Method for manufacturing laminate

Abstract

The present invention addresses the problem of providing a method for manufacturing a laminate capable of efficiently manufacturing a laminate including a plurality of light-emitting elements in which light leakage from adjacent light-emitting elements is suppressed. A method for producing a laminate according to the present invention comprises: a step for producing a The light-emitting-element-equipped substrate includes a substrate and a plurality of light-emitting elements disposed on the substrate. The light-emitting-element-side surface of the light-emitting-element-equipped substrate faces the surface of a transfer film, which includes a temporary support and a photosensitive layer, on the opposite side of the temporary support. The light-emitting elements are covered by the photosensitive layer. A step 1 in which the substrate with the light-emitting element is bonded to the transfer film; a step 2 in which the photosensitive layer is subjected to pattern exposure; and a step (3) for developing the exposed photosensitive layer and forming a resin pattern having an opening at a position corresponding to the light-emitting element, and a step for peeling the temporary support between the step (1) and the step (2) or between the step (2) and the step (3).

Description

Technical Field

[0001] The present invention relates to a method for manufacturing a laminated body. Background Art

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

[0003] Previous technical literature

[0004] Patent Literature

[0005] Patent Document 1: Japanese Patent Application Publication No. 2021-163945 Summary of the invention

[0006] Technical issues to be solved by the invention

[0007] The present inventors, with reference to the micro-LED display of patent document 1, produced a laminated body in which a plurality of light-emitting elements (e.g., micro-LED chips) are arranged on a substrate and studied its performance. As a result, it is clear that there is a case where the display performance is reduced due to light leakage from adjacent light-emitting elements. For example, in the case where pixels are composed of light-emitting elements having luminous colors of red (R), green (G), and blue (B), there is a case where the desired display cannot be performed due to light mixing caused by light leakage from adjacent light-emitting elements.

[0008] Based on the above insights, the inventors have found that there is room for research on a method for manufacturing a stacked body including multiple light-emitting elements in which light leakage from adjacent light-emitting elements is suppressed. In addition, in the manufacturing method of the stacked body, it is usually expected that the manufacturing time is short (in other words, it can be manufactured efficiently).

[0009] Therefore, an object of the present invention is to provide a method for producing a stacked body capable of efficiently producing a stacked body including a plurality of light emitting elements in which light leakage from adjacent light emitting elements is suppressed.

[0010] Means for solving technical problems

[0011] The present inventors have found that the above-mentioned problems can be solved by the following structure.

[0012] [1] A method for producing a laminate, comprising:

[0013] Step 1 of laminating the substrate with light-emitting elements to the transfer film in such a manner that the surface of the substrate with light-emitting elements on the light-emitting element side, which includes a substrate and a plurality of light-emitting elements arranged on the substrate, faces the surface of the transfer film on the side opposite to the temporary support, which includes a temporary support and a photosensitive layer, and the light-emitting elements are covered by the photosensitive layer;

[0014] Step 2 of performing pattern exposure on the photosensitive layer; and

[0015] Step 3 of developing the exposed photosensitive layer to form a resin pattern having openings at positions corresponding to the light emitting elements,

[0016] There is 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.

[0017] [2] The method for producing a laminate according to [1], wherein:

[0018] The film thickness of the photosensitive layer in the transfer film is larger than the height of the light emitting element.

[0019] (3) The method for producing a laminate according to [1] or [2], wherein:

[0020] The photosensitive layer in the transfer film includes an alkali-soluble resin, a polymerizable compound, and a photopolymerization initiator.

[0021] [4] The method for producing a laminate according to [1] or [2], wherein:

[0022] The photosensitive layer in the transfer film includes a polymer and a photoacid generator.

[0023] [5] The method for producing a laminate according to any one of [1] to [4], wherein:

[0024] In the photosensitive layer of the transfer film, a content of water is 5.0% by mass or less based on the total mass of the photosensitive layer.

[0025] [6] The method for producing a laminate according to any one of [1] to [5], wherein:

[0026] In the photosensitive layer of the transfer film, a content of the organic solvent is 5.0% by mass or less based on the total mass of the photosensitive layer.

[0027] [7] The method for producing a laminate according to any one of [1] to [6], wherein:

[0028] In the photosensitive layer of the transfer film, a content of chloride ions is 100 ppm by mass or less based on the total mass of the photosensitive layer.

[0029] [8] The method for producing a laminate according to any one of [1] to [7], wherein:

[0030] The photosensitive layer in the transfer film contains a white pigment.

[0031] [9] The method for producing a laminate according to any one of [1] to [7], wherein:

[0032] The photosensitive layer in the transfer film includes a photosensitive light absorbing layer precursor layer and a photosensitive light reflecting layer precursor layer in this order from the temporary support side.

[0033]

[10] The method for producing a laminate according to any one of [1] to [7], wherein:

[0034] The photosensitive layer in the transfer film is a photosensitive light absorbing layer precursor layer.

[0035]

[11] The method for producing a laminate according to any one of [1] to [7], wherein:

[0036] After the step 3, a step 4 of disposing a light reflecting film on the side wall of the opening is further included.

[0037] Effects of the Invention

[0038] According to the present invention, it is possible to provide a method for manufacturing a stacked body capable of efficiently manufacturing a stacked body including a plurality of light emitting elements in which light leakage from adjacent light emitting elements is suppressed. BRIEF DESCRIPTION OF THE DRAWINGS

[0039] Figure 1 This is a schematic diagram for explaining the step (1-1).

[0040] Figure 2 This is a schematic diagram for explaining the step (1-2).

[0041] Figure 3 This is a schematic diagram for explaining the step (1-3).

[0042] Figure 4 It is a schematic diagram for explaining the structure of the transfer film.

[0043] Figure 5 It is a schematic diagram for explaining the structure of the transfer film.

[0044] Figure 6 This is a schematic diagram for explaining the step (2-4). DETAILED DESCRIPTION

[0045] Hereinafter, the present invention will be described in detail.

[0046] In the present specification, a numerical range expressed using "to" means a range including the numerical values ​​described before and after "to" as the lower limit and the upper limit.

[0047] In this specification, in the numerical range recorded in stages, the upper limit or lower limit recorded in a certain numerical range can be replaced by the upper limit or lower limit of the numerical range recorded in other stages. In addition, in the numerical range recorded in this specification, the upper limit or lower limit recorded in a certain numerical range can be replaced by the value shown in the embodiment.

[0048] In the present specification, the term "process" includes not only an independent process but also a process that cannot be clearly distinguished from other processes as long as the intended purpose of the process is achieved.

[0049] In this specification, unless otherwise specified, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are values ​​converted to polystyrene using a standard substance, measured using a gel permeation chromatography (GPC) analyzer using TSKgel GMHxL, TSKgel G4000HxL or TSKgel G2000HxL (all trade names manufactured by TOSOH CORPORATION) as a column, THF (tetrahydrofuran) as an eluent, a differential refractometer as a detector, and polystyrene as a standard substance.

[0050] In addition, in this specification, unless otherwise specified, the molecular weight of a compound having a molecular weight distribution is a weight average molecular weight (Mw).

[0051] In this specification, unless otherwise specified, the content of a metal element is a value measured using an inductively coupled plasma (ICP: Inductively Coupled Plasma) spectrometer.

[0052] In this specification, unless otherwise specified, hue is a value measured using a colorimeter (CR-221, manufactured by Minolta Co., Ltd.).

[0053] In this specification, “(meth)acrylic acid” is a concept including both acrylic acid and methacrylic acid, “(meth)acryloyl” is a concept including both acryloyl and methacryloyl, and “(meth)acrylate” is a concept including both acrylate and methacrylate.

[0054] In this specification, "alkali-soluble" means that the solubility is 0.1 g or more in 100 g of a 1 mass % sodium carbonate aqueous solution at a liquid temperature of 22° C. Therefore, for example, an alkali-soluble resin refers to a resin that satisfies the above solubility condition.

[0055] In this specification, "water-soluble" means that the solubility in 100 g of water with a pH of 7.0 at a liquid temperature of 22° C. is 0.1 g or more. Therefore, for example, a water-soluble resin refers to a resin that satisfies the above solubility condition.

[0056] In this specification, the "solid content" of a composition refers to the components that form a composition layer formed using the composition, and when the composition contains a solvent (organic solvent, water, etc.), it refers to all components other than the solvent. In addition, if it is a component that forms a composition layer, a liquid component is also considered a solid component.

[0057] In this specification, "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, a "transparent layer" means a layer with an average transmittance of visible light with a wavelength of 400 to 700 nm of 80% or more. The average transmittance is measured for linear transmitted light per 1 nm.

[0058] 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.

[0059] In addition, in this specification, unless otherwise specified, the thickness of each layer (for example, the photosensitive layer, the light reflecting layer precursor layer, and the light absorbing layer precursor layer) is a value obtained by observing a cross section cut by a microtome using a SEM (scanning electron microscope) or a TEM (transmission electron microscope) and measuring the thickness at 10 points. The thickness of 1 μm or more is measured using the SEM, and the thickness of less than 1 μm is measured using the TEM.

[0060] In addition, in this specification, unless otherwise specified, the refractive index refers to the refractive index at a wavelength of 550 nm measured at 25° C. using a measuring device in accordance with ellipsometry.

[0061] [Method for producing laminated body]

[0062] The method for producing a laminated body of the present invention comprises: step 1 of laminating the substrate with light-emitting elements to the transfer film in such a manner that the surface of the substrate with light-emitting elements on the light-emitting element side of the substrate including the substrate and a plurality of light-emitting elements arranged on the substrate faces the surface of the transfer film including the temporary support and the photosensitive layer on the side opposite to the temporary support and the light-emitting elements are covered by the photosensitive layer;

[0063] Step 2 of performing pattern exposure on the photosensitive layer; and

[0064] Step 3 of developing the exposed photosensitive layer to form a resin pattern having openings at positions corresponding to the light emitting elements,

[0065] There is 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.

[0066] According to the manufacturing method of the laminated body of the present invention having the above structure, by using the photolithography of the transfer film, a laminated body having a substrate with a light-emitting element on which a plurality of light-emitting elements are arranged and a partition layer arranged around each light-emitting element on the substrate with the light-emitting element can be efficiently manufactured. The laminated body obtained by the above manufacturing method has a partition layer around each light-emitting element, so that the light leakage of the adjacent light-emitting elements is suppressed.

[0067] Furthermore, compared with a manufacturing method in which, for example, a partition layer is preliminarily formed at a predetermined position on a substrate where a light-emitting element is to be arranged (i.e., a resin pattern having an opening at a predetermined position where the light-emitting element is to be arranged) by photolithography using a transfer film, and then the light-emitting element is arranged at the specified position, the manufacturing method of the stacked body of the present invention can significantly shorten the manufacturing time.

[0068] Examples of uses of the laminate obtained by the method for producing a laminate of the present invention include micro LED display elements.

[0069] In addition, in the laminate obtained by the method for producing a laminate of the present invention, the ability to further suppress light leakage from adjacent light-emitting elements and / or the efficiency of the method for producing the laminate of the present invention is sometimes referred to as "the effect of the present invention is more excellent".

[0070] Hereinafter, a method for producing a laminated body of the present invention will be described with reference to the drawings.

[0071] [First embodiment]

[0072] A first embodiment of the method for producing a laminate of the present invention (hereinafter, also simply referred to as "the first embodiment of the present invention") comprises the following steps (1-1) to (1-3).

[0073] Step (1-1) (laminating step): a step of laminating the substrate with light-emitting elements and the transfer film in such a manner that the surface of the substrate with light-emitting elements on the light-emitting element side, which includes a substrate and a plurality of light-emitting elements arranged on the substrate, faces the surface of the transfer film on the side opposite to the temporary support body, which includes a temporary support body and a photosensitive layer, and the light-emitting elements are covered by the photosensitive layer.

[0074] Step (1-2) (exposure step): a step of pattern-exposing the photosensitive layer

[0075] Step (1-3) (Development Step): A step of developing the exposed photosensitive layer to form a resin pattern having openings at positions corresponding to the light-emitting elements.

[0076] Furthermore, the first embodiment of the present invention includes the following step (1-A) between the step (1-1) and the step (1-2) or between the step (1-2) and the step (1-3).

[0077] Step (1-A) (temporary support peeling step): a step of peeling off the temporary support.

[0078] 《Process (1-1), Laminating process》

[0079] Step (1-1) is a step of bonding the substrate with light-emitting elements to the transfer film in such a manner that the surface on the light-emitting element side of the substrate with light-emitting elements, which includes a substrate and a plurality of light-emitting elements arranged on the substrate, is opposed to the surface on the side opposite to the temporary support of the transfer film including a temporary support and a photosensitive layer, and the light-emitting elements are covered by the photosensitive layer.

[0080] refer to Figure 1 , the specific steps of step (1-1) are described.

[0081] In step (1-1), the substrate 10 with the light-emitting element and the transfer film 20 are bonded together in such a manner that the surface of the substrate 10 with the light-emitting element on the side opposite to the substrate 12 (i.e., the surface on the side having the light-emitting element 14) and the surface of the transfer film 20 on the side opposite to the temporary support 22 (i.e., the surface on the photosensitive layer 24 side) are opposed to each other. Figure 1 The state after the substrate 10 with a light-emitting element and the transfer film 20 are bonded together is shown.

[0082] Furthermore, from the viewpoint that the light-emitting element is easily covered by the photosensitive layer during the lamination process and the effect of the present invention is more easily excellent, the thickness of the photosensitive layer in the transfer film is preferably greater than the height of the light-emitting element. Here, the height of the light-emitting element refers to the thickness of the light-emitting element in the normal direction of the reference plane when the substrate surface of the substrate with the light-emitting element at the part where the light-emitting element is not arranged is used as the reference plane. That is, Figure 1 In the case of the stacked body shown, the height of the light emitting element 14 refers to the thickness T1 of the light emitting element 14 in the normal direction of the reference surface 12A when the substrate surface 12A of the portion where the light emitting element 14 is not arranged in the substrate 10 with the light emitting element is used as the reference surface.

[0083] When the transfer film has a protective film described below, it is preferred to perform the laminating step after peeling off the protective film.

[0084] During the bonding, it is preferred that the surface of the transfer film on the side opposite to the temporary support body side and the surface of the substrate with light-emitting elements on the side of the light-emitting element be brought into contact and pressure-bonded.

[0085] As the pressure bonding method, for example, known transfer methods and lamination methods can be cited, and preferably a method in which the surface of the transfer film on the side opposite to the temporary support body is overlapped with the surface on the light-emitting element side of the substrate with the light-emitting element and pressurized and heated by a roller or the like.

[0086] As a lamination method, the method using a well-known laminator, such as a vacuum laminator and an automatic cutting laminator, is mentioned, for example.

[0087] The lamination temperature is preferably 70 to 130°C.

[0088] <Substrate with light-emitting element>

[0089] The substrate with light emitting elements includes a substrate and a plurality of light emitting elements arranged on the substrate.

[0090] Examples of the substrate include a resin substrate, a glass substrate, a ceramic substrate, and a semiconductor substrate.

[0091] Examples of the material of the resin substrate include polyethylene terephthalate resins, polynaphthalene terephthalate resins, cycloolefin resins, polyimide resins, polycarbonate resins, polyacrylate resins, polyethersulfone resins, silicone resins, and epoxy resins.

[0092] The thickness of the resin substrate is preferably 5 to 200 μm, more preferably 10 to 100 μm.

[0093] As the substrate, a transparent substrate is preferably used in consideration of the exposure step (step (1-2)).

[0094] As the transparent substrate, for example, a resin substrate (for example, a resin film) and a glass substrate can be cited. The resin substrate is preferably a resin substrate that transmits visible light. As a preferred component of the resin substrate that transmits visible light, for example, polyamide resins, polyethylene terephthalate resins, polyethylene naphthalate resins, cycloolefin resins, polyimide resins and polycarbonate resins can be cited.

[0095] Among them, the transparent substrate is preferably a polyamide film, a polyethylene terephthalate film, a cycloolefin polymer, a polyethylene naphthalate film, a polyimide film or a polycarbonate film, and more preferably a polyethylene terephthalate film.

[0096] The thickness of the transparent substrate is not limited, but is preferably 10 to 200 μm, more preferably 20 to 120 μm, and even more preferably 20 to 100 μm.

[0097] The substrate is preferably a substrate having at least one of an electrode and a lead wiring.

[0098] The electrode is preferably composed of a metal oxide film such as ITO (indium tin oxide) and IZO (indium zinc oxide), and a metal fine wire such as a metal mesh and a metal nanowire.

[0099] Examples of the metal thin wires include metal thin wires such as silver and copper, and silver conductive materials such as silver mesh and silver nanowires are preferred.

[0100] As a material of the lead wiring, metal is preferable.

[0101] Examples of the metal include gold, silver, copper, molybdenum, aluminum, titanium, chromium, zinc, and manganese, and alloys of these metals in combination. Copper, molybdenum, aluminum, or titanium is preferred, and copper is more preferred.

[0102] As the light-emitting element, a micro LED chip can be mentioned.

[0103] In a substrate with light-emitting elements, there is no particular restriction on the configuration of the plurality of light-emitting elements. As an example of the configuration of the plurality of light-emitting elements, there can be cited a method of providing a plurality of units on the substrate (for example, equivalent to 1 pixel or 1 pixel), and configuring N light-emitting elements having red (R), green (G) and blue (B) luminous colors in the unit (for example, 1, 2, 3 each). There is no particular restriction on the shape of the unit, and for example, a grid shape and the like can be cited. Furthermore, there is no particular restriction on the configuration method of the light-emitting elements in the unit (for example, a linear array). In addition, R, G, and B are cited as an example of the luminous color of the light-emitting element, but the light-emitting element is not particularly limited as long as it emits light, and its luminous color can be appropriately selected.

[0104] Furthermore, a light-emitting element generally has a terminal for connection to an external electrode.

[0105] When the light-emitting element is a micro LED chip, the type of LED may be an LED having a peak wavelength in the visible light region (hereinafter also referred to as a “visible light LED”) or an LED having a peak wavelength in the ultraviolet light region (hereinafter also referred to as a “UV-LED”).

[0106] <Transfer film>

[0107] The transfer film that can be used in the step (1-1) will be described in the later stage.

[0108] 《Process (1-2), exposure process》

[0109] The exposure step is a step of pattern-exposing the photosensitive layer.

[0110] “Pattern exposure” is a method of exposing in a pattern, and means exposure in which exposed areas and non-exposed areas exist.

[0111] The positional relationship between the exposure portion (exposure region) and the non-exposure portion (non-exposure region) in pattern exposure can be adjusted as appropriate.

[0112] The exposure direction may be from the photosensitive layer side or the side opposite to the photosensitive layer side (substrate side).

[0113] The exposure step is typically a step of performing pattern exposure via a photomask. In the exposure step, the photomask may or may not be in contact with the laminated body as the object to be exposed to light.

[0114] When the temporary support peeling step described later is performed between the lamination step and the exposure step, as the exposure step, it is preferred that the surface of the laminated body from which the temporary support has been peeled off, obtained in the temporary support peeling step, on the side opposite to the substrate side, is brought into contact with a photomask to perform pattern exposure. In other words, it is preferred that the surface (the surface of the photosensitive layer, etc.) of the laminated body from which the temporary support has been peeled off is brought into contact with a photomask to perform pattern exposure on the photosensitive layer.

[0115] In the case where the photosensitive layer is a negative photosensitive layer, a curing reaction of the components contained in the photosensitive layer can be generated in the exposed area (the area corresponding to the opening of the photomask) through an exposure process of performing pattern exposure. By performing a development process (process (1-3)) after the exposure, the non-exposed area of ​​the photosensitive layer is removed to form a pattern. In the exposure process, the exposure process can be performed using a photomask having a pattern in which the portion corresponding to the position where the light-emitting element is arranged is a non-opening portion and the portion corresponding to the position corresponding to the adjacent light-emitting element (in other words, the position where the partition layer is formed) is an opening portion, so that a resin pattern having a prescribed opening at the position corresponding to the light-emitting element can be formed after the development process (process (1-3)). Through the above-mentioned exposure process, the photosensitive layer can be exposed according to the pattern shape of the photomask. In addition, in Figure 2 The pattern exposure process when the photosensitive layer is a negative photosensitive layer is shown in FIG. Figure 2 In the laminated body, a curing reaction of the components contained in the photosensitive layer 24 can occur in the opening portion (exposure area) of the photomask 30. On the other hand, the photosensitive layer in the non-opening portion (non-exposure area) of the photomask 30 is removed by performing a development step (step (1-3)) after exposure.

[0116] On the other hand, when the photosensitive layer is a positive photosensitive layer, a structural change of a component contained in the photosensitive layer may occur in an exposed region (a region corresponding to the opening of the photomask), and a development step (step (1-3)) is performed after exposure to remove the exposed region of the photosensitive layer, thereby forming a pattern. That is, a structural change of a component contained in the photosensitive layer in the exposed region generates a dissolution contrast with a developer between the exposed region and the non-exposed region, and as a result, the exposed region of the photosensitive layer is removed by the development step (step (1-3)) after exposure to form a pattern.

[0117] In the exposure step, the exposure step can be carried out using a photomask having a pattern in which a portion corresponding to a position where a light-emitting element is arranged is an opening portion, and a portion corresponding to a position between adjacent light-emitting elements (in other words, a position where a partition layer is formed) is a non-opening portion, so that a resin pattern having a predetermined opening can be formed at a position corresponding to the light-emitting element after the development step (step (1-3)). Through the above-mentioned exposure step, the photosensitive layer can be exposed according to the pattern shape of the photomask.

[0118] The method for producing a laminated body of the present invention also preferably includes a photomask peeling step of peeling off the photomask used in the exposure step between the exposure step and the development treatment.

[0119] As the photomask peeling step, for example, a known peeling step can be mentioned.

[0120] As a light source for pattern exposure, for example, if it can irradiate light of a wavelength region that can cure the photosensitive layer (for example, 365nm and 405nm), it can be appropriately selected and used. Among them, the main wavelength of the exposure light for exposure is preferably 365nm. In addition, the main wavelength refers to the wavelength with the highest intensity.

[0121] Examples of the light source include various lasers, light emitting diodes (LEDs), ultrahigh pressure mercury lamps, high pressure mercury lamps, and metal halide lamps.

[0122] The exposure dose is preferably 5 to 200 mJ / cm 2 , more preferably 10 to 200 mJ / cm 2 .

[0123] 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, and these contents are incorporated into this specification.

[0124] Furthermore, it is also preferred that the cross section (cross section perpendicular to the substrate) of the resin pattern obtained through the development step (step (1-3)) is tapered. Specifically, the resin pattern preferably has an opening whose opening area increases from the substrate side to the opposite side.

[0125] When the photosensitive layer is a negative photosensitive layer, the cross-sectional shape of the resin pattern can be made tapered by, for example, introducing a light scattering plate into an exposure machine and irradiating exposure light from an oblique direction.

[0126] When the cross section of the resin pattern is tapered, the angle ("taper angle") formed between the side wall of the opening and the substrate surface of the substrate with the light-emitting element on which the light-emitting element is not arranged is equivalent to Figure 3 The angle θ in the embodiment is preferably less than 90°, more preferably 10 to 80°, further preferably 15 to 80°, particularly preferably 20 to 80°, and most preferably 40 to 60°.

[0127] <<Step (1-A), temporary support peeling step>>

[0128] The temporary support peeling step is performed between the laminating step and the exposure step or between the exposure step and the development step.

[0129] Among them, it is more preferable to include a peeling step between the laminating step and the exposure step.

[0130] The peeling step is a step of peeling the temporary support from the laminate of the transfer film and the substrate with a light-emitting element.

[0131] As a method for peeling the temporary support, for example, a known peeling method can be mentioned. Specifically, a cover film peeling mechanism described in paragraphs

[0161] to

[0162] of Japanese Patent Application Laid-Open No. 2010-072589 can be mentioned.

[0132] 《Process (1-3), Development process》

[0133] The development step is a step of developing the exposed photosensitive layer using a developer to form a resin pattern.

[0134] As the developer, an alkaline aqueous solution is preferred. Examples of alkaline compounds that may be contained in the alkaline aqueous solution include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, and choline (2-hydroxyethyltrimethylammonium hydroxide).

[0135] Examples of the method of development include spin immersion development, shower development, spin development, and immersion development.

[0136] Examples of the developer preferably used in this specification include the developer described in paragraph

[0194] of International Publication No. 2015 / 093271, and examples of the development method preferably used include the development method described in paragraph

[0195] of International Publication No. 2015 / 093271.

[0137] It is also preferable to perform a rinsing treatment after development and before transferring to the next step. Water or the like can be used for the rinsing treatment.

[0138] By going through the development process, a resin pattern can be formed on the substrate with the light-emitting element. The resin pattern is arranged at a position corresponding to the position between the adjacent light-emitting elements, and the position corresponding to the light-emitting element becomes an opening. That is, a partition layer can be formed around each light-emitting element to separate it from the adjacent light-emitting element and suppress its light leakage.

[0139] Figure 3 FIG. 4 is a schematic cross-sectional view of a 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. Specifically, the resin pattern 42 is arranged at a position corresponding to the position between adjacent light emitting elements 14, and the position corresponding to the light emitting element 14 becomes an opening 44. Figure 2 In the case of the laminated body of the negative photosensitive layer shown, the resin pattern 42 corresponds to the cured film of the negative photosensitive layer.

[0140] "Step (1-B) (Post-exposure step) and Step (1-C) (Post-baking step)"

[0141] The first embodiment of the present invention may also have a step of further exposing the resin pattern obtained by the development step (step (1-3)) (hereinafter also referred to as "step (1-B)" or "post-exposure step") and / or a heating step (hereinafter also referred to as "step (1-C)" or "post-baking step").

[0142] When the first embodiment of the present invention includes both the post-exposure step and the post-bake step, it is preferable to perform the post-bake step after performing the post-exposure step.

[0143] The exposure amount in the post-exposure step is preferably 100 to 5000 mJ / cm 2 , more preferably 200 to 3000 mJ / cm 2 .

[0144] The post-baking temperature in the post-baking step is preferably 80 to 250°C, more preferably 90 to 160°C.

[0145] The time of the post-baking in the post-baking step is preferably 1 to 180 minutes, more preferably 10 to 60 minutes.

[0146] 《Transfer film》

[0147] Hereinafter, the transfer film which can be used in the first embodiment of the present invention will be described.

[0148] The structure of the transfer film is not particularly limited as long as it has a temporary support and a photosensitive layer (a layer showing photosensitivity).

[0149] The photosensitive layer may be any of a positive photosensitive layer and a negative photosensitive layer, and is preferably a negative photosensitive layer.

[0150] The photosensitive layer may be a single layer or may be two or more layers.

[0151] The transfer film may include other composition layers (for example, a water-soluble resin layer, etc.) in addition to the photosensitive layer.

[0152] The transfer film may have a protective film.

[0153] Figure 4 Specific examples of the transfer film are shown below. Figure 4 The transfer film 20A shown in the figure has a temporary support 22, a photosensitive layer 24 and a protective film 50 in this order. The photosensitive layer 24 is a layer showing photosensitivity, and can be any one of a positive photosensitive layer and a negative photosensitive layer, preferably a negative photosensitive layer. When the photosensitive layer 24 is a negative photosensitive layer, the components contained in the layer undergo a curing reaction by exposure to form a resin layer (cured layer).

[0154] in addition, Figure 4 The transfer film 20A shown is in a form in which the protective film 50 is provided, but the protective film 50 may not be provided.

[0155] and, Figure 4 The transfer film 20A shown may have other composition layers in addition to the photosensitive layer 24 .

[0156] As the structure of the transfer film, in the laminate formed according to the first embodiment of the present invention, the following method is also preferred from the viewpoint of better brightness of the light-emitting element, easier suppression of external light reflection, and / or ability to absorb stray light that is unnecessarily generated when the light-emitting element is lit.

[0157] (N1) Temporary support / photosensitive light absorbing layer precursor layer / protective film

[0158] (N2) Temporary support / photosensitive light reflection layer precursor layer / protective film

[0159] (N3) Temporary support / photosensitive light absorbing layer precursor layer / photosensitive light reflecting layer precursor layer / protective film

[0160] In addition, although the transfer film shown in the above (N1) to (N3) is a form in which a protective film is arranged, it is not necessary to arrange a protective film.

[0161] The photosensitive light absorbing layer precursor layer (hereinafter referred to as “light absorbing layer precursor layer”) and the photosensitive light reflecting layer precursor layer (hereinafter referred to as “light reflecting layer precursor layer”) are layers showing photosensitivity, and are typically negative photosensitive layers.

[0162] exist Figure 4 In the transfer film 20A shown, the transfer films of the above-mentioned forms (N1) and (N2) correspond to the case where the photosensitive layer 24 is a photosensitive light absorbing layer precursor layer and the case where the photosensitive layer 24 is a photosensitive light reflecting layer precursor layer, respectively.

[0163] In addition, in the first embodiment of the present invention, when the transfer film of the form of (N1) is used, in the exposure portion in the pattern exposure of step (1-2), the light absorbing layer precursor layer undergoes a curing reaction, and a patterned light absorbing layer can be formed. That is, the resin pattern can function as a light absorbing partition layer. The laminate having such a resin pattern as a partition layer easily absorbs external light or stray light. As a result, when the light emitting element is not lit, the blackness performance is more excellent.

[0164] Furthermore, in the first embodiment of the present invention, when the transfer film of the form of (N2) is used, in the exposure portion in the pattern exposure of step (1-2), the light reflection layer precursor layer undergoes a curing reaction, and a patterned light reflection layer can be formed. That is, the resin pattern can function as a light-reflective partition layer. When the light-emitting element is turned on, the laminate having such a resin pattern as a partition layer is easy to be reflected by the partition wall from the light-emitting element, thereby improving the brightness.

[0165] exist Figure 4 In the transfer film 20A shown, the transfer film of the form (N3) described above corresponds to a case where the photosensitive layer 24 is a two-layer structure, one side is a photosensitive light absorbing layer precursor layer, and the other side is a photosensitive light reflecting layer precursor layer.

[0166] Figure 5 A schematic cross-sectional view of the transfer film of the above-mentioned form (N3) is shown. Figure 5 The transfer film 20A shown has a temporary support 22, a photosensitive layer 24, and a protective film 50 in this order. The photosensitive layer 24 has 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.

[0167] In addition, in the first embodiment of the present invention, when using the transfer film of the form of (N3) above, in the exposure portion in the pattern exposure of step (1-2), the light absorbing layer precursor layer and the light reflecting layer precursor layer undergo a curing reaction, and through the development step (step (1-3)), a resin pattern having a light reflecting layer and a light absorbing layer in sequence from the substrate side with the light emitting element can be formed. In a laminate having such a resin pattern as a partition layer, external light or stray light is easily absorbed by the light absorbing layer, and as a result, when the light emitting element is not lit, the blackness performance is better. In addition, due to the light reflecting layer, when the light emitting element is lit, the light from the light emitting element is easily reflected by the partition, thereby improving the brightness.

[0168] As described later, the light absorbing layer precursor layer corresponds to a negative photosensitive layer containing a light absorbing substance, and the light reflecting layer precursor layer corresponds to a negative photosensitive layer containing a reflectivity adjusting agent.

[0169] As the structure of the transfer film, in the laminate formed according to the first embodiment of the present invention, the following method is also preferred from the viewpoint of better brightness of the light-emitting element, easier suppression of external light reflection, and / or ability to absorb stray light that is unnecessarily generated when the light-emitting element is lit.

[0170] (P1) Temporary support / photosensitive light absorbing layer / protective film

[0171] (P2) Temporary support / photosensitive light reflecting layer / protective film

[0172] (P3) Temporary support / photosensitive light absorbing layer / photosensitive light reflecting layer / protective film

[0173] In addition, although the transfer films shown in (P1) to (P3) above are in a form in which a protective film is arranged, a protective film may not be arranged.

[0174] The photosensitive light absorbing layer and the photosensitive light reflecting layer are layers showing photosensitivity, and are typically positive photosensitive layers.

[0175] In addition, the light absorbing layer corresponds to a positive photosensitive layer containing a light absorbing substance, and the light reflecting layer corresponds to a positive photosensitive layer containing a reflectivity adjusting agent.

[0176] Hereinafter, each element constituting the transfer film will be described.

[0177] <Temporary Support Body>

[0178] The transfer film has a temporary support.

[0179] The temporary support is a member that supports the photosensitive layer and is finally removed by a peeling process.

[0180] The temporary support may be a single-layer structure or a multi-layer structure.

[0181] The temporary support is preferably a film, more preferably a resin film. As the temporary support, a film which is flexible and does not significantly deform, shrink or elongate under pressure or under pressure and heating is preferred.

[0182] Examples of the film include a polyethylene terephthalate film (for example, a biaxially stretched polyethylene terephthalate film), a polymethyl methacrylate film, a cellulose triacetate film, a polystyrene film, a polyimide film, and a polycarbonate film.

[0183] Among them, a polyethylene terephthalate film is preferable as the temporary support.

[0184] Furthermore, it is preferred that the film used as a temporary support body has no deformation such as wrinkles or scratches.

[0185] From the viewpoint of being able to carry out pattern exposure across the temporary support, the temporary support preferably has high transparency, and the transmittance at 365nm, 405nm and 436nm is preferably 60% or more, more preferably 70% or more, further preferably 80% or more, and especially preferably 90% or more. As the preferred value of transmittance, for example, 87%, 92% and 98% etc. can be cited.

[0186] From the viewpoint of pattern formation during pattern exposure via a temporary support and transparency of the temporary support, the temporary support preferably has a small haze value. Specifically, the temporary support preferably has a haze value of 2% or less, more preferably 0.5% or less, and even more preferably 0.1% or less.

[0187] From the viewpoint of pattern formation during pattern exposure via a temporary support and the transparency of the temporary support, it is preferred that the number of particles, impurities and defects contained in the temporary support is small. The number of particles, foreign matter and defects with a diameter of 1 μm or more in the temporary support is preferably 50 / 10 mm. 2 Below, more preferably 10 / 10mm 2 Below, more preferably 3 / 10mm 2 Below, especially preferably 0 / 10mm 2 .

[0188] The thickness of the temporary support is not particularly limited, but is preferably 5 to 200 μm, more preferably 5 to 150 μm, further preferably 5 to 50 μm, and particularly preferably 5 to 25 μm from the viewpoint of ease of handling and versatility. The thickness of the temporary support can be calculated by the average value of any five points measured by cross-sectional observation using a SEM (Scanning Electron Microscope).

[0189] Furthermore, in order to improve the adhesion between the temporary support and the photosensitive layer formed on the temporary support, the surface of the temporary support in contact with the photosensitive layer may be surface-modified by UV (ultraviolet) irradiation, corona discharge, plasma, or the like.

[0190] When the surface modification of the temporary support is performed by UV irradiation, the exposure dose is preferably 10 to 2000 mJ / cm 2 , more preferably 50 to 1000 mmJ / cm 2 In addition, as the light source, there can be cited low-pressure mercury lamps, high-pressure mercury lamps, super-pressure mercury lamps, carbon arc lamps, metal halide lamps, xenon lamps, chemical lamps, electrodeless discharge lamps, and light-emitting diodes (LEDs) that emit light in the wavelength region of 150 to 450 nm. As long as the light irradiation amount can be within this range, there is no particular limitation on the lamp output or illumination.

[0191] Examples of the temporary support include a biaxially stretched polyethylene terephthalate film having a thickness of 16 μm, a biaxially stretched polyethylene terephthalate film having a thickness of 12 μm, and a biaxially stretched polyethylene terephthalate film having a thickness of 9 μm.

[0192] The temporary support may also be a recycled product. As a recycled product, a used film or the like is washed and chipped, and the used film is used as a material to form a film, etc. As a specific example of a recycled product, the Ecouse series of TORAY INDUSTRIES, INC. can be cited.

[0193] As a preferred method of the temporary support body, for example, there can be cited paragraphs

[0017] to

[0018] of Japanese Patent Publication No. 2014-085643, paragraphs

[0019] to

[0026] of Japanese Patent Publication No. 2016-027363, paragraphs

[0041] to

[0057] of International Publication No. 2012 / 081680, and paragraphs

[0029] to

[0040] of International Publication No. 2018 / 179370, and the contents of these publications are incorporated into this specification.

[0194] From the viewpoint of providing handleability, a layer containing fine particles (lubricant layer) may be provided on the surface of the temporary support. The lubricant layer may be provided on one surface or both surfaces of the temporary support. The diameter of the particles contained in the lubricant layer is preferably 0.05 to 0.8 μm.

[0195] The thickness of the lubricant layer is preferably 0.05 to 1.0 μm. Commercially available products of temporary supports include Lumirror 16KS40, Lumirror 16FB40, Lumirror #38-U48, Lumirror #75-U34, and Lumirror #25T60 (all manufactured by TORAY INDUSTRIES, INC.); COSMOSHINE A4100, COSMOSHINE A4300, COSMOSHINE A4160, COSMOSHINE A4360, and COSMOSHINE A8300 (all manufactured by TOYOBO Co., Ltd.).

[0196] <Photosensitive Layer>

[0197] (Components of the Photosensitive Layer)

[0198] The photosensitive layer may be any of a positive photosensitive layer and a negative photosensitive layer, and is preferably a negative photosensitive layer.

[0199] When the photosensitive layer is a negative photosensitive layer, the photosensitive layer is preferably a structure containing at least an alkali-soluble resin, a polymerizable compound, and a photopolymerization initiator. In addition, as described above, the photosensitive layer may also be a light-reflecting layer precursor layer and a light-absorbing layer precursor layer. When the photosensitive layer is a light-reflecting layer precursor layer, the photosensitive layer contains a reflectivity adjusting agent described below, and when the photosensitive layer is a light-absorbing layer precursor layer, the photosensitive layer contains a light-absorbing substance described below.

[0200] When the photosensitive layer is a positive photosensitive layer, the photosensitive layer is preferably a structure containing at least a polymer and a photoacid generator, for example. In addition, as described above, the photosensitive layer may also be a photosensitive light reflecting layer and a photosensitive light absorbing layer. When the photosensitive layer is a photosensitive light reflecting layer, the photosensitive layer contains a reflectivity adjusting agent described later, and when the photosensitive layer is a photosensitive light absorbing layer, the photosensitive layer contains a light absorbing substance described later.

[0201] (Impurities in the Photosensitive Layer)

[0202] The photosensitive layer may also contain impurities selected from metals and metal ions (hereinafter also referred to as "impurities A"). Specific examples of impurities A include sodium, potassium, magnesium, calcium, iron, manganese, copper, aluminum, titanium, chromium, cobalt, nickel, zinc, tin, halogens, and ions thereof. Among them, halide ions, sodium ions, and potassium ions are easily mixed in as impurities, so it is preferably set to the following content.

[0203] The upper limit of the content of impurity A is preferably 150 mass ppm or less, more preferably 100 mass ppm or less, further preferably 10 mass ppm or less, and particularly preferably 2 mass ppm or less, relative to the total mass of the photosensitive layer. The lower limit of the content of impurity A can be 1 mass ppb or more or 0.1 mass ppm or more, relative to the total mass of the photosensitive layer.

[0204] Wherein, as the upper limit of the content of chloride ions, relative to the gross mass of the photosensitive layer, preferably 100 mass ppm or less, more preferably 50 mass ppm or less, further preferably 10 mass ppm or less, particularly preferably 2 mass ppm or less. As the lower limit of the content of chloride ions, relative to the gross mass of the photosensitive layer, it can be set to 1 mass ppb or more or 0.1 mass ppm or more.

[0205] As a method for setting the impurity A within the above range, there are: selecting a material with a low impurity content as a raw material for the photosensitive layer; preventing the impurities from being mixed when forming the photosensitive layer; and washing and removing the impurities. By this method, the impurity amount can be set within the above range.

[0206] Impurity A can be quantified by a known method such as ICP (Inductively Coupled Plasma) emission spectrometry, atomic absorption spectrometry, and ion chromatography.

[0207] Furthermore, in the photosensitive layer, the smaller the content of the organic solvent, the more preferably.

[0208] The content of the organic solvent is preferably 100 ppm by mass or less, more preferably 20 ppm by mass or less, and further preferably 4 ppm by mass or less relative to the total mass of the photosensitive layer. The lower limit of the content of the organic solvent may be 10 ppb by mass or more relative to the total mass of the photosensitive layer.

[0209] The content of the organic solvent can be quantified by a known method such as ICP (Inductively Coupled Plasma) emission spectrometry, atomic absorption spectrometry, and ion chromatography.

[0210] Specific examples of the organic solvent include those selected from the group consisting of benzene, formaldehyde, trichloroethylene, 1,3-butadiene, carbon tetrachloride, chloroform, N,N-dimethylformamide, N,N-dimethylacetamide, and hexane.

[0211] As the content of water in the photosensitive layer, from the viewpoint of improving reliability and lamination, it is preferably 5.0 mass % or less, more preferably 3.0 mass % or less, and further preferably 1.0 mass % or less relative to the total mass of the photosensitive layer. In addition, as the lower limit of the content of water in the photosensitive layer, the less the better, but it can also be, for example, 0.01 mass % or more relative to the total mass of the layer.

[0212] Hereinafter, the negative photosensitive layer and the positive photosensitive layer will be described respectively.

[0213] 《Negative photosensitive layer》

[0214] Hereinafter, components that may be contained in the negative photosensitive layer will be described in detail.

[0215] -Alkali soluble resin-

[0216] The photosensitive layer preferably contains an alkali-soluble resin.

[0217] Examples of the alkali-soluble resin include (meth)acrylic resins, styrene resins, epoxy resins, amide resins, amide epoxy resins, alkyd resins, phenolic resins, ester resins, urethane resins, epoxy acrylate resins obtained by reaction of epoxy resins with (meth)acrylic acid, and acid-modified epoxy acrylate resins obtained by reaction of epoxy acrylate resins with acid anhydrides.

[0218] (Preferred embodiment 1 of the alkali-soluble resin)

[0219] As one of the preferred aspects of the alkali-soluble resin, a (meth)acrylic resin is mentioned from the viewpoint of being excellent in alkali developability and thin film formability.

[0220] In addition, in this specification, a (meth)acrylic resin means a resin which has a structural unit derived from a (meth)acrylic compound.

[0221] The content of the constituent units derived from the (meth)acrylic compound is preferably 50% by mass or more, more preferably 70% by mass or more, and further preferably 90% by mass or more relative to all the constituent units of the (meth)acrylic resin. The (meth)acrylic resin may be composed only of constituent units derived from the (meth)acrylic compound, or may have constituent units derived from polymerizable monomers other than the (meth)acrylic compound. That is, the upper limit of the content of the constituent units derived from the (meth)acrylic compound relative to all the constituent units of the (meth)acrylic resin is 100% by mass or less.

[0222] Furthermore, the content of the constituent units derived from the (meth)acrylic compound is preferably 50 mol% or more, more preferably 70 mol% or more, and further preferably 90 mol% or more relative to all the constituent units of the (meth)acrylic resin. The (meth)acrylic resin may be composed only of constituent units derived from the (meth)acrylic compound, or may have constituent units derived from polymerizable monomers other than the (meth)acrylic compound. That is, the upper limit of the content of the constituent units derived from the (meth)acrylic compound relative to all the constituent units of the (meth)acrylic resin is 100 mol% or less.

[0223] In addition, in this specification, when the content of a "constituent unit" is specified by a molar ratio, the above-mentioned "constituent unit" has the same meaning as a "monomer unit". In addition, 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.

[0224] As a (meth)acrylic-type compound, (meth)acrylic acid, (meth)acrylic acid ester, (meth)acrylamide, and (meth)acrylonitrile are mentioned, for example.

[0225] Examples of the (meth)acrylate include alkyl (meth)acrylates, tetrahydrofurfuryl (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, glycidyl (meth)acrylate, benzyl (meth)acrylate, 2,2,2-trifluoroethyl (meth)acrylate, and 2,2,3,3-tetrafluoropropyl (meth)acrylate, and alkyl (meth)acrylates are preferred.

[0226] As (meth)acrylic acid amide, acrylamides, such as diacetone acrylamide, are mentioned, for example.

[0227] The alkyl group of the alkyl (meth)acrylate may be straight-chain or branched. Specific examples thereof include alkyl (meth)acrylates having an alkyl group having 1 to 12 carbon atoms, such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, and dodecyl (meth)acrylate.

[0228] Furthermore, 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.

[0229] As the (meth)acrylate, an alkyl (meth)acrylate having an alkyl group having 1 to 4 carbon atoms is preferred, and methyl (meth)acrylate or ethyl (meth)acrylate is more preferred.

[0230] The (meth)acrylic resin may have a structural unit other than the structural unit derived from the (meth)acrylic compound.

[0231] The polymerizable monomer forming the above-mentioned constituent units 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. Examples thereof include styrene compounds that may have a substituent at the α position or on the aromatic ring, such as styrene, vinyltoluene and α-methylstyrene, vinyl alcohol esters such as acrylonitrile and vinyl-n-butyl ether, maleic acid, maleic anhydride, maleic acid monoesters such as monomethyl maleate, monoethyl maleate and monoisopropyl maleate, fumaric acid, cinnamic acid, α-cyanocinnamic acid, itaconic acid and crotonic acid.

[0232] These polymerizable monomers can be used alone or in combination of two or more.

[0233] Furthermore, from the viewpoint of further improving the alkali developability, the (meth)acrylic resin preferably contains a structural unit having an acid group. Examples of the acid group include a carboxyl group, a sulfonic acid group, a phosphoric acid group, and a phosphonic acid group.

[0234] Among them, the (meth)acrylic resin more preferably contains a structural unit having a carboxyl group, and further preferably contains a structural unit derived from the above-mentioned (meth)acrylic acid.

[0235] From the viewpoint of better developability, the content of the constituent unit having an acid group in the (meth)acrylic resin (preferably a constituent unit derived from (meth)acrylic acid) is preferably 10% by mass or more relative to all constituent units of the (meth)acrylic resin. 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.

[0236] From the viewpoint of better developability, the content of the constituent unit having an acid group in the (meth)acrylic resin (preferably a constituent unit derived from (meth)acrylic acid) is preferably 10 mol% or more relative to all constituent units of the (meth)acrylic resin. The upper limit is not particularly limited, but from the viewpoint of excellent alkali resistance, it is preferably 50 mol% or less, and more preferably 40 mol% or less.

[0237] Furthermore, the (meth)acrylic resin more preferably has a structural unit derived from the above-mentioned alkyl (meth)acrylate.

[0238] The content of the structural unit derived from the alkyl (meth)acrylate in the (meth)acrylic resin is preferably 50 to 90 mass %, more preferably 60 to 90 mass %, and further preferably 65 to 90 mass % relative to all structural units in the (meth)acrylic resin.

[0239] The content of the structural units derived from the alkyl (meth)acrylate in the (meth)acrylic resin is preferably 50 to 90 mol %, more preferably 60 to 90 mol %, and even more preferably 65 to 90 mol % relative to all structural units in the (meth)acrylic resin.

[0240] The (meth)acrylic resin is preferably a resin having both a structural unit derived from (meth)acrylic acid and a structural unit derived from an alkyl (meth)acrylate, and more preferably a resin consisting only of a structural unit derived from (meth)acrylic acid and a structural unit derived from an alkyl (meth)acrylate.

[0241] Furthermore, as the (meth)acrylic resin, an acrylic resin having a structural unit derived from methacrylic acid, a structural unit derived from methyl methacrylate, and a structural unit derived from ethyl acrylate is also preferred.

[0242] The (meth)acrylic resin preferably has at least one selected from a constituent unit derived from methacrylic acid and a constituent unit derived from an alkyl methacrylate, and preferably has both a constituent unit derived from methacrylic acid and a constituent unit derived from an alkyl methacrylate.

[0243] The total content of the constituent units derived from methacrylic acid and the constituent units derived from the alkyl methacrylate in the (meth)acrylic resin is preferably 40% by mass or more, more preferably 60% by mass or more, relative to all the constituent units of the (meth)acrylic resin. The upper limit is not particularly limited and may be 100% by mass or less, preferably 80% by mass or less.

[0244] The total content of the constituent units derived from methacrylic acid and the constituent units derived from the alkyl methacrylate in the (meth)acrylic resin is preferably 40 mol% or more, more preferably 60 mol% or more, relative to all the constituent units of the (meth)acrylic resin. The upper limit is not particularly limited and may be 100 mol% or less, preferably 80 mol% or less.

[0245] Furthermore, the (meth)acrylic resin also preferably has at least one selected from constituent units derived from methacrylic acid and constituent units derived from methacrylic acid alkyl esters and at least one selected from constituent units derived from acrylic acid and constituent units derived from acrylate alkyl esters.

[0246] The total content of the structural unit derived from methacrylic acid and the structural unit derived from the alkyl methacrylate is preferably 60 / 40 to 80 / 20 in mass ratio relative to the total content of the structural unit derived from acrylic acid and the structural unit derived from the alkyl acrylate.

[0247] The (meth)acrylic resin preferably has an ester group at the terminal from the viewpoint of excellent developability of the photosensitive layer after transfer.

[0248] 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 terminal can be synthesized by using a polymerization initiator that generates a radical having an ester group.

[0249] (Preferred embodiment 2 of the alkali-soluble resin)

[0250] In addition, as other preferred embodiments of the alkali-soluble resin, from the viewpoint of being more excellent in developability, an alkali-soluble resin having an acid value of 60 mgKOH / g or more can be cited. In such alkali-soluble resins, from the viewpoint of being easily thermally cross-linked with a cross-linking component by heating to form a firm film, a resin having a carboxyl group having an acid value of 60 mgKOH / g or more (hereinafter also referred to as "resin containing a carboxyl group") is more preferably used, and a (meth) acrylic resin having a carboxyl group having an acid value of 60 mgKOH / g or more (hereinafter also referred to as "(meth) acrylic resin containing a carboxyl group") is further preferably used. If the alkali-soluble resin is a resin having a carboxyl group, then, for example, by adding a thermally cross-linkable compound such as a blocked isocyanate compound to perform thermal cross-linking, the three-dimensional cross-linking density can be increased. Moreover, at this time, if the carboxyl group of the resin having a carboxyl group is dehydrated and hydrophobized, the wet heat resistance can be improved.

[0251] As the carboxyl-containing (meth) acrylic resin having an acid value of 60 mgKOH / g or more, there is no particular limitation as long as the above-mentioned acid value condition is satisfied, and it can be appropriately selected from known (meth) acrylic resins. For example, the carboxyl-containing acrylic resin having an acid value of 60 mgKOH / g or more in the polymer described in paragraph

[0025] of Japanese Patent Publication No. 2011-095716 and the carboxyl-containing acrylic resin having an acid value of 60 mgKOH / g or more in the polymer described in paragraphs

[0033] to

[0052] of Japanese Patent Publication No. 2010-237589 can be preferably used.

[0252] (Preferred embodiment 3 of the alkali-soluble resin)

[0253] Furthermore, another preferred embodiment of the alkali-soluble resin is an alkali-soluble resin having an aromatic ring structure from the viewpoint of better developability. Among the alkali-soluble resin having an aromatic ring structure, an alkali-soluble resin containing a structural unit having an aromatic ring structure is more preferred.

[0254] Examples of monomers that form the constituent unit having an aromatic ring structure include monomers having an aralkyl group, styrene, and polymerizable styrene derivatives (e.g., methylstyrene, vinyltoluene, tert-butoxystyrene, acetoxystyrene, 4-vinylbenzoic acid, styrene dimer, and styrene trimer). Among them, monomers having an aralkyl group or styrene are preferred.

[0255] Examples of the aralkyl group include a substituted or unsubstituted phenylalkyl group (excluding benzyl) and a substituted or unsubstituted benzyl group, and a substituted or unsubstituted benzyl group is preferred.

[0256] Examples of the monomer having a phenylalkyl group include phenylethyl (meth)acrylate and the like.

[0257] Examples of the monomer having a benzyl group include (meth)acrylates having a benzyl group, such as benzyl (meth)acrylate and benzyl (meth)acrylate chloride, and the like; and vinyl monomers having a benzyl group, such as vinylbenzyl chloride and vinylbenzyl alcohol, and the like. Among them, benzyl (meth)acrylate is preferred.

[0258] Furthermore, the alkali-soluble resin more preferably has a structural unit represented by the following formula (S) (structural unit derived from styrene).

[0259] [Chemical formula 1]

[0260]

[0261] When the alkali-soluble resin contains a structural unit having an aromatic ring structure, the content of the structural unit having an aromatic ring structure is preferably 5 to 90 mass %, more preferably 10 to 80 mass %, further preferably 10 to 70 mass %, and particularly preferably 20 to 60 mass % relative to all the structural units of the alkali-soluble resin.

[0262] The content of the structural unit having an aromatic ring structure in the alkali-soluble resin is preferably 5 to 70 mol %, more preferably 10 to 60 mol %, and even more preferably 20 to 60 mol % based on all structural units of the alkali-soluble resin.

[0263] 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 %, further preferably 20 to 60 mol %, and particularly preferably 20 to 50 mol % relative to all structural units of the alkali-soluble resin.

[0264] The alkali-soluble resin preferably has an aliphatic hydrocarbon ring structure. That is, the alkali-soluble resin preferably contains a constituent unit having an aliphatic hydrocarbon ring structure. The aliphatic hydrocarbon ring structure may be a monocyclic ring or a polycyclic ring. Among them, the alkali-soluble resin more preferably has a ring structure formed by condensing an aliphatic hydrocarbon ring of more than two rings.

[0265] Examples of the ring constituting the aliphatic hydrocarbon ring structure in the structural unit having the aliphatic hydrocarbon ring structure include a tricyclodecane ring, a cyclohexane ring, a cyclopentane ring, a norbornane ring, and an isophorone ring.

[0266] Among them, a ring formed by condensing two or more aliphatic hydrocarbon rings is preferred, and a tetrahydrodicyclopentadiene ring (tricyclo[5.2.1.0 2，6 ]decane ring).

[0267] Examples of the monomer that forms the structural unit having an aliphatic hydrocarbon ring structure include dicyclopentanyl (meth)acrylate, cyclohexyl (meth)acrylate, and isobornyl (meth)acrylate.

[0268] Furthermore, the alkali-soluble resin preferably has a structural unit represented by the following formula (Cy), and more preferably has a structural unit represented by the above formula (S) and a structural unit represented by the following formula (Cy).

[0269] [Chemical formula 2]

[0270]

[0271] In the formula (Cy), R M represents a hydrogen atom or a methyl group, R Cy It represents a monovalent group having an aliphatic hydrocarbon ring structure.

[0272] R in formula (Cy) M Preferred is methyl.

[0273] R in formula (Cy) Cy It is preferably a monovalent group having an aliphatic hydrocarbon ring structure having 5 to 20 carbon atoms, more preferably a monovalent group having an aliphatic hydrocarbon ring structure having 6 to 16 carbon atoms, and still more preferably a monovalent group having an aliphatic hydrocarbon ring structure having 8 to 14 carbon atoms.

[0274] Furthermore, R of formula (Cy) Cy The aliphatic hydrocarbon ring structure in is preferably a cyclopentane ring structure, a cyclohexane ring structure, a tetrahydrodicyclopentadiene ring structure, a norbornane ring structure or an isophorone ring structure, more preferably a cyclohexane ring structure or a tetrahydrodicyclopentadiene ring structure, further preferably a tetrahydrodicyclopentadiene ring structure.

[0275] In addition, R of formula (Cy) Cy The aliphatic hydrocarbon ring structure in is preferably a ring structure formed by condensing two or more aliphatic hydrocarbon rings, and more preferably a ring formed by condensing 2 to 4 aliphatic hydrocarbon rings.

[0276] In addition, R in formula (Cy) Cy It is preferably a group in which the oxygen atom of -C(=O)O- in the formula (Cy) is directly bonded to the aliphatic hydrocarbon ring structure, that is, an aliphatic hydrocarbon ring group, more preferably a cyclohexyl group or a dicyclopentyl group, and still more preferably a dicyclopentyl group.

[0277] The alkali-soluble resin may have one type of constituent unit having an aliphatic hydrocarbon ring structure alone, or may have two or more types.

[0278] When the alkali-soluble resin contains a structural unit having an aliphatic hydrocarbon ring structure, the content of the structural unit having an aliphatic hydrocarbon ring structure is preferably 5 to 90 mass %, more preferably 10 to 80 mass %, and further preferably 20 to 70 mass % based on all the structural units of the alkali-soluble resin.

[0279] 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 further preferably 20 to 50 mol % based on all structural units of the alkali-soluble resin.

[0280] The content of the structural unit represented by the above formula (Cy) in the alkali-soluble resin is preferably 5 to 70 mol %, more preferably 10 to 60 mol %, and even more preferably 20 to 50 mol % based on all structural units of the alkali-soluble resin.

[0281] When the alkali-soluble resin contains constituent units having an aromatic ring structure and constituent units having an aliphatic hydrocarbon ring structure, the total content of the constituent units having an aromatic ring structure and the constituent units having an aliphatic hydrocarbon ring structure is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, and further preferably 40 to 75% by mass, relative to all the constituent units of the alkali-soluble resin.

[0282] The total content of the constituent units having an aromatic ring structure and the constituent units having an aliphatic hydrocarbon ring structure in the alkali-soluble resin is preferably 10 to 80 mol %, more preferably 20 to 70 mol %, and further preferably 40 to 60 mol % relative to all constituent units in the alkali-soluble resin.

[0283] 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 preferably 10 to 80 mol %, more preferably 20 to 70 mol %, and further preferably 40 to 60 mol % relative to all the structural units of the alkali-soluble resin.

[0284] Furthermore, from the viewpoint of achieving a more excellent effect of the present invention, the molar amount nS of the constituent unit represented by the above formula (S) in the alkali-soluble resin and the molar amount nCy of the constituent unit represented by the above formula (Cy) preferably satisfy the relationship shown by the following formula (SCy), more preferably satisfy the following formula (SCy-1), and further preferably satisfy the following formula (SCy-2).

[0285] 0.2≤nS / (nS+nCy)≤0.8 Formula (SCy)

[0286] 0.30≤nS / (nS+nCy)≤0.75 formula (SCy-1)

[0287] 0.40≤nS / (nS+nCy)≤0.70 formula (SCy-2)

[0288] The alkali-soluble resin also preferably contains a structural unit having an acid group.

[0289] Examples of the acid group include a carboxyl group, a sulfonic acid group, a phosphonic acid group, and a phosphoric acid group, and a carboxyl group is preferred.

[0290] As the structural unit having the acid group, the structural unit derived from (meth)acrylic acid shown below is preferred, and the structural unit derived from methacrylic acid is more preferred.

[0291] [Chemical formula 3]

[0292]

[0293] The alkali-soluble resin may have a single type of structural unit having an acid group, or may have two or more types.

[0294] When the alkali-soluble resin contains a structural unit having an acid group, the content of the structural unit having an acid group is preferably 5 to 50% by mass, more preferably 5 to 40% by mass, further preferably 10 to 40% by mass, and particularly preferably 10 to 30% by mass, relative to all the structural units of the alkali-soluble resin.

[0295] The content of the structural unit having an acid group in the alkali-soluble resin is preferably 5 to 70 mol %, more preferably 10 to 50 mol %, and even more preferably 20 to 40 mol % based on all structural units of the alkali-soluble resin.

[0296] The alkali-soluble resin preferably has a reactive group, and more preferably contains a structural unit having a reactive group.

[0297] The reactive group is preferably a radical polymerizable group, and more preferably an ethylenically unsaturated group. When the alkali-soluble resin has an ethylenically unsaturated group, the alkali-soluble resin preferably has a structural unit having an ethylenically unsaturated group in a side chain.

[0298] In the present specification, the “main chain” refers to the relatively longest bond chain in the molecule of the polymer compound constituting the resin, and the “side chain” refers to an atomic group branched from the main chain.

[0299] As the ethylenically unsaturated group, an allyl group or a (meth)acryloyloxy group is more preferred.

[0300] Examples of the structural unit having a reactive group include the following, but are not limited to these.

[0301] [Chemical formula 4]

[0302]

[0303] The alkali-soluble resin may have a constituent unit having a reactive group alone or in combination of two or more.

[0304] When the alkali-soluble resin contains a structural unit having a reactive group, the content of the structural unit having a reactive group is preferably 5 to 70 mass %, more preferably 10 to 50 mass %, and further preferably 20 to 40 mass % based on all the structural units of the alkali-soluble resin.

[0305] The content of the structural unit having a reactive group in the alkali-soluble resin is preferably 5 to 70 mol %, more preferably 10 to 60 mol %, and even more preferably 10 to 50 mol % based on all structural units of the alkali-soluble resin.

[0306] As a mechanism for introducing a reactive group into an alkali-soluble resin, there can be mentioned a method of reacting a functional group such as a hydroxyl group, a carboxyl group, a primary amino group, a secondary amino group, an acetoacetyl group and a sulfonic acid group with a compound such as an epoxy compound, a blocked isocyanate compound, an isocyanate compound, a vinyl sulfone compound, an aldehyde compound, a methylol group and a carboxylic anhydride.

[0307] As a preferred example of a method for introducing a reactive group into an alkali-soluble resin, there is mentioned a method in which a polymer having a carboxyl group is synthesized by a polymerization reaction, and then glycidyl (meth)acrylate is reacted with a part of the carboxyl group of the obtained polymer by a polymer reaction to introduce a (meth)acryloyloxy group into the polymer. By this mechanism, an alkali-soluble resin having a (meth)acryloyloxy group in a side chain can be obtained.

[0308] The polymerization reaction is preferably carried out at a temperature of 70 to 100° C., more preferably at a temperature of 80 to 90° C. As the polymerization initiator used in the polymerization reaction, an azo initiator is preferred, for example, V-601 (trade name) or V-65 (trade name) manufactured by FUJIFILM Wako Pure Chemical Corporation is more preferred. The polymer reaction is preferably carried out at a temperature of 80 to 110° C. In the polymer reaction, a catalyst such as an ammonium salt is preferably used.

[0309] Furthermore, the alkali-soluble resin also preferably has a structural unit derived from an alkyl (meth)acrylate.

[0310] Examples of the structural unit derived from the alkyl (meth)acrylate include the structural units described above, and among them, methyl (meth)acrylate is preferred.

[0311] The alkali-soluble resin may have a single type of structural unit derived from an alkyl (meth)acrylate, or may have two or more types.

[0312] When the alkali-soluble resin has a structural unit derived from an alkyl (meth)acrylate, the content of the structural unit derived from an alkyl (meth)acrylate is preferably 1 to 10% by mass, more preferably 1 to 5% by mass, based on all the structural units of the alkali-soluble resin.

[0313] Furthermore, the content of the structural unit derived from the alkyl (meth)acrylate in the alkali-soluble resin is preferably 1 to 10 mol %, more preferably 1 to 5 mol %, based on all the structural units of the alkali-soluble resin.

[0314] (Specific example of the alkali-soluble resin of preferred embodiments 1 to 3)

[0315] As the alkali-soluble resin, the polymers X1 to X4 shown below are preferred. In addition, the content ratio (a to d) of each structural unit relative to all structural units and the weight average molecular weight Mw shown below can be appropriately changed according to the purpose, but from the viewpoint of more excellent effects of the present invention, the following constitution is preferred.

[0316] (Polymer X1) 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.

[0317] (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.

[0318] (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.

[0319] (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.

[0320] [Chemical formula 5]

[0321]

[0322]

[0323] (Preferred embodiment 4 of the alkali-soluble resin)

[0324] As the alkali-soluble resin, a polymer containing a structural unit having a carboxylic acid anhydride structure (hereinafter also referred to as “polymer X”) is preferably used.

[0325] The carboxylic acid anhydride structure may be any of a chain carboxylic acid anhydride structure and a cyclic carboxylic acid anhydride structure, but is preferably a cyclic carboxylic acid anhydride structure.

[0326] The ring of the cyclic carboxylic acid anhydride structure is preferably a 5- to 7-membered ring, more preferably a 5-membered ring or a 6-membered ring, and still more preferably a 5-membered ring.

[0327] The structural unit having a carboxylic acid anhydride structure is preferably a structural unit containing a divalent group obtained by removing two hydrogen atoms from a compound represented by the following formula P-1 in the main chain, or a structural unit in which a monovalent group obtained by removing one hydrogen atom from a compound represented by the following formula P-1 is bonded directly or via a divalent linking group.

[0328] [Chemical formula 6]

[0329]

[0330] In formula P-1, R A1a represents a substituent, n 1a R A1a Can be the same or different, Z 1a represents a divalent group forming a ring containing -C(=O)-OC(=O)-, n 1a Indicates an integer greater than 0.

[0331] As R A1a Examples of the substituent represented by include an alkyl group.

[0332] As Z 1a , preferably an alkylene group having 2 to 4 carbon atoms, more preferably an alkylene group having 2 or 3 carbon atoms, and further preferably an alkylene group having 2 carbon atoms.

[0333] n 1a represents an integer greater than 0. 1a When it represents an alkylene group having 2 to 4 carbon atoms, n 1a It is preferably an integer of 0 to 4, more preferably an integer of 0 to 2, and still more preferably 0.

[0334] When n 1a When it represents an integer greater than 2, there are multiple R A1a can be the same or different. Also, there are multiple R A1a They may be bonded to each other to form a ring, but preferably are not bonded to each other to form a ring.

[0335] The structural unit having a carboxylic acid anhydride structure is preferably a structural unit derived from an unsaturated carboxylic acid anhydride, more preferably a structural unit derived from an unsaturated cyclic carboxylic acid anhydride, further preferably a structural unit derived from an unsaturated aliphatic cyclic carboxylic acid anhydride, particularly preferably a structural unit derived from maleic anhydride or itaconic anhydride, and most preferably a structural unit derived from maleic anhydride.

[0336] Specific examples of the structural unit having a carboxylic acid anhydride structure are given below, but the structural unit having a carboxylic acid anhydride structure is not limited to these specific examples. In the following structural unit, Rx represents a hydrogen atom, a methyl group, a CH2OH group or a CF3 group, and Me represents a methyl group.

[0337] [Chemical formula 7]

[0338]

[0339] [Chemical formula 8]

[0340]

[0341] The structural unit having a carboxylic acid anhydride structure in the polymer X may be a single type or two or more types.

[0342] The total content of the structural units having a carboxylic acid anhydride structure is preferably 0 to 60 mol %, more preferably 5 to 40 mol %, and further preferably 10 to 35 mol % based on all the structural units of the polymer X.

[0343] The polymer X is preferably used in combination with any one of the alkali-soluble resins in the above-mentioned preferred aspects 1 to 3.

[0344] When the photosensitive layer contains the polymer X, the content of the polymer X is preferably 0.1 to 30 mass %, more preferably 0.2 to 20 mass %, further preferably 0.5 to 20 mass %, particularly preferably 1 to 20 mass % relative to the total mass of the photosensitive layer.

[0345] The photosensitive layer may contain only one type of polymer X, or may contain two or more types.

[0346] The weight average molecular weight (Mw) of the alkali-soluble resin is preferably 3,500 or more, more preferably 5,000 or more, further preferably 10,000 or more, and particularly preferably 20,000 or more. The upper limit is preferably 50,000 or less, and more preferably 30,000 or less.

[0347] The acid value of the alkali-soluble resin is preferably 10 to 200 mgKOH / g, more preferably 60 to 200 mgKOH / g, further 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 by the method described in JIS K0070:1992.

[0348] From the viewpoint of developability, the dispersion degree of the alkali-soluble resin is preferably 1.0 to 6.0, more preferably 1.0 to 5.0, further preferably 1.0 to 4.0, and particularly preferably 1.0 to 3.0.

[0349] The photosensitive layer may contain only one kind of alkali-soluble resin, or may contain two or more kinds.

[0350] 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, further preferably 20.0% by mass or more, and particularly preferably 30.0% by mass or more, relative to the total mass of the photosensitive layer, and the upper limit is preferably 90.0% by mass or less, more preferably 80.0% by mass or less, and further preferably 70.0% by mass or less.

[0351] -Polymerizable compounds-

[0352] The photosensitive layer preferably contains a polymerizable compound.

[0353] The polymerizable compound is a compound having a polymerizable group. Examples of the polymerizable group include radical polymerizable groups and cation polymerizable groups, and radical polymerizable groups are preferred.

[0354] The polymerizable compound preferably contains a radical polymerizable compound having an ethylenically unsaturated group (hereinafter, also simply referred to as an "ethylenically unsaturated compound").

[0355] As the ethylenically unsaturated group, a (meth)acryloyloxy group is preferred.

[0356] In addition, 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.

[0357] One preferred embodiment of the polymerizable compound includes a compound represented by the following formula (M) (also simply referred to as "compound M").

[0358] Q 2 -R 1 -Q 1 Formula (M)

[0359] In formula (M), Q 1 and Q 2 Each independently represents a (meth)acryloyloxy group, R 1 It represents a divalent linking group having a chain structure.

[0360] Q in formula (M) 1 and Q 2 From the viewpoint of ease of synthesis, Q 1 and Q 2 The same groups are preferred.

[0361] Furthermore, from the viewpoint of reactivity, Q in formula (M) 1 and Q 2An acryloyloxy group is preferred.

[0362] As R in formula (M) 1 , preferably alkylene, alkyleneoxyalkylene (-L 1_ OL 1 -) or polyalkyleneoxyalkylene (-(L 1_ O) p -L 1 -), more preferably a hydrocarbon group or polyalkyleneoxyalkylene group having 2 to 20 carbon atoms, further preferably an alkylene group having 4 to 20 carbon atoms, and particularly preferably a straight-chain alkylene group having 6 to 18 carbon atoms.

[0363] The above-mentioned hydrocarbon group only needs to have a chain structure in at least a part. There is no particular limitation on the part other than the above-mentioned chain structure. For example, it can be any one of a branched, cyclic or straight-chain alkylene group having 1 to 5 carbon atoms, an arylene group, an ether bond and a combination thereof. It is preferably an alkylene group or a group composed of two or more alkylene groups and one or more arylene groups. It is more preferably an alkylene group, and even more preferably a straight-chain alkylene group.

[0364] In addition, the above L 1 Each independently represents an alkylene group, and is 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, and is preferably an integer of 2 to 10.

[0365] Furthermore, the connection Q in compound M 1 With Q 2 The number of atoms in the shortest connecting chain between the two is preferably 3 to 50, more preferably 4 to 40, further preferably 6 to 20, and particularly preferably 8 to 12.

[0366] In this manual, "Connect Q 1 With Q 2 The number of atoms in the shortest link between the two is the number of atoms in the shortest link between the two atoms. 1 Linked R 1 The atoms in Q 2 Linked R 1 The number of atoms in the shortest bond.

[0367] Specific examples of compound M include 1,3-butanediol di(meth)acrylate, tetramethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,7-heptanediol di(meth)acrylate, 1,8-octanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, di(meth)acrylate of hydrogenated bisphenol A, di(meth)acrylate of hydrogenated bisphenol F, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, poly(ethylene glycol / propylene glycol) di(meth)acrylate, and polybutylene glycol di(meth)acrylate. The above ester monomers may also be used as a mixture.

[0368] Among the above compounds, at least one compound selected from 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate and neopentyl glycol di(meth)acrylate is preferred, at least one compound selected from 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate and 1,10-decanediol di(meth)acrylate is more preferred, and at least one compound selected from 1,9-nonanediol di(meth)acrylate and 1,10-decanediol di(meth)acrylate is further preferred.

[0369] Furthermore, as one of the preferred aspects of the polymerizable compound, there is mentioned a bifunctional or higher-functional ethylenically unsaturated compound.

[0370] In the present specification, the "bifunctional or higher-functional ethylenically unsaturated compound" refers to a compound having two or more ethylenically unsaturated groups in one molecule.

[0371] As the ethylenically unsaturated group in the ethylenically unsaturated compound, a (meth)acryloyl group is preferred.

[0372] As the ethylenically unsaturated compound, a (meth)acrylate compound is preferred.

[0373] The bifunctional ethylenically unsaturated compound can be appropriately selected from known compounds.

[0374] Examples of the bifunctional ethylenically unsaturated compound other than the compound M include tricyclodecane dimethanol di(meth)acrylate and 1,4-cyclohexanediol di(meth)acrylate.

[0375] Examples of commercially available 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 DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.), 1,9-nonanediol diacrylate (trade name: NK Ester A-NOD-N, manufactured by Shin-Nakamura Chemical Co., Ltd.), and 1,6-hexanediol diacrylate (trade name: NK Ester A-HD-N, manufactured by Shin-Nakamura Chemical Co., Ltd.).

[0376] The trifunctional or higher-functional ethylenically unsaturated compound can be appropriately selected from known compounds.

[0377] Examples of trifunctional or higher-functional ethylenically unsaturated compounds include dipentaerythritol (tri / tetra / penta / hexa) (meth)acrylate, pentaerythritol (tri / tetra) (meth)acrylate, trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, isocyanuric acid (meth)acrylate, and (meth)acrylate compounds having a glycerol tri(meth)acrylate skeleton.

[0378] Here, “(tri / tetra / penta / hexa) (meth)acrylate” is a concept including tri(meth)acrylate, tetra(meth)acrylate, penta(meth)acrylate and hexa(meth)acrylate, and “(tri / tetra) (meth)acrylate” is a concept including tri(meth)acrylate and tetra(meth)acrylate.

[0379] Another preferred embodiment of the polymerizable compound is a urethane (meth)acrylate compound.

[0380] As urethane (meth)acrylate, urethane di(meth)acrylate is mentioned, For example, propylene oxide-modified urethane di(meth)acrylate, and ethylene oxide and propylene oxide-modified urethane di(meth)acrylate are mentioned.

[0381] Furthermore, as the urethane (meth) acrylate, urethane (meth) acrylates with three or more functional groups may also be mentioned. As the lower limit of the number of functional groups, it is more preferably 6 or more functional groups, and further preferably 8 or more functional groups. In addition, as the upper limit of the number of functional groups, it is preferably 20 or less functional groups. Examples of trifunctional or higher-functional urethane (meth)acrylates include 8UX-015A (manufactured by Taisei Fine Chemical Co., Ltd.), UA-32P (manufactured by Shin-Nakamura Chemical Co., Ltd.), U-15HA (manufactured by Shin-Nakamura Chemical Co., Ltd.), UA-1100H (manufactured by Shin-Nakamura Chemical Co., Ltd.), AH-600 (trade name) manufactured by Kyoeisha Chemical Co., Ltd., and UA-306H, UA-306T, UA-306I, UA-510H and UX-5000 (all manufactured by Nippon Kayaku Co., Ltd.), etc.

[0382] Another preferred embodiment of the polymerizable compound is an ethylenically unsaturated compound having an acid group.

[0383] Examples of the acid group include a phosphoric acid group, a sulfonic acid group, and a carboxyl group.

[0384] Among these, as the acid group, a carboxyl group is preferred.

[0385] Examples of the ethylenically unsaturated compound having an acid group include tri- to tetra-functional ethylenically unsaturated compounds having an acid group [those having carboxyl groups introduced into the skeleton of pentaerythritol tri- and tetra-acrylate (PETA) (acid value: 80 to 120 mgKOH / g)], and 5- to 6-functional ethylenically unsaturated compounds having an acid group (those having carboxyl groups introduced into the skeleton of dipentaerythritol penta- and hexa-acrylate (DPHA) [acid value: 25 to 70 mgKOH / g)].

[0386] These trifunctional or higher ethylenically unsaturated compounds having an acid group may be used together with a bifunctional ethylenically unsaturated compound having an acid group as needed.

[0387] As the ethylenically unsaturated compound having an acid group, at least one selected from bifunctional or higher-functional ethylenically unsaturated compounds having a carboxyl group and carboxylic acid anhydrides thereof is preferred.

[0388] When the ethylenically unsaturated compound having an acid group is at least one selected from bifunctional or higher-functional ethylenically unsaturated compounds having a carboxyl group and carboxylic anhydrides thereof, developability and film strength are further improved.

[0389] The bifunctional or higher-functional ethylenically unsaturated compound having a carboxyl group is not particularly limited and can be appropriately selected from known compounds.

[0390] Examples of the bifunctional or higher-functional 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.), and ARONIX (registered trademark) M-510 (manufactured by TOAGOSEI CO., LTD.).

[0391] As the ethylenically unsaturated compound having an acid group, a polymerizable compound having an acid group described in paragraphs

[0025] to

[0030] of JP-A-2004-239942 is preferred, and the contents described in the publication are incorporated into the present specification.

[0392] Examples of the polymerizable compound include compounds obtained by reacting an α,β-unsaturated carboxylic acid with a polyol, compounds obtained by reacting an α,β-unsaturated carboxylic acid with a compound containing a glycidyl group, urethane monomers such as (meth)acrylate compounds having a urethane bond, phthalic acid compounds such as γ-chloro-β-hydroxypropyl-β'-(meth)acryloyloxyethyl-phthalate, β-hydroxyethyl-β'-(meth)acryloyloxyethyl-phthalate and β-hydroxypropyl-β'-(meth)acryloyloxyethyl-phthalate, and alkyl (meth)acrylates.

[0393] These are used alone or in combination of two or more.

[0394] Examples of the compound obtained by reacting an α,β-unsaturated carboxylic acid with a polyol include bisphenol A (meth)acrylate compounds such as 2,2-bis(4-((meth)acryloxypolyethoxy)phenyl)propane, 2,2-bis(4-((meth)acryloxypolypropoxy)phenyl)propane, and 2,2-bis(4-((meth)acryloxypolyethoxypolypropoxy)phenyl)propane; polyethylene glycol di(meth)acrylate having 2 to 14 ethylene oxide groups; polypropylene glycol di(meth)acrylate having 2 to 14 propylene oxide groups; and polyethylene polypropylene glycol having 2 to 14 ethylene oxide groups and 2 to 14 propylene oxide groups. trimethylolpropane) di(meth)acrylate, trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolpropane ethoxy tri(meth)acrylate, trimethylolpropane diethoxy tri(meth)acrylate, trimethylolpropane triethoxy tri(meth)acrylate, trimethylolpropane tetraethoxy tri(meth)acrylate, trimethylolpropane pentaethoxy tri(meth)acrylate, di(trimethylolpropane) tetraacrylate, tetramethylolmethane tri(meth)acrylate, tetramethylolmethane tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate and dipentaerythritol hexa(meth)acrylate.

[0395] Among them, an ethylenically unsaturated compound having a tetramethylolmethane structure or a trimethylolpropane structure is preferred, and tetramethylolmethane tri(meth)acrylate, tetramethylolmethane tetra(meth)acrylate, trimethylolpropane tri(meth)acrylate, or di(trimethylolpropane)tetraacrylate is more preferred.

[0396] Examples of the polymerizable compound include caprolactone-modified compounds of ethylenically unsaturated compounds (e.g., KAYARAD (registered trademark) DPCA-20 manufactured by Nippon Kayaku Co., Ltd., A-9300-1CL manufactured by Shin-Nakamura Chemical Co., Ltd., etc.), alkylene oxide-modified compounds of ethylenically unsaturated compounds (e.g., KAYARAD RP-1040 manufactured by Nippon Kayaku Co., Ltd., ATM-35E and A-9300 manufactured by Shin-Nakamura Chemical Co., Ltd., EBECRYL (registered trademark) 135 manufactured by DAICEL-ALLNEX LTD., etc.), and ethoxylated glyceryl triacrylate (A-GLY-9E manufactured by Shin-Nakamura Chemical Co., Ltd., etc.).

[0397] In addition, examples of the polymerizable compound include (2,2-dimethylethylene)(5-ethyl-1,3-dioxane-2,5-diyl)methylene bisacrylate (KAYARAD R-604 manufactured by Nippon Kayaku Co., Ltd.) and the like.

[0398] As the polymerizable compound (particularly, an ethylenically unsaturated compound), a compound including an ester bond is particularly preferred from the viewpoint of excellent developability of the photosensitive layer after transfer.

[0399] The ethylenically unsaturated compound containing an ester bond is not particularly limited as long as it contains an ester bond in the molecule, but from the viewpoint of more excellent effects of the present invention, an ethylenically unsaturated compound having a tetramethylolmethane structure or a trimethylolpropane structure is preferred, and tetramethylolmethane tri(meth)acrylate, tetramethylolmethane tetra(meth)acrylate, trimethylolpropane tri(meth)acrylate or di(trimethylolpropane)tetraacrylate is more preferred.

[0400] From the viewpoint of imparting reliability, the ethylenically unsaturated compound preferably includes an ethylenically unsaturated compound having an aliphatic group having 6 to 20 carbon atoms and an ethylenically unsaturated compound having the above-mentioned tetramethylolmethane structure or trimethylolpropane structure.

[0401] Examples of the ethylenically unsaturated compound 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.

[0402] One preferred embodiment of the polymerizable compound is a polymerizable compound having an aliphatic hydrocarbon ring structure (preferably a bifunctional ethylenically unsaturated compound).

[0403] The above-mentioned polymerizable compound is preferably a polymerizable compound having a ring structure formed by the condensation of two or more aliphatic hydrocarbon rings (preferably a structure selected from a tricyclodecane structure and a tricyclodecene structure), more preferably a bifunctional ethylenically unsaturated compound having a ring structure formed by the condensation of two or more aliphatic hydrocarbon rings, and further preferably tricyclodecane dimethanol di(meth)acrylate.

[0404] The aliphatic hydrocarbon ring structure is preferably a cyclopentane structure, a cyclohexane structure, a tricyclodecane structure, a tricyclodecene structure, a norbornane structure or an isophorone structure.

[0405] The molecular weight of the polymerizable compound is preferably 200 to 3,000 or less, more preferably 250 to 2,600, further preferably 280 to 2,200, and particularly preferably 300 to 2,200.

[0406] As one preferred embodiment of the photosensitive layer, the photosensitive layer preferably contains a compound represented by formula (M) and an ethylenically unsaturated compound having an acid group, and more preferably contains 1,9-nonanediol diacrylate and a polyfunctional ethylenically unsaturated compound having a carboxylic acid group.

[0407] Furthermore, as one of the preferred aspects of the photosensitive layer, from the viewpoint of development residue inhibition and rust resistance, the photosensitive layer preferably contains a difunctional ethylenically unsaturated compound (preferably a difunctional (meth)acrylate compound) and a trifunctional or higher ethylenically unsaturated compound (preferably a trifunctional or higher (meth)acrylate compound).

[0408] The mass ratio of the content of the bifunctional ethylenically unsaturated compound to the trifunctional or higher-functional ethylenically unsaturated compound (mass of the bifunctional ethylenically unsaturated compound / mass of the trifunctional or higher-functional ethylenically unsaturated compound) is preferably 10 / 90 to 90 / 10, more preferably 30 / 70 to 70 / 30.

[0409] The content of the bifunctional ethylenically unsaturated compound is preferably 20.0% by mass or more, more preferably 30.0% by mass or more, and further preferably 40.0% by mass or more relative to the total amount of all ethylenically unsaturated compounds. The upper limit is not particularly limited, for example, 100% by mass or less, preferably 90.0% by mass or less, and more preferably 80.0% by mass or less.

[0410] The content of 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.

[0411] The photosensitive layer may contain a monofunctional ethylenically unsaturated compound as the ethylenically unsaturated compound.

[0412] The content of the bifunctional or higher-functional ethylenically unsaturated compound is preferably 50 to 100% by mass relative to the total content of all ethylenically unsaturated compounds contained in the photosensitive layer.

[0413] The polymerizable compound (especially, an ethylenically unsaturated compound) may be used alone or in combination of two or more.

[0414] The lower limit of the content of the polymerizable compound (especially the ethylenically unsaturated compound) in the photosensitive layer is preferably 10.0% by mass or more, more preferably 15.0% by mass or more, relative to the total mass of the photosensitive layer. And, as the upper limit, it is preferably 70.0% by mass or less, more preferably 60.0% by mass or less, further preferably 50.0% by mass or less, and particularly preferably 40.0% by mass or less.

[0415] -Photopolymerization initiator-

[0416] The photosensitive layer preferably contains a photopolymerization initiator.

[0417] The photopolymerization initiator is not particularly limited, and a known photopolymerization initiator can be used.

[0418] Examples of the photopolymerization initiator include a photopolymerization initiator having an oxime ester structure (hereinafter, also referred to as an “oxime-based photopolymerization initiator”), a photopolymerization initiator having an α-aminoalkylphenol structure (hereinafter, also referred to as an “α-aminoalkylphenol-based photopolymerization initiator”), a photopolymerization initiator having an α-hydroxyalkylphenol structure (hereinafter, also referred to as an “α-hydroxyalkylphenol-based polymerization initiator”), a photopolymerization initiator having an acylphosphine oxide structure (hereinafter, also referred to as an “acylphosphine oxide-based photopolymerization initiator”), and a photopolymerization initiator having an N-phenylglycine structure (hereinafter, also referred to as an “N-phenylglycine-based photopolymerization initiator”).

[0419] The photopolymerization initiator preferably includes at least one selected from oxime-based photopolymerization initiators, α-aminoalkylphenol-based photopolymerization initiators, α-hydroxyalkylphenol-based photopolymerization initiators and N-phenylglycine-based photopolymerization initiators, and more preferably includes at least one selected from oxime-based photopolymerization initiators, α-aminoalkylphenol-based photopolymerization initiators and N-phenylglycine-based photopolymerization initiators.

[0420] Furthermore, as the photopolymerization initiator, for example, the polymerization initiators described in paragraphs

[0031] to

[0042] of JP-A-2011-095716 and paragraphs

[0064] to

[0081] of JP-A-2015-014783 can also be used.

[0421] Furthermore, from the viewpoints of photosensitivity, visibility of the exposed and non-exposed parts, and resolution, the photopolymerization initiator preferably contains at least one selected from 2,4,5-triarylimidazole dimers and derivatives thereof as a photoradical polymerization initiator. In addition, the two 2,4,5-triarylimidazole structures in the 2,4,5-triarylimidazole dimer and derivatives thereof may be the same or different.

[0422] Examples of the derivatives of 2,4,5-triarylimidazole dimers include 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(o-chlorophenyl)-4,5-di(methoxyphenyl)imidazole dimer, 2-(o-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(o-methoxyphenyl)-4,5-diphenylimidazole dimer, and 2-(p-methoxyphenyl)-4,5-diphenylimidazole dimer.

[0423] Examples of the derivative of the 2,4,5-triarylimidazole dimer include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole.

[0424] Examples of the photoradical polymerization initiator include ethyl dimethylaminobenzoate (DBE, CAS No. 10287-53-3), benzoin methyl ether, (p,p'-dimethoxybenzyl) anisate, TAZ-110 (trade name: manufactured by Midori Kagaku Co., Ltd.), benzophenone, 4,4'-bis(diethylamino)benzophenone, TAZ-111 (trade name: manufactured by Midori Kagaku Co., Ltd.), Irgacure OXE01, OXE02, OXE03, OXE04 (manufactured by BASF), Omnirad 651 and 369 (trade name: manufactured by IGM Resins BV), and 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.).

[0425] Examples of commercially available photoradical polymerization initiators include 1-[4-(phenylthio)phenyl]-1,2-octanedione-2-(0-benzoyloxime) (trade name: IRGACURE (registered trademark) OXE-01, manufactured by BASF), 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone-1-(O-acetyloxime) (trade name: IRGACURE OXE-02, manufactured by BASF), IRGACURE OXE-03 (manufactured by BASF), IRGACURE OXE-04 (manufactured by BASF), 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone (trade name: Omnirad 379EG, manufactured by IGM Resins BV), 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one (trade name: Omnirad 907, manufactured by IGM Resins BV), 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)benzyl]phenyl}-2-methylpropan-1-one (trade name: Omnirad 127, manufactured by IGM Resins BV), 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone-1 (trade name: Omnirad 369, manufactured by IGM Resins BV), 2-hydroxy-2-methyl-1-phenylpropan-1-one (trade name: Omnirad 1173, manufactured by IGM Resins BV), 1-hydroxycyclohexyl phenyl ketone (trade name: Omnirad 184, manufactured by IGM Resins BV), BV), 2,2-dimethoxy-1,2-diphenylethane-1-one (trade name: Omnirad 651, manufactured by IGM Resins BV), 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (trade name: Omnirad TPO H, manufactured by IGM Resins BV), bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (trade name: Omnirad 819, manufactured by IGM Resins BV), oxime ester-based photopolymerization initiator (trade name: Lunar 6, manufactured by DKSH Japan KK), 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole (2-(2-chlorophenyl)-4,5-diphenylimidazole dimer) (trade name: B-CIM, manufactured by Hampford) and 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer (trade name: BCTB, manufactured by Tokyo Chemical Industry Co., Ltd.manufactured by Changzhou Tronly New Electronic Materials Co., Ltd.), 1-[4-(phenylthio)phenyl]-3-cyclopentylpropane-1,2-dione-2-(O-benzoyl oxime) (trade name: TR-PBG-305, manufactured by Changzhou Tronly New Electronic Materials Co., Ltd.), 1,2-propanedione, 3-cyclohexyl-1-[9-ethyl-6-(2-furylcarbonyl)-9H-carbazole-3-yl]-, 2-(O-acetyl oxime) (trade name: TR-PBG-326, manufactured by Changzhou Tronly New Electronic Materials Co., Ltd.) and 3-cyclohexyl-1-(6-(2-(benzoyloxyimino)octanoyl)-9-ethyl-9H-carbazole-3-yl)-propane-1,2-dione-2-(O-benzoyl oxime) (trade name: TR-PBG-391, manufactured by Changzhou Tronly New Electronic Materials CO., LTD.).

[0426] In addition, as a commercially available product of the photoradical polymerization initiator, an alkylphenone-based compound having a trade name of "Omnirad 379" (manufactured by IGM Resins BV) can be mentioned.

[0427] The photopolymerization initiator may be used alone or in combination of two or more.

[0428] When two or more types are used in combination, it is preferred to use an oxime-based photopolymerization initiator and at least one selected from the group consisting of an α-aminoalkylphenone-based photopolymerization initiator and an α-hydroxyalkylphenone-based polymerization initiator.

[0429] When the photosensitive layer contains a photopolymerization initiator, the content of the photopolymerization initiator is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, and further preferably 0.5% by mass or more, relative to the total mass of the photosensitive layer. And, as an upper limit, it is preferably 10.0% by mass or less, and more preferably 7.0% by mass or less, relative to the total mass of the photosensitive layer.

[0430] -Heterocyclic compounds-

[0431] The photosensitive layer may contain a heterocyclic compound.

[0432] The heterocyclic ring of the heterocyclic compound may be either a monocyclic ring or a polycyclic ring.

[0433] Examples of the hetero atom possessed by 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 has a nitrogen atom.

[0434] Examples of the heterocyclic compound include triazole compounds, benzotriazole compounds, tetrazole compounds, thiadiazole compounds, triazine compounds, rhodanine compounds, thiazole compounds, benzothiazole compounds, benzimidazole compounds, benzoxazole compounds, and pyrimidine compounds.

[0435] Among the above, the heterocyclic compound is preferably at least one compound selected from the group consisting of triazole compounds, benzotriazole compounds, tetrazole compounds, thiadiazole compounds, triazine compounds, rhodanine compounds, thiazole compounds, benzimidazole compounds and benzoxazole compounds, and more preferably at least one compound selected from the group consisting of triazole compounds, benzotriazole compounds, tetrazole compounds, thiadiazole compounds, thiazole compounds, benzothiazole compounds, benzimidazole compounds and benzoxazole compounds.

[0436] Preferred specific examples of the heterocyclic compound are shown below. As the triazole compound and the benzotriazole compound, the following compounds can be exemplified.

[0437] [Chemical formula 9]

[0438]

[0439] As the tetrazole compound, the following compounds can be exemplified.

[0440] [Chemical formula 11]

[0441]

[0442] [Chemical formula 12]

[0443]

[0444] As the thiadiazole compound, the following compounds can be exemplified.

[0445] [Chemical formula 13]

[0446]

[0447] As the triazine compound, the following compounds can be exemplified.

[0448] [Chemical formula 14]

[0449]

[0450] Examples of the rhodanine compound include the following compounds.

[0451] [Chemical formula 15]

[0452]

[0453] As the thiazole compound, the following compounds can be exemplified.

[0454] [Chemical formula 16]

[0455]

[0456] As the benzothiazole compound, the following compounds can be exemplified.

[0457] [Chemical formula 17]

[0458]

[0459] As the benzimidazole compound, the following compounds can be exemplified.

[0460] [Chemical formula 18]

[0461]

[0462] [Chemical formula 19]

[0463]

[0464] As the benzoxazole compound, the following compounds can be exemplified.

[0465] [Chemical formula 20]

[0466]

[0467] The heterocyclic compound may be used alone or in combination of two or more.

[0468] When the photosensitive layer contains a heterocyclic compound, the content of the heterocyclic compound is preferably 0.01 to 20.0 mass %, more preferably 0.10 to 10.0 mass %, further preferably 0.30 to 8.0 mass %, particularly preferably 0.50 to 5.0 mass % relative to the total mass of the photosensitive layer.

[0469] -Aliphatic thiol compounds-

[0470] The photosensitive layer may contain an aliphatic thiol compound.

[0471] When the photosensitive layer contains an aliphatic thiol compound, an ene-thiol reaction occurs between the aliphatic thiol compound and the radical polymerizable compound having an ethylenically unsaturated group, so that cure shrinkage of the formed film is suppressed and stress is relaxed.

[0472] The aliphatic thiol compound is preferably a monofunctional aliphatic thiol compound or a polyfunctional aliphatic thiol compound (ie, a bifunctional or higher-functional aliphatic thiol compound).

[0473] Among the above, the aliphatic thiol compound is preferably a polyfunctional aliphatic thiol compound from the viewpoint of the adhesion of the formed pattern (particularly, the adhesion after exposure).

[0474] In the present specification, the "polyfunctional aliphatic thiol compound" refers to an aliphatic compound having two or more thiol groups (also referred to as "mercapto groups") in the molecule.

[0475] As the polyfunctional aliphatic thiol compound, a low molecular weight compound having a molecular weight of not less than 100 is preferred. Specifically, the molecular weight of the polyfunctional aliphatic thiol compound is more preferably 100 to 1,500, and further preferably 150 to 1,000.

[0476] The number of functional groups of the polyfunctional aliphatic thiol compound is preferably 2 to 10 functional groups, more preferably 2 to 8 functional groups, and even more preferably 2 to 6 functional groups, from the viewpoint of the adhesion of the pattern to be formed.

[0477] Examples of the polyfunctional aliphatic thiol compound 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-thiobutyryloxy)ethyl)-1,3,5-triazine-2,4,6-trione, trimethylolethane tris(3-mercaptobutyrate), tris[(3

[0043] The invention also includes the following:

[0044] bis(3-mercaptopropionyloxy)ethyl] isocyanurate, trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptopropionate), tetraethylene glycol bis(3-mercaptopropionate), dipentaerythritol hexa(3-mercaptopropionate), ethylene glycol dithiopropionate, 1,4-bis(3-mercaptobutyryloxy)butane, 1,2-ethanedithiol, 1,3-propanedithiol, 1,6-hexamethylenedithiol, 2,2'-(ethylenedithio)diethanethiol, meso-2,3-dimercaptosuccinic acid and bis(mercaptoethyl) ether.

[0478] Among the above, the polyfunctional aliphatic thiol compound is preferably at least one compound selected from trimethylolpropane tris(3-mercaptobutyrate), 1,4-bis(3-mercaptobutyryloxy)butane and 1,3,5-tris(3-mercaptobutyryloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione.

[0479] Examples of the monofunctional aliphatic thiol compound include 1-octanethiol, 1-dodecylthiol, β-mercaptopropionic acid, methyl 3-mercaptopropionate, 2-ethylhexyl-3-mercaptopropionate, n-octyl-3-mercaptopropionate, methoxybutyl 3-mercaptopropionate, and stearyl 3-mercaptopropionate.

[0480] The photosensitive layer may contain a single aliphatic thiol compound, or may contain two or more aliphatic thiol compounds.

[0481] When the photosensitive layer contains an aliphatic thiol compound, the content of the aliphatic thiol compound is preferably 5 mass % or more, more preferably 5 to 50 mass %, further preferably 5 to 30 mass %, particularly preferably 8 to 20 mass % based on the total mass of the photosensitive layer.

[0482] -Thermal cross-linking compound-

[0483] From the viewpoint of the strength of the obtained cured film and the adhesiveness of the obtained uncured film, the photosensitive layer also preferably contains a thermally crosslinkable compound. In addition, in this specification, the thermally crosslinkable compound having an ethylenically unsaturated group described later is not treated as an ethylenically unsaturated compound, but is treated as a thermally crosslinkable compound.

[0484] Examples of the heat-crosslinkable compound include epoxy compounds, cyclohexane compounds, methylol compounds, and blocked isocyanate compounds. Among these, blocked isocyanate compounds are preferred from the viewpoint of the strength of the resulting cured film and the adhesiveness of the resulting uncured film.

[0485] The blocked isocyanate compound reacts with a hydroxyl group and a carboxyl group. Therefore, for example, when at least one of the alkali-soluble resin and the radically polymerizable compound having an ethylenically unsaturated group has at least one of a hydroxyl group and a carboxyl group, the hydrophilicity of the formed film tends to decrease and the function as a protective film tends to increase.

[0486] The blocked isocyanate compound refers to a "compound having a structure in which the isocyanate group of isocyanate is protected (so-called masked) by a blocking agent".

[0487] 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.

[0488] The dissociation temperature of the blocked isocyanate refers to "the temperature of an endothermic peak accompanying the deprotection reaction of the blocked isocyanate when measured by DSC (Differential scanning calorimetry) analysis using a differential scanning calorimeter."

[0489] As the differential scanning calorimeter, for example, a differential scanning calorimeter (model: DSC6200) manufactured by Seiko Instruments Inc. can be preferably used. However, the differential scanning calorimeter is not limited thereto.

[0490] Examples of the end-capping agent having a dissociation temperature of 100 to 160° C. include active methylene compounds [malonic acid diesters (dimethyl malonate, diethyl malonate, di-n-butyl malonate, di-2-ethylhexyl malonate, etc.)] and oxime compounds (formaldehyde oxime, acetaldehyde oxime, acetone oxime, methyl ethyl ketone oxime, cyclohexanone oxime, etc., compounds having a structure represented by -C(=N-OH)- in the molecule).

[0491] Among these, as a blocking agent having a dissociation temperature of 100 to 160° C., for example, at least one selected from oxime compounds is preferred from the viewpoint of storage stability.

[0492] For example, from the viewpoints of improving the brittleness of the film and improving the adhesion to the transfer target, the blocked isocyanate compound preferably has an isocyanurate structure.

[0493] For example, hexamethylene diisocyanate is protected by isocyanation to obtain a blocked isocyanate compound having an isocyanurate structure.

[0494] Among blocked isocyanate compounds having an isocyanurate structure, compounds having an oxime structure using an oxime compound as a blocking agent are preferred from the viewpoint that the dissociation temperature can be more easily set within a preferred range and development residues can be easily reduced compared to compounds not having an oxime structure.

[0495] The blocked isocyanate compound may have a polymerizable group.

[0496] The polymerizable group is not particularly limited, and a known polymerizable group can be used, but a radical polymerizable group is preferred.

[0497] Examples of the polymerizable group include ethylenically unsaturated groups such as a (meth)acryloyloxy group, a (meth)acrylamide group, and a styryl group, and groups having an epoxy group such as a glycidyl group.

[0498] Among these, as the polymerizable group, an ethylenically unsaturated group is preferred, a (meth)acryloyloxy group is more preferred, and an acryloyloxy group is further preferred.

[0499] As the blocked isocyanate compound, a commercially available product can be used.

[0500] Examples of commercially available blocked isocyanate compounds include Karenz (registered trademark) AOI-BM, Karenz (registered trademark) MOI-BM, Karenz (registered trademark) MOI-BP, etc. (all manufactured by SHOWA DENKO KK), and blocked Duranate series (for example, Duranate (registered trademark) TPA-B80E, Duranate (registered trademark) WT32-B75P, etc., manufactured by Asahi Kasei Chemicals Corporation).

[0501] The heat-crosslinkable compound may be used alone or in combination of two or more.

[0502] When the photosensitive layer contains a thermally crosslinkable compound, the content of the thermally crosslinkable compound is preferably 1.0 to 50.0% by mass, more preferably 5.0 to 30.0% by mass, and further preferably 5.0 to 25.0% by mass, based on the total mass of the photosensitive layer.

[0503] -Surfactant-

[0504] The photosensitive layer may contain a surfactant.

[0505] Examples of the surfactant include surfactants described in paragraph

[0017] of Japanese Patent No. 4502784 and paragraphs

[0060] to

[0071] of Japanese Unexamined Patent Application Publication No. 2009-237362.

[0506] As the surfactant, a fluorine-based surfactant or a silicone-based surfactant is preferred.

[0507] Examples of commercially available fluorine-based surfactants include MEGAFACE F-171, F-172, F-173, F-176, F-177, F-141, F-142, F-143, F-144, F-437, F-475, F-477, F-479, F-482, F-551-A, F-552, F-554, F-555-A, F-556, F-557, F-558, F-559, F-600, F-601, F-602, F-603, F-604, F-605, F-606, F-607, F-608, F-609, F-610, F-611, F-612, F-613, F-614, F-615, F-616, F-617, F-618, F-619, F-620, F-621 59, F-560, F-561, F-565, F-563, F-568, F-575, F-780, EXP, MFS-330, R-41, R-41-LM, R-01, R-40, R-40-LM, RS-43, TF-1956, RS-90, R-94, RS-72-K, DS-21 (the above are DIC Corporation), FLUORAD FC430, FC431, FC171 (all manufactured by Sumitomo 3M Limited), Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, KH-40 (all manufactured by AGC Inc.), PolyFox PF636, PF656, PF6320, PF6520, PF7002 (all manufactured by OMNOVA Solutions Inc.), Footgent 710FM, 710FL, 610FM, 601AD, 601ADH2, 602A, 215M, 245F, 251, 212M, 250, 209F, 222F, 208G, 710LA, 710FS, 730LM, 650AC, 681 (all manufactured by NEOS COMPANY LIMITED), etc.

[0508] In addition, the fluorine-based surfactant can also preferably use an acrylic compound, which has a molecular structure containing a functional group containing a fluorine atom, and when heat is applied, the functional group containing a fluorine atom is partially cut off, so that the fluorine atom volatilizes. As such a fluorine-based surfactant, the MEGAFACE DS series manufactured by DIC Corporation (The Chemical Daily (February 22, 2016), NIKKEI BUSINESS DAILY (February 23, 2016)) can be cited, for example, MEGAFACE DS-21.

[0509] Furthermore, as the fluorine-based surfactant, it is also preferable to use a polymer of a fluorine-containing vinyl ether compound having a fluorinated alkyl group or a fluorinated alkylene ether group and a hydrophilic vinyl ether compound.

[0510] Furthermore, as the fluorine-based surfactant, a terminal polymer can also be used.

[0511] Furthermore, as the fluorine-based surfactant, a fluorine-containing polymer compound can also be preferably used, which contains a constituent unit derived from a (meth)acrylate compound having a fluorine atom and a constituent unit derived from a (meth)acrylate compound having two or more (preferably five or more) alkyleneoxy groups (preferably ethyleneoxy and propyleneoxy).

[0512] Furthermore, as the fluorine-based surfactant, a fluorine-containing polymer having a group containing an ethylenically unsaturated bond in a side chain can also be used, such as MEGAFACE RS-101, RS-102, RS-718K, RS-72-K (all manufactured by DIC Corporation).

[0513] As the fluorinated surfactant, from the viewpoint of improving environmental suitability, a surfactant derived from an alternative material of a compound having a perfluoroalkyl group having 7 or more carbon atoms, such as perfluorooctane acid (PFOA) and perfluorooctane sulfonic acid (PFOS), is preferred.

[0514] Examples of the nonionic surfactant include glycerin, trimethylolpropane, trimethylolethane, and ethoxylates and propoxylates thereof (e.g., glycerin propoxylate, glycerin ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid esters, Pluronic (registered trademark) L10, L31, L61, L62, 10R5, 17R2, 25R2 (all manufactured by BASF), Tetronie 304, 701, 704, 901, 904, 150R1 (all manufactured by BASF), Solsperse 20000 (all manufactured by Lubrizol Japan Limited.), NCW-101, NCW-1001, NCW-1002 (all manufactured by FUJIFILM Wako Pure Chemical Corporation), PI0NIN D-6112, D-6112-W, D-6315 (all manufactured by Takemoto Oil & Fat Co., Ltd.), Olfine E1010, Surfynol 104, 400, 440 (all manufactured by Nissin Chemical Co., Ltd.), etc.

[0515] Examples of the silicone-based surfactant include linear polymers formed of siloxane bonds and modified siloxane polymers having an organic group introduced into a side chain or a terminal.

[0516] Specific examples of the surfactant include DOWSIL 8032 ADDITIVE, Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, and Toray Silicone SH8400 (all of which are Dow Corning Toray Silicone Co., Ltd.), and X-22-4952, X-22-4272, X-22-6266, KF-351A, K354L, KF-355A, KF-945, KF-640, KF-642, KF-643, X-22-6191, X-22-4515, KF-6004, KP-341, KF-6001, KF-6002 (all manufactured by Shin-Etsu Silicone Co., Ltd.), F-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (all manufactured by Momentive Performance Materials Inc.), BYK307, BYK323, BYK330 (all manufactured by BYK Chemie), etc.

[0517] The surfactant may be used alone or in combination of two or more.

[0518] When the photosensitive layer contains a surfactant, the content of the surfactant is preferably 0.01 to 3.0 mass %, more preferably 0.01 to 1.0 mass %, and further preferably 0.05 to 0.80 mass % relative to the total mass of the photosensitive layer.

[0519] -Inhibitors-

[0520] The photosensitive layer may contain a polymerization inhibitor.

[0521] The polymerization inhibitor is a compound having a function of delaying or inhibiting a polymerization reaction. As the polymerization inhibitor, for example, a known compound used as a polymerization inhibitor can be used.

[0522] Examples of the polymerization inhibitor include phenothiazine compounds such as phenothiazine, bis-(1-dimethylbenzyl)phenothiazine and 3,7-dioctylphenothiazine; bis[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate][vinylbis(ethylene oxide)]2,4-bis[(stearylthio)methyl]-o-cresol, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl), 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl), 2,4-bis-(n-octylthio)-6-(4-hydroxy-3,5-di-tert-butylanilino)-1,3,5-triazine and Hindered phenol compounds such as pentaerythritol tetrakis 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate; nitroso compounds or their salts such as 4-nitrosophenol, N-nitrosodiphenylamine, N-nitrosocyclohexylhydroxylamine and N-nitrosophenylhydroxylamine; quinone compounds such as methylhydroquinone, tert-butylhydroquinone, 2,5-di-tert-butylhydroquinone and 4-benzoquinone; phenol compounds such as 4-methoxyphenol, 4-methoxy-1-naphthol and tert-butylcatechol; metal salt compounds such as copper dibutyldithiocarbamate, copper diethyldithiocarbamate, manganese diethyldithiocarbamate and manganese diphenyldithiocarbamate.

[0523] Among them, from the viewpoint of more excellent effects of the present invention, the polymerization inhibitor is preferably at least one selected from phenothiazine compounds, nitroso compounds or their salts, and hindered phenol compounds, and more preferably phenothiazine, bis[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionic acid][vinylbis(ethylene oxide)]2,4-bis[(stearylthio)methyl]-o-cresol, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl) and N-nitrosophenylhydroxylamine aluminum salt.

[0524] The polymerization inhibitor may be used alone or in combination of two or more.

[0525] When the photosensitive layer contains a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.001 to 5.0% by mass, more preferably 0.01 to 3.0% by mass, and further preferably 0.02 to 2.0% by mass relative to the total mass of the photosensitive layer. 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 further preferably 0.01 to 1.0% by mass relative to the total mass of the polymerizable compound.

[0526] -Hydrogen Donating Compounds-

[0527] The photosensitive layer may contain a hydrogen donating compound.

[0528] The hydrogen-donating compound has the functions of further improving the sensitivity of the photopolymerization initiator to active light and suppressing the polymerization inhibition of the polymerizable compound caused by oxygen.

[0529] Examples of the hydrogen-donating compound include amines and amino acid compounds.

[0530] Examples of the amines include compounds described in "Journal of Polymer Society" by MR Sander et al., Vol. 10, p. 3173 (1972), JP-44-020189, JP-51-082102, JP-52-134692, JP-59-138205, JP-60-084305, JP-62-018537, JP-64-033104, and Research Disclosure No. 33825. More specifically, 4,4′-bis(diethylamino)benzophenone, tris(4-dimethylaminophenyl)methane (another name: colorless crystal violet), triethanolamine, ethyl p-dimethylaminobenzoate, p-formyldimethylaniline, and p-methylthiodimethylaniline are mentioned.

[0531] Among them, from the viewpoint of achieving more excellent effects of the present invention, the amine is preferably at least one selected from 4,4′-bis(diethylamino)benzophenone and tris(4-dimethylaminophenyl)methane.

[0532] Examples of the amino acid compound include N-phenylglycine, N-methyl-N-phenylglycine, and N-ethyl-N-phenylglycine.

[0533] Among them, N-phenylglycine is preferred as the amino acid compound from the viewpoint of achieving more excellent effects of the present invention.

[0534] In addition, examples of hydrogen-donating compounds include organic metal 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 (trithiane, etc.) described in Japanese Patent Application Laid-Open No. 6-308727.

[0535] The hydrogen-donating compound may be used alone or in combination of two or more.

[0536] When the photosensitive layer contains a hydrogen donating compound, from the viewpoint of improving the curing rate by balancing the polymerization growth rate and chain transfer, the content of the hydrogen donating compound is preferably 0.01 to 10.0 mass %, more preferably 0.01 to 8.0 mass %, and further preferably 0.03 to 5.0 mass % relative to the total mass of the photosensitive layer.

[0537] -Residual Monomers-

[0538] The photosensitive layer may contain residual monomers of each structural unit of the above-mentioned alkali-soluble resin.

[0539] From the viewpoint of patterning and reliability, the content of residual monomers is preferably 5,000 mass ppm or less, more preferably 2,000 mass ppm or less, and further preferably 500 mass ppm or less relative to the total mass of the alkali-soluble resin. The lower limit is not particularly limited, but is preferably 1 mass ppm or more, and more preferably 10 mass ppm or more.

[0540] From the viewpoint of patterning and reliability, the residual monomer of each constituent unit of the alkali-soluble resin is preferably 3,000 mass ppm or less, more preferably 600 mass ppm or less, and further preferably 100 mass ppm or less relative to the total mass of the photosensitive layer. The lower limit is not particularly limited, but is preferably 0.1 mass ppm or more, and more preferably 1 mass ppm or more.

[0541] The residual monomer amount of monomers when synthesizing an alkali-soluble resin by polymer reaction is also preferably within the above range. For example, when synthesizing an alkali-soluble resin by reacting a carboxylic acid side chain with glycidyl acrylate, the content of glycidyl acrylate is preferably within the above range.

[0542] The amount of residual monomers can be measured by a known method such as liquid chromatography and gas chromatography.

[0543] -Other ingredients-

[0544] The photosensitive layer may contain components other than the components described above (hereinafter also referred to as "other components"). Examples of other components include particles (e.g., metal oxide particles), colorants, antioxidants, reflectivity adjusters, light absorbing substances, sensitizers, and chain transfer agents. Other components include other additives described in paragraphs

[0058] to

[0071] of Japanese Patent Application Laid-Open No. 2000-310706.

[0545] --particle--

[0546] The particles are preferably metal oxide particles.

[0547] The metal in the metal oxide particles also includes semi-metals such as B, Si, Ge, As, Sb and Te.

[0548] For example, from the viewpoint of transparency of a cured film, the average primary particle diameter of the particles is preferably 1 to 200 nm, more preferably 3 to 80 nm.

[0549] The average primary particle diameter of the particles was calculated by measuring the particle diameters of 200 random particles using an electron microscope and averaging the measurement results. In addition, when the shape of the particles is not spherical, the longest side is used as the particle diameter.

[0550] --Colorants--

[0551] The photosensitive layer may contain a trace amount of a colorant (pigment, dye, etc.).

[0552] --Antioxidants--

[0553] Examples of the antioxidant include 3-pyrazolones such as 1-phenyl-3-pyrazolidone (also known as phenidone), 1-phenyl-4,4-dimethyl-3-pyrazolone and 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolone; polyhydroxybenzenes such as hydroquinone, catechol, gallol, methylhydroquinone and chlorohydroquinone; p-methylaminophenol, p-aminophenol, p-hydroxyphenylglycine and p-phenylenediamine.

[0554] Among them, from the viewpoint of more excellent effects of the present invention, the antioxidant is preferably 3-pyrazolones, and more preferably 1-phenyl-3-pyrazolone.

[0555] -Reflectivity adjuster-

[0556] The photosensitive layer preferably contains one or more reflectivity adjusting agents selected from white pigments, metal particles, hollow particles, and liquid crystal compounds (especially, pigment particles of cholesteric liquid crystal compounds). When the photosensitive layer contains a reflectivity adjusting agent, it can be a light reflective layer precursor layer.

[0557] When the photosensitive layer includes a reflective adjusting agent, the light reflectivity of the resin pattern of the laminate formed according to the first embodiment of the present invention is more excellent. In addition, when the photosensitive layer includes a white pigment or hollow particles, the photosensitive layer is easy to become a white layer, and it is easy to obtain a light reflecting layer of the characteristic X1 described later. On the other hand, when the photosensitive layer includes metal particles or liquid crystal compounds (especially, pigment particles of cholesterol-type liquid crystal compounds), due to the reflectivity caused by the metal particles or liquid crystal compounds, it is easy to obtain light reflecting layers of the characteristics X2 and X3 described later.

[0558] --White pigment--

[0559] Examples of white pigments include titanium oxide, zinc oxide, lithopone, light calcium carbonate, white carbon, aluminum oxide, aluminum hydroxide, and barium sulfate. In addition, as white pigments, particles having a higher refractive index than the cured product of the polymerizable compound contained in the photosensitive layer are preferred from the viewpoint of achieving a more excellent effect of the present invention, among which titanium oxide is more preferred, rutile or anatase titanium oxide is further preferred, and rutile titanium oxide is particularly preferred.

[0560] The surface of the white pigment may be subjected to treatments such as silica treatment, alumina treatment, titania treatment, zirconium dioxide treatment, and organic treatment.

[0561] Furthermore, when the photosensitive layer contains a white pigment, the photosensitive layer may further contain a pigment dispersant.

[0562] The shape of the white pigment is not particularly limited, and examples thereof include spherical, amorphous, plate-like, needle-like, and polyhedral shapes.

[0563] The average primary particle size of the white pigment is not particularly limited, but is, for example, preferably 50 to 1000 nm, more preferably 100 to 500 nm.

[0564] In addition, the average primary particle diameter of the white pigment is a value obtained by measuring the diameters of any 100 particles by observation using a transmission electron microscope (TEM) and calculating the arithmetic average of the 100 diameters. In addition, the diameter of the white pigment refers to the diameter when the observation image based on the transmission electron microscope (TEM) is set to a circle of the same area.

[0565] --Metal Particles--

[0566] From the viewpoint of having high reflectivity, 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, more preferably silver, gold, tin, nickel, aluminum or cobalt, and from the viewpoint of showing higher reflectivity in the visible light region, further preferably gold, silver or aluminum, particularly preferably silver.

[0567] The metal particles may be metal single body particles or metal alloy particles. When the metal particles are metal alloy particles, the metal alloy particles are preferably alloy particles of two or more of the above-mentioned metal types.

[0568] The shape of the metal particles is not particularly limited, and examples thereof include spherical, irregular, plate-like, needle-like, and polyhedral shapes.

[0569] The average primary particle size of the metal particles is not particularly limited, but is, for example, preferably 1 to 5000 nm, more preferably 5 to 1000 nm.

[0570] The average primary particle diameter of the metal particles is a value obtained by measuring the diameters of any 100 particles by observation using a transmission electron microscope (TEM) and calculating the arithmetic average of the 100 diameters. The diameter of the metal particles refers to the diameter when the observation image based on the transmission electron microscope (TEM) is set to a circle of the same area.

[0571] The metal particles can be produced by a method such as reduction of an organic metal compound as disclosed in, for example, Japanese Patent Application Laid-Open No. 10-183207.

[0572] --Hollow particles--

[0573] 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.

[0574] As the hollow inorganic particles, for example, preferably, the shell portion of the hollow inorganic particles is formed of a metal oxide selected from the group consisting of silica, alumina, zirconia, titania, and composite oxides thereof.

[0575] Examples of hollow resin particles include hollow resin particles having a shell composed of organic substances such as polymers such as styrene resins, acrylic resins, silicone resins, acrylic-styrene resins, vinyl chloride resins, vinylidene chloride resins, amide resins, urethane resins, phenol resins, styrene-conjugated diene resins, acrylic-conjugated diene resins and olefin resins, and crosslinked products of these polymers.

[0576] The hollow particles may be subjected to physical surface treatment such as plasma discharge treatment and corona discharge treatment, or chemical surface treatment using a surfactant, a coupling agent, or the like.

[0577] The shape of the hollow particles is not particularly limited, and examples thereof include spherical, crushed, fibrous, needle-like, and scaly shapes.

[0578] The average primary particle size of the hollow particles is not particularly limited, but is, for example, preferably 50 to 5000 nm, more preferably 100 to 1000 nm.

[0579] In addition, the average primary particle diameter of the hollow particles is a value obtained by measuring the diameters of any 100 particles by observation using a transmission electron microscope (TEM) and calculating the arithmetic average of the 100 diameters. In addition, the diameter of the hollow particles refers to the diameter when the observation image based on the transmission electron microscope (TEM) is set to a circle of the same area.

[0580] --Liquid Crystalline Compounds--

[0581] As the liquid crystal compound, there can be mentioned compounds having liquid crystal properties. In addition, the liquid crystal compound can also be fixed in a predetermined orientation state. That is, the photosensitive layer can include a polymer formed by polymerizing the oriented polymerizable liquid crystal compound. In the above polymer, the orientation state is fixed.

[0582] As a liquid crystal compound, from the viewpoint of having better reflectivity, a polymer obtained by polymerizing a polymerizable liquid crystal compound having a cholesteric liquid crystal orientation (in other words, a polymer having a fixed cholesteric liquid crystal orientation) is preferably used. A cholesteric liquid crystal composition comprising a nematic liquid crystal compound and a chiral agent is used, and the liquid crystal composition is cured in a state of presenting a cholesteric liquid crystal phase to obtain a polymer having a fixed cholesteric liquid crystal orientation. A polymer having a fixed cholesteric liquid crystal orientation generally has a circularly polarized light selective reflection function of selectively reflecting circularly polarized light.

[0583] Furthermore, the polymer having a fixed cholesteric liquid crystal orientation is contained in the photosensitive layer in the form of liquid crystal particles. In other words, the photosensitive layer preferably contains liquid crystal particles including the polymer having a fixed cholesteric liquid crystal orientation.

[0584] The shape of the liquid crystal particles is not particularly limited, but is preferably a flake from the viewpoint of better dispersibility. The average primary particle diameter of the flakes is, for example, preferably 1 to 120 μm, and more preferably 1 to 100 μm.

[0585] The average primary particle diameter of the liquid crystal particles is a value obtained by measuring the diameters of any 100 particles by observation using a transmission electron microscope (TEM) and calculating the arithmetic average of the 100 diameters. Furthermore, the diameter of the liquid crystal particles refers to the diameter when the observation image based on the transmission electron microscope (TEM) is set to a circle of the same area.

[0586] Examples of commercially available liquid crystal particles include "HELICONE HC Sapphire", "HELICONE HC Aquarius", "HELICONE HC Scarabeus", "HELICONE HC Jade", and "HELICONE HC Maple" (all manufactured by Wacker Asahikasei Silicone Co., Ltd.).

[0587] When the photosensitive layer contains a reflectivity adjusting agent, the content of the reflectivity adjusting agent is preferably 10 to 90% by mass, more preferably 20 to 85% by mass, and further preferably 30 to 80% by mass, based on the total mass of the photosensitive layer.

[0588] In particular, when the reflective adjuster includes a white pigment, the content of the white pigment is preferably 30 to 80% by mass, more preferably 40 to 70% by mass, relative to the total mass of the photosensitive layer. In addition, when the reflective adjuster includes metal particles, the content of the metal particles is preferably 20 to 95% by mass, more preferably 30 to 90% by mass, relative to the total mass of the photosensitive layer. In addition, when the reflective adjuster includes hollow particles, the content of the hollow particles is preferably 20 to 80% by mass, more preferably 30 to 70% by mass, relative to the total mass of the photosensitive layer. In addition, when the reflective adjuster includes a liquid crystal compound (preferably liquid crystal particles), the content of the liquid crystal compound (preferably liquid crystal particles) is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, and further preferably 30 to 70% by mass, relative to the total mass of the photosensitive layer.

[0589] -Light absorbing substances-

[0590] The photosensitive layer also preferably contains a light absorbing substance. When the photosensitive layer contains a light absorbing substance, a light absorbing layer precursor layer can be formed.

[0591] When 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 stray light that can be generated when the light-emitting element is turned on is easily absorbed, resulting in a better blackness when the light-emitting element is not turned on. In addition, when the photosensitive layer contains a light-absorbing substance, it is easy to obtain a light-absorbing layer having the characteristic Y1 and / or the characteristic Y2 described later.

[0592] 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. Carbon black is more preferred.

[0593] When the light absorbing substance is a black pigment, its shape is not particularly limited, and examples thereof include spherical, amorphous, plate-like, needle-like, and polyhedral shapes.

[0594] The average primary particle size of the light absorbing substance is not particularly limited, but is preferably, for example, 1 to 1000 nm, and more preferably 2 to 500 nm.

[0595] The average primary particle diameter of the light absorbing substance is a value obtained by measuring the diameters of any 100 particles by observation using a transmission electron microscope (TEM) and calculating the arithmetic average of the 100 diameters. Furthermore, the diameter of the light absorbing substance refers to the diameter when the observation image based on the transmission electron microscope (TEM) is set to a circle with the same area.

[0596] The light absorbing material may be subjected to a physical surface treatment such as a plasma discharge treatment or a corona discharge treatment, or a chemical surface treatment using a surfactant, a coupling agent, a resin, or the like.

[0597] In addition to the black dye, the light absorbing substance may include compounds that turn black by exposure to light or heating, etc. Examples of the compound that turns black by exposure to light or heating, etc. include the following compound (1).

[0598] [Chemical formula 21]

[0599]

[0600] When the photosensitive layer contains a light absorbing substance, the content of the light absorbing substance is preferably 5 to 80 mass %, more preferably 10 to 70 mass %, further preferably 10 to 60 mass %, particularly preferably 10 to 50 mass % relative to the total mass of the photosensitive layer.

[0601] The thickness of the photosensitive layer is, for example, preferably 1 μm or more, more preferably 2 μm or more. The upper limit is not particularly limited, but is, for example, preferably 100 μm or less, more preferably 50 μm or less.

[0602] (Preferred Embodiments of Light Reflecting Layer Precursor Layer and Light Absorbing Layer Precursor Layer)

[0603] As described above, when the photosensitive layer contains a reflectivity adjusting agent, 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.

[0604] Hereinafter, the light absorbing layer precursor layer and each preferred embodiment of the light absorbing layer precursor layer will be described.

[0605] Light reflecting layer precursor layer

[0606] ··Thickness of the light reflecting layer precursor layer

[0607] The thickness of the light reflection layer precursor is preferably 3 μm or more, more preferably 5 μm or more, further preferably 10 μm or more, and particularly preferably 16 μm or more. The upper limit is not particularly limited, but is preferably 100 μm or less, and more preferably 50 μm or less.

[0608] ··Characteristics of the light reflecting layer formed from the light reflecting layer precursor layer

[0609] The light reflecting layer formed from the light reflecting layer precursor layer is preferably a layer satisfying at least one of the following characteristics X1, X2, and X3. In particular, when the light emitting element is a visible light LED, the light reflecting layer is preferably a layer satisfying 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 is preferably a layer satisfying the characteristic X3.

[0610] 《Characteristic X1》

[0611] Total reflection of the light reflection layer (incident angle 8°, light source: D-65 (2° field of view)) in CIE1976 (L * 、a * 、b * ) color space, L * The value is preferably 80 or more.

[0612] In addition, the above CIE 1976 (L * 、a * 、b * )L in color space * The value is a value measured using a spectrophotometer for a light reflecting layer having a thickness of 30 μm at 25° C. As the spectrophotometer, for example, a spectrophotometer V-570 manufactured by JASCO Corporation can be used.

[0613] As the above L * The value is more preferably 90 or more. The upper limit is 100 or less.

[0614] 《Characteristic X2》

[0615] The total reflectivity 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. In addition, the total reflectivity at a wavelength of 550 nm is a value measured at 25° C. using a spectrophotometer for a light reflecting layer with a thickness of 30 μm. As a spectrophotometer, for example, a spectrophotometer V-570 manufactured by JASCO Corporation can be used.

[0616] 《Feature X3》

[0617] The total reflectivity 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 reflectivity at a wavelength of 385 nm is a value measured at 25° C. using a spectrophotometer for a light reflecting layer having a thickness of 30 μm. As a spectrophotometer, for example, a spectrophotometer V-570 manufactured by JASCO Corporation can be used.

[0618] Light absorbing layer precursor layer

[0619] ··Thickness of the light absorbing layer precursor layer

[0620] The thickness of the light absorbing layer precursor layer is preferably 1 μm or more, more preferably 2 μm or more. The upper limit is not particularly limited, but is, for example, preferably 10 μm or less, more preferably 5 μm or less.

[0621] ··Optical concentration of the light absorbing layer precursor layer

[0622] The optical density (OD) of the light absorbing layer precursor layer at a wavelength of 550nm is preferably 0.5 or more, more preferably 1.0 or more, further preferably 2.0 or more, and particularly preferably 3.0 or more. The upper limit is not particularly limited, for example, it is preferably 6.0 or less. The optical density of the light absorbing layer precursor layer can be measured by a Macbeth concentration meter (manufactured by Macbeth, TD-904, using a visible filter) or the like.

[0623] The optical density (OD) of the light absorbing layer precursor layer at a wavelength of 385 nm is preferably 0.5 or more, more preferably 1.0 or more, further preferably 2.0 or more, and particularly preferably 3.0 or more. The upper limit is not particularly limited, but is preferably 6.0 or less, for example. The optical density of the light absorbing layer precursor layer at a wavelength of 385 nm can be measured by an ultraviolet spectrophotometer U-3310 (manufactured by Hitachi, Ltd.) or the like.

[0624] ··Characteristics of the light absorbing layer formed from the light absorbing layer precursor layer

[0625] The light absorbing layer formed from the light absorbing layer precursor layer preferably satisfies the characteristic Y1 and / or the characteristic Y2. In particular, when the light emitting element is a visible light LED, the light absorbing layer is preferably a layer satisfying the characteristic Y1 from the viewpoint of having a better anti-reflection property against external light, and when the light emitting element is a UV-LED, the light absorbing layer is preferably a layer satisfying the characteristic Y2 from the viewpoint of having a better anti-reflection property against external light and a better stray light suppression property.

[0626] "Feature Y1"

[0627] The optical density (OD) at a wavelength of 550 nm as the light absorbing layer is preferably 0.5 or more, more preferably 1.0 or more, further preferably 2.0 or more, and particularly preferably 3.0 or more. As an upper limit value, it is not particularly limited, for example, it is preferably 6.0 or less. The optical density of the light absorbing layer can be measured by a Macbeth concentration meter (manufactured by Macbeth, TD-904, using a visible filter) or the like.

[0628] 《Characteristic Y2》

[0629] The optical density (OD) of the light absorbing layer at a wavelength of 385 nm is preferably 0.5 or more, more preferably 1.0 or more, further preferably 2.0 or more, and particularly preferably 3.0 or more. The upper limit is not particularly limited, but is preferably 6.0 or less, for example. The optical density of the light absorbing layer at a wavelength of 385 nm can be measured by an ultraviolet spectrophotometer U-3310 (manufactured by Hitachi, Ltd.) or the like.

[0630] 《Positive photosensitive layer》

[0631] Hereinafter, the positive photosensitive layer will be described in detail.

[0632] The photosensitive layer may include a photosensitive layer comprising at least a polymer and a photoacid generator. The polymer is preferably a polymer comprising a repeating unit having a group whose hydrophilicity is increased by the action of an acid (e.g., an acid-decomposable group in which a polar group is protected by a leaving group that leaves by the action of an acid).

[0633] As the photosensitive layer, a known positive photosensitive layer can be used.

[0634] In addition, the photosensitive layer may also be a photosensitive light reflecting layer and a photosensitive light absorbing layer. When the photosensitive layer is a photosensitive light reflecting layer, the photosensitive layer contains a reflective adjusting agent, and when the photosensitive layer is a photosensitive light absorbing layer, the photosensitive layer contains a light absorbing substance. The types of the reflective adjusting agent and the light absorbing substance, and the contents of the reflective adjusting agent and the light absorbing substance relative to the total mass of the photosensitive layer are the same as the types of the reflective adjusting agent and the light absorbing substance in the negative photosensitive layer, and the contents of the reflective adjusting agent and the light absorbing substance relative to the total mass of the photosensitive layer, and the preferred ranges are also the same.

[0635] The thickness of the photosensitive layer is, for example, preferably 1 μm or more, more preferably 2 μm or more. The upper limit is not particularly limited, but is, for example, preferably 100 μm or less, more preferably 50 μm or less.

[0636] (Preferred Embodiments of Photosensitive Light Reflecting Layer and Photosensitive Light Absorbing Layer)

[0637] Hereinafter, each preferred embodiment of the photosensitive light reflecting layer and the photosensitive light absorbing layer will be described.

[0638] ·Photosensitive light reflecting layer

[0639] ··Thickness of the photosensitive light reflecting layer

[0640] The thickness of the photosensitive light reflective layer is preferably 3 μm or more, more preferably 5 μm or more, further preferably 10 μm or more, and particularly preferably 16 μm or more. The upper limit is not particularly limited, but is preferably 100 μm or less, and more preferably 50 μm or less.

[0641] ··Characteristics of the photosensitive light reflecting layer

[0642] The photosensitive light reflecting layer is preferably a layer satisfying at least one of the above-mentioned characteristics X1, X2 and X3. In particular, when the light-emitting element is a visible light LED, the photosensitive light reflecting layer is preferably a layer satisfying 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 satisfying the characteristic X3.

[0643] ·Photosensitive light absorbing layer

[0644] ··Thickness of the photosensitive light absorbing layer

[0645] The thickness of the photosensitive light absorbing layer is preferably 1 μm or more, more preferably 2 μm or more. The upper limit is not particularly limited, but is, for example, preferably 10 μm or less, more preferably 5 μm or less.

[0646] ··Characteristics of the photosensitive light absorbing layer

[0647] The photosensitive light absorbing layer preferably satisfies the above-mentioned characteristic Y1 and / or characteristic Y2. In particular, when the light emitting element is a visible light LED, the photosensitive light absorbing layer is preferably a layer satisfying characteristic Y1 from the viewpoint of having a better anti-reflection property against external light, and when the light emitting element is a UV-LED, the photosensitive light absorbing layer is preferably a layer satisfying characteristic Y2 from the viewpoint of having a better anti-reflection property against external light and a better stray light suppression property.

[0648] Protective film

[0649] The transfer film may have a protective film.

[0650] As the protective film, a resin film having heat resistance and solvent resistance can be used, and examples thereof include polyolefin films such as polypropylene films and polyethylene films, polyester films such as polyethylene terephthalate films, polycarbonate films, and polystyrene films.

[0651] Furthermore, as the protective film, a resin film made of the same material as that of the temporary support body described above can be used.

[0652] Among them, the protective film is preferably a polyolefin film, more preferably a polypropylene film or a polyethylene film, and still more preferably a polyethylene film.

[0653] The thickness of the protective film is preferably 1 to 100 μm, more preferably 5 to 50 μm, further preferably 5 to 40 μm, and particularly preferably 15 to 30 μm. The thickness of the protective film can be calculated as the average value of five arbitrary points measured by cross-sectional observation using a SEM (Scanning Electron Microscope).

[0654] The thickness of the protective film is preferably 1 μm or more from the viewpoint of excellent mechanical strength, and is preferably 100 μm or less from the viewpoint of being relatively inexpensive.

[0655] Furthermore, the number of fisheyes with a diameter of 80 μm or more contained in the protective film is preferably 5 / m. 2 the following.

[0656] In addition, "fish eyes" refer to defects caused by foreign matter, undissolved matter, oxidative degradation products, etc. of the material being introduced into the film when the material is heated and melted and then manufactured into a film through kneading, extrusion, biaxial stretching, casting, etc.

[0657] The number of particles with a diameter of 3 μm or more contained in the protective film is preferably 30 particles / mm. 2 Below, more preferably 10 / mm 2 Below, more preferably 5 / mm 2 the following.

[0658] This can suppress defects caused by the unevenness due to the particles contained in the protective film being transferred to the photosensitive layer.

[0659] From the viewpoint of providing windability, the arithmetic mean roughness Ra of the surface of the protective film on the side opposite to the surface in contact with the photosensitive layer is preferably 0.01 μm or more, more preferably 0.02 μm or more, and further preferably 0.03 μm or more. On the other hand, it is preferably less than 0.50 μm, more preferably 0.40 μm or less, and further preferably 0.30 μm or less.

[0660] From the viewpoint of suppressing defects during transfer, the surface roughness Ra of the protective film in contact with the photosensitive layer is preferably 0.01 μm or more, more preferably 0.02 μm or more, and further preferably 0.03 μm or more. On the other hand, it is preferably less than 0.50 μm, more preferably 0.40 μm or less, and further preferably 0.30 μm or less.

[0661] [Second embodiment]

[0662] The second embodiment of the method for producing a laminate of the present invention (hereinafter, also simply referred to as "the second embodiment of the present invention") comprises the following steps (2-1) to (2-4).

[0663] Step (2-1) (laminating step): a step of laminating the substrate with light-emitting elements and the transfer film in such a manner that the surface of the substrate with light-emitting elements on the light-emitting element side, which includes a substrate and a plurality of light-emitting elements arranged on the substrate, faces the surface of the transfer film on the side opposite to the temporary support, which includes a temporary support and a photosensitive layer, and the light-emitting elements are covered by the photosensitive layer.

[0664] Step (2-2) (exposure step): a step of pattern-exposing the photosensitive layer

[0665] Step (2-3) (Development Step): A step of developing the exposed photosensitive layer to form a resin pattern having openings at positions corresponding to the light-emitting elements.

[0666] Step (2-4) (light-reflecting film forming step): a step of disposing a light-reflecting film on the side wall of the opening

[0667] Furthermore, the second embodiment of the present invention includes the following step (2-A) between the step (2-1) and the step (2-2) or between the step (2-2) and the step (2-3).

[0668] Step (2-A) (temporary support peeling step): a step of peeling off the temporary support.

[0669] <Steps (2-1) to (2-3), (2-A) to (2-C)>

[0670] Steps (2-1) to (2-3) and (2-A) in the second embodiment of the present invention are the same as the steps (1-1) to (1-3) and (1-A) described in the first embodiment of the present invention, respectively.

[0671] Furthermore, in the second embodiment of the present invention, after implementing step (2-3) (development step), there may also be a step of further exposing the formed resin pattern (hereinafter also referred to as "step (2-B)" or "post-exposure step") and / or a step of heating (hereinafter also referred to as "step (2-C)" or "post-baking step").

[0672] The steps (2-B) and (2-C) in the second embodiment of the present invention are the same as the steps (1-B) and (1-C) described in the first embodiment of the present invention, respectively.

[0673] <Step (2-4) Light Reflective Film Forming Step>

[0674] The second embodiment of the present invention is a process of forming a light-reflecting film on the side wall of the opening in the resin pattern formed on the substrate with the light-emitting element after the development process (process (2-3)) (in addition, when the above-mentioned process (2-B) and / or process (2-C) are implemented, after the process). In the resin pattern that functions as a partition layer that separates the light-emitting elements from each other, when the light-reflecting film is arranged on the side wall of the opening, the light from the light-emitting element is reflected by the light-reflecting film, so that the brightness is more excellent.

[0675] Figure 6 The schematic cross-sectional view of the laminated body formed through the light reflecting film forming step (step (2-4)) is shown. The laminated body 60 is composed of the substrate 10 with light emitting elements, the resin pattern 42, and the light reflecting film 62 disposed on the side wall of the opening 43 in the resin pattern 42.

[0676] The light reflecting film preferably contains metal.

[0677] The type of metal is not particularly limited, but from the viewpoint of having high reflectivity, silver, nickel, cobalt, iron, copper, palladium, gold, platinum, tin, zinc, aluminum, tungsten or titanium is preferred, and silver, gold, tin, nickel, aluminum or cobalt is more preferred. From the viewpoint of showing higher reflectivity in the visible light region, gold, silver or aluminum is further preferred, and silver is particularly preferred.

[0678] The light reflective film forming step (step (2-4)) can be applied by sputtering, vapor deposition, electroplating, and printing of ink containing metal particles (screen printing, inkjet, etc.). In addition, it can also be formed by patterning in a manner that only necessary parts remain by known methods such as wet etching and dry etching.

[0679] The thickness of the light reflective film is preferably 10 nm or more, more preferably 50 nm or more, and further preferably 250 nm or more. The upper limit is not particularly limited, but is, for example, preferably 100 μm or less, more preferably 50 μm or less, further preferably 10 μm or less, particularly preferably 1 μm or less, and most preferably 800 nm or less.

[0680] The light reflective film preferably satisfies at least one of the following characteristics Z1 and Z2: When the light emitting element is a visible light LED, the light reflective film preferably satisfies the characteristic Z1, and when the light emitting element is a UV-LED, the light reflective film preferably satisfies the characteristic Z2.

[0681] (Characteristic Z1)

[0682] The total reflectivity of the light reflective 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 reflectivity at a wavelength of 550 nm is a value measured at 25° C. using a spectrophotometer for a light reflective film with a thickness of 30 μm. As a spectrophotometer, for example, a spectrophotometer V-570 manufactured by JASCO Corporation can be used.

[0683] (Feature Z2)

[0684] The total reflectance of the light reflective 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 reflective film at a wavelength of 385 nm is a value measured at 25° C. using a spectrophotometer for a light reflective film with a thickness of 30 μm. As a spectrophotometer, for example, a spectrophotometer V-570 manufactured by JASCO Corporation can be used.

[0685] As the transfer film that can be used in the second embodiment of the present invention, for example, the various transfer films described as the transfer film that can be used in the first embodiment of the present invention can be used.

[0686] An example of a preferred embodiment of the transfer film that can be used in the second embodiment of the present invention is shown below.

[0687] Hereinafter, the light reflecting layer precursor layer, the light absorbing layer precursor layer, the protective film and the temporary support have the same meanings as the light reflecting layer precursor layer, the light absorbing layer precursor layer, the protective film and the temporary support in the transfer film that can be used in the first embodiment of the present invention, and the preferred embodiments are also the same. Other photosensitive layers refer to photosensitive layers that do not belong to any of the light reflecting layer precursor layer and the light absorbing layer precursor layer.

[0688] (N4) Temporary support / light absorbing layer precursor layer / protective film

[0689] (N5) Temporary support / light absorbing layer precursor layer / other photosensitive layers / protective film

[0690] When the transfer film (N5) is used in the second embodiment of the present invention, a light reflecting film may be arranged at least at a position corresponding to the resin layer from another photosensitive layer in the side wall of the opening of the resin pattern.

[0691] Example

[0692] The present invention will be described in more detail below according to the examples. The materials, usage amounts, ratios, processing contents and processing steps shown in the following examples can be appropriately changed without departing from the gist of the present invention. Therefore, the scope of the present invention should not be interpreted in a limited manner by the examples shown below.

[0693] In addition, unless otherwise specified, the following "parts" and "%" are based on mass.

[0694] [Preparation of Composition for Forming Light-Absorbing Layer Precursor Layer]

[0695] Compositions for forming a light-absorbing layer precursor layer (A-1 to A-2) were prepared according to the components and blending amounts shown in Table 1. The unit of the blending amount of each component shown in Table 1 is part by mass.

[0696] [Table 1]

[0697] Table 1: Light absorbing layer precursor layer composition

[0698]

[0699] The details of other abbreviations and product names in Table 1 are shown below.

[0700] "Compound (1)": a compound having the following structure: Compound (1) corresponds to a compound that changes from transparent to black by heat treatment.

[0701] [Chemical formula 22]

[0702]

[0703] “Polymer P-1 solution”: PGMEA solution (solid content: 40.5% by mass) of polymer P-1 [copolymer of benzyl methacrylate / methacrylic acid, copolymer composition ratio (by mass) = 70 / 30, weight average molecular weight (Mw) = 5000].

[0704] "ARONIX T0-2349": Monomer containing a carboxyl group (manufactured by TOAGOSEI CO., LTD.)

[0705] "SB-PI 701": 4,4'-bis(diethylamino)benzophenone (manufactured by Sanyo Traditional Co., Ltd.)

[0706] "TDP-G": Phenothiazine (manufactured by Kawaguchi Chemical Industry Company, Limited)

[0707] "MEGAFACE F551A": Fluorine-based surfactant (manufactured by DIC Corporation)

[0708] [Preparation of Light Reflective Layer Precursor Forming Composition (B-1) and Photosensitive Composition (B-2)]

[0709] The light-reflecting layer precursor layer-forming composition (B-1) and the photosensitive composition (B-2) were prepared according to the components and blending amounts shown in Table 2. The unit of the blending amount of each component shown in Table 2 is part by mass.

[0710] [Table 2]

[0711] Table 2: Light reflection layer precursor layer composition (composition B-1), other photosensitive composition (composition B-2)

[0712]

[0713] [Method for preparing P-2 solution (solid content 36.2% by mass solution of polymer P-2)]

[0714] A P-2 solution (a solution containing 36.2% by mass of the polymer P-2 solid content) was prepared by the polymerization step and the addition step described below.

[0715] 113.5 g of propylene glycol monomethyl ether was placed in a flask and heated to 90° C. under a nitrogen stream. A solution obtained by dissolving 172 g of styrene, 4.7 g of methyl methacrylate and 112.1 g of methacrylic acid in 30 g of propylene glycol monomethyl ether, and a solution obtained by dissolving 27.6 g of polymerization initiator V-601 (manufactured by FUJIFILM Wako Pure Chemical Corporation) in 57.7 g of propylene glycol monomethyl ether were simultaneously added dropwise to the solution over 3 hours. After the addition was completed, 2.5 g of V-601 was added three times every 1 hour. Then, it was further reacted for 3 hours. Then, it was diluted with 160.7 g of propylene glycol monomethyl ether acetate and 233.3 g of propylene glycol monomethyl ether. Under an air stream, the reaction solution was heated to 100° C., and 1.8 g of tetraethylammonium bromide and 0.86 g of p-methoxyphenol were added. 71.9 g of glycidyl methacrylate (Brenmar G manufactured by NOF CORPORATION) was added dropwise thereto over 20 minutes. After the addition, the reaction solution was reacted at 100 ° C for 7 hours to obtain a solution of resin P-2. The solid content concentration of the obtained solution was 36.2% by mass. The weight average molecular weight converted to standard polystyrene in GPC was 18000, the number average molecular weight was 7800, the dispersity 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 in any monomer relative to the polymer solid content. The structure of polymer P-2 is shown below.

[0716] Polymer P-2: The composition of the constituent units in the following structural formula represents a molar ratio.

[0717] In addition, the polymer P-2 corresponds to an alkali-soluble resin.

[0718] [Chemical formula 23]

[0719]

[0720] The details of the abbreviations and product names of other components in Table 2 are shown below.

[0721] "A-NOD-N": 1,9-nonanediol diacrylate (manufactured by Shi n-Nakamura Chemical Co., Ltd.)

[0722] "A-DPH": dipentaerythritol hexaacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.)

[0723] "ARONIX TO-2349": Monomer containing a carboxyl group (manufactured by TOAGOSEICO., LTD.)

[0724] "B-CIM": 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole (manufactured by Hampford Corporation)

[0725] "SB-PI 701": 4,4'-bis(diethylamino)benzophenone (manufactured by Sanyo Trading Co., Ltd.)

[0726] "TDP-G": Phenothiazine (manufactured by Kawaguchi Chemical Industry Company, Limited)

[0727] "CBT-1": Carboxybenzotriazole (manufactured by Johoku Chemical Co., Ltd.)

[0728] "MEGAFACE F551A": Fluorine-based surfactant (manufactured by DIC Corporation)

[0729] [Example 1]

[0730] 〔Production of transfer film〕

[0731] As a temporary support, a polyethylene terephthalate film (Lumirror 16KS40, manufactured by TORAY INDUSTRIES, INC., thickness: 16 μm) was prepared. On the temporary support, the light absorbing layer precursor layer forming composition A-1 was applied in a manner that the thickness after drying was 3 μm, and dried at 100° C. for 1 minute, thereby forming a light absorbing layer precursor layer. On the light absorbing layer precursor layer, the light reflecting layer precursor layer forming composition B-1 was applied in a manner that the thickness after drying was 30 μm, and dried at 100° C. for 3 minutes, thereby forming a light reflecting layer precursor layer. A polyethylene terephthalate film (Lumirror 16KS40, manufactured by TORAY INDUSTRIES, INC., thickness: 16 μm) was crimped onto the light reflecting layer precursor layer. Through the above steps, a transfer film 1 including a temporary support, a light absorbing layer precursor layer, a light reflecting layer precursor layer and a protective film in sequence was obtained.

[0732] 〔Production of micro-LED display components〕

[0733] According to the following steps, a micro LED display element was produced using the transfer film 1. Specifically, after the LED chip was 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.

[0734] [[Installation of LED chips]]

[0735] First, according to the method described in Japanese Patent Application Laid-Open No. 2021-163945 (especially claims, paragraphs 0013 to 0041), 200 LED chips on the peeling sapphire substrate were bonded together to the array substrate, and the peeling sapphire substrate was peeled off.

[0736] [[Formation of resin pattern (partition layer)]]

[0737] Next, the protective film of the transfer film 1 is peeled off, and under the lamination conditions shown below, the transfer film 1 is bonded to an array substrate to which an LED chip is bonded, thereby producing a substrate with precursor layers, in which a light reflecting layer precursor layer, a light absorbing layer precursor layer and a temporary support body are sequentially stacked on a substrate with a light-emitting element (a substrate with a chip).

[0738] Heating temperature of substrate with chip: 40℃

[0739] Rubber roller temperature: 110°C

[0740] Line pressure: 3N / cm

[0741] Conveying speed: 2m / min

[0742] The distance between the surface of the exposure mask (a mask having a pattern for forming the opening) and the surface of the temporary support was set to 125 μm. A proximity exposure machine (Hitachi High-Tech Corporation) with an ultra-high pressure mercury lamp was used to expose the light reflecting layer precursor layer and the light absorbing layer precursor layer through the temporary support at a rate of 100 mJ / cm 2 At this time, the pattern and position of the exposure mask are adjusted so that the taper angle of the partition layer is formed at the portion where the LED chip is mounted (reference Figure 3 The cone angle θ) becomes the opening portion of the angle shown in Table 3.

[0743] After the temporary support was peeled off after the exposure treatment, the light reflecting layer precursor layer and the light absorbing layer precursor layer after exposure were developed for 60 seconds using a 1 mass % sodium carbonate aqueous solution at a temperature of 32° C. Then, ultrapure water was sprayed from an ultrahigh pressure washing nozzle onto the laminated body obtained after the development treatment to remove residues, and then air was blown to remove moisture.

[0744] Next, the pattern on the obtained laminate was exposed to light at an exposure dose of 1000 mJ / cm using a post-exposure machine equipped with a high-pressure mercury lamp (manufactured by USHIO INC.). 2 After the exposure, a post-baking process was performed at 210° C. for 5 minutes.

[0745] According to the above steps, a resin pattern (a partition layer in which a light reflecting layer and a light absorbing layer are stacked in this order) having an opening at the position of the LED chip is formed on the array substrate.

[0746] In this way, a micro LED display element is manufactured.

[0747] [Example 2]

[0748] [Preparation of transfer film of example]

[0749] As a temporary support, a polyethylene terephthalate film (Lumirror 16KS40, manufactured by TORAY INDUSTRIES, INC., thickness: 16 μm) was prepared. On the temporary support, the light absorbing layer precursor layer forming composition A-1 was applied in a manner that the thickness after drying was 3 μm, and dried at 100°C for 1 minute, thereby forming a light absorbing layer precursor layer. On the light absorbing layer precursor layer, the photosensitive layer forming composition B-2 was applied in a manner that the thickness after drying was 30 μm, and dried at 100°C for 3 minutes to form a photosensitive layer (other photosensitive layer). A polyethylene terephthalate film (Lumirror16KS40, manufactured by TORAY INDUSTRIES, INC., thickness: 16 μm) was crimped onto the photosensitive layer. Through the above steps, a transfer film 2 including a temporary support, a light absorbing layer precursor layer, a photosensitive layer and a protective film in sequence was obtained.

[0750] [Fabrication of Micro LED Display Element of Example 2]

[0751] First, in the same manner as [[Mounting of LED chips]] in Example 1, LED chips were mounted on the array substrate.

[0752] Next, the process conditions are appropriately adjusted so as to obtain the tapered angle of the partition layer shown in Table 3. In addition, a resin pattern (a partition layer formed by stacking resin layers and light absorption layers in order) having an opening is formed on the array substrate on which the LED chip is mounted according to the same steps as the [[Formation of resin pattern (partition layer)]] in the above-mentioned Example 1.

[0753] After the partition wall was formed, a 300 nm silver layer was evaporated on the opening of the partition wall by a known evaporation method. At this time, by shielding the position on the chip and the surface of the partition wall layer on the side opposite to the substrate side, a light reflection layer was formed only on the side of the opening of the partition wall layer. In this way, the micro LED display element of Example 2 was manufactured.

[0754] [Example 3]

[0755] A transfer film 3 was obtained in the same manner as in Example 1 except that A-2 was used as the light absorbing layer precursor layer composition and was applied to a thickness of 30 μm after drying and a light reflecting layer precursor layer was not laminated.

[0756] [Fabrication of Micro LED Display Element of Example 3]

[0757] First, in the same manner as [[Mounting of LED chips]] in Example 1, LED chips were mounted on the array substrate.

[0758] Next, the process conditions are appropriately adjusted so as to obtain the tapered angle of the partition layer shown in Table 3. Otherwise, a resin pattern (light absorption layer) having an opening is formed on the array substrate with the chip in accordance with the same steps as the [[Formation of resin pattern (partition layer)]] in the above-mentioned Example 1.

[0759] [Fabrication of micro LED display element of comparative example 1]

[0760] 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.

[0761] As described above, in each micro LED element produced, the LED chip size is 20 μm square, the thickness is 8 μm, the pitch of the LED chips is 400 μm, the through hole size is 30 μm square, and the width of the partition wall between the LED chips is 370 μm.

[0762] (Evaluation of light bleed-through to adjacent pixels)

[0763] Using the micro-LED display element produced as described above, the light leakage of adjacent pixels was evaluated. Using the microscopic UV-visible near-infrared spectrophotometer MSV-5500 (manufactured by JASCO Corporation), the light intensity of 530nm was measured at the position of the adjacent pixel when the green pixel with a central wavelength of 530nm emitted light. At this time, the 530nm light intensity of the adjacent pixel when the light intensity of 530nm in the emitting pixel was set to 100% was evaluated according to the following criteria.

[0764] (Evaluation Criteria)

[0765] "A": Light intensity in adjacent pixels is less than 0.1%

[0766] "B": The light intensity in the adjacent pixel is 0.1% or more and less than 1%

[0767] "C": Light intensity in adjacent pixels is more than 1%

[0768] Table 3 shows the evaluation results of each example.

[0769] [Table 3]

[0770]

[0771] From the results in Table 3, it can be seen that the laminated body including a plurality of light-emitting elements obtained by the method for producing a laminated body of the example suppresses light leakage from adjacent light-emitting elements.

[0772] On the other hand, it is found that the laminate including a plurality of light-emitting elements obtained by the method for producing a laminate in Comparative Example 1 cannot obtain the above-mentioned effect.

[0773] Furthermore, it was confirmed that the laminated bodies obtained by the laminated body manufacturing methods of Examples 1 and 2 were able to display at a higher brightness than that of Example 1 and Comparative Example 1 when the light emitting element was turned on.

[0774] [Fabrication of micro LED display element of comparative example 2]

[0775] On the array substrate before connecting the LED chip, a partition wall structure is formed in advance using the transfer film 1, and then the LED chip is mounted on the substrate, thereby manufacturing a micro LED display element.

[0776] At this time, since the array substrate has a partition wall structure with a thickness of 33μm, it is difficult to install multiple micro LED chips together on the array substrate as in [[Installation of LED chips]] of Example 1. Therefore, a micro LED display element is produced by repeatedly joining the LED chips to the connecting parts one by one and peeling them off from the peeling sapphire substrate.

[0777] As a result, in Comparative Example 2, it took more than 100 times as long to manufacture the micro LED display element as in any of Examples 1 to 3.

[0778] Explanation of symbols

[0779] 10-substrate with light-emitting element, 12-substrate, 12A-substrate surface, T1-height of light-emitting element, 14-light-emitting element, 20, 20A, 20B-transfer film, 22-temporary support body, 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, θ-cone angle.

Claims

1. A method for producing a laminate, comprising: Step 1 of laminating the substrate with light-emitting elements and the transfer film so that the surface of the substrate with light-emitting elements on the light-emitting element side, which includes a substrate and a plurality of light-emitting elements arranged on the substrate, faces the surface of the transfer film on the side opposite to the temporary support, which includes a temporary support and a photosensitive layer, and the light-emitting elements are covered by the photosensitive layer; Step 2 of performing pattern exposure on the photosensitive layer; and Step 3 of developing the exposed photosensitive layer to form a resin pattern having an opening at a position corresponding to the light emitting element, There is a step of peeling off the temporary support between the step 1 and the step 2 or between the step 2 and the step 3.

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

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

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

5. The method for producing a laminate according to claim 1 or 2, wherein: In the photosensitive layer in the transfer film, a content of water is 5.0% by mass or less relative to the total mass of the photosensitive layer.

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

7. The method for producing a laminate according to claim 1 or 2, wherein: In the photosensitive layer in the transfer film, a content of chloride ions is 100 mass ppm or less relative to the total mass of the photosensitive layer.

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

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

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

11. The method for producing a laminate according to claim 1 or 2, wherein: After the step 3, the method further includes a step 4 of disposing a light reflecting film on the side wall of the opening.

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