less than ppm.
  • the lower limit of the content of chloride ions can be 1 mass ppb or more or 0.1 mass ppm or more with respect to the total mass of the photosensitive layer.
  • the method of keeping impurity A within the above range is to select a material with a low content of impurities as the raw material for the photosensitive layer, to prevent the impurity from being mixed in when forming the photosensitive layer, and to remove it by washing. can be mentioned. By such a method, the amount of impurities can be kept within the above range.
  • Impurity A can be quantified by known methods such as ICP (Inductively Coupled Plasma) emission spectroscopy, atomic absorption spectroscopy, and ion chromatography.
  • ICP Inductively Coupled Plasma
  • the content of the organic solvent in the photosensitive layer is preferably as small as possible.
  • the content of the organic solvent is preferably 100 mass ppm or less, more preferably 20 mass ppm or less, and even more preferably 4 mass ppm or less, based on the total mass of the photosensitive layer.
  • the lower limit of the content of the organic solvent may be 10 mass ppb or more based on the total mass of the photosensitive layer.
  • the content of the organic solvent can be determined by known methods such as ICP (Inductively Coupled Plasma) emission spectroscopy, atomic absorption spectroscopy, and ion chromatography.
  • the organic solvent is selected from the group consisting of benzene, formaldehyde, trichloroethylene, 1,3-butadiene, carbon tetrachloride, chloroform, N,N-dimethylformamide, N,N-dimethylacetamide, and hexane. There are many things that can be done.
  • the content of water in the photosensitive layer is preferably 5.0% by mass or less, more preferably 3.0% by mass or less, based on the total mass of the photosensitive layer, from the viewpoint of improving reliability and lamination properties. , more preferably 1.0% by mass or less.
  • the lower limit of the water content in the photosensitive layer is preferably as small as possible, but it may be, for example, 0.01% by mass or more with respect to the total mass of the layer.
  • the photosensitive layer contains an alkali-soluble resin.
  • alkali-soluble resins include (meth)acrylic resins, styrene resins, epoxy resins, amide resins, amide epoxy resins, alkyd resins, phenol resins, ester resins, urethane resins, and reactions between epoxy resins and (meth)acrylic acid. and acid-modified epoxy acrylate resins obtained by reacting an epoxy acrylate resin with an acid anhydride.
  • a (meth)acrylic resin means resin which has a structural unit derived from a (meth)acrylic compound.
  • the content of the structural units derived from the (meth)acrylic compound is preferably 50% by mass or more, more preferably 70% by mass or more, and still more preferably 90% by mass or more, based on all the structural units of the (meth)acrylic resin. .
  • the (meth)acrylic resin may be composed only of structural units derived from a (meth)acrylic compound, or may have structural units derived from a polymerizable monomer other than the (meth)acrylic compound. . That is, the upper limit of the content of the structural units derived from the (meth)acrylic compound is 100% by mass or less based on all the structural units of the (meth)acrylic resin. Further, the content of the structural units derived from the (meth)acrylic compound is preferably 50 mol% or more, more preferably 70 mol% or more, and 90 mol% or more with respect to all the structural units of the (meth)acrylic resin. More preferred.
  • the (meth)acrylic resin may be composed only of structural units derived from a (meth)acrylic compound, or may have structural units derived from a polymerizable monomer other than the (meth)acrylic compound. . That is, the upper limit of the content of the structural units derived from the (meth)acrylic compound is 100 mol% or less based on all the structural units of the (meth)acrylic resin.
  • the above-mentioned “constituent unit” when the content of a "constituent unit” is defined by a molar ratio, the above-mentioned “constituent unit” shall have the same meaning as a “monomer unit.” Moreover, in this specification, the above-mentioned “monomer unit” may be modified after polymerization by a polymer reaction or the like. The same applies to the following.
  • Examples of the (meth)acrylic compound include (meth)acrylic acid, (meth)acrylic acid ester, (meth)acrylamide, and (meth)acrylonitrile.
  • Examples of (meth)acrylic acid ester include (meth)acrylic acid alkyl ester, (meth)acrylic acid tetrahydrofurfuryl ester, (meth)acrylic acid dimethylaminoethyl ester, (meth)acrylic acid diethylaminoethyl ester, (meth)acrylic acid diethylaminoethyl ester, ) Acrylic acid glycidyl ester, (meth)acrylic acid benzyl ester, 2,2,2-trifluoroethyl (meth)acrylate, and 2,2,3,3-tetrafluoropropyl (meth)acrylate, ( Preferred are meth)acrylic acid alkyl esters.
  • Examples of (meth)acrylamide include acrylamide such as diacetone
  • the alkyl group of the (meth)acrylic acid alkyl ester may be linear or branched. Specific examples include 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 (meth)acrylic acid Examples include (meth)acrylic acid alkyl esters having an alkyl group having 1 to 12 carbon atoms such as dodecyl.
  • 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 and the like.
  • As the (meth)acrylic ester a (meth)acrylic acid alkyl ester having an alkyl group having 1 to 4 carbon atoms is preferred, and methyl (meth)acrylate or ethyl (meth)acrylate is more preferred.
  • the (meth)acrylic resin may have structural units other than the structural units derived from the (meth)acrylic compound.
  • the polymerizable monomer forming the above structural unit is not particularly limited as long as it is a compound other than a (meth)acrylic compound that can be copolymerized with a (meth)acrylic compound, such as styrene, vinyltoluene, and ⁇ .
  • - Styrene compounds that may have substituents at the ⁇ -position or aromatic ring such as methylstyrene, vinyl alcohol esters such as acrylonitrile and vinyl-n-butyl ether, maleic acid, maleic anhydride, monomethyl maleate, maleic acid
  • maleic acid monoesters such as monoethyl and monoisopropyl maleate, fumaric acid, cinnamic acid, ⁇ -cyanocinnamic acid, itaconic acid, and crotonic acid.
  • These polymerizable monomers may be used alone or in combination of two or more.
  • the (meth)acrylic resin has a structural unit having an acid group in order to improve the alkali developability.
  • the acid group include a carboxy group, a sulfo group, a phosphoric acid group, and a phosphonic acid group.
  • 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.
  • the content of structural units having an acid group (preferably structural units derived from (meth)acrylic acid) in the (meth)acrylic resin is determined based on the total structural units of the (meth)acrylic resin in terms of excellent developability. , preferably 10% by mass or more. Further, 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 (preferably structural units derived from (meth)acrylic acid) in the (meth)acrylic resin is determined based on the total structural units of the (meth)acrylic resin in terms of excellent developability. , preferably 10 mol% or more. Further, the upper limit is not particularly limited, but from the viewpoint of excellent alkali resistance, it is preferably 50 mol% or less, more preferably 40 mol% or less.
  • the (meth)acrylic resin has a structural unit derived from the above-mentioned (meth)acrylic acid alkyl ester.
  • the content of structural units derived from (meth)acrylic acid alkyl ester in the (meth)acrylic resin is preferably 50 to 90% by mass, and 60 to 90% by mass based on the total structural units of the (meth)acrylic resin. More preferably, 65 to 90% by mass is even more preferred.
  • the content of structural units derived from (meth)acrylic acid alkyl ester in the (meth)acrylic resin is preferably 50 to 90 mol%, and 60 to 90 mol%, based on the total structural units of the (meth)acrylic resin. % is more preferable, and 65 to 90 mol% is even more preferable.
  • 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 preferable. More preferred is a resin composed only of structural units derived from (meth)acrylic acid alkyl ester. Moreover, 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 preferable.
  • the (meth)acrylic resin preferably has at least one kind selected from the group consisting of a structural unit derived from methacrylic acid and a structural unit derived from a methacrylic acid alkyl ester, and the structural unit derived from methacrylic acid and It is preferable to have both structural units derived from methacrylic acid alkyl ester.
  • the total content of structural units derived from methacrylic acid and structural units derived from methacrylic acid alkyl ester in the (meth)acrylic resin is preferably 40% by mass or more, and 60% by mass or more based on the total structural units of the (meth)acrylic resin. More preferably, the amount is % by mass or more.
  • 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, and 60% by mole or more based on the total structural units of the (meth)acrylic resin. More preferably mol% or more.
  • the upper limit is not particularly limited and may be 100 mol% or less, preferably 80 mol% or less.
  • the (meth)acrylic resin includes at least one kind selected from the group consisting of a structural unit derived from methacrylic acid and a structural unit derived from a methacrylic acid alkyl ester, and a structural unit derived from acrylic acid and an acrylic acid alkyl ester. It is also preferable to have at least one kind selected from the group consisting of structural units derived from.
  • the total content of the structural units derived from methacrylic acid and the structural units derived from methacrylic acid alkyl esters is the mass ratio of the structural units derived from acrylic acid and the structural units derived from acrylic acid alkyl esters. The ratio is preferably 60/40 to 80/20.
  • the (meth)acrylic resin preferably has an ester group at the end, since the photosensitive layer after transfer has excellent developability.
  • the terminal portion of the (meth)acrylic resin is composed of a site derived from the polymerization initiator used in the synthesis.
  • a (meth)acrylic resin having an ester group at the end can be synthesized by using a polymerization initiator that generates a radical having an ester group.
  • alkali-soluble resin examples include an alkali-soluble resin having an acid value of 60 mgKOH/g or more in terms of better developability.
  • alkali-soluble resins resins having a carboxy group with an acid value of 60 mgKOH/g or more (hereinafter referred to as "carboxy group-containing resins") are preferred because they are easily thermally crosslinked with the crosslinking component and form a strong film when heated.
  • a (meth)acrylic resin having a carboxy group with an acid value of 60 mgKOH/g or more (hereinafter also referred to as "carboxy group-containing (meth)acrylic resin") is even more preferred.
  • the alkali-soluble resin is a resin having a carboxyl group
  • the three-dimensional crosslink density can be increased by, for example, adding a thermally crosslinkable compound such as a blocked isocyanate compound and thermally crosslinking the resin.
  • the carboxyl group of the resin having a carboxyl group is anhydrous and made hydrophobic, the resistance to wet heat can be improved.
  • the carboxy 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 acid value condition, and can be appropriately selected from known (meth)acrylic resins.
  • carboxy group-containing acrylic resins with an acid value of 60 mgKOH/g or more among the polymers described in paragraph [0025] of JP-A-2011-095716, carboxy group-containing acrylic resins with an acid value of 60 mgKOH/g or more, and paragraphs [0033] to [ of JP-A-2010-237589]
  • carboxy group-containing acrylic resins having an acid value of 60 mgKOH/g or more can be preferably used.
  • alkali-soluble resin examples include an alkali-soluble resin having an aromatic ring structure, since it has better developability.
  • an alkali-soluble resin having an aromatic ring structure an alkali-soluble resin having a structural unit having an aromatic ring structure is especially preferable.
  • Monomers forming structural units having an aromatic ring structure include monomers having an aralkyl group, styrene, and polymerizable styrene derivatives (for example, methylstyrene, vinyltoluene, tert-butoxystyrene, acetoxystyrene, 4-vinylbenzoic acid).
  • styrene dimer styrene trimer, etc.
  • monomers having an aralkyl group or styrene are preferred.
  • the aralkyl group include a substituted or unsubstituted phenylalkyl group (excluding a benzyl group), a substituted or unsubstituted benzyl group, and a substituted or unsubstituted benzyl group is preferred.
  • Examples of the monomer having a phenylalkyl group include phenylethyl (meth)acrylate and the like.
  • Examples of monomers having a benzyl group include (meth)acrylates having a benzyl group, such as benzyl (meth)acrylate and chlorobenzyl (meth)acrylate; vinyl monomers having a benzyl group, such as vinylbenzyl chloride; Examples include vinylbenzyl alcohol. Among these, benzyl (meth)acrylate is preferred.
  • the alkali-soluble resin has a structural unit (a structural unit derived from styrene) represented by the following formula (S).
  • the content of the structural unit having an aromatic ring structure is preferably 5 to 90% by mass, and 10 to 80% by mass based on the total structural units of the alkali-soluble resin. %, more preferably 10 to 70% by weight, and particularly preferably 20 to 60% by weight. Further, 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 20 to 60 mol% based on the total structural units of the alkali-soluble resin. % is more preferable.
  • the content of the structural unit represented by the above formula (S) in the alkali-soluble resin is preferably 5 to 70 mol%, more preferably 10 to 60 mol%, based on the total structural units of the alkali-soluble resin. 20 to 60 mol% is more preferable, and 20 to 50 mol% is particularly preferable.
  • the alkali-soluble resin has an aliphatic hydrocarbon ring structure. That is, it is preferable that the alkali-soluble resin has a structural unit having an aliphatic hydrocarbon ring structure.
  • the aliphatic hydrocarbon ring structure may be monocyclic or polycyclic. Among these, it is more preferable that the alkali-soluble resin has a ring structure in which two or more aliphatic hydrocarbon rings are condensed.
  • Examples of the ring constituting 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.
  • a ring in which two or more aliphatic hydrocarbon rings are condensed is preferable, and a tetrahydrodicyclopentadiene ring (tricyclo[5.2.1.0 2,6 ]decane ring) is more preferable.
  • Monomers forming the structural unit having an aliphatic hydrocarbon ring structure include dicyclopentanyl (meth)acrylate, cyclohexyl (meth)acrylate, and isobornyl (meth)acrylate.
  • the alkali-soluble resin preferably has a structural unit represented by the following formula (Cy), a structural unit represented by the above formula (S), and a structural unit represented by the following formula (Cy). It is more preferable to have.
  • R M represents a hydrogen atom or a methyl group
  • R Cy represents a monovalent group having an aliphatic hydrocarbon ring structure
  • R M in formula (Cy) is preferably a methyl group.
  • R Cy in formula (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.
  • a monovalent group having an aliphatic hydrocarbon ring structure having 8 to 14 carbon atoms is more preferable.
  • the aliphatic hydrocarbon ring structure in R Cy of 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, and a cyclohexane ring structure, Alternatively, a tetrahydrodicyclopentadiene ring structure is more preferable, and a tetrahydrodicyclopentadiene ring structure is even more preferable.
  • the aliphatic hydrocarbon ring structure in R Cy of formula (Cy) is preferably a ring structure in which two or more aliphatic hydrocarbon rings are condensed; A ring is more preferred.
  • the alkali-soluble resin may have one type of structural unit having an aliphatic hydrocarbon ring structure, or may have two or more types of structural units.
  • the content of the constitutional unit having an aliphatic hydrocarbon ring structure is 5 to 90% by mass based on the total constitutional units of the alkali-soluble resin. It is preferably 10 to 80% by weight, more preferably 20 to 70% by weight.
  • 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 20 to 60 mol%, based on the total structural units of the alkali-soluble resin.
  • 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%, based on the total structural units of the alkali-soluble resin. More preferably 20 to 50 mol%.
  • the total content of the constitutional unit having an aromatic ring structure and the constitutional unit having an aliphatic hydrocarbon ring structure is It is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, and even more preferably 40 to 75% by mass, based on the total structural units of the alkali-soluble resin. Further, the total content of structural units having an aromatic ring structure and structural units having an aliphatic hydrocarbon ring structure in the alkali-soluble resin is preferably 10 to 80 mol%, and 20 It is more preferably 70 mol%, and even more preferably 40 to 60 mol%.
  • the total content of the structural units represented by the above formula (S) and the structural units represented by the above formula (Cy) in the alkali-soluble resin is 10 to 80 mol with respect to all the structural units of the alkali-soluble resin. %, more preferably 20 to 70 mol%, even more preferably 40 to 60 mol%.
  • the molar amount nS of the structural unit represented by the above formula (S) and the molar amount nCy of the structural unit represented by the above formula (Cy) in the alkali-soluble resin are as follows from the viewpoint that the effect of the present invention is more excellent. It is preferable that the relationship shown in the formula (SCy) is satisfied, it is more preferable that the following formula (SCy-1) is satisfied, and it is even more preferable that the following formula (SCy-2) is satisfied. 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)
  • the alkali-soluble resin has a structural unit having an acid group.
  • the acid group include a carboxy group, a sulfo group, a phosphonic acid group, and a phosphoric acid group, with a carboxy group being preferred.
  • the above-mentioned structural unit having an acid group the following structural units derived from (meth)acrylic acid are preferable, and structural units derived from methacrylic acid are more preferable.
  • the alkali-soluble resin may have one type of structural unit having an acid group, or may have two or more types.
  • the content of the structural unit having an acid group is preferably 5 to 50% by mass, and 5 to 40% by mass based on the total constitutional units of the alkali-soluble resin. It is more preferably 10 to 40% by weight, even more preferably 10 to 30% by weight.
  • 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 20 to 40 mol% based on the total structural units of the alkali-soluble resin. is even more preferable.
  • the alkali-soluble resin preferably has a reactive group, and more preferably has a structural unit having a reactive group.
  • a reactive group a radically polymerizable group is preferable, and an ethylenically unsaturated group is more preferable.
  • the alkali-soluble resin has an ethylenically unsaturated group, it is preferable that the alkali-soluble resin has a structural unit having an ethylenically unsaturated group in a side chain.
  • the "main chain” refers to the relatively longest bond chain in the molecules of the polymer compound that constitutes the resin
  • the "side chain” refers to the atomic group branching from the main chain. represent.
  • the ethylenically unsaturated group an allyl group or a (meth)acryloyloxy group is more preferable.
  • the structural unit having a reactive group include, but are not limited to, those shown below.
  • the alkali-soluble resin may have one type of structural unit having a reactive group, or may have two or more types of structural units.
  • the content of the constitutional unit having a reactive group is preferably 5 to 70% by mass, and 10 to 50% by mass based on the total constitutional units of the alkali-soluble resin. % is more preferable, and 20 to 40% by mass is even more preferable.
  • 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 10 to 50 mol% based on the total structural units of the alkali-soluble resin. % is more preferable.
  • an epoxy compound As a means of introducing a reactive group into an alkali-soluble resin, an epoxy compound, a block Examples include methods of reacting compounds such as isocyanate compounds, isocyanate compounds, vinyl sulfone compounds, aldehyde compounds, methylol compounds, and carboxylic acid anhydrides.
  • a preferable example of a means for introducing a reactive group into an alkali-soluble resin is to synthesize a polymer having a carboxyl group by a polymerization reaction, and then add glycidyl (meth) to some of the carboxyl groups of the obtained polymer by a polymer reaction. Examples include a method of reacting acrylate to introduce a (meth)acryloxy group into the polymer.
  • an alkali-soluble resin having a (meth)acryloyloxy group in the side chain can be obtained.
  • the above polymerization reaction is preferably carried out at a temperature of 70 to 100°C, more preferably 80 to 90°C.
  • an azo initiator is preferable, and for example, V-601 (trade name) or V-65 (trade name) manufactured by Fuji Film Wako Pure Chemical Industries, Ltd. is more preferable.
  • the above polymer reaction is preferably carried out at a temperature of 80 to 110°C. In the above polymer reaction, it is preferable to use a catalyst such as an ammonium salt.
  • the alkali-soluble resin has a structural unit derived from a (meth)acrylic acid alkyl ester.
  • the structural unit derived from the above-mentioned (meth)acrylic acid alkyl ester include those mentioned above, and among them, methyl (meth)acrylate is preferable.
  • the alkali-soluble resin may have one type of structural unit derived from an alkyl (meth)acrylate ester, or may have two or more types of structural units.
  • the content of the structural unit derived from the (meth)acrylic acid alkyl ester is 1 to 1 with respect to all the structural units of the alkali-soluble resin. It is preferably 10% by weight, more preferably 1 to 5% by weight. Further, the content of structural units derived from (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. .
  • polymers X1 to X4 As the alkali-soluble resin, polymers X1 to X4 shown below are preferred. Note that the content ratios (a to d) of each structural unit to all structural units and the weight average molecular weight Mw, etc. shown below can be changed as appropriate depending on the purpose, but in particular, in terms of the effects of the present invention, The following configuration is preferable.
  • Polymer X2 a: 20 to 60% by mass, b: 10 to 50% by mass, c: 5.0 to 25% by mass, d: 10 to 50% by mass.
  • Polymer X3 a: 30 to 65% by mass, b: 1.0 to 30% by mass, c: 0.5 to 15% by mass, d: 10 to 50% by 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.
  • the alkali-soluble resin it is preferable to use a polymer having a structural unit having a carboxylic acid anhydride structure (hereinafter also referred to as "polymer X").
  • the carboxylic anhydride structure may be either a chain carboxylic anhydride structure or a cyclic carboxylic anhydride structure, but is preferably a cyclic carboxylic 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.
  • the structural unit having a carboxylic acid anhydride structure is a structural unit containing a divalent group in the main chain obtained by removing two hydrogen atoms from the compound represented by the following formula P-1, or a structural unit having the following formula P-1. It is preferable to use a structural unit in which a monovalent group obtained by removing one hydrogen atom from the represented compound is bonded to the main chain directly or via a divalent linking group.
  • R A1a represents a substituent
  • n 1a R A1a 's may be the same or different
  • Examples of the substituent represented by R A1a include an alkyl group.
  • Z 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.
  • n 1a represents an integer of 0 or more.
  • Z 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.
  • multiple R A1a 's may be the same or different.
  • a plurality of R A1a may be bonded to each other to form a ring, but it is preferable that they are not bonded to each other to form a ring.
  • the structural unit having a carboxylic acid anhydride structure is preferably a structural unit derived from an unsaturated carboxylic anhydride, more preferably a structural unit derived from an unsaturated cyclic carboxylic acid anhydride, and a structural unit derived from an unsaturated aliphatic cyclic carboxylic acid anhydride is more preferable.
  • Structural units derived from acid anhydrides are more preferred, structural units derived from maleic anhydride or itaconic anhydride are particularly preferred, and structural units derived from maleic anhydride are most preferred.
  • Rx represents a hydrogen atom, a methyl group, a CH 2 OH group, or a CF 3 group
  • Me represents a methyl group
  • the number of structural units having a carboxylic acid anhydride structure in the polymer X may be one type alone, or two or more types may be used.
  • the total content of 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 the total structural units of polymer X. preferable.
  • Polymer X is preferably used in combination with any of the alkali-soluble resins of preferred embodiments 1 to 3 described above.
  • the content of polymer X is preferably 0.1 to 30% by mass, more preferably 0.2 to 20% by mass, based on the total mass of the photosensitive layer More preferably 0.5 to 20% by weight, particularly preferably 1 to 20% by weight.
  • the photosensitive layer may contain only one type of polymer X, or may contain two or more types of polymer X.
  • 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.
  • the upper limit is preferably 50,000 or less, more preferably 30,000 or less.
  • 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.
  • the degree of dispersion 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 1.0 to 6.0. 3.0 is particularly preferred.
  • the photosensitive layer may contain only one kind of alkali-soluble resin, or may contain two or more kinds.
  • the lower limit of the content of the alkali-soluble resin is preferably 10.0% by mass or more, more preferably 15.0% by mass or more, and even more preferably 20.0% by mass or more, based on the total mass of the photosensitive layer. , 30.0% by mass or more is particularly preferred.
  • 90.0 mass % or less is preferable, 80.0 mass % or less is more preferable, and 70.0 mass % or less is still more preferable.
  • the photosensitive layer preferably contains a polymerizable compound.
  • a polymerizable compound is a compound having a polymerizable group. Examples of the polymerizable group include radically polymerizable groups and cationic polymerizable groups, with radically polymerizable groups being preferred.
  • the polymerizable compound preferably includes a radically polymerizable compound having an ethylenically unsaturated group (hereinafter also simply referred to as an "ethylenic unsaturated compound").
  • ethylenic unsaturated compound a radically polymerizable compound having an ethylenically unsaturated group
  • a (meth)acryloyloxy group is preferred.
  • the ethylenically unsaturated compound in this specification is a compound other than the above-mentioned alkali-soluble resin, and preferably has a molecular weight of less than 5,000.
  • One of the preferred embodiments of the polymerizable compound is a compound represented by the following formula (M) (also simply referred to as "compound M”).
  • Q 2 -R 1 -Q 1 formula (M) Q 1 and Q 2 each independently represent a (meth)acryloyloxy group, and R 1 represents a divalent linking group having a chain structure.
  • Q 1 and Q 2 in formula ( M ) are preferably the same group from the viewpoint of ease of synthesis. Furthermore, Q 1 and Q 2 in formula (M) are preferably acryloyloxy groups from the viewpoint of reactivity.
  • R 1 in formula (M) is an alkylene group, 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 above-mentioned hydrocarbon group only needs to have a chain structure at least in part, and the part other than the above-mentioned chain structure is not particularly limited.
  • it is branched, cyclic, or has 1 to 1 carbon atoms
  • It may be a linear alkylene group, an arylene group, an ether bond, or a combination thereof as shown in No. 5, and an alkylene group or a group combining two or more alkylene groups and one or more arylene groups is preferable.
  • an alkylene group is more preferable, and a linear alkylene group is even more preferable.
  • each of the above L 1 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.
  • the number of atoms in the shortest linking chain connecting Q 1 and Q 2 in compound M is preferably 3 to 50, more preferably 4 to 40, even more preferably 6 to 20, and 8 to 50 atoms. Twelve pieces are particularly preferred.
  • the number of atoms in the shortest connecting chain connecting Q 1 and Q 2 refers to the number of atoms in R 1 connecting to Q 1 to the atom in R 1 connecting to Q 2 . This is the shortest number of atoms.
  • compound M examples 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, hydrogenated Bisphenol A di(meth)acrylate, hydrogenated bisphenol F di(meth)acrylate, 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.
  • 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, and neopentylglycol di(meth)acrylate, ) acrylate is preferred, and 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 preferred.
  • At least one compound selected from the group consisting of (meth)acrylates 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. More preferably, at least one compound is used.
  • one of the preferred embodiments of the polymerizable compound includes an ethylenically unsaturated compound having two or more functionalities.
  • the term "bifunctional or more ethylenically unsaturated compound” means a compound having two or more ethylenically unsaturated groups in one molecule.
  • a (meth)acryloyl group is preferable.
  • (meth)acrylate compounds are preferred.
  • the bifunctional ethylenically unsaturated compound can be appropriately selected from known compounds.
  • Examples of bifunctional ethylenically unsaturated compounds other than the above compound M include tricyclodecane dimethanol di(meth)acrylate and 1,4-cyclohexanediol di(meth)acrylate.
  • bifunctional ethylenically unsaturated compounds include tricyclodecane dimethanol diacrylate (trade name: NK ester A-DCP, manufactured by Shin Nakamura Chemical Co., Ltd.), tricyclodecane dimethanol dimethacrylate (trade name: NK Ester A-DCP, manufactured by Shin Nakamura Chemical Co., Ltd.), Product name: NK ester DCP, manufactured by Shin Nakamura Chemical Co., Ltd.), 1,9-nonanediol diacrylate (Product name: NK ester A-NOD-N, manufactured by Shin Nakamura Chemical Co., Ltd.), 1,6 -hexanediol diacrylate (trade name: NK ester A-HD-N, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.).
  • the trifunctional or higher-functional ethylenically unsaturated compound can be appropriately selected from known compounds.
  • trifunctional or more ethylenically unsaturated compounds include dipentaerythritol (tri/tetra/penta/hexa) (meth)acrylate, pentaerythritol (tri/tetra) (meth)acrylate, trimethylolpropane tri(meth)acrylate, Examples include ditrimethylolpropane tetra(meth)acrylate, isocyanuric acid (meth)acrylate, and (meth)acrylate compounds having a glycerin tri(meth)acrylate skeleton.
  • (tri/tetra/penta/hexa)(meth)acrylate is a concept that includes tri(meth)acrylate, tetra(meth)acrylate, penta(meth)acrylate, and hexa(meth)acrylate.
  • (tri/tetra)(meth)acrylate” is a concept that includes tri(meth)acrylate and tetra(meth)acrylate.
  • urethane (meth)acrylate compound One of the preferred embodiments of the polymerizable compound is a urethane (meth)acrylate compound.
  • urethane (meth)acrylates include urethane di(meth)acrylates, such as propylene oxide-modified urethane di(meth)acrylates, and ethylene oxide- and propylene oxide-modified urethane di(meth)acrylates.
  • examples of urethane (meth)acrylates include trifunctional or higher functional urethane (meth)acrylates.
  • the lower limit of the number of functional groups is more preferably 6 functional groups or more, and even more preferably 8 functional groups or more. Note that the upper limit of the number of functional groups is preferably 20 or less functional groups.
  • trifunctional or higher functional urethane (meth)acrylates examples include 8UX-015A (manufactured by Taisei Fine Chemical Co., Ltd.), UA-32P (manufactured by Shin Nakamura Chemical Co., Ltd.), and U-15HA (manufactured by Shin Nakamura Chemical Co., Ltd.). ), UA-1100H (manufactured by Shin-Nakamura Chemical Co., Ltd.), AH-600 (product name) manufactured by Kyoeisha Chemical Co., Ltd., as well as UA-306H, UA-306T, UA-306I, UA-510H , and UX-5000 (all manufactured by Nippon Kayaku Co., Ltd.).
  • One of the preferred embodiments of the polymerizable compound is an ethylenically unsaturated compound having an acid group.
  • acid groups include phosphoric acid groups, sulfo groups, and carboxy groups. Among these, a carboxy group is preferred as the acid group.
  • Examples of ethylenically unsaturated compounds having an acid group include tri- to tetrafunctional ethylenically unsaturated compounds having an acid group [pentaerythritol tri- and tetraacrylate (PETA) with a carboxy group introduced into the skeleton (acid value: 80 ⁇ 120mgKOH/g)], a penta- to hexa-functional ethylenically unsaturated compound having an acid group (dipentaerythritol penta and hexaacrylate (DPHA) with a carboxy group introduced into the skeleton [acid value: 25-70mgKOH/g)] etc.
  • PETA penta- to hexa-functional ethylenically unsaturated compound having an acid group
  • DPHA dipentaerythritol penta and hexaacrylate
  • These trifunctional or higher functional ethylenically unsaturated compounds having an acid group may be used
  • the ethylenically unsaturated compound having an acid group is preferably at least one selected from the group consisting of bifunctional or more ethylenically unsaturated compounds having a carboxy group and their carboxylic acid anhydrides.
  • the ethylenically unsaturated compound having an acid group is at least one selected from the group consisting of bifunctional or more ethylenically unsaturated compounds having a carboxy group and their carboxylic acid anhydrides, developability and film strength are improved. It increases.
  • the bifunctional or more ethylenically unsaturated compound having a carboxy group is not particularly limited, and can be appropriately selected from known compounds.
  • Examples of the bifunctional or more ethylenically unsaturated compound having a carboxyl group include Aronix (registered trademark) TO-2349 (manufactured by Toagosei Co., Ltd.), Aronix (registered trademark) M-520 (manufactured by Toagosei Co., Ltd.), Aronix (registered trademark) M-510 (manufactured by Toagosei Co., Ltd.) is mentioned.
  • the polymerizable compounds having an acid group described in paragraphs [0025] to [0030] of JP-A No. 2004-239942 are preferable, and the contents described in this publication are similar to those described in this publication. Incorporated into the specification.
  • polymerizable compounds examples include compounds obtained by reacting polyhydric alcohols with ⁇ , ⁇ -unsaturated carboxylic acids, compounds obtained by reacting glycidyl group-containing compounds with ⁇ , ⁇ -unsaturated carboxylic acids, and urethane.
  • Urethane monomers such as (meth)acrylate compounds having bonds, ⁇ -chloro- ⁇ -hydroxypropyl- ⁇ '-(meth)acryloyloxyethyl-o-phthalate, ⁇ -hydroxyethyl- ⁇ '-(meth)acryloyloxyethyl
  • phthalic acid compounds such as -o-phthalate and ⁇ -hydroxypropyl- ⁇ '-(meth)acryloyloxyethyl-o-phthalate, and (meth)acrylic acid alkyl esters. These may be used alone or in combination of two or more.
  • Examples of compounds obtained by reacting polyhydric alcohols with ⁇ , ⁇ -unsaturated carboxylic acids include 2,2-bis(4-((meth)acryloxypolyethoxy)phenyl)propane, 2,2-bis Bisphenol A-based (meth)acrylate compounds such as (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, and polypropylene glycol di(meth)acrylate having 2 to 14 ethylene oxide groups.
  • polyethylene polypropylene glycol di(meth)acrylate trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolpropane ethoxytri(meth)acrylate having 2 to 14 propylene oxide groups.
  • ethylenically unsaturated compounds having a tetramethylolmethane structure or a trimethylolpropane structure are preferable, and tetramethylolmethane tri(meth)acrylate, tetramethylolmethanetetra(meth)acrylate, trimethylolpropane tri(meth)acrylate, or dimethylolmethane tri(meth)acrylate is preferred. (Trimethylolpropane)tetraacrylate is more preferred.
  • Examples of the polymerizable compound include caprolactone-modified compounds of ethylenically unsaturated compounds (for example, KAYARAD (registered trademark) DPCA-20 manufactured by Nippon Kayaku Co., Ltd., A-9300-1CL manufactured by Shin Nakamura Chemical Industry Co., Ltd.), Alkylene oxide modified compounds of ethylenically unsaturated compounds (for example, KAYARAD RP-1040 manufactured by Nippon Kayaku Co., Ltd., ATM-35E and A-9300 manufactured by Shin Nakamura Chemical Co., Ltd., EBECRYL (registered trademark) manufactured by Daicel Allnex Co., Ltd.
  • KAYARAD registered trademark
  • DPCA-20 manufactured by Nippon Kayaku Co., Ltd., A-9300-1CL manufactured by Shin Nakamura Chemical Industry Co., Ltd.
  • Alkylene oxide modified compounds of ethylenically unsaturated compounds for example, KAYARAD RP-1040 manufactured by Nippon Kayaku Co
  • polymerizable compounds particularly ethylenically unsaturated compounds
  • those containing an ester bond are also preferred, since they provide 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 its molecule, but since the effects of the present invention are excellent, ethylenically unsaturated compounds having a tetramethylolmethane structure or a trimethylolpropane structure are preferred.
  • the ethylenically unsaturated compounds include ethylenically unsaturated compounds having an aliphatic group having 6 to 20 carbon atoms, and ethylenically unsaturated compounds having the above-mentioned tetramethylolmethane structure or trimethylolpropane structure. It is preferable to include a compound.
  • Examples of ethylenically unsaturated compounds having an aliphatic structure having 6 or more carbon atoms include 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, and tricyclodecane dimethanol di(meth)acrylate. Examples include (meth)acrylates.
  • polymerizable compound is a polymerizable compound having an aliphatic hydrocarbon ring structure (preferably a difunctional ethylenically unsaturated compound).
  • the above-mentioned polymerizable compound is 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).
  • a bifunctional ethylenically unsaturated compound having a ring structure in which two or more aliphatic hydrocarbon rings are condensed is more preferable, and tricyclodecane dimethanol di(meth)acrylate is even more preferable.
  • 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.
  • the molecular weight of the polymerizable compound is preferably 200 to 3,000, more preferably 250 to 2,600, even more preferably 280 to 2,200, and particularly preferably 300 to 2,200.
  • the photosensitive layer preferably contains a compound represented by formula (M) and an ethylenically unsaturated compound having an acid group, and 1,9-nonane. More preferably, it contains diol diacrylate and a polyfunctional ethylenically unsaturated compound having a carboxylic acid group.
  • the photosensitive layer is made of a difunctional ethylenically unsaturated compound (preferably a difunctional (meth)acrylate compound) from the viewpoint of development residue suppression and rust prevention properties. ) and a trifunctional or higher functional ethylenically unsaturated compound (preferably a trifunctional or higher functional (meth)acrylate compound).
  • a difunctional ethylenically unsaturated compound preferably a difunctional (meth)acrylate compound
  • a trifunctional or higher functional ethylenically unsaturated compound preferably a trifunctional or higher functional (meth)acrylate compound
  • the mass ratio of the content of the bifunctional ethylenically unsaturated compound and the trifunctional or more functional ethylenically unsaturated compound is 10/90 to 90/10 is preferred, and 30/70 to 70/30 is more preferred.
  • 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 40.0% by mass or more. is even more preferable.
  • the upper limit is not particularly limited, but 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 bifunctional ethylenically unsaturated compound in the photosensitive layer is preferably 5.0 to 60.0% by mass, more preferably 5.0 to 40.0% by mass, and even more preferably 5.0 to 40.0% by mass. preferable.
  • the photosensitive layer may contain a monofunctional ethylenically unsaturated compound as the ethylenically unsaturated compound.
  • the content of the ethylenically unsaturated compound having two or more functionalities is preferably 50 to 100% by mass based on the total content of all ethylenically unsaturated compounds contained in the photosensitive layer.
  • the polymerizable compounds may be used alone or in combination of two or more.
  • the lower limit of the content of polymerizable compounds (especially ethylenically unsaturated compounds) in the photosensitive layer is preferably 10.0% by mass or more, and 15.0% by mass or more based on the total mass of the photosensitive layer. is more preferable.
  • 70.0 mass % or less is preferable, 60.0 mass % or less is more preferable, 50.0 mass % or less is still more preferable, and 40.0 mass % or less is especially preferable.
  • the photosensitive layer contains a photopolymerization initiator.
  • photopolymerization initiator there are no particular limitations on the photopolymerization initiator, and any known photopolymerization initiator can be used.
  • photopolymerization initiators include photopolymerization initiators having an oxime ester structure (hereinafter also referred to as "oxime-based photopolymerization initiators”), and photopolymerization initiators having an ⁇ -aminoalkylphenone structure (hereinafter referred to as " ⁇ - ), a photopolymerization initiator having an ⁇ -hydroxyalkylphenone structure (hereinafter also referred to as an “ ⁇ -hydroxyalkylphenone polymerization initiator”), an acylphosphine oxide structure A photopolymerization initiator having an N-phenylglycine structure (hereinafter also referred to as an "acylphosphine oxide photopolymerization initiator”) and a photopolymerization initiator having an
  • the photopolymerization initiator is selected from the group consisting of oxime photopolymerization initiators, ⁇ -aminoalkylphenone photopolymerization initiators, ⁇ -hydroxyalkylphenone photopolymerization initiators, and N-phenylglycine photopolymerization initiators. It preferably contains at least one kind selected from the group consisting of oxime-based photopolymerization initiators, ⁇ -aminoalkylphenone-based photopolymerization initiators, and N-phenylglycine-based photopolymerization initiators. It is more preferable.
  • photopolymerization initiator for example, those described in paragraphs [0031] to [0042] of JP-A No. 2011-095716 and paragraphs [0064] to [0081] of JP-A No. 2015-014783, A polymerization initiator may also be used.
  • 2,4,5-triarylimidazole dimer and It is preferable to include at least one selected from the group consisting of derivatives thereof.
  • the two 2,4,5-triarylimidazole structures in the 2,4,5-triarylimidazole dimer and its derivatives may be the same or different.
  • Examples of derivatives of 2,4,5-triarylimidazole dimer include 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer and 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer.
  • (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 is mentioned.
  • Examples of the 2,4,5-triarylimidazole dimer derivative include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-bis Mention may also be made of imidazoles.
  • Examples of the photoradical polymerization initiator include ethyl dimethylaminobenzoate (DBE, CAS No. 10287-53-3), benzoin methyl ether, anisyl (p,p'-dimethoxybenzyl), and TAZ-110 (trade name: Midori Kagaku Co., Ltd.), benzophenone, 4,4'-bis(diethylamino)benzophenone, TAZ-111 (product name: Midori Kagaku Co., Ltd.), Irgacure OXE01, OXE02, OXE03, OXE04 (BASF Co., Ltd.), Omnirad651 and 369 (product name: Midori Kagaku Co., Ltd.) Name: IGM Resins manufactured by B.V.), and 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole (Tokyo Chemical Industry Co., Ltd.) ).
  • photoradical polymerization initiators include, for example, 1-[4-(phenylthio)]-1,2-octanedione-2-(O-benzoyloxime) (trade name: IRGACURE (registered trademark) OXE-01).
  • the photopolymerization initiators may be used alone or in combination of two or more. When two or more types are used in combination, an oxime photopolymerization initiator and at least one selected from ⁇ -aminoalkylphenone photopolymerization initiators and ⁇ -hydroxyalkylphenone polymerization initiators may be used. preferable.
  • the content of the photopolymerization initiator is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, based on the total mass of the photosensitive layer. More preferably, the content is 0.5% by mass or more. Further, the upper limit thereof is preferably 10.0% by mass or less, more preferably 7.0% by mass or less, based on the total mass of the photosensitive layer.
  • the photosensitive layer may contain a heterocyclic compound.
  • the heterocycle possessed by the heterocyclic compound may be either a monocyclic or polycyclic heterocycle.
  • Examples of the heteroatom contained in the heterocyclic compound include a nitrogen atom, an oxygen atom, and a sulfur atom.
  • the heterocyclic compound preferably has at least one atom selected from the group consisting of a nitrogen atom, an oxygen atom, and a sulfur atom, and more preferably a nitrogen atom.
  • heterocyclic compound examples include a triazole compound, a benzotriazole compound, a tetrazole compound, a thiadiazole compound, a triazine compound, a rhodanine compound, a thiazole compound, a benzothiazole compound, a benzimidazole compound, a benzoxazole compound, and a pyrimidine compound.
  • the heterocyclic compound is at least one 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.
  • a type of compound is preferred, and at least one compound selected from the group consisting of a triazole compound, a benzotriazole compound, a tetrazole compound, a thiadiazole compound, a thiazole compound, a benzothiazole compound, a benzimidazole compound, and a benzoxazole compound is more preferred.
  • heterocyclic compound Preferred specific examples of the heterocyclic compound are shown below.
  • examples of the triazole compound and benzotriazole compound include the following compounds.
  • Examples of the tetrazole compound include the following compounds.
  • thiadiazole compounds include the following compounds.
  • triazine compounds include the following compounds.
  • rhodanine compounds include the following compounds.
  • thiazole compounds include the following compounds.
  • benzothiazole compounds include the following compounds.
  • benzimidazole compounds include the following compounds.
  • benzoxazole compounds include the following compounds.
  • the heterocyclic compounds may be used alone or in combination of two or more.
  • the content of the heterocyclic compound is preferably 0.01 to 20.0% by mass, and 0.10 to 10.0% by mass based on the total mass of the photosensitive layer. is more preferable, 0.30 to 8.0% by weight is still more preferable, and 0.50 to 5.0% by weight is particularly preferable.
  • the photosensitive layer may contain an aliphatic thiol compound. Since the photosensitive layer contains an aliphatic thiol compound, the aliphatic thiol compound undergoes an ene-thiol reaction with a radically polymerizable compound having an ethylenically unsaturated group, thereby suppressing curing shrinkage of the formed film. and the stress is relieved.
  • aliphatic thiol compound a monofunctional aliphatic thiol compound or a polyfunctional aliphatic thiol compound (that is, a bifunctional or more functional aliphatic thiol compound) is preferable.
  • polyfunctional aliphatic thiol compounds are preferred from the viewpoint of the adhesion of the formed pattern (particularly the adhesion after exposure).
  • polyfunctional aliphatic thiol compound means an aliphatic compound having two or more thiol groups (also referred to as “mercapto groups”) in the molecule.
  • the polyfunctional aliphatic thiol compound a low molecular compound with a molecular weight of 100 or more is preferable. 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.
  • the number of functional groups in the polyfunctional aliphatic thiol compound is preferably 2 to 10 functional, more preferably 2 to 8 functional, and even more preferably 2 to 6 functional, from the viewpoint of adhesion of the formed pattern.
  • 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), tris[(3-mercaptopropionyloxy)ethyl] Isocyanurate, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionat
  • polyfunctional aliphatic thiol compounds include trimethylolpropane tris(3-mercaptobutyrate), 1,4-bis(3-mercaptobutyryloxy)butane, and 1,3,5-tris At least one compound selected from the group consisting of (3-mercaptobutyryloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione is preferred.
  • Examples of monofunctional aliphatic thiol compounds include 1-octanethiol, 1-dodecanethiol, ⁇ -mercaptopropionic acid, methyl-3-mercaptopropionate, 2-ethylhexyl-3-mercaptopropionate, n- Included are octyl-3-mercaptopropionate, methoxybutyl-3-mercaptopropionate, and stearyl-3-mercaptopropionate.
  • the photosensitive layer may contain one type of aliphatic thiol compound alone, or may contain two or more types of aliphatic thiol compounds.
  • the content of the aliphatic thiol compound is preferably 5% by mass or more, more preferably 5 to 50% by mass, and more preferably 5 to 30% by mass based on the total mass of the photosensitive layer. % by weight is more preferable, and 8 to 20% by weight is particularly preferable.
  • the photosensitive layer contains a thermally crosslinkable compound from the viewpoint of the strength of the resulting cured film and the tackiness of the resulting uncured film.
  • the thermally crosslinkable compound having an ethylenically unsaturated group which will be described later, is not treated as an ethylenically unsaturated compound, but as a thermally crosslinkable compound.
  • thermally crosslinkable compounds include epoxy compounds, oxetane compounds, methylol compounds, and blocked isocyanate compounds. Among these, blocked isocyanate compounds are preferred from the viewpoint of the strength of the cured film obtained and the tackiness of the uncured film obtained.
  • blocked isocyanate compounds react with hydroxy groups and carboxy groups. , the hydrophilicity of the formed film tends to decrease and its function as a protective film tends to be strengthened.
  • the blocked isocyanate compound refers to "a compound having a structure in which the isocyanate group of isocyanate is protected (so-called masked) with a blocking agent.”
  • the dissociation temperature of the blocked isocyanate compound is not particularly limited, but is preferably 100 to 160°C, more preferably 130 to 150°C.
  • the dissociation temperature of the blocked isocyanate means "the temperature of the endothermic peak associated with the deprotection reaction of the blocked isocyanate when measured by DSC (differential scanning calorimetry) analysis using a differential scanning calorimeter.”
  • DSC differential scanning calorimetry
  • a differential scanning calorimeter model: DSC6200 manufactured by Seiko Instruments Inc. can be suitably used.
  • the differential scanning calorimeter is not limited to this.
  • the blocking agent having a dissociation temperature of 100 to 160° C. is preferably at least one selected from oxime compounds, for example, from the viewpoint of storage stability.
  • 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 isocyanate compound having an isocyanurate structure can be obtained, for example, by converting hexamethylene diisocyanate into isocyanurate and protecting it.
  • blocked isocyanate compounds having an isocyanurate structure a compound having an oxime structure using an oxime compound as a blocking agent is easier to maintain the dissociation temperature in a preferable range than a compound without an oxime structure, and produces less development residue. This is preferable because it is easy to do.
  • the blocked isocyanate compound may have a polymerizable group.
  • the polymerizable group is not particularly limited, and any known polymerizable group can be used, with radically polymerizable groups being preferred.
  • the polymerizable group include ethylenically unsaturated groups such as a (meth)acryloxy group, (meth)acrylamide group, and styryl group, and groups having an epoxy group such as a glycidyl group.
  • the polymerizable group is preferably an ethylenically unsaturated group, more preferably a (meth)acryloxy group, and even more preferably an acryloxy group.
  • blocked isocyanate compound commercially available products can be used.
  • block isocyanate compounds include Karenz (registered trademark) AOI-BM, Karenz (registered trademark) MOI-BM, Karenz (registered trademark) MOI-BP (all manufactured by Showa Denko K.K.), Block Examples include the Duranate series of molds (eg, Duranate (registered trademark) TPA-B80E, Duranate (registered trademark) WT32-B75P, etc., manufactured by Asahi Kasei Chemicals Co., Ltd.).
  • Thermal crosslinkable compounds may be used alone or in combination of two or more.
  • the content of the thermally crosslinkable compound is preferably 1.0 to 50.0% by mass, and 5.0 to 30.0% by mass based on the total mass of the photosensitive layer.
  • the amount is more preferably 5.0 to 25.0% by weight, and even more preferably 5.0 to 25.0% by weight.
  • the photosensitive layer may contain a surfactant.
  • the surfactant include the surfactants described in paragraph [0017] of Japanese Patent No. 4502784 and paragraphs [0060] to [0071] of JP-A-2009-237362.
  • fluorine-based surfactants or silicone-based surfactants are preferred.
  • Commercially available fluorosurfactants include Megafac F-171, F-172, F-173, F-176, F-177, F-141, F-142, F-143, F-144.
  • fluorine-based surfactants include acrylic compounds that have a molecular structure with a functional group containing a fluorine atom, and when heat is applied, the functional group containing the fluorine atom is severed and the fluorine atom evaporates.
  • fluorine-based surfactants include the Megafac DS series manufactured by DIC Corporation (Kagaku Kogyo Nippo (February 22, 2016), Nikkei Sangyo Shimbun (February 23, 2016)); An example is DS-21.
  • the fluorine-based surfactant it is also preferable to use a polymer of a fluorine atom-containing vinyl ether compound having a fluorinated alkyl group or a fluorinated alkylene ether group and a hydrophilic vinyl ether compound.
  • block polymers can also be used as the fluorosurfactant.
  • the fluorine-based surfactant has a structural unit derived from a (meth)acrylate compound having a fluorine atom and two or more (preferably five or more) alkyleneoxy groups (preferably ethyleneoxy groups, propyleneoxy groups).
  • a fluorine-containing polymer compound containing a structural unit derived from a (meth)acrylate compound can also be preferably used.
  • fluorine-containing surfactant a fluorine-containing polymer having an ethylenically unsaturated bond-containing group in its side chain can also be used.
  • fluorosurfactants are derived from alternative materials for compounds with perfluoroalkyl groups having 7 or more carbon atoms, such as perfluorooctanoic acid (PFOA) and perfluorooctane sulfonic acid (PFOS).
  • 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 ester, Pluronic (registered trademark) L10, L31, L61, L62, 10R5, 17R2 , 25R2 (manufactured by BASF), Tetronic 304, 701, 704, 901, 904, 150R1 (manufactured by BASF), Solsperse 20000 (manufactured by Japan Lubrizol
  • silicone surfactants include linear polymers consisting of siloxane bonds and modified siloxane polymers with organic groups introduced into side chains or terminals.
  • surfactants include DOWSIL 8032 ADDITIVE, Tore Silicone DC3PA, Tore Silicone SH7PA, Tore Silicone DC11PA, Tore Silicone SH21PA, Tore Silicone SH28PA, Tore Silicone SH29PA, Tore Silicone SH30PA, Tore Silicone SH 8400 (or more, Toray Dow (manufactured by Corning Corporation), X-22-4952, X-22-4272, 643, X-22-6191, X-22-4515, KF-6004, KP-341, KF-6001, KF-6002 (manufactured by Shin-Etsu Silicone Co., Ltd.), F-4440, TSF-4300, TSF-4445 , TSF-4460, TSF-4452 (manufactured by Momentive Performance Materials), BYK307, BYK323, BYK330 (manufactured by BYK Chemie), and the like.
  • the surfactants may be used alone or in combination of two or more.
  • the content of the surfactant is preferably 0.01 to 3.0% by mass, and 0.01 to 1.0% by mass based on the total mass of the photosensitive layer. is more preferable, and even more preferably 0.05 to 0.80% by mass.
  • the photosensitive layer may contain a polymerization inhibitor.
  • a polymerization inhibitor means a compound that has the function of delaying or inhibiting a polymerization reaction.
  • the polymerization inhibitor for example, known compounds used as polymerization inhibitors can be used.
  • polymerization inhibitor examples include phenothiazine compounds such as phenothiazine, bis-(1-dimethylbenzyl)phenothiazine, and 3,7-dioctylphenothiazine; bis[3-(3-tert-butyl-4-hydroxy-5-methyl); phenyl)propionic acid][ethylenebis(oxyethylene)]2,4-bis[(laurylthio)methyl]-o-cresol, 1,3,5-tris(3,5-di-t-butyl-4-hydroxy benzyl), 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl), 2,4-bis-(n-octylthio)-6-(4-hydroxy-3, Hindered phenol compounds such as 5-di-tert-butylanilino)-1,3,5-triazine, and pentaerythritol tetrakis 3-(3,5-di-d
  • the polymerization inhibitor is preferably at least one selected from the group consisting of phenothiazine compounds, nitroso compounds or salts thereof, and hindered phenol compounds; -(3-tert-butyl-4-hydroxy-5-methylphenyl)propionic acid][ethylenebis(oxyethylene)]2,4-bis[(laurylthio)methyl]-o-cresol, 1,3,5- More preferred are tris(3,5-di-t-butyl-4-hydroxybenzyl) and N-nitrosophenylhydroxylamine aluminum salt.
  • the polymerization inhibitors may be used alone or in combination of two or more.
  • the content of the polymerization inhibitor is preferably 0.001 to 5.0% by mass, and 0.01 to 3.0% by mass based on the total mass of the photosensitive layer. is more preferable, and even more preferably 0.02 to 2.0% by mass.
  • the content of the polymerization inhibitor is preferably 0.005 to 5.0% by mass, more preferably 0.01 to 3.0% by mass, and 0.01 to 1.0% by mass based on the total mass of the polymerizable compound. Mass % is more preferred.
  • the photosensitive layer may contain a hydrogen donating compound.
  • the hydrogen-donating compound has effects such as further improving the sensitivity of the photopolymerization initiator to actinic rays and suppressing inhibition of polymerization of the polymerizable compound by oxygen.
  • Examples of hydrogen-donating compounds include amines and amino acid compounds.
  • Examples of amines include M. R. "Journal of Polymer Society” Vol. 10, p. 3173 (1972) by Sander et al. Examples include compounds described in JP-A-60-084305, JP-A-62-018537, JP-A-64-033104, and Research Disclosure 33825. More specifically, 4,4'-bis(diethylamino)benzophenone, tris(4-dimethylaminophenyl)methane (also known as leuco crystal violet), triethanolamine, p-dimethylaminobenzoic acid ethyl ester, p-formyl Dimethylaniline and p-methylthiodimethylaniline are mentioned.
  • the amine is preferably at least one selected from the group consisting of 4,4'-bis(diethylamino)benzophenone and tris(4-dimethylaminophenyl)methane, in that the effects of the present invention are more excellent. .
  • amino acid compound examples include N-phenylglycine, N-methyl-N-phenylglycine, and N-ethyl-N-phenylglycine.
  • N-phenylglycine is preferred as the amino acid compound since it provides better effects of the present invention.
  • hydrogen-donating compounds examples include organometallic compounds (tributyltin acetate, etc.) described in Japanese Patent Publication No. 48-042965, hydrogen donors described in Japanese Patent Publication No. 55-034414, and Sulfur compounds (such as trithiane) described in Japanese Patent No. 308727 may also be mentioned.
  • organometallic compounds tributyltin acetate, etc.
  • hydrogen donors described in Japanese Patent Publication No. 55-034414
  • Sulfur compounds such as trithiane
  • the hydrogen donating compounds may be used alone or in combination of two or more.
  • the content of the hydrogen-donating compound is 0 with respect to the total mass of the photosensitive layer, from the viewpoint of improving the curing rate due to the balance between polymerization growth rate and chain transfer.
  • the content is preferably from .01 to 10.0% by weight, more preferably from 0.01 to 8.0% by weight, even more preferably from 0.03 to 5.0% by weight.
  • the photosensitive layer may contain residual monomers of each structural unit of the alkali-soluble resin described above. From the point of patterning properties and reliability, the content of the residual monomer is preferably 5,000 mass ppm or less, more preferably 2,000 mass ppm or less, and still more preferably 500 mass ppm or less, based on the total mass of the alkali-soluble resin. preferable.
  • the lower limit is not particularly limited, but is preferably at least 1 ppm by mass, more preferably at least 10 ppm by mass.
  • the residual monomer of each structural unit of the alkali-soluble resin is preferably 3,000 mass ppm or less, more preferably 600 mass ppm or less, and 100 mass ppm or less, based on the total mass of the photosensitive layer, from the viewpoint of patterning properties and reliability. More preferably, it is less than ppm. Although the lower limit is not particularly limited, it is preferably 0.1 mass ppm or more, and more preferably 1 mass ppm or more.
  • the amount of residual monomers in the synthesis of the alkali-soluble resin by polymer reaction is within the above range.
  • the content of glycidyl acrylate is preferably within the above range.
  • the amount of residual monomer can be measured by known methods such as liquid chromatography and gas chromatography.
  • the photosensitive layer may contain components other than those described above (hereinafter also referred to as "other components”).
  • Other components include, for example, particles (eg, metal oxide particles), colorants, antioxidants, reflectance modifiers, light-absorbing substances, sensitizers, and chain transfer agents. Further, other components include other additives described in paragraphs [0058] to [0071] of JP-A-2000-310706.
  • metal oxide particles are preferred.
  • Metals in the metal oxide particles also include semimetals such as B, Si, Ge, As, Sb, and Te.
  • the average primary particle diameter of the particles is, for example, preferably 1 to 200 nm, more preferably 3 to 80 nm, from the viewpoint of transparency of the cured film.
  • the average primary particle diameter of the particles is calculated by measuring the particle diameter of 200 arbitrary particles using an electron microscope and taking the arithmetic average of the measurement results. In addition, when the shape of the particle is not spherical, the longest side is taken as the particle diameter.
  • the photosensitive layer may contain trace amounts of colorants (pigments, dyes, etc.).
  • antioxidants include 1-phenyl-3-pyrazolidone (also known as phenidone), 1-phenyl-4,4-dimethyl-3-pyrazolidone, and 1-phenyl-4-methyl-4-hydroxymethyl-3.
  • 3-pyrazolidones such as pyrazolidone; polyhydroxybenzenes such as hydroquinone, catechol, pyrogallol, methylhydroquinone, and chlorohydroquinone; paramethylaminophenol, paraaminophenol, parahydroxyphenylglycine, and paraphenylenediamine.
  • 3-pyrazolidones are preferable as the antioxidant, and 1-phenyl-3-pyrazolidone is more preferable, since the effects of the present invention are more excellent.
  • the photosensitive layer preferably contains one or more reflectivity modifiers selected from the group consisting of white pigments, metal particles, hollow particles, and liquid crystal compounds (particularly pigment particles of cholesteric liquid crystal compounds).
  • the photosensitive layer contains a reflectance modifier, it can be used as a light reflective layer precursor layer.
  • the photosensitive layer contains a reflectivity modifier, the resin pattern of the laminate formed according to the first embodiment of the present invention has even better light reflectivity.
  • the photosensitive layer contains a white pigment or hollow particles, the photosensitive layer is likely to become a white layer, and a light reflecting layer having the characteristic X1 described below is likely to be obtained.
  • the photosensitive layer contains metal particles or a liquid crystal compound (particularly pigment particles of a cholesteric liquid crystal compound), a light reflecting layer having characteristics X2 and X3, which will be described later, can be obtained due to the reflectivity caused by the metal particles or liquid crystal compound.
  • a light reflecting layer having characteristics X2 and X3 which will be described later, can be obtained due to the reflectivity caused by the metal particles or liquid crystal compound.
  • the white pigment examples include titanium oxide, zinc oxide, lithopone, light calcium carbonate, white carbon, aluminum oxide, aluminum hydroxide, barium sulfate, and the like.
  • the white pigment particles that exhibit a higher refractive index than the cured product of the polymerizable compound contained in the photosensitive layer are preferable in that the effects of the present invention are more excellent, and titanium oxide is particularly preferable.
  • rutile type or anatase type titanium oxide is more preferable, and rutile type titanium oxide is particularly preferable.
  • the surface of the white pigment may be subjected to treatments such as silica treatment, alumina treatment, titania treatment, zirconia treatment, and organic substance treatment.
  • the photosensitive layer may further contain a pigment dispersant.
  • the shape of the white pigment is not particularly limited, and examples include spherical, amorphous, plate-like, acicular, and polyhedral shapes.
  • the average primary particle size of the white pigment is not particularly limited, and is preferably, for example, 50 to 1000 nm, more preferably 100 to 500 nm.
  • the average primary particle diameter of the white pigment is a value determined by measuring the diameters of 100 arbitrary particles through observation using a transmission electron microscope (TEM) and taking the arithmetic mean of the 100 diameters.
  • TEM transmission electron microscope
  • the diameter of the white pigment refers to the diameter when an image observed by a transmission electron microscope (TEM) is a circle with the same area.
  • 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 their high reflectivity. , tin, nickel, aluminum, or cobalt are more preferable, and gold, silver, or aluminum is even more preferable in that they exhibit higher reflectivity in the visible light region, and silver is particularly preferable.
  • the metal particles may be single metal particles or metal alloy particles. In addition, when the metal particles are metal alloy particles, it is preferable that the metal alloy particles are alloy particles of two or more of the above-mentioned metal types.
  • the shape of the metal particles is not particularly limited, and examples include spherical, amorphous, plate-like, acicular, and polyhedral shapes.
  • the average primary particle size of the metal particles is not particularly limited, and is preferably, for example, 1 to 5,000 nm, more preferably 5 to 1,000 nm.
  • the average primary particle diameter of the metal particles is a value determined by measuring the diameters of 100 arbitrary particles by observation using a transmission electron microscope (TEM) and calculating the arithmetic mean of the 100 diameters. Further, the diameter of the metal particles refers to the diameter when an image observed by a transmission electron microscope (TEM) is a circle with the same area.
  • Metal particles can be produced, for example, by a method such as reduction of an organometallic compound, as disclosed in JP-A-10-183207.
  • the hollow particles are not particularly limited as long as they have a cavity inside, and examples thereof include hollow inorganic particles and hollow resin particles.
  • the hollow inorganic particles are preferably hollow inorganic particles whose shell portions are made of a metal oxide selected from the group consisting of silica, alumina, zirconia, titanium oxide, and composite oxides thereof.
  • Examples of hollow resin particles include styrene resin, acrylic resin, silicone resin, acrylic-styrene resin, vinyl chloride resin, vinylidene chloride resin, amide resin, urethane resin, phenol resin, and styrene-conjugated diene.
  • Polymers such as acrylic-based resins, acrylic-conjugated diene-based resins, and olefin-based resins, as well as hollow resin particles whose shell portions are made of organic substances such as crosslinked products of these polymers, can be mentioned.
  • 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, and the like.
  • the shape of the hollow particles is not particularly limited, and examples include spherical, crushed, fibrous, acicular, and scaly shapes.
  • the average primary particle size of the hollow particles is not particularly limited, and is preferably, for example, 50 to 5000 nm, more preferably 100 to 1000 nm.
  • the average primary particle diameter of the hollow particles is a value obtained by measuring the diameters of 100 arbitrary particles by observation using a transmission electron microscope (TEM) and calculating the arithmetic mean of the 100 diameters.
  • the diameter of the hollow particles refers to the diameter when an image observed by a transmission electron microscope (TEM) is a circle with the same area.
  • liquid crystal compound-- examples include compounds having liquid crystal properties.
  • the liquid crystal compound may be fixed in a predetermined alignment state. That is, the photosensitive layer may contain a polymer obtained by polymerizing an oriented polymerizable liquid crystal compound. In the above polymer, the orientation state is fixed.
  • a polymer obtained by polymerizing a polymerizable liquid crystal compound with cholesteric liquid crystal alignment is preferable because it has better reflectivity.
  • a polymer with a fixed cholesteric liquid crystal orientation can be 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 state exhibiting a cholesteric liquid crystal phase.
  • a polymer in which cholesteric liquid crystal alignment is fixed usually has a circularly polarized light selective reflection function that selectively reflects circularly polarized light.
  • the polymer in which the cholesteric liquid crystal alignment is fixed is contained in the photosensitive layer in the form of liquid crystal particles.
  • the photosensitive layer preferably contains liquid crystal particles made of a polymer with fixed cholesteric liquid crystal orientation.
  • the shape of the liquid crystal particles is not particularly limited, flakes are preferable since they have better dispersibility.
  • the average primary particle diameter of the flakes is, for example, preferably 1 to 120 ⁇ m, more preferably 1 to 100 ⁇ m.
  • the average primary particle diameter of the liquid crystal particles is a value determined by measuring the diameters of 100 arbitrary particles through observation using a transmission electron microscope (TEM) and taking the arithmetic mean of the 100 diameters. Further, the diameter of the liquid crystal particles refers to the diameter when an image observed by a transmission electron microscope (TEM) is a circle with the same area.
  • TEM transmission electron microscope
  • liquid crystal particles include, for example, "HELICONE HC Sapphire,” “HELICONE HC Aquarius,” “HELICONE HC Scarabeus,” “HELICONE HC Jade,” and “HELICONE HC Aquarius.”
  • ICONE HC Maple (all manufactured by Asahi Kasei Wacker Silicone Co., Ltd.), etc. can be mentioned.
  • the content of the reflection modifier is preferably 10 to 90% by mass, more preferably 20 to 85% by mass, and 30 to 85% by mass, based on the total mass of the photosensitive layer. 80% by mass is more preferred.
  • the content of the white pigment is preferably 30 to 80% by mass, more preferably 40 to 70% by mass, based on the total mass of the photosensitive layer.
  • the reflectance modifier contains metal particles
  • the content of the metal particles is preferably 20 to 95% by mass, more preferably 30 to 90% by mass, based on the total mass of the photosensitive layer.
  • the content of the hollow particles is preferably 20 to 80% by mass, more preferably 30 to 70% by mass, based on the total mass of the photosensitive layer.
  • the reflectivity modifier contains a liquid crystal compound (preferably liquid crystal particles)
  • the content of the liquid crystal compound is preferably 10 to 90% by mass based on the total mass of the photosensitive layer. More preferably 20 to 80% by weight, even more preferably 30 to 70% by weight.
  • the photosensitive layer contains a light-absorbing substance.
  • a light-absorbing layer precursor layer may be formed.
  • the photosensitive layer contains a light-absorbing substance, the external light reflectivity of the resin pattern of the laminate formed according to the first embodiment of the present invention is reduced, and/or the external light reflectivity is reduced when the light emitting element is turned on. The obtained stray light is easily absorbed, and as a result, the black density is better when the light emitting element is not lit.
  • a light-absorbing layer having characteristics Y1 and/or Y2, which will be described later, is likely to be obtained.
  • 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. preferable.
  • the light-absorbing substance is a black pigment
  • its shape is not particularly limited, and examples include spherical, amorphous, plate-like, needle-like, and polyhedral.
  • the average primary particle size of the light-absorbing substance is not particularly limited, and is preferably, for example, 1 to 1000 nm, more preferably 2 to 500 nm.
  • the average primary particle diameter of the light-absorbing substance is a value determined by measuring the diameters of 100 arbitrary particles through observation using a transmission electron microscope (TEM) and taking the arithmetic mean of the 100 diameters.
  • the diameter of the light-absorbing substance refers to the diameter when an image observed by a transmission electron microscope (TEM) is a circle with the same area.
  • 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.
  • light-absorbing substances include compounds that turn black when exposed to light, heated, etc.
  • Examples of compounds that turn black due to the action of exposure, heating, etc. include the following compound (1).
  • the content of the light-absorbing substance is preferably 5 to 80% by mass, more preferably 10 to 70% by mass, and 10 to 70% by mass, based on the total mass of the photosensitive layer. More preferably 60% by weight, particularly preferably 10 to 50% by weight.
  • the thickness of the photosensitive layer is, for example, preferably 1 ⁇ m or more, more preferably 2 ⁇ m or more.
  • the upper limit is not particularly limited, and is preferably, for example, 100 ⁇ m or less, more preferably 50 ⁇ m or less.
  • the photosensitive layer contains a reflectivity modifier, it can be used as a light-reflecting layer precursor layer, and when the photosensitive layer contains a light-absorbing substance, it can be used as a light-absorbing layer precursor layer. can.
  • the light absorption layer precursor layer and the light absorption layer precursor layer will be described.
  • the thickness of the light reflective layer precursor layer is preferably 3 ⁇ m or more, more preferably 5 ⁇ m or more, even more preferably 10 ⁇ m or more, particularly preferably 16 ⁇ m or more.
  • the upper limit is not particularly limited, and is preferably, for example, 100 ⁇ m or less, more preferably 50 ⁇ m or less.
  • the light reflective layer formed from the light reflective layer precursor layer is a layer that satisfies at least one of the following characteristics X1, X2, and X3. It is preferable that 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 the characteristics X1 and X2, and when the LED in the light-emitting element is a UV-LED, the light-reflecting layer As such, it is preferable that the layer satisfies characteristic X3.
  • the total internal reflection (incident angle: 8°, light source: D-65 (2° field of view)) of the light reflective layer has an L * value of 80 or more in the CIE1976 (L * , a * , b * ) color space. is preferred.
  • L * value in the CIE 1976 (L * , a * , b * ) color space is a value measured using a spectrophotometer at 25° C. for a light reflecting layer with a thickness of 30 ⁇ m.
  • spectrophotometer for example, spectrophotometer V-570 manufactured by JASCO Corporation can be used.
  • the above L * value is more preferably 90 or more.
  • the upper limit is 100 or less.
  • the total reflectance of the light reflecting layer 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 at 25° C. for a light reflecting layer with a thickness of 30 ⁇ m.
  • spectrophotometer for example, spectrophotometer V-570 manufactured by JASCO Corporation can be used.
  • ⁇ Characteristics X3 ⁇ The total reflectance of the light reflecting layer 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 at a wavelength of 385 nm is a value measured using a spectrophotometer at 25° C. for a light reflecting layer with a thickness of 30 ⁇ m.
  • a spectrophotometer for example, spectrophotometer V-570 manufactured by JASCO Corporation can be used.
  • the thickness of the light absorption layer precursor layer is preferably 1 ⁇ m or more, more preferably 2 ⁇ m or more.
  • the upper limit is not particularly limited, and is preferably, for example, 10 ⁇ m or less, more preferably 5 ⁇ m or less.
  • Optical density of light absorption layer precursor layer The optical density (OD) of the light absorption layer precursor layer at a wavelength of 550 nm is preferably 0.5 or more, more preferably 1.0 or more, and still more preferably 2.0 or more. Preferably, 3.0 or more is particularly preferable.
  • the upper limit is not particularly limited, and is preferably 6.0 or less, for example.
  • the optical density of the light absorption layer precursor layer can be measured with a Macbeth densitometer (manufactured by Macbeth, TD-904, using a visual filter) or the like.
  • the optical density (OD) of the light absorption 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.
  • the upper limit is not particularly limited, and is preferably 6.0 or less, for example.
  • the optical density of the light absorption 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.
  • the light absorption layer formed from the light absorption layer precursor layer preferably satisfies the characteristics Y1 and/or the characteristics Y2.
  • the light-absorbing layer is preferably a layer that satisfies characteristic Y1 in that it has better antireflection properties for external light
  • the light-emitting element is a UV-LED
  • the light absorption layer is preferably a layer that satisfies characteristic Y2 in that it has better antireflection properties for external light and better suppressing properties for stray light.
  • the optical density (OD) of the light absorption 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.
  • the upper limit is not particularly limited, and is preferably 6.0 or less, for example.
  • the optical density of the light absorption layer can be measured with a Macbeth densitometer (manufactured by Macbeth, TD-904, using a visual filter) or the like.
  • the optical density (OD) of the light absorption 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.
  • the upper limit is not particularly limited, and is preferably 6.0 or less, for example.
  • the optical density of the light absorption layer at a wavelength of 385 nm can be measured using an ultraviolet spectrophotometer U-3310 (manufactured by Hitachi, Ltd.) or the like.
  • the positive photosensitive layer will be described in detail below.
  • the photosensitive layer include a photosensitive layer containing at least a polymer and a photoacid generator.
  • the above-mentioned polymer is a polymer containing a repeating unit having a group whose hydrophilicity is increased by the action of an acid (for example, an acid-decomposable group in which a polar group is protected by a leaving group that is eliminated by the action of an acid). It is preferable to have one.
  • the photosensitive layer a known positive type photosensitive layer can be used. Note that the photosensitive layer may be a photosensitive light reflection layer or a photosensitive light absorption layer.
  • the photosensitive layer When the photosensitive layer is a photosensitive light-reflecting layer, the photosensitive layer contains a reflection modifier, and when the photosensitive layer is a photosensitive light-absorbing layer, the photosensitive layer contains a light-absorbing substance.
  • the types of the reflectivity modifier and light-absorbing substance, and the respective contents of the reflectivity modifier and light-absorbing substance relative to the total mass of the photosensitive layer are as follows: The types of the photosensitive substances and the respective contents of the reflection modifier and the light-absorbing substance relative to the total mass of the photosensitive layer are the same, and the preferred ranges are also the same.
  • the thickness of the photosensitive layer is, for example, preferably 1 ⁇ m or more, more preferably 2 ⁇ m or more.
  • the upper limit is not particularly limited, and is preferably, for example, 100 ⁇ m or less, more preferably 50 ⁇ m or less.
  • Preferred embodiments of the photosensitive light-reflecting layer and the photosensitive light-absorbing layer Preferred embodiments of the photosensitive light-reflecting layer and the photosensitive light-absorbing layer will be described below.
  • the thickness of the photosensitive light reflective layer is preferably 3 ⁇ m or more, more preferably 5 ⁇ m or more, even more preferably 10 ⁇ m or more, particularly preferably 16 ⁇ m or more.
  • the upper limit is not particularly limited, and is preferably, for example, 100 ⁇ m or less, more preferably 50 ⁇ m or less.
  • the photosensitive light-reflecting layer is preferably a layer that satisfies at least one of the above characteristics X1, X2, and X3.
  • 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 characteristic X3.
  • the thickness of the photosensitive light absorption layer is preferably 1 ⁇ m or more, more preferably 2 ⁇ m or more.
  • the upper limit is not particularly limited, and is preferably, for example, 10 ⁇ m or less, more preferably 5 ⁇ m or less.
  • the photosensitive light-absorbing layer preferably satisfies the above-mentioned characteristics Y1 and/or characteristics Y2.
  • the photosensitive light-absorbing layer is preferably a layer that satisfies characteristic Y1 in that it has better antireflection properties for external light
  • the photosensitive light-absorbing layer is preferably a layer that satisfies characteristic Y2 in that it has better antireflection properties for external light and better suppressing properties for stray light.
  • the transfer film may have a protective film.
  • a resin film having heat resistance and solvent resistance can be used, and examples thereof include polyolefin films such as polypropylene films and polyethylene films, polyester films such as polyethylene terephthalate films, polycarbonate films, and polystyrene films. It will be done.
  • a resin film made of the same material as the above-mentioned temporary support may be used as the protective film.
  • the protective film is preferably a polyolefin film, more preferably a polypropylene film or a polyethylene film, and even more preferably a polyethylene film.
  • the thickness of the protective film is preferably 1 to 100 ⁇ m, more preferably 5 to 50 ⁇ m, even more preferably 5 to 40 ⁇ m, and particularly preferably 15 to 30 ⁇ m.
  • the thickness of the protective film can be calculated as the average value of five arbitrary points measured by cross-sectional observation using a SEM (Scanning Electron Microscope).
  • the thickness of the protective film is preferably 1 ⁇ m or more in terms of excellent mechanical strength, and preferably 100 ⁇ m or less in terms of being relatively inexpensive.
  • the number of fish eyes with a diameter of 80 ⁇ m or more contained in the protective film is 5 pieces/m 2 or less.
  • “Fisheye” refers to foreign matter, undissolved matter, oxidized deterioration products, etc. of the material when manufacturing the film by methods such as heat-melting, kneading, extrusion, biaxial stretching, and casting. It was captured in the film.
  • the number of particles with a diameter of 3 ⁇ m or more contained in the protective film is preferably 30 particles/mm 2 or less, more preferably 10 particles/mm 2 or less, and even more preferably 5 particles/mm 2 or less. This makes it possible to suppress defects caused by the transfer of unevenness caused by particles contained in the protective film onto the photosensitive layer.
  • 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 ⁇ m or more, more preferably 0.02 ⁇ m or more, and 0.03 ⁇ m.
  • the above is more preferable.
  • it is preferably less than 0.50 ⁇ m, more preferably 0.40 ⁇ m or less, and even more preferably 0.30 ⁇ m or less.
  • the surface roughness Ra of the surface of the protective film in contact with the photosensitive layer is preferably 0.01 ⁇ m or more, more preferably 0.02 ⁇ m or more, and even more preferably 0.03 ⁇ m or more.
  • the second embodiment of the method for manufacturing a laminate of the present invention includes the following steps (2-1) to (2-4).
  • Step (2-1) (bonding step): The surface of the light emitting element side of the light emitting element-equipped substrate, which includes a substrate and a plurality of light emitting elements arranged on the substrate, the temporary support and the photosensitive layer. A step of laminating the light emitting element-equipped substrate and the transfer film so that the surface of the transfer film opposite to the temporary support faces each other and the light emitting element is covered with the photosensitive layer.
  • Step (2-2) exposure step: A step of exposing the photosensitive layer in a pattern.
  • Step (2-3) developer step: Developing the exposed photosensitive layer to form the light emitting element.
  • the embodiment includes 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: Step of peeling off the temporary support.
  • 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 respectively steps (1-1) to (1-3) in the first embodiment of the present invention. , (1-A).
  • step (2-B) or “ (also referred to as "post-exposure step")
  • 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. It is.
  • Step (2-4) Light reflective film formation step>
  • a light reflecting film is formed on the side wall of the opening in the resin pattern formed on the substrate with a light emitting element.
  • a resin pattern that functions as a partition layer that separates light-emitting elements from each other when a light-reflecting film is disposed on the side wall of the opening, the light from the light-emitting elements is reflected by the light-reflecting film, resulting in better brightness.
  • the laminate 60 includes a substrate 10 with a light emitting element, a resin pattern 42, and a light reflecting film 62 disposed on a side wall of an opening 43 in the resin pattern 42.
  • the light-reflecting film contains 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 preferable because of its high reflectivity. , tin, nickel, aluminum, or cobalt are more preferable, and gold, silver, or aluminum is even more preferable in that they exhibit higher reflectivity in the visible light region, and silver is particularly preferable.
  • step (2-4) sputtering method, vapor deposition method, plating method, printing of ink containing metal particles (screen printing, inkjet, etc.), etc. can be applied.
  • it may be formed by patterning using a known method such as wet etching or dry etching so that only necessary portions are left.
  • 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.
  • the upper limit is not particularly limited, and for example, is preferably 100 ⁇ m or less, more preferably 50 ⁇ m or less, even more preferably 10 ⁇ m or less, particularly preferably 1 ⁇ m or less, and most preferably 800 nm or less.
  • the light reflecting film is preferably a film that satisfies at least one of the following characteristics Z1 and Z2.
  • the light-reflecting film preferably satisfies characteristic Z1
  • the light-reflecting film preferably satisfies characteristic Z2.
  • characteristic Z1 characteristic Z1
  • UV-LED characteristic Z2
  • 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 at 25° C. for a light reflecting film with a thickness of 30 ⁇ m.
  • spectrophotometer V-570 manufactured by JASCO Corporation can be used.
  • 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 reflection film at a wavelength of 385 nm is a value measured using a spectrophotometer at 25° C. for a light reflection film with a thickness of 30 ⁇ m.
  • spectrophotometer V-570 manufactured by JASCO Corporation can be used.
  • the various transfer films shown as the transfer film that can be used in the first embodiment of the present invention can be used.
  • An example of a preferred embodiment of the transfer film that can be used in the second embodiment of the present invention will be shown below.
  • the light-reflecting layer precursor layer, the light-absorbing layer precursor layer, the protective film, and the temporary support are referred to as the light-reflecting layer precursor layer, the light-absorbing layer in the transfer film that can be used in the first embodiment of the present invention. It has the same meaning as a precursor layer, a protective film, and a temporary support, and the preferred embodiments are also the same.
  • the other photosensitive layer means a photosensitive layer that does not fall under either the light-reflecting layer precursor layer or the light-absorbing layer precursor layer.
  • Temporary support/light absorption layer precursor layer/protective film ⁇ (N5) Temporary support/light absorption layer precursor layer/other photosensitive layer/protective film
  • the transfer film (N5) is used in the second embodiment of the present invention, on the side wall of the opening of the resin pattern, at least a position corresponding to the resin layer originating from another photosensitive layer has light reflection. Just place the membrane.
  • composition for forming light-absorbing layer precursor layer [Preparation of composition for forming light-absorbing layer precursor layer]
  • Light absorption layer precursor layer forming compositions (A-1 to A-2) were prepared based on the components and blending amounts shown in Table 1. Note that the unit of the amount of each component shown in Table 1 is parts by mass.
  • Compound (1) A compound having the following structure.
  • compound (1) corresponds to a compound that changes from transparent to black by heat treatment.
  • a composition for forming a light reflective layer precursor layer (B-1) and a photosensitive composition (B-2) were prepared based on the components and blending amounts shown in Table 2. Note that the unit of the amount of each component shown in Table 2 is parts by mass.
  • P-2 solution solid content 36.2% by mass solution of polymer P-2
  • a P-2 solution (a solution of polymer P-2 with a solid content of 36.2% by mass) was prepared by the polymerization step and addition step shown below. 113.5 g of propylene glycol monomethyl ether was charged into a flask and heated to 90° C. under a nitrogen stream.
  • the weight average molecular weight in terms of standard polystyrene in GPC was 18,000, the number average molecular weight was 7,800, the degree of dispersion was 2.3, and the acid value of the polymer was 124 mgKOH/g.
  • the amount of residual monomer measured using gas chromatography was less than 0.1% by mass based on the solid content of the polymer in all monomers.
  • the structure of polymer P-2 is shown below.
  • Polymer P-2 The composition of the structural units in the following structural formula represents the molar ratio. Note that the polymer P-2 corresponds to an alkali-soluble resin.
  • Example 1 [Preparation of transfer film] A polyethylene terephthalate film (Lumirror 16KS40, manufactured by Toray Industries, Inc., thickness: 16 ⁇ m) was prepared as a temporary support.
  • the composition A-1 for forming a light-absorbing layer precursor layer is applied onto the temporary support so that the thickness after drying is 3 ⁇ m, and the light-absorbing layer precursor layer is formed by drying at 100° C. for 1 minute. was formed.
  • the composition B-1 for forming a light-reflecting layer precursor layer is applied so that the thickness after drying is 30 ⁇ m, and the light-reflecting layer precursor layer is dried at 100° C. for 3 minutes. formed a layer.
  • a polyethylene terephthalate film (Lumirror 16KS40, manufactured by Toray Industries, Inc., thickness: 16 ⁇ m) was pressure-bonded onto the light reflective layer precursor layer.
  • a micro LED display element was produced using the transfer film 1 according to the following procedure. Specifically, after the LED chips were bonded to the bonding member on the array substrate, a resin pattern (partition layer) was formed using the transfer film 1. The specific steps are shown below.
  • a substrate with a precursor layer was prepared by laminating a light-reflecting layer precursor layer, a light-absorbing layer precursor layer, and a temporary support in this order. Heating temperature of substrate with chip: 40°C Rubber roller temperature: 110°C Linear pressure: 3N/cm Conveying speed: 2m/min
  • the distance between the surface of the exposure mask (mask having a pattern for forming openings) and the surface of the temporary support was set to 125 ⁇ m.
  • a proximity type exposure machine (Hitachi High-Tech Electronics Engineering Co., Ltd.) equipped with an ultra-high pressure mercury lamp, i-rays were applied at 100 mJ/cm to the light-reflecting layer precursor layer and the light-absorbing layer precursor layer through a temporary support. It was irradiated in a pattern at an exposure dose of 2 .
  • the exposure mask is patterned and positioned so that an opening is formed in the part where the LED chip is mounted so that the taper angle of the partition layer (see taper angle ⁇ in FIG. 3) is as shown in Table 3. adjusted.
  • 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% by mass aqueous solution of sodium carbonate at a temperature of 32°C.
  • ultrapure water was sprayed from an ultra-high pressure cleaning nozzle to the laminate obtained after the development treatment to remove the residue, and then air was further sprayed to remove moisture.
  • the pattern in the obtained laminate was exposed to light using a post-exposure machine (manufactured by Ushio Inc.) equipped with a high-pressure mercury lamp at an exposure dose of 1000 mJ/cm 2 (i-line) (post-exposure).
  • a post-bake treatment was performed at 210° C. for 5 minutes.
  • a resin pattern (a partition layer in which a light reflection layer and a light absorption layer were laminated in this order) having openings at the positions of the LED chips was formed on the array substrate.
  • Example 2 [Preparation of transfer film of Example] A polyethylene terephthalate film (Lumirror 16KS40, manufactured by Toray Industries, Inc., thickness: 16 ⁇ m) was prepared as a temporary support.
  • the composition A-1 for forming a light-absorbing layer precursor layer is applied onto the temporary support so that the thickness after drying is 3 ⁇ m, and the light-absorbing layer precursor layer is formed by drying at 100° C. for 1 minute. was formed.
  • Composition B-2 for forming a photosensitive layer is applied onto the light-absorbing layer precursor layer so that the thickness after drying is 30 ⁇ m, and dried at 100°C for 3 minutes to form a photosensitive layer (other photosensitive layers). layer) was formed.
  • a polyethylene terephthalate film (Lumirror 16KS40, manufactured by Toray Industries, Inc., thickness: 16 ⁇ m) was pressure-bonded onto the photosensitive layer.
  • Example 2 [Production of micro LED display element of Example 2] First, an LED chip was mounted on an array substrate in the same manner as in Example 1 [[Mounting of LED chip]]. Next, the LED was formed using the same procedure as [[Formation of resin pattern (partition layer)]] in Example 1 described above, except that the process conditions were adjusted appropriately so that the taper angle of the partition layer was as shown in Table 3. A resin pattern (a partition layer in which a resin layer and a light absorption layer were laminated in this order) having an opening was formed on the array substrate on which the chips were mounted. After the barrier ribs were fabricated, a 300 nm thick silver layer was deposited in the openings of the barrier ribs by a known vapor deposition method. At this time, the light reflecting layer was formed only on the side surface of the opening of the barrier layer by masking the chip and the surface of the barrier layer on the side opposite to the substrate. In this way, the micro LED display element of Example 2 was produced.
  • Example 3 A-2 was used as the light-absorbing layer precursor layer composition and coated to a thickness of 30 ⁇ m after drying, and the light-reflecting layer precursor layer was not laminated, but in the same manner as in Example 1. Transfer film 3 was obtained.
  • Example 3 [Production of micro LED display element of Example 3] First, an LED chip was mounted on an array substrate in the same manner as in Example 1 [[Mounting of LED chip]]. Next, the chip was fabricated using the same procedure as [[Formation of resin pattern (barrier layer)]] in Example 1 above, except that the process conditions were adjusted appropriately so that the taper angle of the barrier layer was as shown in Table 3. A resin pattern (light absorption layer) having openings was formed on the attached array substrate.
  • micro LED display element of Comparative Example 1 A micro LED display element of Comparative Example 1 was produced in the same manner as in Example 1 except that the partition layer was not formed.
  • the size of the LED chip was 20 ⁇ m square and the thickness was 8 ⁇ m. Further, the pitch at which the LED chips were arranged was 400 ⁇ m, the through hole size was 30 ⁇ m square, and the width of the partition between the LED chips was 370 ⁇ m.
  • Table 3 shows the evaluation results for each example.
  • micro LED display element of Comparative Example 2 A barrier rib structure was previously formed on the array substrate before the LED chips were connected using the transfer film 1, and then the LED chips were mounted on the substrate to produce a micro LED display element. At this time, since the array substrate has a partition wall structure with a thickness of 33 ⁇ m, it is difficult to mount multiple micro LED chips on the array substrate at once, as in Example 1 [[Mounting LED chips]]. Therefore, a micro LED display element was manufactured by repeatedly bonding the LED chips to the connecting portion and peeling them from the sapphire substrate for peeling one by one. As a result, in Comparative Example 2, it took 100 times more time to manufacture the micro LED display element than in any of Examples 1 to 3.
  • 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 Laminated body 42 Resin pattern 44 Opening 50
  • Protective film 62 Light reflecting film ⁇ Taper angle

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