Transfer film, pattern formation method, laminate, semiconductor package

Abstract

The present invention addresses the problem of providing a transfer film that makes it possible to form a film that contributes to suppression of migration between wirings. This transfer film includes, in order, a temporary support, a water-soluble resin layer, and a photosensitive composition layer. The photosensitive composition layer includes at least one specific compound selected from the group that consists of polyimide precursors, polyimides, polybenzoxazole precursors, polybenzoxazoles, phenol resins, epoxy resins, polyphenylene ether resins, silicone resins, benzocyclobutene resins, fluorine resins, liquid crystal polymers, polyether sulfones, polyarylates, polyetherimides, polybenzimidazoles, polyphenyl sulfones, polycarbonates, acrylonitrile-butadiene-styrene copolymer resins, and polyphenylene sulfides.

Description

Transfer film, pattern forming method, laminate, semiconductor package

[0001] The present invention relates to a transfer film, a pattern forming method, a laminate, and a semiconductor package.

[0002] In display devices (e.g., organic electroluminescence (EL) display devices and liquid crystal display devices) equipped with a touch panel such as a capacitance-type input device, conductive patterns such as an electrode pattern corresponding to a sensor in the viewing area, and wiring for peripheral wiring and lead-out wiring are provided inside the touch panel. An insulating film is used for the purpose of forming and protecting such electrode patterns and conductive patterns. Similarly, in multilayer printed wiring boards and build-up substrates for semiconductor packages, insulating films are provided between each layer for the purpose of insulating and protecting the wiring between the wiring.

[0003] As a composition capable of forming the above-described insulating layer, for example, Patent Document 1 discloses a resin composition for an insulating film of a high-frequency circuit board, which contains a resin, a porous compound, and a heterocyclic compound.

[0004] Japanese Patent Application Laid-Open No. 2020-045385

[0005] In terms of manufacturing efficiency, the insulating film described above is preferably formed using a transfer film. Furthermore, as described above, for example, in multilayer printed circuit boards and semiconductor packages, insulating films are provided above and below wiring layers, and in such configurations, it is required that migration between wirings be suppressed. The present inventors produced the transfer film disclosed in the above document and examined its properties, and found that there was room for improvement in the migration resistance evaluated using a film formed from the transfer film.

[0006] Therefore, an object of the present invention is to provide a transfer film capable of forming a film that contributes to suppressing migration between wirings. Another object of the present invention is to provide a pattern formation method, a laminate, and a semiconductor package related to the transfer film.

[0007] As a result of extensive research into solving the above problems, the present inventors have found that the problems can be solved by the following configuration.

[0008] [1] A transfer film comprising, in this order, a temporary support, a water-soluble resin layer, and a photosensitive composition layer, wherein the photosensitive composition layer contains at least one specific compound selected from the group consisting of polyimide precursors, polyimides, polybenzoxazole precursors, polybenzoxazole, phenolic resins, epoxy resins, polyphenylene ether resins, silicone resins, benzocyclobutene resins, fluorene resins, liquid crystal polymers, polyethersulfones, polyarylates, polyetherimides, polybenzimidazoles, polyphenylsulfones, polycarbonates, acrylonitrile-butadiene-styrene copolymer resins, and polyphenylene sulfides. [2] The transfer film according to [1], wherein the photosensitive composition layer contains a photopolymerization initiator. [3] The transfer film according to [1], wherein the surface free energy measured by measurement X is 40 mJ / m or less. ２ Measurement X: The temporary support is peeled off from a laminate obtained by laminating the transfer film and the substrate so that the photosensitive composition layer of the transfer film faces the substrate, the entire surface of the photosensitive composition layer is exposed from the exposed water-soluble resin layer side, the water-soluble resin layer is removed, and the exposed photosensitive composition layer is heated at 200°C for 1.5 hours in a nitrogen atmosphere to obtain a cured layer, and the surface free energy of the surface opposite to the substrate side is measured. [4] The polar component of the surface free energy is 10 mJ / m ２[5] The transfer film according to any one of [1] to [4], which satisfies at least one of the following requirements 1 and 2: Requirement 1: The specific compound has an ethylenically unsaturated double bond. Requirement 2: The photosensitive composition layer contains a compound having an ethylenically unsaturated double bond. [6] The transfer film according to [5], in which the molecular weight of the compound having an ethylenically unsaturated double bond is 800 or less. [7] The transfer film according to any one of [1] to [6], in which the specific compound contains at least one selected from the group consisting of a polyimide precursor, a polyimide, a polybenzoxazole precursor, and a polybenzoxazole. [8] The transfer film according to [2], in which the photopolymerization initiator contains a compound represented by formula (P1) described below. [9] The transfer film according to any one of [1] to [8], in which the photosensitive composition layer contains a chain transfer agent.

[10] The transfer film according to any one of [1] to [9], wherein the photosensitive composition layer contains a filler.

[11] The transfer film according to

[10] , wherein the filler contains at least one selected from the group consisting of silicon dioxide, boron nitride, barium sulfate, and silicates.

[12] The transfer film according to

[10] or

[11] , wherein the filler has an average particle size of 300 nm or less.

[13] The transfer film according to any one of

[10] to

[12] , wherein the filler has an average particle size of 150 nm or less.

[14] The transfer film according to any one of

[10] to

[13] , wherein the content of the filler is 30.0 mass% or more, relative to the total mass of the photosensitive composition layer.

[15] The transfer film according to any one of

[10] to

[14] , wherein the content of the filler is 90.0 mass% or less, relative to the total mass of the photosensitive composition layer.

[16] The transfer film according to any one of [1] to

[15] , wherein the photosensitive composition layer has a thickness of 3 to 30 μm.

[17] The transfer film according to any one of [1] to

[16] , wherein the water-soluble resin layer has a thickness of 5 μm or less.

[18] The transfer film according to any one of [1] to

[17] , wherein the water-soluble resin layer contains polyvinyl alcohol.

[19] The transfer film according to

[18] , wherein the content of the polyvinyl alcohol is 15.0 to 90.0% by mass relative to the total mass of the water-soluble resin layer.

[20] The transfer film according to any one of [1] to

[19] , wherein the water-soluble resin layer contains hydroxypropyl methylcellulose.

[21] The transfer film according to any one of [1] to

[20] , which is used for forming an insulating film.

[22] A pattern forming method comprising: Step 1: obtaining a laminate by laminating the transfer film according to any one of [1] to

[21] to a substrate so that the photosensitive composition layer of the transfer film faces the substrate; Step 2: removing the temporary support from the laminate obtained in Step 1; Step 3: pattern-exposing the photosensitive composition layer from the water-soluble resin layer side of the laminate from which the temporary support has been removed in Step 2; and Step 4: removing the water-soluble resin layer and the unexposed photosensitive composition layer from the pattern-exposed laminate to form a pattern having vias.

[23] A laminate comprising a pattern formed by the pattern forming method according to

[22] .

[24] A semiconductor package comprising the laminate according to

[23] .

[0009] According to the present invention, a transfer film capable of forming a film that contributes to suppressing migration between wirings can be provided. The present invention also provides a pattern formation method, a laminate, and a semiconductor package related to the transfer film.

[0010] FIG. 2 is a schematic diagram illustrating an example of a layer structure of a transfer film.

[0011] The present invention will be described in detail below. The following description of the components may be based on representative embodiments of the present invention, but the present invention is not limited to such embodiments.

[0012] In this specification, a numerical range expressed using "to" means a range that includes the numerical values ​​written before and after "to" as the lower and upper limits. Furthermore, in this specification, when two or more types of a certain component are present, the "content" of that component means the total content of those two or more components. In this specification, in a numerical range described in stages, the upper or lower limit value described in a certain numerical range may be replaced with the upper or lower limit value of another numerical range described in stages. Furthermore, in a numerical range described in this specification, the upper or lower limit value described in a certain numerical range may be replaced with a value shown in the Examples. In this specification, a combination of two or more preferred embodiments is a more preferred embodiment.

[0013] The term "step" in this specification includes not only an independent step, but also a step that cannot be clearly distinguished from other steps, as long as the intended purpose of the step is achieved.

[0014] In this specification, unless otherwise specified, the temperature condition may be 25° C. For example, the temperature when performing each of the above steps may be 25° C. unless otherwise specified.

[0015] In this specification, "transparent" means that the average transmittance of visible light in the wavelength range of 400 to 700 nm is 80% or more, and preferably 90% or more. The average transmittance of visible light is a value measured using a spectrophotometer, and can be measured using, for example, a spectrophotometer U-3310 manufactured by Hitachi, Ltd.

[0016] In this specification, unless otherwise specified, "exposure" includes not only exposure using far ultraviolet light, extreme ultraviolet light, X-rays, EUV light, etc., as typified by mercury lamps and excimer lasers, but also exposure using particle beams such as electron beams and ion beams.

[0017] In this specification, the "solid content" of the photosensitive composition layer refers to the components that form a film formed using the photosensitive composition layer. Typically, when the photosensitive composition layer contains a solvent (e.g., organic solvent and water, etc.), it refers to all components excluding the solvent. Furthermore, if it is a component that forms a film, liquid components are also considered to be solids. In this specification, the "solid content" of the water-soluble resin layer refers to all components excluding the solvent (e.g., organic solvent and water, etc.) from the components that form the water-soluble resin layer.

[0018] In this specification, unless otherwise specified, the content ratio of each repeating unit of the resin is a molar ratio. In this specification, unless otherwise specified, the molecular weight when there is a molecular weight distribution is the weight average molecular weight (Mw). In this specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are values ​​obtained by gel permeation chromatography (GPC) in terms of polystyrene.

[0019] In this specification, "(meth)acrylic acid" is a concept that encompasses both acrylic acid and methacrylic acid, "(meth)acryloyl group" is a concept that encompasses both acryloyl group and methacryloyl group, "(meth)acrylate" is a concept that encompasses both acrylate and methacrylate, and "(meth)acrylamide group" is a concept that encompasses both acrylamide group and methacrylamide group.

[0020] In this specification, the bonding direction of a divalent group (e.g., -CO-O-) is not limited unless otherwise specified. For example, when Y is -CO-O- in a compound represented by the formula "X-Y-Z," the compound may be "X-O-CO-Z" or "X-CO-O-Z." Unless otherwise specified, the compounds described in this specification may contain isomers (compounds having the same number of atoms but different structures), optical isomers, and isotopes. Furthermore, only one type of isomer or isotope may be contained, or multiple types may be contained.

[0021] In this specification, unless otherwise specified, the thickness (film thickness) of a layer is the average thickness measured using a scanning electron microscope (SEM) for thicknesses of 0.5 μm or more, and the average thickness measured using a transmission electron microscope (TEM) for thicknesses of less than 0.5 μm. The average thickness is obtained by cutting a sample to be measured using an ultramicrotome, measuring the thickness at any five points, and calculating the arithmetic average of the thicknesses.

[0022] In this specification, unless otherwise specified, the boiling point means the boiling point under normal pressure (1 atmosphere, 760 mmHg). In this specification, unless otherwise specified, the refractive index is a value measured by an ellipsometer at a wavelength of 550 nm.

[0023] [Transfer Film] The transfer film of the present invention will be described in detail below. The transfer film of the present invention comprises a temporary support, a water-soluble resin layer, and a photosensitive composition layer in this order, and the photosensitive composition layer comprises at least one specific compound selected from the group consisting of polyimide precursors, polyimides, polybenzoxazole precursors, polybenzoxazole, phenolic resins, epoxy resins, polyphenylene ether resins, silicone resins, benzocyclobutene resins, fluorene resins, liquid crystal polymers, polyethersulfones, polyarylates, polyetherimides, polybenzimidazoles, polyphenylsulfones, polycarbonates, acrylonitrile-butadiene-styrene copolymer resins, and polyphenylene sulfides.

[0024] While the reason why the transfer film having the above configuration can solve the problems of the present invention is not entirely clear, the inventors speculate as follows. The following speculation does not limit the mechanism by which the effect is obtained. In other words, even if the effect is obtained by a mechanism other than the one described below, it is still within the scope of the present invention. The transfer film of the present invention contains a predetermined specific compound in the photosensitive composition layer, thereby forming a film with excellent heat resistance. Furthermore, the transfer film contains a water-soluble resin layer on the photosensitive composition layer, which affects the surface properties of the cured film derived from the photosensitive composition layer on the water-soluble resin layer side. As a result, adhesion between the cured film and a layer laminated on the surface of the cured film exposed after the water-soluble resin layer is removed is improved, thereby blocking the effects of moisture, etc. It is speculated that these effects enable the film formed by the transfer film of the present invention to suppress migration between wirings. Hereinafter, the property of the film formed by the transfer film of the present invention to suppress migration between wirings will also be simply referred to as "excellent migration suppression."

[0025] As described above, the transfer film of the present invention has a temporary support, a water-soluble resin layer, and a photosensitive composition layer in this order. FIG. 1 is a cross-sectional schematic diagram showing an example of an embodiment of a transfer film. The transfer film 100 shown in FIG. 1 has a configuration in which a temporary support 12, a water-soluble resin layer 14, and a photosensitive composition layer 16 are laminated in this order. The transfer film 100 shown in FIG. 1 may have other layers not shown, for example, a cover film on the surface of the photosensitive composition layer 16 opposite the water-soluble resin layer 14. It is preferable that the photosensitive composition layer 16 and the water-soluble resin layer 14 are adjacent to each other. Each component of the transfer film will be described in detail below.

[0026] [Temporary Support] The transfer film includes a temporary support. The temporary support is a member that supports the photosensitive composition layer and is ultimately removed by a peeling treatment. In terms of excellent pattern formability, it is preferable that the temporary support is removed before exposure. The above-mentioned pattern formability refers to the property of easily forming a pattern of a designed size by photolithography, and means, for example, that when a pattern is formed using a mask, a pattern corresponding to the size of the opening of the mask is easily formed.

[0027] The temporary support may have either a single-layer structure or a multi-layer structure. The temporary support is preferably a film, more preferably a resin film. The temporary support is also preferably a film that is flexible and does not significantly deform, shrink, or stretch under pressure, or under pressure and heat. Examples of the film include polyethylene terephthalate (PET) films (e.g., biaxially oriented polyethylene terephthalate films), polymethyl methacrylate films, cellulose triacetate films, polystyrene films, polyimide films, and polycarbonate films, with polyethylene terephthalate films being preferred. Furthermore, the temporary support is preferably free of deformations such as wrinkles and scratches.

[0028] The temporary support preferably has high transparency. Specifically, the transmittance at each of the wavelengths of 313 nm, 365 nm, 405 nm, and 436 nm is preferably 60% or more, more preferably 70% or more, even more preferably 80% or more, and most preferably 90% or more. The upper limit is preferably less than 100%. Preferred values ​​of the transmittance at each of the above wavelengths include, for example, 87%, 92%, and 98%. The haze of the temporary support is preferably small. Specifically, the haze value of the temporary support is preferably 2% or less, more preferably 0.5% or less, and even more preferably 0.1% or less. The lower limit is preferably 0% or more. The number of fine particles, foreign matter, and defects contained in the temporary support is preferably small. The number of fine particles, foreign matter, and defects with a diameter of 1 μm or more in the temporary support is 50 / 10 mm ２ Preferably, 10 pieces / 10 mm or less ２More preferably, 3 pieces / 10 mm or less ２ More preferably, 0 pieces / 10 mm or less ２ is particularly preferred.

[0029] The thickness of the temporary support is preferably 5 to 200 μm, and from the viewpoint of ease of handling and versatility, more preferably 5 to 150 μm, still more preferably 5 to 50 μm, and particularly preferably 5 to 35 μm. The thickness of the temporary support can be calculated as the average value of any five points measured by cross-sectional observation using an SEM (scanning electron microscope).

[0030] In order to improve the adhesion between the temporary support and the adjacent layer, the surface of the temporary support may be modified by UV irradiation, corona discharge, plasma, etc. When the surface is modified by UV irradiation, the exposure dose of UV irradiation is 10 to 2000 mJ / cm. ２ is preferred, and 50 to 1000 mJ / cm ２ Examples of light sources for UV irradiation include low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, carbon arc lamps, metal halide lamps, xenon lamps, chemical lamps, electrodeless discharge lamps, and light-emitting diodes that emit light in the wavelength range of 150 to 450 nm. The lamp output and illuminance can be adjusted as appropriate.

[0031] Examples of the temporary support include a biaxially oriented polyethylene terephthalate film having a thickness of 16 μm, a biaxially oriented polyethylene terephthalate film having a thickness of 12 μm, and a biaxially oriented polyethylene terephthalate film having a thickness of 9 μm. The temporary support may be a recycled product. Examples of the recycled product include a film obtained by cleaning and chipping used films. Examples of commercially available recycled products include the Ecouse series (manufactured by Toray Industries, Inc.).

[0032] Examples of the temporary support include those described in paragraphs 0017 to 0018 of JP-A-2014-085643, paragraphs 0019 to 0026 of JP-A-2016-027363, paragraphs 0041 to 0057 of WO 2012 / 081680, and paragraphs 0029 to 0040 of WO 2018 / 179370, the contents of which are incorporated herein by reference.

[0033] The temporary support may have a layer containing fine particles (lubricant layer) on one or both sides of the temporary support for the purpose of imparting handleability. The diameter of the fine particles contained in the lubricant layer is preferably 0.05 to 0.8 μm. The film thickness of the lubricant layer is preferably 0.05 to 1.0 μm. Commercially available temporary supports include, for example, Lumirror 16FB40, Lumirror 16KS40, Lumirror #38-U48, Lumirror #75-U34, and Lumirror #25T60 (all manufactured by Toray Industries, Inc.); and Cosmoshine A4100, Cosmoshine A4160, Cosmoshine A4300, Cosmoshine A4360, and Cosmoshine A8300 (all manufactured by Toyobo Co., Ltd.).

[0034] [Water-soluble resin layer] The transfer film includes a water-soluble resin layer. The water-soluble resin layer is a layer containing a water-soluble resin. The water-soluble resin layer is preferably soluble in water or an alkaline developer, since it is easily removed when forming a pattern using the transfer film. The alkaline developer will be described later.

[0035] <Water-Soluble Resin> The water-soluble resin refers to a resin having a solubility of 0.1 g or more in 100 g of water having a pH of 7.0 and a liquid temperature of 22° C. Examples of the water-soluble resin include polyvinyl alcohol (PVA), polyvinylpyrrolidone (PVP), water-soluble cellulose derivatives, water-soluble salts of carboxyalkyl starch, polyacrylamide, water-soluble polyamides, water-soluble salts of poly(meth)acrylic acid, gelatin, polyethylene oxide, polyvinyl ether / maleic anhydride polymers, and styrene / maleic acid copolymers, with PVA, PVP, or water-soluble cellulose ethers being preferred.

[0036] The water-soluble cellulose derivatives include water-soluble cellulose ethers and water-soluble salts of carboxyalkyl celluloses. Examples of water-soluble cellulose ethers include hydroxypropylmethylcellulose (HPMC), hydroxyethylmethylcellulose (HEMC), methylcellulose (MC), and hydroxyethylcellulose (HEC), with HPMC being preferred. Examples of water-soluble salts of carboxyalkyl celluloses include carboxymethylcellulose (CMC) and metal salts of carboxyethylcellulose (e.g., alkali metal salts and alkaline earth metal salts). Examples of water-soluble cellulose derivatives include water-soluble cellulose ethers or metal salts of carboxymethylcellulose, with HPMC being more preferred.

[0037] The water-soluble resin may be used alone or in combination of two or more, preferably in combination of two or more. The water-soluble resin layer preferably contains at least one selected from PVA and PVP, more preferably PVA, and even more preferably PVA and PVP. The water-soluble resin layer also preferably contains a water-soluble cellulose derivative, more preferably HPMC. When the water-soluble resin layer contains a crystalline polymer such as PVA, the oxygen permeability of the water-soluble resin layer is reduced. This suppresses deactivation of radicals by oxygen during the process of patternwise exposing the photosensitive composition layer from the water-soluble resin layer side described below, improving pattern formability. In particular, when a compound represented by formula (P1) described below is used as the photopolymerization initiator, pattern formability (particularly fine pattern formability) is significantly improved. The reason for this is presumed to be as follows. The radicals generated from the compound represented by formula (P1) have a large molecular structure, and diffusion of the radicals is suppressed, so that deactivation of the radicals by oxygen is the dominant factor that reduces pattern formability. By combining the compound with the water-soluble resin layer as described above, deactivation of the radicals by oxygen is also suppressed, and therefore pattern formability (particularly fine pattern formability) is remarkably excellent.

[0038] The content of the water-soluble resin in the water-soluble resin layer is preferably 70.0% by mass or more, more preferably 80.0% by mass or more, and even more preferably 90.0% by mass or more, relative to the total mass of the water-soluble resin layer. The upper limit of the water-soluble resin content is 100% by mass or less, and preferably 99.0% by mass or less, relative to the total mass of the water-soluble resin layer. The content of PVA is preferably 15.0 to 90.0% by mass, more preferably 40.0 to 80.0% by mass, and even more preferably 60.0 to 70.0% by mass, relative to the total mass of the water-soluble resin layer. The content of PVP is preferably 10.0 to 50.0% by mass, more preferably 20.0 to 40.0% by mass, and even more preferably 25.0 to 35.0% by mass, relative to the total mass of the water-soluble resin layer. The content of the water-soluble cellulose derivative is preferably from 0.01 to 10.0% by mass, more preferably from 0.1 to 5.0% by mass, and even more preferably from 0.5 to 3.0% by mass, based on the total mass of the water-soluble resin layer.

[0039] <Surfactant> The water-soluble resin layer preferably contains a surfactant. Examples of the surfactant include a fluorine-based surfactant, a hydrocarbon-based surfactant, and a silicone-based surfactant. A silicone-based surfactant is preferred as the surfactant. From the viewpoint of improving environmental compatibility, it is also preferred that the surfactant does not contain a fluorine atom.

[0040] Examples of fluorosurfactants include acrylic compounds that have a molecular structure containing a functional group having a fluorine atom, and when heated, the functional group having the fluorine atom is cleaved, causing the fluorine atom to volatilize. Examples of such fluorosurfactants include the Megafac DS series (manufactured by DIC Corporation, Chemical Daily (February 22, 2016), Nikkei Business Daily (February 23, 2016), and Megafac DS-21). Furthermore, the fluorosurfactant may be 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. The fluorosurfactant may be a block polymer. The fluorosurfactant may also be a fluorine-containing polymer compound containing a repeating unit derived from a (meth)acrylate compound having a fluorine atom and a repeating unit derived from a (meth)acrylate compound having two or more (preferably five or more) alkyleneoxy groups (preferably ethyleneoxy groups or propyleneoxy groups). Further, examples of fluorine-based surfactants include fluorine-containing polymers having a group with an ethylenically unsaturated double bond in the side chain, such as Megafac RS-101, RS-102, RS-718K, and RS-72-K (all manufactured by DIC Corporation).

[0041] As the fluorine-based surfactant, from the viewpoint of improving environmental compatibility, surfactants derived from alternative materials to compounds having a linear perfluoroalkyl group having 7 or more carbon atoms, such as perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic acid (PFOS), are preferred.

[0042] Commercially available fluorine-based surfactants include, for example, Megafac F-171, F-172, F-173, F-176, F-177, F-141, F-142, F-143, F-144, F-437, F-475, F-477, F-479, F-482, F-551-A, F-552, F-554, F-555-A, F-556, F-557, F-558, F-559, F-560, F-561, F-565, F-563, F-568, F-575, and F-780 (all manufactured by DIC Corporation); EXP. MFS-324, EXP. MFS-330, EXP. MFS-578, EXP. MFS-578-2, EXP. MFS-579, EXP. MFS-586, EXP. MFS-587, EXP. MFS-628, EXP. MFS-631, EXP. MFS-603, R-41, R-41-LM, R-01, R-40, R-40-LM, RS-43, TF-1956, RS-90, R-94, RS-72-K, and DS-21 (all manufactured by DIC Corporation); Fluorad FC430, FC431, and 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, and KH-40 (all manufactured by AGC); PolyFox Examples of such products include PF636, PF656, PF6320, PF6520, and PF7002 (manufactured by OMNOVA); Ftergent 710FL, 710FM, 610FM, 601AD, 601ADH2, 602A, 215M, 245F, 251, 212M, 250, 209F, 222F, 208G, 710LA, 710FS, 730LM, 650AC, 681, and 683 (manufactured by NEOS Corporation); and U-120E (manufactured by Unichem).

[0043] Examples of hydrocarbon surfactants include glycerol, trimethylolpropane, trimethylolethane, and their ethoxylates and propoxylates (e.g., glycerol propoxylate and glycerol ethoxylate), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, and sorbitan fatty acid ester. Commercially available hydrocarbon surfactants include, for example, Pluronic (registered trademark) L10, L31, L61, L62, 10R5, 17R2, and 25R2, Tetronic 304, 701, 704, 901, 904, and 150R1, and HYDROPALAT WE 3323 (all manufactured by BASF); Solsperse 20000 (manufactured by Lubrizol Japan Corporation); NCW-101, NCW-1001, and NCW-1002 (all manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.); Paionin D-1105, D-6112, D-6112-W, and D-6315 (all manufactured by Takemoto Yushi Co., Ltd.); Olfine E1010, Surfynol 104, 400, and 440 (all manufactured by Nissin Chemical Industry Co., Ltd.).

[0044] Examples of silicone surfactants include linear polymers consisting of siloxane bonds, modified siloxane polymers with organic groups introduced into the side chains and / or terminals, and polymers having a repeating unit with a hydrophilic group in the side chain and a repeating unit with a group having a siloxane bond in the side chain.Preferred silicone surfactants are polymers having a repeating unit with a hydrophilic group in the side chain and a repeating unit with a group having a siloxane bond in the side chain.The polymers may be either random copolymers or block copolymers.

[0045] Commercially available silicone surfactants include, for example, EXP. S-309-2, EXP. S-315, EXP. S-503-2, EXP. S-505-2, and S-506 (all manufactured by DIC Corporation); DOWSIL 8032 ADDITIVE, Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, and Toray Silicone SH8400 (all manufactured by Dow Corning Toray Co., Ltd.); X-22-4952, X-22-4272, and X-22-626 6, KF-351A, K354L, KF-355A, KF-945, KF-640, KF-642, KF-643, X-22-6191, X-22-4515, KF-6004, KF-6001 , KF-6002, KP-101, KP-103, KP-104, KP-105, KP-106, KP-109, KP-112, KP-120, KP-121, KP-124, KP-125, KP -301, KP-306, KP-310, KP-322, KP-323, KP-327, KP-341, KP-368, KP-369, KP-611, KP-620, KP-621, KP-626, and KP-652 (all manufactured by Shin-Etsu Silicone Co., Ltd.); F-4440, TSF-4300, TSF-4445, TSF-4460, and TSF-4452 (all manufactured by Momentive Performance BYK300, BYK306, BYK307, BYK310, BYK320, BYK323, BYK325, BYK330, BYK313, BYK315N, BYK331, BYK333, BYK345, BYK347, BYK348, BYK349, BYK370, BYK377, BYK378, and BYK323 (all manufactured by BYK-Chemie).

[0046] Other examples of the surfactant include nonionic surfactants other than those mentioned above, such as those described in paragraph 0017 of Japanese Patent No. 04502784 and paragraphs 0060 to 0071 of JP-A-2009-237362.

[0047] The surfactant may be used alone or in combination of two or more. The content of the surfactant is preferably 0.1 to 10.0% by mass, more preferably 0.5 to 5.0% by mass, and even more preferably 1.0 to 3.0% by mass, based on the total mass of the water-soluble resin layer.

[0048] <Other Additives> The water-soluble resin layer may contain additives other than those described above, such as solvents, plasticizers, polymerization inhibitors, and impurities, as long as they do not impair water solubility.

[0049] The water-soluble resin layer may contain a solvent. Examples of the solvent include water and organic solvents. The organic solvent is preferably a water-miscible organic solvent that is miscible with water at any ratio. Examples of the water-miscible organic solvent include alcohol solvents having 1 to 3 carbon atoms, acetone, ethylene glycol, glycerin, and tetrahydrofuran. The solvent may be used alone or in combination of two or more.

[0050] When a composition containing an alkaline aqueous solution is used as a solvent in forming the water-soluble resin layer, the water-soluble resin layer may contain a basic compound component contained in the alkaline aqueous solution.

[0051] The thickness of the water-soluble resin layer is not particularly limited, but is preferably 10 μm or less, more preferably 5 μm or less, from the viewpoint of better pattern formability. The lower limit of the thickness of the water-soluble resin layer is preferably 0.3 μm or more, more preferably 0.5 μm or more.

[0052] The water-soluble resin layer preferably has high transparency in terms of excellent pattern formation when exposing the photosensitive composition layer from the water-soluble resin layer side. Specifically, the transmittance at wavelengths of 313 nm, 365 nm, 405 nm, and 436 nm is preferably 60% or more, more preferably 70% or more, even more preferably 80% or more, and most preferably 90% or more. The upper limit is preferably less than 100%. Preferred values ​​of the transmittance at each of the above wavelengths include, for example, 87%, 92%, and 98%. The haze of the water-soluble resin layer is preferably small. Specifically, the haze value of the water-soluble resin layer is preferably 2% or less, more preferably 0.5% or less, and even more preferably 0.1% or less. The lower limit is preferably 0% or more.

[0053] [Photosensitive composition layer] The transfer film includes a photosensitive composition layer. The photosensitive composition layer is not particularly limited as long as it contains a specific compound and a component that exhibits photosensitivity. The specific compound may also have photosensitivity.

[0054] <Specific Compound> The photosensitive composition layer contains at least one specific compound selected from the group consisting of polyimide precursors, polyimides, polybenzoxazole precursors, polybenzoxazoles, phenolic resins, epoxy resins, polyphenylene ether resins, silicone resins, benzocyclobutene resins, fluorene resins, liquid crystal polymers, polyethersulfones, polyarylates, polyetherimides, polybenzimidazoles, polyphenylsulfones, polycarbonates, acrylonitrile-butadiene-styrene copolymer resins, and polyphenylene sulfides. The specific compound preferably contains at least one selected from the group consisting of polyimide precursors, polyimides, polybenzoxazole precursors, and polybenzoxazoles, in terms of superior heat resistance, dielectric properties, and migration suppression properties. It is more preferable that the specific compound contains at least one selected from polyimide precursors and polyimides, and even more preferable that the specific compound is a polyimide precursor. The polyimide precursor and polybenzoxazole precursor are compounds that are converted to polyimides and polybenzoxazoles, respectively, by heat treatment, light treatment, or chemical treatment.

[0055] In terms of excellent photosensitivity, the specific compound preferably contains an ethylenically unsaturated double bond, and more preferably has a group having an ethylenically unsaturated double bond. Examples of the group having an ethylenically unsaturated double bond include a (meth)acryloyl group, a (meth)acrylamide group, a vinyl group, a styryl group, an allyl group, and a vinyl ether group, and a (meth)acryloyl group is preferred.

[0056] (Polyimide and polyimide precursor) Polyimide is a resin having an imide structure. As the polyimide, a resin having a cyclic imide structure is preferred, and may have a substituent. As the polyimide, a resin synthesized from a polyimide precursor having a repeating unit represented by formula (1) (for example, a resin obtained by a ring-closing reaction) is preferred. The polyimide precursor preferably has a repeating unit represented by formula (1).

[0057]

[0058] In formula (1), A １ and A ２ R each independently represents an oxygen atom or —NH—. １１１ represents a divalent organic group. １１３ and R １１４ R each independently represents a hydrogen atom or a monovalent organic group. １１５ represents a tetravalent organic group.

[0059] In formula (1), A １ and A ２ each independently represents an oxygen atom or —NH—. １ and A ２ is preferably an oxygen atom.

[0060] In formula (1), R １１１ represents a divalent organic group. Examples of the divalent organic group include a divalent aliphatic group, a divalent aromatic ring group, and a group formed by combining these. The divalent organic group is preferably a divalent aliphatic group having 2 to 20 carbon atoms, a divalent aromatic ring group having 6 to 20 carbon atoms, or a group formed by combining these, and more preferably a divalent aromatic ring group having 6 to 20 carbon atoms. The aliphatic group may be linear, branched, or cyclic. The aromatic ring group may be monocyclic or polycyclic. The aliphatic group and the aromatic ring group may have a heteroatom. Examples of the heteroatom include -O-, -CO-, -S-, and -SO. ２ It may be contained in the divalent organic group as a group such as - and -NHCO-. １１１ As the diamine, a divalent organic group derived from a diamine is also preferred. The diamine is preferably a diamine used in the production of a polyimide precursor, with aliphatic diamines or aromatic diamines being more preferred. The diamine is preferably a diamine having a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic ring group having 6 to 20 carbon atoms, or a group combining these, with diamines having an aromatic ring group having 6 to 20 carbon atoms (aromatic diamines) being more preferred. Examples of the aromatic ring group include groups having the following structure:

[0061]

[0062] In AR-8 to AR-10, A represents a divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms which may have a fluorine atom, —O—, —CO—, —S—, or —SO ２ A represents an alkylene group having 1 to 3 carbon atoms which may have a fluorine atom, -O-, -CO-, -S-, or -SO ２ - is preferred, and -CH ２ -, -O-, -S-, -SO ２ -, -C(CF ３ ) ２ - or -C(CH ３ ) ２ - is more preferred, and -O- is even more preferred.

[0063] R １１１ As for *-Ar ０ -L ０ -Ar ０ -* is also preferred. ０ each independently represents a divalent aromatic hydrocarbon group. ０ represents a divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms which may have a fluorine atom, -O-, -CO-, -S-, -SO ２ represents -, -NHCO-, a group formed by combining these, or a single bond. * represents the bonding position. ０ They may be the same or different from each other.

[0064] Ar ０ The number of carbon atoms in the divalent aromatic hydrocarbon group represented by the formula (I) is preferably 6 to 22, more preferably 6 to 18, and even more preferably 6 to 10. The aromatic hydrocarbon group is preferably a phenylene group. ０ has the same meaning as A described above, and the preferred embodiments are also the same.

[0065] Examples of diamines include 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, 1,6-diaminohexane; 1,2- or 1,3-diaminocyclopentane, 1,2-, 1,3-, or 1,4-diaminocyclohexane, 1,2-, 1,3-, or 1,4-bis(aminomethyl)cyclohexane, bis-(4-aminocyclohexyl)methane, bis-(3-aminocyclohexyl)methane, 4,4'-diamino-3,3'-dimethylcyclohexylmethane, or isophoronediamine; meta- or para- Phenylenediamine, diaminotoluene, 4,4'- or 3,3'-diaminobiphenyl, 4,4'-diaminodiphenyl ether, 3,3-diaminodiphenyl ether, 4,4'- or 3,3'-diaminodiphenylmethane, 4,4'- or 3,3'-diaminodiphenyl sulfone, 4,4'- or 3,3'-diaminodiphenyl sulfide, 4,4'- or 3,3'-diaminobenzophenone, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl (4,4'-diamino-2,2'-dimethyl biphenyl), 3,3'-dimethoxy-4,4'-diaminobiphenyl, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis(3-hydroxy-4-aminophenyl)propane, 2,2-bis(3-hydroxy-4-aminophenyl)hexafluoropropane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, bis(3-amino-4-hydroxyphenyl)sulfone, bis(4 -amino-3-hydroxyphenyl)sulfone, 4,4'-diaminoparaterphenyl, 4,4'-bis(4-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, bis[4-(2-aminophenoxy)phenyl]sulfone, 1,4-bis(4-aminophenoxy)benzene, 9,10-bis(4-aminophenyl)anthracene, 3,3'-dimethyl-4,4'-diaminodiphenylsulfone, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 9,10-bis(4-aminophenyl)anthracene, 3,3'-dimethyl-4,4'-diaminodiphenylsulfone, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenyl)anthracene ...3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenyl)benzene, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 4,4'-diaminooctafluorobiphenyl, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 9,9-bis(4-aminophenyl)-10-hydroanthracene, 3,3',4,4'-tetraafluorobenzoate aminobiphenyl, 3,3',4,4'-tetraaminodiphenyl ether, 1,4-diaminoanthraquinone, 1,5-diaminoanthraquinone, 3,3-dihydroxy-4,4'-diaminobiphenyl, 9,9'-bis(4-aminophenyl)fluorene, 4,4'-dimethyl-3,3'-diaminodiphenyl sulfone, 3,3',5,5'-tetramethyl-4,4'-diaminodiphenylmethane, 2-(3',5'-diaminobenzoyloxy)ethyl methacrylate, 2,4- or 2,5-diaminocumene, 2,5- Dimethyl-paraphenylenediamine, acetoguanamine, 2,3,5,6-tetramethyl-paraphenylenediamine, 2,4,6-trimethyl-metaphenylenediamine, bis(3-aminopropyl)tetramethyldisiloxane, 2,7-diaminofluorene, 2,5-diaminopyridine, 1,2-bis(4-aminophenyl)ethane, diaminobenzanilide, esters of diaminobenzoic acid, 1,5-diaminonaphthalene, diaminobenzotrifluoride, 1,3-bis(4-aminophenyl)hexafluoropropane , 1,4-bis(4-aminophenyl)octafluorobutane, 1,5-bis(4-aminophenyl)decafluoropentane, 1,7-bis(4-aminophenyl)tetradecafluoroheptane, 2,2-bis[4-(3-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(2-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)-3,5-dimethylphenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)-3,4,4'-bis(4-amino-2-trifluoromethylphenoxy)diphenyl sulfone, 4,4'-bis(3-amino-5-trifluoromethylphenoxy)diphenyl sulfone, 2,2-bis[4-(4-amino-3-trifluoromethylphenoxy)phenyl]hexafluoropropane, 3,3',5,5'-tetramethyl-4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, 2,2',5,5',6,6'-hexafluorotolidine, and 4,4'-diaminoquaterphenyl. Further, examples of diamines include compounds represented by any one of formulas (DA-1) to (DA-18).

[0066]

[0067]

[0068] Further, the diamine also includes a diamine having two or more alkylene glycol units in the main chain, and as the diamine having two or more alkylene glycol units in the main chain, a diamine containing two or more ethylene glycol chains and / or two or more propylene glycol chains in one molecule is preferred. Diamines not containing aromatic rings are also preferred. Examples of the diamine include the Jeffamine (registered trademark) series (KH-511, ED-600, ED-900, ED-2003, EDR-148, EDR-176, D-200, D-400, D-2000, and D-4000, manufactured by HUNTSMAN), 1-(2-(2-(2-aminopropoxy)ethoxy)propoxy)propan-2-amine, and 1-(1-(1-(2-aminopropoxy)propan-2-yl)oxy)propan-2-amine.

[0069] In formula (1), R １１３ and R １１４R each independently represents a hydrogen atom or a monovalent organic group. １１３ and R １１４ Preferably, at least one of R represents a group having a polymerizable group, １１３ and R １１４ It is more preferable that both R and R represent a group having a polymerizable group. Examples of the polymerizable group include the groups exemplified as the polymerizable group that the resin may have. The monovalent organic group may be a monovalent organic group X, which will be described later. １１３ and R １１４ As the alkyl group, a group having an ethylenically unsaturated double bond is preferred, and a vinyl group, an allyl group, a (meth)acryloyl group, or a group represented by formula (III) is more preferred.

[0070]

[0071] In formula (III), R ２００ represents a hydrogen atom or a methyl group. ２０１ represents an alkylene group having 2 to 12 carbon atoms, —CH ２ CH(OH)CH ２ - or a (poly)oxyalkylene group having 4 to 30 carbon atoms. * indicates the bonding position.

[0072] In formula (III), R ２００ represents a hydrogen atom or a methyl group. ２００ As the alkyl group, a methyl group is preferred.

[0073] In formula (III), R ２０１ represents an alkylene group having 2 to 12 carbon atoms, —CH ２ CH(OH)CH ２ -, or a (poly)oxyalkylene group having 4 to 30 carbon atoms. The number of carbon atoms in the alkylene group constituting the (poly)oxyalkylene group is preferably 1 to 12, more preferably 1 to 6, and even more preferably 1 to 3. The number of repeating oxyalkylene units constituting the (poly)oxyalkylene group is preferably 1 to 12, more preferably 1 to 6, and even more preferably 1 to 3. The (poly)oxyalkylene group is a concept that encompasses both an oxyalkylene group and a polyoxyalkylene group. R ２０１Examples of the alkyl group include an ethylene group, a propylene group, a trimethylene group, a tetramethylene group, a 1,2-butanediyl group, a 1,3-butanediyl group, a pentamethylene group, a hexamethylene group, an octamethylene group, a dodecamethylene group, and —CH ２ CH(OH)CH ２ -, and examples thereof include an ethylene group, a propylene group, a trimethylene group, or -CH ２ CH(OH)CH ２ - is preferred, and an ethylene group is more preferred.

[0074] R １１３ or R １１４ Examples of the monovalent organic group represented by the formula (I) include an aliphatic group, an aromatic ring group, and an arylalkyl group having 1 to 3 acid groups. Examples include an aromatic ring group having 6 to 20 carbon atoms and having an acid group, and an arylalkyl group having 7 to 25 carbon atoms and having an acid group. More specifically, examples include a phenyl group having an acid group and a benzyl group having an acid group. The acid group is preferably a hydroxyl group or a carboxy group. R １１３ and R １１４ Also preferred as R is a hydrogen atom, a 2-hydroxybenzyl group, a 3-hydroxybenzyl group, or a 4-hydroxybenzyl group. １１３ or R １１４ The monovalent organic group represented by the formula (I) also includes a leaving group which is eliminated by the action of an acid.

[0075] In formula (1), R １１５ represents a tetravalent organic group. As the tetravalent organic group, a tetravalent organic group having an aromatic ring is preferred, and a group represented by formula (5) or a group represented by formula (6) is more preferred.

[0076]

[0077] In formula (5), R １１２ represents a divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms which may have a fluorine atom, -O-, -CO-, -S-, -SO ２ * represents a bonding position. In formula (6), * represents a bonding position.

[0078] In formula (5), R１１２ has the same meaning as A described above, and the preferred embodiments are also the same.

[0079] The tetravalent organic group may be, for example, a tetracarboxylic acid residue remaining after removing the acid dianhydride group from a tetracarboxylic acid dianhydride. The tetracarboxylic acid dianhydride is preferably a compound represented by formula (7).

[0080]

[0081] In formula (7), R １１５ represents a tetravalent organic group. １１５ is R in formula (1). １１５ The same definition and preferred embodiments are also the same.

[0082] Examples of tetracarboxylic dianhydrides include pyromellitic acid, pyromellitic dianhydride (PMDA), 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfidetetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, and 3,3',4,4'-diphenylmethanetetracarboxylic dianhydride. hydrate, 2,2',3,3'-diphenylmethanetetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-benzophenonetetracarboxylic dianhydride, 4,4'-oxydiphthalic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,7-naphthalenetetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl)propane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 1,3-diphenylhexafluoropropane-3,3,4,4-tetracarboxylic dianhydride, 1,4,5,6-naphthalenetetracarboxylic dianhydride, 2,2',3,3'-diphenyltetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 1,2,4,5-naphthalene Examples thereof include tetracarboxylic acid dianhydride, 1,4,5,8-naphthalenetetracarboxylic acid dianhydride, 1,8,9,10-phenanthrenetetracarboxylic acid dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, 1,2,3,4-benzenetetracarboxylic acid dianhydride, and alkyl derivatives having 1 to 6 carbon atoms and alkoxy derivatives having 1 to 6 carbon atoms.

[0083] Examples of the tetracarboxylic dianhydride include compounds represented by any one of formulas (DAA-1) to (DAA-5).

[0084]

[0085] (Monovalent Organic Group X) The monovalent organic group X is preferably an alkyl group which may have a substituent or an aromatic ring group which may have a substituent, and more preferably an alkyl group which may have an aromatic ring group. The alkyl group may be linear, branched, or cyclic. The cyclic group may be monocyclic or polycyclic. The number of carbon atoms in the linear or branched alkyl group is preferably 1 to 30. The number of carbon atoms in the cyclic alkyl group (cycloalkyl group) is preferably 3 to 30. Examples of the alkyl group include linear or branched alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, octadecyl, isopropyl, isobutyl, sec-butyl, t-butyl, 1-ethylpentyl, and 2-ethylhexyl; monocyclic cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl; and polycyclic cycloalkyl groups such as adamantyl, norbornyl, bornyl, camphenyl, decahydronaphthyl, tricyclodecanyl, tetracyclodecanyl, campholoyl, dicyclohexyl, and pinenyl. The substituent that the alkyl group may have is preferably an aromatic ring group, as described below.

[0086] The aromatic ring group may be either an aromatic hydrocarbon ring group or an aromatic heterocyclic group. The aromatic ring group may be either a monocyclic or polycyclic ring. Examples of rings constituting the aromatic ring group include aromatic hydrocarbon rings such as a benzene ring, a naphthalene ring, a biphenyl ring, a fluorene ring, a pentalene ring, an indene ring, an azulene ring, a heptalene ring, an indacene ring, a perylene ring, a pentacene ring, an acenaphthene ring, a phenanthrene ring, an anthracene ring, a naphthacene ring, a chrysene ring, and a triphenylene ring; a pyrrole ring, a furan ring, a thiophene ring, an imidazole ring, an oxazole ring, a thiazole ring, a pyridine ring, a pyrazine ring, and a pyrimidine ring. Examples of aromatic heterocyclic groups include a pyridazine ring, an indolizine ring, an indole ring, a benzofuran ring, a benzothiophene ring, an isobenzofuran ring, a quinolizine ring, a quinoline ring, a phthalazine ring, a naphthyridine ring, a quinoxaline ring, a quinoxazoline ring, an isoquinoline ring, a carbazole ring, a phenanthridine ring, an acridine ring, a phenanthroline ring, a thianthrene ring, a chromene ring, a xanthene ring, a phenoxathiin ring, a phenothiazine ring, and a phenazine ring. As the substituent that the aromatic ring group may have, the above-mentioned alkyl group is preferred.

[0087] The repeating unit represented by formula (1) is preferably a repeating unit represented by formula (1-A) or a repeating unit represented by formula (1-B).

[0088]

[0089] In formula (1-A) and formula (1-B), A １１ and A １２ represents an oxygen atom or —NH—. １１１ and R １１２ R each independently represents a divalent organic group. １１３ and R １１４ each independently represents a hydrogen atom or a monovalent organic group.

[0090] In formula (1-A) and formula (1-B), A １１ , A １２ , R １１１ , R １１３ , and R １１４ are respectively represented by A in formula (1). １ , A２ , R １１１ , R １１３ , and R １１４ In formula (1-A), R １１２ In formula (5), R １１２ The same definition and preferred embodiments are also the same.

[0091] In formula (1-A), the bonding positions of the carbonyl group to the benzene ring are preferably 4, 5, 3', and 4' in formula (1-A).In formula (1-B), the bonding positions of the carbonyl group to the benzene ring are preferably 1, 2, 4, and 5 in formula (1-B).

[0092] The polyimide precursor may contain other repeating units in addition to the repeating unit represented by formula (1).

[0093] The content of the repeating unit represented by formula (1) is preferably 50 mol% or more, more preferably 70 mol% or more, and even more preferably 90 mol% or more, based on the total repeating units of the polyimide precursor. The upper limit is preferably 100 mol% or less.

[0094] The polyimide precursor preferably contains fluorine atoms. The content of fluorine atoms in the polyimide precursor is preferably 10% by mass or more, more preferably 20% by mass or more, based on the total mass of the polyimide precursor. The upper limit is preferably 50% by mass or less.

[0095] The polyimide precursor may be obtained by copolymerizing the repeating unit represented by formula (1) with an aliphatic group having a siloxane structure, which can improve adhesion to a substrate. Examples of the aliphatic group having a siloxane structure include bis(3-aminopropyl)tetramethyldisiloxane and bis(paraaminophenyl)octamethylpentasiloxane.

[0096] The weight-average molecular weight (Mw) of the polyimide precursor is preferably 2,000 to 500,000, more preferably 5,000 to 100,000, and even more preferably 10,000 to 50,000. The number-average molecular weight (Mn) of the polyimide precursor is preferably 800 to 250,000, more preferably 2,000 to 50,000, and even more preferably 4,000 to 25,000. The polyimide precursor has a polydispersity (Mw / Mn) of preferably 1.5 to 3.5, and more preferably 2.0 to 3.0.

[0097] (Polybenzoxazole and polybenzoxazole precursor) Polybenzoxazole is a resin having a benzoxazole ring. The polybenzoxazole is not particularly limited as long as it is a resin having a benzoxazole ring, and may have a substituent. The polybenzoxazole is preferably a resin synthesized from a polybenzoxazole precursor having a repeating unit represented by formula (2) (for example, a resin obtained by a ring-closing reaction). The polybenzoxazole precursor preferably has a repeating unit represented by formula (2).

[0098]

[0099] In formula (2), R １２１ represents a divalent organic group. １２２ represents a tetravalent organic group. １２３ and R １２４ each independently represents a hydrogen atom or a monovalent organic group.

[0100] In formula (2), R １２１ represents a divalent organic group. The divalent organic group may be any of the above-mentioned R １１１ Examples of the divalent organic group include a divalent organic group represented by the following formula:

[0101] In formula (2), R １２２ represents a tetravalent organic group. The tetravalent organic group may be any of the above-mentioned R １１５ Examples of the tetravalent organic group include a tetravalent organic group represented by the following formula:

[0102] In formula (2), R １２３ and R １２４ R each independently represents a hydrogen atom or a monovalent organic group. １２３and R １２４ is R １１３ and R １１４ The same definition and preferred embodiments are also the same.

[0103] The polybenzoxazole precursor may contain other repeating units in addition to the repeating unit represented by formula (2). Examples of the other repeating units include repeating units having a siloxane structure. Examples of the other repeating units include the repeating units described in paragraphs 0150 to 0154 of JP 2020-154205 A.

[0104] The weight-average molecular weight (Mw) of the polybenzoxazole precursor is preferably 2,000 to 500,000, more preferably 5,000 to 100,000, and even more preferably 10,000 to 50,000. The number-average molecular weight (Mn) of the polybenzoxazole precursor is preferably 800 to 250,000, more preferably 2,000 to 50,000, and even more preferably 4,000 to 25,000. The polybenzoxazole precursor has a polydispersity (Mw / Mn) of preferably 1.5 to 3.5, and more preferably 2.0 to 3.0.

[0105] (Phenol Resin) The phenol resin is a resin having a phenolic hydroxyl group. Examples of the phenol resin include phenol novolac resin, cresol novolac resin, biphenyl aralkyl phenol resin, naphthol aralkyl resin, and naphthol novolac resin. Examples of the phenol resin include AV Light series such as TR4020G, TR4050G, TR4080G, TR5020G, TR5050G, TR6020G, TR6050G, and TR6080G manufactured by Asahi Organic Chemicals Co., Ltd.; photoresist resin series manufactured by Sumitomo Bakelite Co., Ltd.; Resitop series manufactured by Gun-ei Chemical Industry Co., Ltd.; PR-30-40P, PR-100L, PR-100H, PR-50, PR-55, PR-56-1, PR-56-2, and WR. Phenolite series such as WR-101, WR-102, WR-103, and WR-104, manufactured by DIC Corporation; photoresist resins such as LF-100, LF-110, LF-120, LF-200, LF-400, and LF-500, manufactured by Lignite Corporation; MEHC-7851SS, MEHC-78004S, MEHC-7851-SS, MEHC-7851-S, MEHC-7851-M, MEHC-7851-H, MEHC-7800-4S, MEHC -7800-SS, MEHC-7800-S, MEHC-7800-M, and MEHC-7800-H, manufactured by Meiwa Kasei; GPH-65, GPH-103, and MEHC-7841-4S, manufactured by Nippon Kayaku; BisP-AP, BisP-MIBK, BisP-B, Bis-Z, BisP-CP, o,o'-BPF, BisP-IOTD, BisP-IBTD, BisP-DED, BisP-BA, Bis-C, Bis26X-A, BisOPP-A, Examples of the phenolic resin include BisOTBP-A, BisOCHP-A, BisOFP-A, BisOC-Z, BisOC-FL, BisOC-CP, BisOCHP-Z, MethylenebisP-CR, TM-BPF, BisOC-F, Bis3M6B-IBTD, BisOC-IST, BisP-IST, BisP-PRM, BisP-LV, BisE, and BisP-TMC manufactured by Honshu Chemical Co., Ltd.; and BisA, BisF, and BisP-M manufactured by Mitsui Chemicals Fine Co., Ltd. Examples of the phenolic resin include the resins described in JP 2021-157174 A.Further, examples of the phenolic resin include phenolic curing agents such as EPICLON series, EXB9451, EXB9460, EXB9460S, and HPC8000-65T (manufactured by DIC Corporation).

[0106] (Epoxy Resin) Epoxy resins are resins having epoxy groups. Examples of epoxy resins include bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, bisphenol AF type epoxy resins, dicyclopentadiene type epoxy resins, trisphenol epoxy resins, naphthol novolac type epoxy resins, phenol novolac type epoxy resins, tert-butyl-catechol type epoxy resins, naphthalene type epoxy resins, naphthol type epoxy resins, anthracene type epoxy resins, glycidylamine type epoxy resins, glycidyl ester type epoxy resins, cresol novolac type epoxy resins, biphenyl type epoxy resins, linear aliphatic epoxy resins, epoxy resins having a butadiene structure, alicyclic epoxy resins, heterocyclic epoxy resins, spiro ring-containing epoxy resins, cyclohexanedimethanol type epoxy resins, naphthylene ether type epoxy resins, and trimethylol type epoxy resins.

[0107] In view of improving the flexibility and breaking strength of the formed film, it is also preferable that the epoxy resin contains an epoxy resin that is liquid at a temperature of 20°C (hereinafter also referred to as "liquid epoxy resin") and an epoxy resin that is solid at a temperature of 20°C (hereinafter also referred to as "solid epoxy resin").

[0108] The liquid epoxy resin is preferably a bisphenol A epoxy resin, a bisphenol F epoxy resin, a phenol novolac epoxy resin, or a naphthalene epoxy resin, and more preferably a bisphenol A epoxy resin, a bisphenol F epoxy resin, or a naphthalene epoxy resin. Examples of liquid epoxy resins include HP4032, HP4032D, EXA4032SS, and HP4032SS (naphthalene epoxy resins) manufactured by DIC Corporation; jER828EL (bisphenol A epoxy resin), jER807 (bisphenol F epoxy resin), and jER152 (phenol novolac epoxy resin) manufactured by Mitsubishi Chemical Corporation; and ZX1059 (a mixture of bisphenol A epoxy resin and bisphenol F epoxy resin) manufactured by Nippon Steel Chemical & Materials Co., Ltd. The liquid epoxy resin is preferably HP4032SS or ZX1059.

[0109] As the solid epoxy resin, tetrafunctional naphthalene type epoxy resin, cresol novolac type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol epoxy resin, naphthol novolac type epoxy resin, biphenyl type epoxy resin, or naphthylene ether type epoxy resin is preferred, tetrafunctional naphthalene type epoxy resin, biphenyl type epoxy resin, or naphthylene ether type epoxy resin is more preferred, and biphenyl type epoxy resin is even more preferred. Examples of solid epoxy resins include HP-4700, HP-4710 (tetrafunctional naphthalene type epoxy resins), N-690 (cresol novolac type epoxy resin), N-695 (cresol novolac type epoxy resin), HP7200, HP7200H, HP7200K-65I (dicyclopentadiene type epoxy resin), EXA7311, EXA7311-G3, and HP6000 (naphthylene ether type epoxy resin), and EPPN-502H (trisphenol epoxy resin) manufactured by DIC Corporation. Examples of suitable epoxy resins include NC7000L (naphthol novolac epoxy resin), NC3000H, NC3000, NC3000L, and NC3100 (biphenyl epoxy resin), manufactured by Nippon Kayaku Co., Ltd.; ESN475 (naphthol novolac epoxy resin) and ESN485 (naphthol novolac epoxy resin), manufactured by Nippon Steel Chemical & Materials; and YX4000H, YL6121 (biphenyl epoxy resin), and YX4000HK (bixylenol epoxy resin), manufactured by Mitsubishi Chemical Corporation. Preferred solid epoxy resins are YX4000HK, NC3000L, and HP7200H.

[0110] (Polyphenylene ether resin) The polyphenylene ether resin is a resin having a phenylene ether group. The polyphenylene ether resin may have either a linear structure or a branched structure, and a branched structure is preferred. In the polyphenylene ether resin having a branched structure, it is preferred that ether bonds are directly bonded to at least three positions, i.e., the ipso position, the ortho position, and the para position, of at least one benzene ring constituting the polyphenylene ether resin.

[0111] The branched polyphenylene ether resin can be obtained, for example, by polymerizing two or more phenolic compounds. The phenolic compounds are preferably a phenolic compound having hydrogen atoms at the ortho- and para-positions and a polymerizable group, or a mixture of a phenolic compound having hydrogen atoms at the ortho- and para-positions but no polymerizable group and a phenolic compound having no hydrogen atom at the ortho-position, a hydrogen atom at the para-position, and a polymerizable group.

[0112] Examples of phenol compounds used in the synthesis of polyphenylene ether resins include o-vinylphenol, m-vinylphenol, o-allylphenol, m-allylphenol, 3-vinyl-6-methylphenol, 3-vinyl-6-ethylphenol, 3-vinyl-5-methylphenol, 3-vinyl-5-ethylphenol, 3-allyl-6-methylphenol, 3-allyl-6-ethylphenol, 3-allyl-5-methylphenol, 3-allyl-5-ethylphenol, phenol, o-cresol, m-cresol, o-ethylphenol, m-ethylphenol, 2,3-xylenol, 2,5-xylenol, 3,5-xylenol, o-tert-butylphenol, m-tert-butylphenol, o-phenylphenol, m-phenylphenol, and 2-dodecylphenol. , 2-allyl-6-methylphenol, 2-allyl-6-ethylphenol, 2-allyl-6-phenylphenol, 2-allyl-6-styrylphenol, 2,6-divinylphenol, 2,6-diallylphenol, 2,6-diisopropenylphenol, 2,6-dibutenylphenol, 2,6-diisobutenylphenol, 2,6-diisopentenylphenol, 2-methyl-6-styrylphenol, 2-vinyl-6-methylphenol, 2-vinyl-6-ethylphenol, 2,6-dimethylphenol, 2,3,6-trimethylphenol, 2-methyl-6-ethylphenol, 2-ethyl-6-n-propylphenol, 2-methyl-6-n-butylphenol, 2-methyl-6-phenylphenol, 2,6-diphenylphenol, and 2,6-ditolylphenol. Of these, 2,6-dimethylphenol or 2-allylphenol is preferred as the phenol compound.

[0113] It is also preferable that the polyphenylene ether resin has a polymerizable group. As the polymerizable group, a group having an ethylenically unsaturated double bond is preferable, and a vinylphenyl group or a (meth)acryloyl group is more preferable. Furthermore, when the polyphenylene ether resin has a polymerizable group, it is preferable that the composition contains a maleimide compound. The maleimide compound reacts with the polyphenylene ether resin to obtain a modified polyphenylene ether. As the modified polyphenylene ether, for example, a resin obtained by curing the resin composition described in WO 2022 / 102756 can be mentioned.

[0114] Examples of polyphenylene ether resins include poly(2,6-diethyl-1,4-phenylene) ether, poly(2-ethyl-6-n-propyl-1,4-phenylene) ether, poly(2,6-di-n-propyl-1,4-phenylene) ether, poly(2-methyl-6-n-butyl-1,4-phenylene) ether, poly(2-ethyl-6-isopropyl-1,4-phenylene) ether, poly(2-methyl-6-chloroethyl-1,4-phenylene) ether, poly(2-methyl-6-hydroxyethyl-1,4-phenylene) ether, and poly(2-methyl-6-chloroethyl-1,4-phenylene) ether. Examples of polyphenylene ether resins include resins described in JP 2022-157695 A.

[0115] (Silicone Resin) Silicone resin is a resin having an organosiloxane structure. Examples of silicone resin include curable silicone resin, silicone graft resin, and modified silicone resin such as alkyl-modified, and curable silicone resin is preferred. Examples of curable silicone resin include addition reaction type silicone resin, condensation reaction type silicone resin, and ultraviolet or electron beam curable silicone resin.

[0116] Examples of addition reaction silicone resins include resins obtained by reacting and curing polydimethylsiloxane having vinyl groups introduced at the end or side chain with hydrogen siloxane using a platinum catalyst. Examples of condensation reaction silicone resins include resins with a three-dimensional crosslinked structure formed by condensing polydimethylsiloxane having hydroxyl groups at the end with polydimethylsiloxane having hydrogen atoms at the end using an organotin catalyst. Examples of ultraviolet curable silicone resins include those that utilize the same radical reaction as silicone rubber crosslinking, those that introduce unsaturated groups and photocure, those that decompose onium salts with ultraviolet or electron beams to generate strong acids and cleave epoxy groups to crosslink, and those that crosslink via the addition reaction of thiol to vinyl siloxane. Specific examples include acrylate-modified polydimethylsiloxane and glycidoxy-modified polydimethylsiloxane. Examples of silicone resins include a dimethylsiloxane-methylvinylsiloxane copolymer capped at both molecular chain terminals with trimethylsiloxy groups, a dimethylsiloxane-diphenylsiloxane-methylvinylsiloxane copolymer capped at both molecular chain terminals with trimethylsiloxy groups, and a dimethylsiloxane-diphenylsiloxane copolymer capped at both molecular chain terminals with dimethylvinylsiloxy groups.

[0117] The silicone resin preferably has an aromatic ring, preferably an aromatic hydrocarbon ring, more preferably an aromatic hydrocarbon ring having 6 to 12 carbon atoms, and even more preferably a benzene ring.

[0118] As the silicone resin, a modified silicone resin obtained by reacting an organosilicon compound with a hydrosilylation agent is also preferred. The organosilicon compound preferably further has a polymerizable group. Examples of the polymerizable group include polymerizable groups contained in the resin. Examples of the organosilicon compound include compounds containing a silyl group, and 1,4-bis(dimethylsilyl)benzene or trivinylphenylsilane are preferred. The reaction temperature is preferably 100 to 200°C, and the reaction time is preferably 1 to 10 hours.

[0119] Examples of silicone resins include resins obtained from organosiloxanes and curable compositions described in JP-A-2020-026502.

[0120] (Other resins)

[0121] Benzocyclobutene resins are resins having a benzocyclobutene ring, such as divinylsiloxane-bisbenzocyclobutene resins (e.g., CYCLOTENE resins, manufactured by The Dow Chemical Company).

[0122] Fluorene resins are resins having a fluorene ring. Examples of fluorene resins include resins obtained by reacting a fluorene compound having a hydroxyaryl structure with an aldehyde compound, and derivatives thereof. Examples of the fluorene compound include 9,9-bis(4-hydroxyphenyl)fluorene, 9,9-bis(4-hydroxyphenyl)fluorene, and 9,9-bis(6-hydroxynaphthyl)fluorene.

[0123] A liquid crystal polymer is a resin that exhibits liquid crystallinity. A thermotropic liquid crystal polymer is preferred as the liquid crystal polymer. A thermotropic liquid crystal polymer refers to a polymer that exhibits liquid crystallinity within a predetermined temperature range. The thermotropic liquid crystal polymer may be any liquid crystal polymer that can be melt-molded, and examples thereof include thermoplastic liquid crystal polyesters and thermoplastic liquid crystal polyester amides in which an amide bond is introduced into a thermoplastic liquid crystal polyester.

[0124] The liquid crystal polymer preferably has a repeating unit having an aromatic ring. The aromatic ring is preferably an aromatic hydrocarbon ring, more preferably an aromatic hydrocarbon ring having 6 to 12 carbon atoms, and even more preferably a benzene ring. The monomer from which the repeating unit having an aromatic ring is derived is preferably p-hydroxybenzoic acid, 4,4'-dihydroxybiphenyl, hydroquinone, terephthalic acid, or isophthalic acid. The liquid crystal polymer preferably contains two or more repeating units derived from a compound selected from p-hydroxybenzoic acid, 4,4'-dihydroxybiphenyl, hydroquinone, terephthalic acid, and isophthalic acid, and more preferably contains four or five repeating units derived from the above compounds. The liquid crystal polymer may also contain repeating units derived from compounds other than the above compounds. Examples of liquid crystal polymers include the liquid crystal polymers described in JP 2006-299254 A and WO 2015 / 064437 A.

[0125] Examples of known resins include polyethersulfone, polyarylate, polyetherimide, polybenzimidazole, polyphenylsulfone, polycarbonate, acrylonitrile-butadiene-styrene copolymer resin (ABS resin), and polyphenylene sulfide.

[0126] As described above, the specific compound contained in the composition may be a precursor of each of the resins described above.

[0127] The weight average molecular weight (Mw) of the specific compound is preferably 2,000 to 500,000, more preferably 5,000 to 100,000, and even more preferably 5,000 to 50,000. The number average molecular weight (Mn) of the specific compound is preferably 800 to 250,000, more preferably 2,000 to 50,000, and even more preferably 4,000 to 25,000. The polydispersity (Mw / Mn) of the specific compound is preferably 1.0 to 3.5, and more preferably 2.0 to 3.0.

[0128] The specific compound may be used alone or in combination of two or more. The content of the specific compound is preferably 1.0 to 99.0 mass %, more preferably 5.0 to 90.0 mass %, and even more preferably 20.0 to 50.0 mass %, based on the total mass of the photosensitive composition layer excluding the filler. The content of the specific compound is preferably 5.0 to 99.0 mass %, based on the total mass of the photosensitive composition layer excluding the filler.

[0129] <Photopolymerization Initiator> The photosensitive composition layer preferably contains a photopolymerization initiator in terms of achieving better pattern formability.

[0130] Examples of the photopolymerization initiator include an oxime ester compound (a photopolymerization initiator having an oxime ester structure), an aminoacetophenone compound (a photopolymerization initiator having an aminoacetophenone structure), a hydroxyacetophenone compound (a photopolymerization initiator having a hydroxyacetophenone structure), an acylphosphine oxide compound (a photopolymerization initiator having an acylphosphine oxide structure), and a bistriphenylimidazole compound (a photopolymerization initiator having a bistriphenylimidazole structure). As the photopolymerization initiator, an oxime ester compound or an aminoacetophenone compound is preferred, and an oxime ester compound is more preferred.

[0131] Examples of the oxime ester compound include 1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2-(O-benzoyloxime)] (trade name: IRGACURE OXE-01, manufactured by BASF), ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime) (trade name: IRGACURE OXE-02, manufactured by BASF), [8-[5-(2,4,6-trimethylphenyl)-11-(2-ethylhexyl)-11H-benzo[a]carbazol-3-yl]-[2-(2,2,3,3-tetrafluoropropoxy)phenyl]methanone-(O-acetyloxime) (trade name: IRGACURE OXE-03, manufactured by BASF), and OXE-03, manufactured by BASF), 1-[4-[4-(2-benzofuranylcarbonyl)phenyl]thio]phenyl]-4-methylpentanone-1-(O-acetyloxime) (trade name: IRGACURE OXE-04, manufactured by BASF and trade name: Lunar 6, manufactured by DKSH Japan Co., Ltd.), 1-[4-(phenylthio)phenyl]-3-cyclopentylpropane-1,2-dione-2-(O-benzoyloxime) (trade name: TR-PBG-305, manufactured by Changzhou New Power Electronic Materials Co., Ltd.), 1,2-propanedione,3-cyclohexyl-1-[9-ethyl-6-(2-furanylcarbonyl)-9H-carbazol-3-yl]-,2-(O-acetyloxime) (trade name: TR-PBG-326, manufactured by Changzhou New Power Electronic Materials Co., Ltd.), and 3-cyclohexyl-1-(6-(2-(benzoyloxyimino)hexanoyl)-9-ethyl-9H-carbazol-3-yl)-propane-1,2-dione-2-(O-benzoyloxime) (trade name: TR-PBG-391, manufactured by Changzhou New Power Electronic Materials Co., Ltd.).

[0132] Examples of aminoacetophenone compounds include 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone (trade name: Omnirad 379EG, Omnirad series, manufactured by IGM Resins B.V.), 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one (trade name: Omnirad 907), and APi-307 (1-(biphenyl-4-yl)-2-methyl-2-morpholinopropan-1-one, manufactured by Shenzhen UV-ChemTech Ltd.).

[0133] Examples of the photopolymerization initiator include 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]phenyl}-2-methyl-propan-1-one (trade name: Omnirad 127), 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1 (trade name: Omnirad 369), 2-hydroxy-2-methyl-1-phenyl-propan-1-one (trade name: Omnirad 1173), 1-hydroxy-cyclohexyl-phenyl-ketone (trade name: Omnirad 184), 2,2-dimethoxy-1,2-diphenylethan-1-one (trade name: Omnirad 651), 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (trade name: Omnirad TPO), and H), and bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (trade name: Omnirad 819). Examples of the photopolymerization initiator include the photopolymerization initiators described in paragraphs 0031 to 0042 of JP 2011-095716 A and paragraphs 0064 to 0081 of JP 2015-014783 A.

[0134] The photopolymerization initiator is also preferably a compound represented by formula (P1), in that it has better fine pattern formability.

[0135]

[0136] In formula (P1), each R independently represents a substituent. The substituent represented by R is not particularly limited, and examples thereof include a halogen atom, an alkyl group, an alkoxy group, an alkynyl group, an alkenyl group, an aryl group, an aryloxy group, a formyl group, an acyl group, an alkoxycarbonyl group, an acyloxy group, a hydroxy group, an amino group, a carboxy group, a nitro group, and a cyano group. From the viewpoint of achieving superior effects of the present invention, a halogen atom, an alkyl group, or an alkoxy group is preferred, and an alkoxy group is more preferred. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, with a chlorine atom being preferred. The number of carbon atoms in the alkyl group and alkoxy group is preferably 1 to 10, more preferably 1 to 6, and even more preferably 1 to 3. The number of carbon atoms in the alkynyl group, alkenyl group, acyl group, alkoxycarbonyl group, and acyloxy group is preferably 2 to 10, more preferably 2 to 6, and even more preferably 2 to 4. Each of the groups shown as the substituents above may further have a substituent if possible. Such a substituent is preferably a halogen atom, a hydroxy group, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, and more preferably a halogen atom or a hydroxy group. When a plurality of Rs are present, the plurality of Rs may be the same or different.

[0137] In formula (P1), each n independently represents an integer of 0 to 5, preferably an integer of 0 to 3, and more preferably an integer of 0 to 2. The sum of all n's is an integer of 0 or greater, preferably an integer of 1 or greater, more preferably an integer of 0 to 10, and even more preferably an integer of 0 to 5. When n is 1 or greater, R is preferably located at at least one of the ortho-position and the para-position relative to the bonding position with the biimidazole skeleton.

[0138] Of the compounds represented by formula (P1), compounds represented by formula (P1-1) or formula (P1-2) are preferred, and compounds represented by formula (P1-1) are more preferred. In formulas (P1-1) and (P1-2), the definitions and preferred embodiments of R and n are the same as those in formula (P1).

[0139]

[0140] Examples of the compound represented by formula (P1) include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,1'-biimidazole, 2,2',4-tris(2-chlorophenyl)-5-(3,4-dimethoxyphenyl)-4',5'-diphenyl-1,1'-biimidazole, 2,2'-bis(2-methoxyphenyl)-4,4',5,5'-tetraphenyl-1,1'-biimidazole, 2-(o-chlorophenyl)-4,5-diphenylbiimidazole, and 2-(o-chlorophenyl)-4,5-bis-(m-methoxyphenyl) ) biimidazole, 2-(p-methoxyphenyl)-4,5-diphenylbiimidazole, 2,2',5-tris-(o-chlorophenyl)-4-(3,4-dimethoxyphenyl)-4',5'-diphenylbiimidazole, 2,4-bis-(o-chlorophenyl)-5-(3,4-dimethoxyphenyl)-diphenylbiimidazole, 2,4,5-tris-(o-chlorophenyl)-diphenylbiimidazole, 2-(o-chlorophenyl)-bis-4,5-(3,4-dimethoxyphenyl)-biimidazole, 2,2'-bis-(2-fluorophenyl) 2,2'-bis-(2,3-difluoromethylphenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,4-difluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,5-difluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,6-difluorophenyl)- phenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3,4-trifluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3,5-trifluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3,6-trifluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,4,2,2'-bis-(2,4,6-trifluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3,4,5-tetrafluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3,4,6-tetrafluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3,4,6-tetrafluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3,4,5,6-pentafluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2',4-tris(2-fluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, Examples of the biimidazole include 2,2'-bis(2-chlorophenyl)-5-(3,4-dimethoxyphenyl)-4',5'-diphenyl-1,1'-biimidazole, 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,1'-biimidazole, and 2,2'-bis(2-methoxyphenyl)-4,4',5,5'-tetraphenyl-1,1'-biimidazole. Preferred are 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,1'-biimidazole, 2,2',4-tris(2-chlorophenyl)-5-(3,4-dimethoxyphenyl)-4',5'-diphenyl-1,1'-biimidazole, and 2,2'-bis(2-methoxyphenyl)-4,4',5,5'-tetraphenyl-1,1'-biimidazole.

[0141] The content of the photopolymerization initiator is preferably 0.01 to 10.0% by mass, more preferably 0.1 to 5.0% by mass, and even more preferably 0.1 to 3.0% by mass, based on the total mass of the photosensitive composition layer.

[0142] <Chain Transfer Agent> In order to obtain superior fine pattern formability, the photosensitive composition layer preferably contains a chain transfer agent. Known compounds can be used as the chain transfer agent, and examples thereof include N-phenylglycine compounds, phenoxyacetic acid compounds, thiol compounds, disulfide compounds, thiophenoxy compounds, halogenated hydrocarbons, and secondary alcohols, with N-phenylglycine compounds being preferred. Examples of the N-phenylglycine compound include N-phenylglycine and derivatives thereof, with a compound represented by the following formula (II) being preferred:

[0143]

[0144] In formula (II), X represents a hydrogen atom or a monovalent organic group. The monovalent organic group is preferably a hydrocarbon group or a carboxy group, which may have a substituent. The hydrocarbon group, which may have a substituent, preferably has 1 to 10 carbon atoms, more preferably 2 to 9 carbon atoms. Examples of the hydrocarbon group include an alkyl group, a phenyl group, and a benzyl group. Examples of the substituent that the hydrocarbon group may have include a carboxy group, an amino group, an alkylamino group, and an anilinocarbonyl group. Examples of the monovalent organic group include an alkyl group having 1 to 10 carbon atoms, a carboxyalkyl group having 2 to 9 carbon atoms, a carboxyphenyl group, a carboxybenzyl group, an anilinocarbonylalkyl group having 2 to 9 carbon atoms, an anilinocarbonylphenyl group, and an anilinocarbonylbenzyl group.

[0145] In formula (II), R ｃ represents a hydroxy group, an alkoxy group, and —O － M ＋ Represents M ＋ represents an alkali metal cation. The number of carbon atoms in the alkoxy group is preferably 1 to 3, and more preferably 1. Examples of the alkali metal cation include Li ＋ , Na ＋ , and K ＋ Examples include:

[0146] Examples of the compound represented by formula (II) include the following compounds:

[0147]

[0148] The chain transfer agent may be used alone or in combination of two or more. The content of the chain transfer agent is preferably 5.0% by mass or less, more preferably 3.0% by mass or less, based on the total mass of the photosensitive composition layer. The content of the chain transfer agent is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, based on the total mass of the photosensitive composition layer.

[0149] <Compound Having an Ethylenically Unsaturated Double Bond (Polymerizable Compound)> The photosensitive composition layer preferably contains a compound having an ethylenically unsaturated double bond (hereinafter also referred to as a "polymerizable compound") in terms of more excellent pattern formability. The polymerizable compound is a compound different from the specific compound and the photopolymerization initiator described above. Examples of the ethylenically unsaturated double bond contained in the polymerizable compound include a (meth)acryloyl group, a (meth)acrylamide group, a vinyl group, a styryl group, an allyl group, and a vinyl ether group, and a (meth)acryloyl group is preferred.

[0150] The polymerizable compound is preferably a low-molecular-weight compound, and specifically, the molecular weight of the polymerizable compound is preferably 2000 or less, more preferably 1000 or less, and even more preferably 800 or less. The lower limit of the molecular weight of the polymerizable compound is preferably 120 or more, more preferably 200 or more. When the polymerizable compound has a molecular weight distribution, it is preferable that the weight-average molecular weight falls within the above range.

[0151] The number of ethylenically unsaturated double bonds in the polymerizable compound is 1 or more, preferably 2 or more, more preferably 2 to 10, and even more preferably 2 to 6. Examples of the polymerizable compound include a polymerizable compound having one ethylenically unsaturated double bond in one molecule (hereinafter also referred to as a "monofunctional polymerizable compound"), a polymerizable compound having two ethylenically unsaturated double bonds in one molecule (hereinafter also referred to as a "bifunctional polymerizable compound"), and a polymerizable compound having three or more ethylenically unsaturated double bonds in one molecule (hereinafter also referred to as a "trifunctional or higher functional polymerizable compound"). The polymerizable compound is preferably a bifunctional polymerizable compound or a trifunctional or higher functional polymerizable compound.

[0152] Examples of bifunctional polymerizable compounds include polyethylene glycol (meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, tricyclodecane dimenanol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, and 1,6-hexanediol di(meth)acrylate. Commercially available bifunctional polymerizable compounds include, for example, diethylene glycol dimethacrylate (2G, manufactured by Shin-Nakamura Chemical Co., Ltd.), triethylene glycol dimethacrylate (3G, manufactured by Shin-Nakamura Chemical Co., Ltd.), polyethylene glycol #200 dimethacrylate (4G, manufactured by Shin-Nakamura Chemical Co., Ltd.), tricyclodecane dimethanol diacrylate (A-DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.), tricyclodecane dimenanol dimethacrylate (DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.), 1,9-nonanediol diacrylate (A-NOD-N, manufactured by Shin-Nakamura Chemical Co., Ltd.), 1,6-hexanediol diacrylate (A-HD-N, manufactured by Shin-Nakamura Chemical Co., Ltd.), SR205NS (manufactured by Sartomer Inc.), and SR209 (manufactured by Sartomer Inc.).

[0153] Examples of trifunctional or higher functional polymerizable 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 with a glycerin tri(meth)acrylate skeleton. "(Tri / tetra / penta / hexa)(meth)acrylate" is a concept that encompasses tri(meth)acrylate, tetra(meth)acrylate, penta(meth)acrylate, and hexa(meth)acrylate, and "(tri / tetra)(meth)acrylate" is a concept that encompasses tri(meth)acrylate and tetra(meth)acrylate.

[0154] Examples of the polymerizable compound include caprolactone-modified (meth)acrylate compounds (KAYARAD (registered trademark) DPCA-20, etc., manufactured by Nippon Kayaku Co., Ltd., and A-9300-1CL, etc., manufactured by Shin-Nakamura Chemical Co., Ltd.), alkylene oxide-modified (meth)acrylate compounds (KAYARAD RP-1040, etc., manufactured by Nippon Kayaku Co., Ltd., ATM-35E and A-9300, etc., manufactured by Shin-Nakamura Chemical Co., Ltd., and EBECRYL (registered trademark) 135, etc., manufactured by Daicel-Allnex Corporation), and ethoxylated glycerin triacrylate (A-GLY-9E, etc., manufactured by Shin-Nakamura Chemical Co., Ltd.).

[0155] Examples of the polymerizable compound include urethane (meth)acrylates (preferably tri- or higher functional urethane (meth)acrylates). The number of polymerizable groups in the urethane (meth)acrylate is preferably 6 or more, and more preferably 8 or more. The upper limit is preferably 20 or less. Examples of tri- or higher functional urethane (meth)acrylates include 8UX-015A (manufactured by Taisei Fine Chemical Co., Ltd.); UA-32P, U-15HA, and UA-1100H (all manufactured by Shin-Nakamura Chemical Co., Ltd.); AH-600 (manufactured by Kyoeisha Chemical Co., Ltd.); UA-306H, UA-306T, UA-306I, UA-510H, and UX-5000 (all manufactured by Nippon Kayaku Co., Ltd.).

[0156] The polymerizable compound may have liquid crystallinity. The polymerizable compound having liquid crystallinity may be either a rod-shaped liquid crystal compound or a discotic liquid crystal compound, with a rod-shaped liquid crystal compound being preferred. Examples of polymerizable compounds having liquid crystallinity include compounds having a polymerizable group and a mesogenic group exhibiting liquid crystallinity, and compounds in which the polymerizable group and the mesogenic group are linked via a spacer are preferred. Examples of the spacer include linear aliphatic hydrocarbon groups and (poly)oxyalkylene groups. Examples of mesogenic groups include known mesogenic groups, such as groups in which two or more (preferably two or three) optionally substituted divalent cyclic groups (e.g., divalent aromatic cyclic groups and divalent alicyclic groups) are linked by a single bond or a divalent linking group. Examples of polymerizable compounds having liquid crystallinity include the compounds described in JP-A-11-513019.

[0157] The polymerizable compound may be used alone or in combination of two or more. The content of the polymerizable compound is preferably 0.1 to 40.0% by mass, more preferably 1.0 to 25.0% by mass, based on the total mass of the photosensitive composition layer.

[0158] <Filler> The photosensitive composition layer preferably contains a filler, since the dielectric properties of the film formed are more excellent. Since insulation reliability is more excellent, the average particle diameter of the filler is preferably 500 nm or less, more preferably 300 nm or less, and even more preferably 150 nm or less. The lower limit of the average particle diameter of the filler is greater than 0 nm, preferably 5 nm or more, more preferably 10 nm or more, even more preferably 50 nm or more, and particularly preferably 60 nm or more. The average particle diameter of the filler is also preferably 5 to 300 nm, more preferably 10 to 150 nm. The average particle diameter of the filler is a value calculated by the following particle diameter measurement method. Particle diameter measurement method: A rectangular region of 3 μm × 10 μm in a cross section of the photosensitive composition layer taken along the normal direction to the surface is observed with a scanning electron microscope, and the major axes of all fillers observed within the region are measured at five different locations on the photosensitive composition layer. The average value of the major axes of all fillers measured in each measurement is defined as the average particle diameter of the filler.

[0159] The particle size measurement method is described in detail below. A photosensitive composition layer is formed on a substrate (preferably a glass substrate). The thickness of the photosensitive composition layer is preferably 3 μm or more. Furthermore, to form the photosensitive composition layer, a drying treatment may be performed, if necessary, after applying the photosensitive composition layer-forming composition. A cross section of the obtained photosensitive composition layer along the normal direction to the surface (the surface opposite the substrate side) is cut out, and a rectangular region of 3 μm x 10 μm on the cross section is observed with a scanning electron microscope, and the major diameters of all fillers observed within the region are measured. The scanning electron microscope used is a Hitachi High-Tech S-4800. The magnification for observation is 50,000x. The above procedure is performed at five different locations on the photosensitive composition layer, and the average (arithmetic mean) of the major diameters of all fillers measured in each procedure is taken as the average particle size of the filler. The major diameter refers to the length of the longest line segment connecting any two points on the outline of the filler's outer shape in the observed image. Furthermore, when fillers are aggregated to form aggregates in the observed image, the major axis of each filler constituting the aggregate is measured.

[0160] Examples of fillers include organic fillers and inorganic fillers, with inorganic fillers being preferred. Examples of fillers include silicon dioxide (silica); silicates such as kaolinite, kaolin clay, calcined clay, talc, and glass fillers such as undoped glass; alumina, barium sulfate, mica powder, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum borate, barium titanate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, barium zirconate, calcium zirconate, zirconium phosphate, cordierite, zirconium tungstate, and manganese nitride. The filler preferably contains at least one selected from the group consisting of silicon dioxide (silica), boron nitride, barium sulfate, and silicates, and more preferably contains silicon dioxide (silica).

[0161] The shape of the filler may be either spherical or non-spherical (e.g., crushed or fibrous), with spherical being preferred. The filler may be surface-treated. Examples of surface treatments include treatments to introduce functional groups and treatments using known surface treatment agents. Examples of the functional groups include polymerizable groups (e.g., polymerizable groups possessed by polymerizable compounds) and hydrophobic groups. Examples of surface treatment agents include silane coupling agents, titanate coupling agents, and silazane compounds. Examples of methods for surface treatment of the filler include a dry method in which surface treatment is performed in a gas phase and a wet method in which surface treatment is performed in a liquid phase.

[0162] Examples of fillers include NHM-5N (manufactured by Tokuyama Corporation, silicon dioxide, solid content concentration 100% by mass), NHM-3N (manufactured by Tokuyama Corporation, silicon dioxide, solid content concentration 100% by mass), Seahoster KE-S30 (manufactured by Nippon Shokubai Co., Ltd., silicon dioxide, solid content concentration 100% by mass), YA050C-MJE (manufactured by Admatechs Co., Ltd., silicon dioxide, solid content concentration 50% by mass MEK slurry), SFP-20M (manufactured by Denka Co., Ltd., silicon dioxide), PMA-ST (manufactured by Nissan Chemical Industries, Ltd., silicon dioxide), and M Examples of such an emulsion include EK-ST-L (manufactured by Nissan Chemical Industries, Ltd., silicon dioxide), MEK-AC-5140Z (manufactured by Nissan Chemical Industries, Ltd., silicon dioxide), MEK-EC-2430Z (manufactured by Nissan Chemical Industries, Ltd., solids concentration 30% by mass), barium sulfate (manufactured by Nippon Solvay K.K., solids concentration 100% by mass), Y50SP-AM1 (manufactured by Admatechs Co., Ltd., silicon dioxide, MEK slurry with a solids concentration of 50% by mass), and Y50SZ-AM1 (manufactured by Admatechs Co., Ltd., silicon dioxide, MEK slurry with a solids concentration of 50% by mass).

[0163] The refractive index of the filler is preferably 0.5 to 30.0, and more preferably 1.2 to 1.8. The refractive index can be measured by the method described above.

[0164] The filler may be used alone or in combination of two or more. The content of the filler, relative to the total mass of the photosensitive composition layer, is preferably 20.0% by mass or more, and more preferably 30.0% by mass or more, in terms of superior dielectric properties and heat resistance. Furthermore, the content of the filler, relative to the total mass of the photosensitive composition layer, is preferably 90.0% by mass or less, more preferably 80.0% by mass or less, and even more preferably 70.0% by mass or less, in terms of step-conforming ability. The mass ratio of the filler content to the content of the specific compound is preferably 0.5 to 30.0, more preferably 1.0 to 20.0, and even more preferably 1.0 to 4.0.

[0165] <Thermal Base Generator> The photosensitive composition layer preferably contains a thermal base generator. When the photosensitive composition layer contains a resin precursor (for example, a polyimide precursor or a polybenzoxazole precursor), the photosensitive composition layer further contains a thermal base generator, which promotes the reaction of the resin precursor.

[0166] The thermal base generator is preferably an acidic compound or an onium salt compound (a compound consisting of a cation and an anion) that generates a base upon heating. The onium salt compound is preferably an ammonium salt compound (a compound consisting of an ammonium cation and an anion), an iminium salt compound (a compound consisting of an iminium cation and an anion), a sulfonium salt compound (a compound consisting of a sulfonium cation and an anion), an iodonium salt compound (a compound consisting of an iodonium cation and an anion), or a phosphonium salt compound (a compound consisting of a phosphonium cation and an anion), with an ammonium salt compound or an iminium salt compound being more preferred. The anion constituting the onium salt compound is preferably a carboxylate anion, a phenol anion, a phosphate anion, or a sulfate anion, with a carboxylate anion being more preferred. The anion constituting the ammonium salt compound also preferably has an aromatic ring. The aromatic ring may be, for example, A in the formula (A1) described below. ａ１ Examples of aromatic rings that constitute aromatic ring groups represented by the following formula are given.

[0167] The base generated by the thermal base generator is preferably a secondary amine or a tertiary amine, more preferably a tertiary amine. The base may be linear, branched, or cyclic, and is preferably cyclic.

[0168] The acidic compound is preferably a compound represented by formula (A1).

[0169]

[0170] In formula (A1), A ａ１ represents a p-valent organic group. ａ１ represents a monovalent organic group. ａ１ represents an (m+1)-valent linking group, m represents an integer of 1 or more, and p represents an integer of 1 or more.

[0171] In formula (A1), A ａ１ represents a p-valent organic group. Examples of the organic group include an aliphatic hydrocarbon group and an aromatic ring group, with an aromatic ring group being preferred. Examples of the monovalent aliphatic hydrocarbon group include an alkyl group and an alkenyl group. The alkyl group may be linear, branched, or cyclic. The alkyl group preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and even more preferably 1 to 10 carbon atoms. Examples of the alkyl group include a methyl group, an ethyl group, a tert-butyl group, a dodecyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and an adamantyl group. The alkenyl group may be linear, branched, or cyclic. The alkenyl group preferably has 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, and even more preferably 2 to 10 carbon atoms. Examples of the alkenyl group include a vinyl group, an allyl group, and a methallyl group. Examples of p-valent aliphatic hydrocarbon groups (where p is an integer of 2 or greater) include groups formed by removing (p-1) hydrogen atoms from the above-mentioned monovalent aliphatic hydrocarbon groups. The aliphatic hydrocarbon groups may further have a substituent.

[0172] The aromatic ring group may be either a monocyclic or polycyclic ring. The aromatic ring group may be either an aromatic hydrocarbon ring group or an aromatic heterocyclic group. Examples of the aromatic ring group include a benzene ring group, a naphthalene ring group, a pentalene ring group, an indene ring group, an azulene ring group, a heptalene ring group, an indacene ring group, a perylene ring group, a pentacene ring group, an acenaphthene ring group, a phenanthrene ring group, an anthracene ring group, a naphthacene ring group, a chrysene ring group, a triphenylene ring group, a fluorene ring group, a biphenyl ring group, a pyrrole ring group, a furan ring group, a thiophene ring group, an imidazole ring group, an oxazole ring group, a thiazole ring group, a pyridine ring group, a pyrazine ring group, a pyrimidine ring group, a pyridazine ... phenanthrene ring group, an anthracene ring group, a naphthacene ring group, a chrysene ring group, a triphenylene ring group, a fluorene ring group, a biphenyl ring group, a pyrrole ring group, a furan ring group, a thiophene ring group, an imidazole ring group, an oxazole ring group, a thiazole ring group, a pyr Examples of the aromatic ring group include a benzene ring group, an indolizine ring group, an indole ring group, a benzofuran ring group, a benzothiophene ring group, an isobenzofuran ring group, a quinolizine ring group, a quinoline ring group, a phthalazine ring group, a naphthyridine ring group, a quinoxaline ring group, a quinoxazoline ring group, an isoquinoline ring group, a carbazole ring group, a phenanthridine ring group, an acridine ring group, a phenanthroline ring group, a thianthrene ring group, a chromene ring group, a xanthene ring group, a phenoxathiin ring group, a phenothiazine ring group, and a phenazine ring group, and a benzene ring group is preferred. The aromatic ring group may further have a substituent.

[0173] In formula (A1), R ａ１ represents a monovalent organic group. Examples of the monovalent organic group include A ａ１ Examples of the monovalent organic group include a monovalent aliphatic hydrocarbon group and a monovalent aromatic ring group represented by the following formula: The monovalent organic group may further have a substituent. The substituent is preferably a carboxy group.

[0174] In formula (A1), L ａ１ represents an (m+1)-valent linking group. Examples of the (m+1)-valent linking group include an ether group (—O—), a carbonyl group (—CO—), an ester group (—COO—), a thioether group (—S—), and —SO ２ -, -NR Ｎ - (R Ｎrepresents a hydrogen atom or a substituent), divalent linking groups such as alkylene groups (preferably having 1 to 10 carbon atoms) and alkenylene groups (preferably having 2 to 10 carbon atoms); trivalent linking groups having a group represented by "-N<" and trivalent linking groups having a group represented by "-CR<" (R represents a hydrogen atom or a substituent); tetravalent linking groups having a group represented by ">C<"; k-valent linking groups having a cyclic group such as an aromatic ring group or an alicyclic group; and groups combining these.

[0175] In formula (A1), m represents an integer of 1 or greater. m is preferably 1 or 2, and more preferably 1.

[0176] In formula (A1), p represents an integer of 1 or greater. p is preferably 1 or 2, and more preferably 1.

[0177] Examples of the thermal base generator include the thermal base generators described in WO 2018 / 038002.

[0178] The temperature at which the thermal base generator generates a base is preferably the heating temperature in step 5 of the pattern formation method described below. The temperature at which the thermal base generator generates a base is, for example, preferably 50 to 400°C, more preferably 100 to 250°C. The temperature at which the thermal base generator generates a base can be a measured value obtained by a known measurement method or a literature value. For example, the base generation temperature can be determined by differential scanning calorimetry, where a compound to be measured is heated to 250°C at 5°C / min in a pressure-resistant capsule, and the peak temperature of the lowest exothermic peak is the base generation temperature.

[0179] The thermal base generator may be used alone or in combination of two or more. The content of the thermal base generator is preferably 0.01 to 10.0 mass %, more preferably 0.1 to 5.0 mass %, relative to the total mass of the photosensitive composition layer. The mass ratio of the content of the thermal base generator to the content of the specific compound is preferably 0.0005 to 1.0, more preferably 0.001 to 0.1, and even more preferably 0.01 to 0.05.

[0180] <Plasticizer> The photosensitive composition layer may contain a plasticizer. When a plasticizer is contained, the photosensitive composition layer has excellent step conformability when laminated to an object to be laminated, and has excellent pattern formability, which is preferable. The plasticizer is a compound different from the various components described above, and preferably does not have a polymerizable group.

[0181] The molecular weight of the plasticizer is preferably from 200 to 1000, more preferably from 250 to 800, and even more preferably from 300 to 600. When the plasticizer has a molecular weight distribution, the above molecular weight refers to the weight average molecular weight.

[0182] The boiling point of the plasticizer is preferably 230 to 500°C, more preferably 280 to 480°C, even more preferably 300 to 450°C, and particularly preferably 350 to 450°C. The above boiling point is the boiling point under normal pressure (760 mmHg). In this specification, the boiling point of a compound is a value determined by the following measurement method. When a compound is distilled under normal pressure (760 mmHg), the boiling point is the gas temperature at which condensation of the evaporated gas begins (measured from 23 to 300°C, temperature rise rate 1°C / min). The compound is distilled using a Liebig condenser, and if distillation does not begin at 300°C under normal pressure, the distillation is carried out under reduced pressure. Similar distillation was carried out sequentially at pressures of 100 mmHg, 50 mmHg, and 5 mmHg (measurement from 23 to 300°C, temperature increase rate 1°C / min, if distillation did not start at 300°C, distillation was carried out at the next pressure), and the boiling point at atmospheric pressure was calculated using the nomograph described in Science of Petroleum, Vol. II, p. 1281 (1938) from the temperature and pressure at which condensation of the evaporated gas began. The boiling point at atmospheric pressure was taken as the calculated boiling point. If distillation did not start at 300°C under 5 mmHg, the boiling point at atmospheric pressure was deemed to be greater than 500°C. The method of using a nomograph is well known. Specifically, a straight line was drawn between the boiling point at reduced pressure on line A and the degree of reduced pressure on line C (Procedure 1), and the value at the intersection of the line drawn in Procedure 1 and line B was read (Procedure 2), and this was deemed to be the boiling point at atmospheric pressure.

[0183] The viscosity of the plasticizer at 25° C. is preferably 0.01 to 500 mPa·s, more preferably 0.05 to 300 mPa·s, and even more preferably 0.1 to 100 mPa·s. The viscosity can be measured using a B-type viscometer.

[0184] Examples of the plasticizer include polycarboxylic acid esters, phosphoric acid esters, polyether esters, alkylene glycol monoalkyl ethers, alkylene glycol dialkyl ethers, and benzyl benzoate, with polycarboxylic acid esters being preferred.

[0185] Examples of polycarboxylic acid esters include aliphatic dicarboxylic acid esters (e.g., adipic acid esters, azelaic acid esters, and sebacate esters); aromatic dicarboxylic acid esters (e.g., phthalic acid esters); trimellitic acid esters; and citrate esters (e.g., tributyl acetyl citrate). Examples of polycarboxylic acid esters include ethyl phthalyl ethyl glycolate, dihexyl phthalate, tributyl o-acetyl citrate, benzyl 2-ethylhexyl phthalate, bis(2-ethylhexyl) isophthalate, tris(2-ethylhexyl) trimellitate, and bis(2-butoxyethyl) adipate.

[0186] Examples of phosphate esters include triamyl phosphate and tris(2-butoxyethyl) phosphate.

[0187] The polyether esters are preferably organic acid esters of polyalkylene glycol. Examples of organic acids include monocarboxylic acids (e.g., butanoic acid, isobutanoic acid, 2-ethylbutyric acid, 2-ethylhexyl acid, and decanoic acid). Specific examples of polyether esters include triethylene glycol bis-2-ethylhexanoate.

[0188] Examples of alkylene glycol monoalkyl ethers and alkylene glycol dialkyl ethers include hexaethylene glycol monomethyl ether (mPEG6-OH), pentaethylene glycol monomethyl ether, tetraethylene glycol monomethyl ether, heptaethylene glycol monomethyl ether, octaethylene glycol monomethyl ether, nonaethylene glycol monomethyl ether, pentaethylene glycol dimethyl ether, hexaethylene glycol dimethyl ether, heptaethylene glycol dimethyl ether, octaethylene glycol dimethyl ether, and nonaethylene glycol dimethyl ether.

[0189] The plasticizer may be used alone or in combination of two or more. The content of the plasticizer is preferably 1.0 to 50.0% by mass, and more preferably 3.0 to 30.0% by mass, relative to the total mass of the photosensitive composition layer. The mass ratio of the plasticizer content to the specific compound content is preferably 0.1 to 10.0, and more preferably 0.5 to 7.0. The mass ratio of the plasticizer content to the filler content is preferably 0.01 to 1.0, and more preferably 0.2 to 0.7.

[0190] <Surfactant> The photosensitive composition layer preferably contains a surfactant.

[0191] Examples of surfactants include fluorine-based surfactants, hydrocarbon-based surfactants, and silicone-based surfactants. Silicone-based surfactants are preferred as surfactants. From the viewpoint of improving environmental compatibility, it is also preferred that the surfactant does not contain fluorine atoms.

[0192] Examples of the surfactant include the surfactants that may be contained in the water-soluble resin layer described above.

[0193] The surfactant may be used alone or in combination of two or more. The content of the surfactant is preferably from 0.01 to 3.0% by mass, more preferably from 0.05 to 1.0% by mass, and still more preferably from 0.1 to 0.8% by mass, based on the total mass of the photosensitive composition layer.

[0194] <Rust inhibitor> The photosensitive composition layer preferably contains a rust inhibitor. Examples of the rust inhibitor include heterocyclic compounds. 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, pyrimidine compounds, and pyridine compounds, and triazole compounds, benzotriazole compounds, or tetrazole compounds are preferred. Examples of the heterocyclic compound include compounds described in International Publication No. 2022 / 039027.

[0195] The content of the rust inhibitor is preferably 0.01 to 3.0% by mass, more preferably 0.05 to 1.0% by mass, and even more preferably 0.1 to 0.8% by mass, based on the total mass of the photosensitive composition layer.

[0196] <Other Additives> The photosensitive composition layer may contain other additives in addition to those described above. Examples of the other additives include a photoacid generator, a curing agent, an aliphatic thiol compound, a thermally crosslinkable compound, a polymerization inhibitor, a hydrogen donor compound, a solvent, impurities, a sensitizer, an alkoxysilane compound, a maleimide compound, and a hydrosilylation agent.

[0197] (Solvent) The photosensitive composition layer may contain a solvent. The solvent is not particularly limited as long as it can dissolve or disperse various components other than the solvent that may be contained in the photosensitive composition layer. Examples of solvents include water, alkylene glycol ether solvents, alkylene glycol ether acetate solvents, alcohol solvents (e.g., methanol and ethanol), ketone solvents (e.g., acetone and methyl ethyl ketone), aromatic hydrocarbon solvents (e.g., toluene), aprotic polar solvents (e.g., N,N-dimethylformamide), cyclic ether solvents (e.g., tetrahydrofuran), ester solvents (e.g., n-propyl acetate), amide solvents, lactone solvents, and solvents containing two or more of these. The solvents may be used alone or in combination. The content of the solvent is preferably 50 to 1900 parts by mass, more preferably 100 to 1200 parts by mass, and even more preferably 100 to 900 parts by mass, relative to 100 parts by mass of the total solids content of the photosensitive composition layer.

[0198] (Polymerization Inhibitor) The photosensitive composition layer preferably contains a polymerization inhibitor, in order to obtain a more excellent fine pattern formability. Examples of the polymerization inhibitor include radical scavengers, and specific examples thereof include imino compounds such as phenothiazine, phenoxazine, and bis(2,2,6,6-tetramethyl-4-piperidyl)-sebacate, hydroquinone, 4-t-butylcatechol, 2-t-butylhydroquinone, hydroquinone monomethyl ether, 2,6-di-t-butyl-p-cresol, 2,2-methylene-bis(4-methyl-6-t-butylphenol), 1,1,3-tris(2-methyl-4-hydroxy- phenolic compounds such as 1,3,5-tris(3,5-di-t-butyl-4-hydroxybenzyl)-S-triazine-2,4,6-(1H,3H,5H)trione, quinone compounds such as methaquinone and benzoquinone, nitro compounds, and nitroso compounds, with phenothiazine, phenoxazine, or quinone compounds being preferred.

[0199] The polymerization inhibitor may be used alone or in combination of two or more. The content of the polymerization inhibitor is preferably 0.01 to 5.0% by mass, more preferably 0.1 to 3.0% by mass, based on the total mass of the photosensitive composition layer.

[0200] (Sensitizer) The photosensitive composition layer preferably contains a sensitizer, as this provides better fine pattern formability. The sensitizer is not particularly limited, and examples thereof include benzoin-based compounds, benzophenone-based compounds, xanthone-based compounds, thioxanthone-based compounds, acetophenone-based compounds, anthraquinone-based compounds, ketal-based compounds, fluorene-based compounds, naphthoquinone-based compounds, and coumarin-based compounds. Benzophenone-based or thioxanthone-based compounds are preferred, and benzophenone-based compounds are more preferred. Examples of benzophenone-based compounds include benzophenone, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone (EAB-F), and 4,4'-bis(ethylmethylamino)benzophenone, with EAB-F being preferred.

[0201] Examples of the sensitizer include the compounds described in paragraphs

[0113] to

[0116] of JP-A-2021-120946, the contents of which are incorporated herein by reference.

[0202] The content of the sensitizer is preferably 5.0% by mass or less, more preferably 1.0% by mass or less, based on the total mass of the photosensitive composition layer, and is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, based on the total solid content of the photosensitive composition.

[0203] Examples of the aliphatic thiol compound, thermal crosslinking compound, polymerization inhibitor, and hydrogen donor compound include the various components described in WO 2022 / 039027. Examples of the sensitizer and alkoxysilane compound include the components described in paragraphs 0097 to 0119 of WO 2018 / 179640. Examples of the maleimide compound (a compound having a maleimide ring) include known maleimide compounds and the maleimide compounds described in WO 2022 / 102756. Examples of the hydrosilylation agent include platinum catalysts such as platinum metal-supported carbon powder, platinum black, platinic chloride, chloroplatinic acid, reaction products of chloroplatinic acid and monohydric alcohols, complexes of chloroplatinic acid and olefins, and platinum bisacetoacetate; and platinum group metal catalysts such as palladium-based catalysts and rhodium-based catalysts. The hydrosilylation agent is preferably used as a curing agent when a silicone resin or a precursor thereof is used as the resin.

[0204] The photosensitive composition layer may contain a component derived from the water-soluble resin layer (for example, a water-soluble resin).

[0205] <Requirements 1 and 2> In terms of achieving better pattern formability and heat resistance, the photosensitive composition layer preferably satisfies at least one of the following requirements 1 and 2, and more preferably satisfies requirements 1 and 2. Requirement 1: The specific compound has an ethylenically unsaturated double bond. Requirement 2: The photosensitive composition layer contains a compound (polymerizable compound) having an ethylenically unsaturated double bond.

[0206] The thickness of the photosensitive composition layer is not particularly limited, but is preferably from 1 to 100 μm, more preferably from 3 to 50 μm, and even more preferably from 3 to 30 μm.

[0207] [Other Layers] The transfer film may include other layers.

[0208] <Cover Film> The transfer film may include a cover film. The cover film is preferably provided on the outermost surface of the photosensitive composition layer opposite to the water-soluble resin layer. The number of fisheyes with a diameter of 80 μm or more contained in the cover film is 5 / m. ２ The following are preferred: Fisheyes are foreign matter, undissolved matter, and / or oxidized and deteriorated matter of the material that is introduced into the film when the material is thermally melted and then kneaded, extruded, and / or biaxially stretched, cast, or other methods are used to produce the film.

[0209] The number of particles with a diameter of 3 μm or more contained in the cover film is 30 / mm ２ Preferably, 10 pieces / mm or less ２ More preferably, 5 or less pieces / mm ２ The following is more preferable: This can suppress defects caused by the transfer of irregularities due to particles contained in the cover film to the composition layer.

[0210] The arithmetic mean roughness Ra of the surface of the cover film is preferably 0.01 μm or more, more preferably 0.02 μm or more, and even more preferably 0.03 μm or more.If Ra is within this range, for example, when the transfer film is long, the winding property of the transfer film is excellent.In addition, from the viewpoint of suppressing defects during transfer, Ra is preferably less than 0.50 μm, more preferably 0.40 μm or less, and even more preferably 0.30 μm or less.

[0211] Examples of the cover film include polyethylene terephthalate film, polypropylene film, polystyrene film, and polycarbonate film, and examples of the cover film include the cover films described in paragraphs 0083 to 0087 and 0093 of JP-A No. 2006-259138.

[0212] Examples of cover films include Alphan (registered trademark) FG-201 (manufactured by Oji F-Tex Co., Ltd.), Alphan (registered trademark) E-201F (manufactured by Oji F-Tex Co., Ltd.), Therapeel (registered trademark) 25WZ (manufactured by Toray Advanced Film Co., Ltd.), and Lumirror (registered trademark) 16QS62 (16KS40) (manufactured by Toray Industries, Inc.). The cover film may be a recycled product. Examples of recycled products include those obtained by cleaning and chipping used films and then forming the resulting material into films. Examples of commercially available recycled products include the Ecouse series (manufactured by Toray Industries, Inc.).

[0213] The transfer film may have a high refractive index layer. Examples of high refractive index layers include those described in paragraphs 0168 to 0188 of WO 2021 / 187549, the contents of which are incorporated herein by reference.

[0214] [Surface Free Energy] The transfer film has a surface free energy of 30 mJ / m or less as measured by measurement X, which is indicative of superior adhesion between the film formed by the transfer film and the insulating film and superior effects of the present invention. ２ It is preferable that the concentration is 40 mJ / m or more. ２ It is more preferable that the surface free energy is 80 mJ / m or more. ２ In most cases, it is less than 70 mJ / m ２ Preferably, it is 60 mJ / m or less. ２ The polar component of the surface free energy is more preferably 5 mJ / m or less. ２ It is preferable that the concentration is 10 mJ / m or more. ２ More preferably, 15 mJ / m or more ２ It is more preferable that the polar component of the surface free energy is 50 mJ / m or more. ２ In most cases, it is less than 40 mJ / m ２ Preferably, it is 30 mJ / m or less. ２ More preferably, it is:

[0215] Measurement X: A transfer film and a substrate are laminated together so that the photosensitive composition layer of the transfer film faces the substrate, and the temporary support is peeled off from the resulting laminate. The entire surface of the photosensitive composition layer is exposed from the exposed water-soluble resin layer side, the water-soluble resin layer is removed, and the exposed photosensitive composition layer is heated at 200°C for 1.5 hours in a nitrogen atmosphere to obtain a cured layer, and the surface free energy of the surface opposite to the substrate side is measured.

[0216] The method for laminating the transfer film and the substrate is not particularly limited, and examples thereof include the method described in step 1 of the pattern forming method described below.

[0217] The exposure method for the photosensitive composition layer is not limited as long as it is performed from the water-soluble resin layer side exposed by peeling off the temporary support and on the entire surface of the photosensitive composition layer. The light source used for exposure may be one that irradiates light in a wavelength range to which various photosensitive components in the photosensitive composition layer are photosensitive (e.g., light in wavelength ranges of 254 nm, 313 nm, 365 nm, and 405 nm, etc.). Specific examples include ultra-high pressure mercury lamps, high pressure mercury lamps, metal halide lamps, and LEDs (light-emitting diodes). The exposure dose is 5 to 2000 mJ / cm. ２ is preferred, and 100 to 1500 mJ / cm ２ Among these, the exposure dose (integrated illuminance) measured with an illuminometer at a wavelength of 365 nm is more preferably 1000 mJ / cm. ２ is preferred.

[0218] The method for removing the water-soluble resin layer is not particularly limited, and examples thereof include removal using water or an alkaline developer. Examples of the alkaline developer include the alkaline developer that can be used in step 4 of the pattern formation method described below.

[0219] Specifically, the surface free energy of the cured layer is measured by the following method in accordance with the Owens and Wendt method (J. Appl. Polym. Sci., 13, 1741-1747 (1969)). A contact angle meter is used to measure the contact angle between the cured layer and each test liquid. Pure water and methylene iodide are used as the test liquids. The contact angle is measured three times at different locations, and the average value is used. As the contact angle meter, for example, a contact angle meter CA-A manufactured by Kyowa Interface Science Co., Ltd. can be used. From the obtained contact angle and the surface free energy of the test liquids (pure water and methylene iodide), the surface free energy of the cured layer, as well as the polar component and dispersive component of the surface free energy of the cured layer, are calculated according to the following formulas (1) to (3): Formula (1): 1 + cos θ = (2 / γ Ｌ ) ((γ Ｓ ｄ gamma Ｌ ｄ ) １／２ + (γ Ｓ ｐ gamma Ｌ ｐ ) １／２ ) Formula (2): γ Ｓ = γ Ｓ ｄ +γ Ｓ ｐ Formula (3): γ Ｌ = γ Ｌ ｄ +γ Ｌ ｐ In the above formulas (1) to (3), θ represents the contact angle between the cured layer and each test liquid. Ｓ represents the surface free energy of the hardened layer, and γ Ｓ ｄ represents the dispersion component of the surface free energy of the hardened layer, and γ Ｓ ｐ represents the polar component of the surface free energy of the hardened layer. Ｌ represents the surface free energy of the test liquid, and γ Ｌ ｄ represents the dispersive component of the surface free energy of the test liquid, and γ Ｌ ｐ represents the polar component of the surface free energy of the test liquid. The surface free energy of the test liquid is as follows: pure water: γ Ｌｄ = 21.8 mJ / m ２ , γ Ｌ ｐ = 51.0 mJ / m ２ , methylene iodide: γ Ｌ ｄ = 49.5 mJ / m ２ , γ Ｌ ｐ = 1.3 mJ / m ２ A more detailed method for measuring the surface free energy of the cured layer by measurement X is as described in the examples below.

[0220] The method for adjusting the surface free energy of the cured layer is not particularly limited, but includes contacting the cured layer with a hydrophilic composition (e.g., a water-soluble resin layer) before curing and adjusting the composition of the photosensitive composition layer. When contacting the cured layer with a hydrophilic composition before curing, it is presumed that some of the components of the hydrophilic composition migrate to the photosensitive composition layer, thereby affecting the surface free energy of the cured layer. By having a photosensitive composition layer and a water-soluble resin layer, the transfer film of the present invention can easily adjust the surface free energy of the cured layer to a suitable value while maintaining the performance of the film formed.

[0221] [Method for manufacturing transfer film] Known manufacturing methods can be applied to the method for manufacturing the transfer film. Specifically, for example, a method can be used in which a water-soluble resin layer-forming composition is applied to a temporary support to form a water-soluble resin layer, and a photosensitive composition layer-forming composition is applied to the water-soluble resin layer to form a photosensitive composition layer. The water-soluble resin layer is preferably formed by applying the water-soluble resin layer-forming composition and then drying the coating film. The photosensitive composition layer is preferably formed by applying the photosensitive composition layer-forming composition and then drying the coating film. Examples of coating methods include slit coating, spin coating, curtain coating, and inkjet coating.

[0222] For example, a method for manufacturing the transfer film 100 shown in FIG. 1 includes the steps of applying a water-soluble resin layer-forming composition to the surface of the temporary support 12 to form a coating film, and then drying the coating film to form the water-soluble resin layer 14, and applying a photosensitive composition layer-forming composition to the surface of the water-soluble resin layer 14 to form a coating film, and then drying the coating film to form the photosensitive composition layer 16. Furthermore, a cover film may be pressed onto the photosensitive composition layer 16 of the transfer film manufactured by the above manufacturing method to manufacture a transfer film including the cover film. Furthermore, the transfer film may be wound up after manufacturing and stored as a roll-form transfer film. The roll-form transfer film can be provided in its original form for the lamination process with a substrate in a roll-to-roll system, which will be described later.

[0223] [Uses] The transfer film is preferably used for forming a pattern and / or a film. The patterns and films can be used for various applications, such as electrode protective films, insulating films, planarizing films, overcoat films, hard coat films, passivation films, partitions, spacers, microlenses, optical filters, anti-reflection films, etching resists, and plating members. More specifically, examples include protective films or insulating films for touch panel electrodes, protective films or insulating films for printed wiring boards, protective films or insulating films for TFT substrates, interlayer insulating films in build-up substrates for semiconductor packages, organic interposers, color filters, overcoat films for color filters, and etching resists for wiring formation. In particular, the transfer film is preferably used for forming an insulating film, and the insulating film is preferably used as an insulating film for semiconductor packages. That is, the transfer film is preferably used for forming an insulating film for semiconductor packages. The transfer film is also preferably used for producing a laminate having a patterned composition layer on a substrate.

[0224] [Pattern Forming Method] The pattern forming method of the present invention is not particularly limited as long as it is a method of forming a pattern derived from the photosensitive composition layer on a substrate using the transfer film, but a method of forming a pattern including vias on a substrate is preferred, and specifically, it preferably includes the following steps 1 to 4. Step 1: A step of laminating a transfer film and a substrate so that the photosensitive composition layer of the transfer film faces the substrate to obtain a laminate Step 2: A step of removing the temporary support from the laminate Step 3: A step of pattern-exposing the photosensitive composition layer from the water-soluble resin layer side of the laminate from which the temporary support has been removed Step 4: A step of removing the water-soluble resin layer and the unexposed photosensitive composition layer from the pattern-exposed laminate to form a pattern having vias Each step is described in detail below.

[0225] [Step 1] Step 1 is a step of obtaining a laminate by laminating a transfer film and a substrate so that the photosensitive composition layer of the transfer film faces the substrate. Examples of lamination methods include known transfer methods and lamination methods. A preferred method involves placing the substrate on the surface of the photosensitive composition layer and applying pressure and heat using a roll or the like. Examples of lamination methods include known laminators such as vacuum laminators and auto-cut laminators. The lamination temperature is not particularly limited, but a temperature of 70 to 130°C is preferred. When a transfer film is used, step 1 is preferably performed using a roll-to-roll system. The substrate to which the transfer film is laminated is preferably a resin film or a resin film having a conductive layer. The roll-to-roll system uses a substrate that can be wound and unwound, and includes a step of unwinding the substrate before any of the steps included in the pattern formation method of the present invention and a step of winding the substrate after any of the steps, and at least one of the steps (preferably all steps or all steps other than the heating step) is performed while the substrate is being transported. As the unwinding method in the unwinding step and the winding method in the winding step, a known method may be used in a manufacturing method that employs a roll-to-roll system.

[0226] <Substrate> Examples of the substrate include a glass substrate, a glass epoxy substrate, a silicon substrate, a resin substrate, and a substrate having a conductive layer. The refractive index of the substrate is preferably 1.50 to 1.52. The substrate may be composed of a light-transmitting substrate such as a glass substrate, and tempered glass, such as Corning Gorilla Glass, can also be used. Materials contained in the substrate include, for example, materials used in JP 2010-086684 A, JP 2010-152809 A, and JP 2010-257492 A. When the substrate includes a resin substrate, a resin film with low optical distortion and / or high transparency is more preferred. Specific examples include polyethylene terephthalate (PET), polyethylene naphthalate, polycarbonate, triacetyl cellulose, cycloolefin polymer, and polyimide.

[0227] The substrate having a conductive layer is preferably a resin substrate having a conductive layer, and more preferably a resin film having a conductive layer, in that it can be produced by a roll-to-roll process. The substrate having a conductive layer may be a laminate obtained by the above-mentioned pattern forming method.

[0228] Examples of the conductive layer include any conductive layer used in general circuit wiring or touch panel wiring. From the viewpoints of conductivity and fine line formability, the conductive layer is preferably one or more layers selected from the group consisting of a metal layer (e.g., metal foil, etc.), a conductive metal oxide layer, a graphene layer, a carbon nanotube layer, and a conductive polymer layer, more preferably a metal layer, and even more preferably a copper layer or a silver layer. The conductive layer in the substrate having a conductive layer may be one layer or two or more layers. When the substrate having a conductive layer includes two or more conductive layers, it is preferable that each conductive layer is made of a different material. Examples of materials for the conductive layer include simple metals and conductive metal oxides. Examples of simple metals include Al, Zn, Cu, Fe, Ni, Cr, Mo, Ag, and Au. Examples of conductive metal oxides include ITO (indium tin oxide), IZO (indium zinc oxide), and SiO ２The conductivity is such that the volume resistivity is 1×10 ６ It means that the volume resistivity is less than 1×10 ４ It is preferably less than Ωcm.

[0229] The conductive layer may be patterned. Examples of methods for producing a patterned conductive layer include subtractive methods such as etching and additive methods. Examples of the etching method include the wet etching method described in paragraphs 0048 to 0054 of JP 2010-152155 A and known dry etching methods such as plasma etching. The etching method may also be a method using an etching resist.

[0230] [Step 2] Step 2 is a step of removing the temporary support from the laminate obtained in step 1, which has a substrate, a photosensitive composition layer, a water-soluble resin layer, and a temporary support in this order. By including step 2, the pattern formation method of the present invention can eliminate the influence of the temporary support during exposure, and has excellent pattern formability. The method for removing the temporary support is not particularly limited, and known methods can be used. For example, a method of peeling off the temporary support can be mentioned, and the peeling may be performed by a roll-to-roll system. Details of the roll-to-roll system are as described above. It is also preferable that the laminate from which the temporary support has been removed by the roll-to-roll system be continuously subjected to the treatment of step 3 without going through a winding step, in order to prevent contamination of the exposed water-soluble resin layer and photosensitive composition layer.

[0231] [Step 3] Step 3 is a step of pattern-exposing the photosensitive composition layer from the water-soluble resin layer side of the laminate obtained in Step 2, which has the substrate, photosensitive composition layer, and water-soluble resin layer in this order. "Pattern exposure" means a form of patterned exposure, i.e., exposure in a form in which exposed areas and unexposed areas exist. The positional relationship between the exposed areas and unexposed areas in the patterned exposure is not particularly limited and can be adjusted as appropriate.

[0232] The light source used for exposure may be any light source that irradiates light in a wavelength range (e.g., light in wavelength ranges of 254 nm, 313 nm, 365 nm, and 405 nm) to which various photosensitive components (e.g., photopolymerization initiators) in the photosensitive composition layer are sensitive. Specific examples include ultra-high pressure mercury lamps, high pressure mercury lamps, metal halide lamps, and LEDs (Light Emitting Diodes). The exposure dose is 5 to 2000 mJ / cm. ２ is preferred, and 10 to 1500 mJ / cm ２ is more preferred.

[0233] The pattern exposure may be exposure through a mask or direct exposure using a laser or the like. When exposure is performed through a mask, exposure may be performed with the mask in contact with the water-soluble resin layer, or without contacting the mask with the water-soluble resin layer. Examples of masks include quartz masks, soda-lime glass masks, and film masks. Quartz masks are preferred because of their excellent dimensional accuracy, and film masks are preferred because they can be easily made into large sizes. As a material for the film mask, polyester film is preferred, and polyethylene terephthalate film is more preferred. As a material for the film mask, for example, XPR-7S SG (manufactured by Fujifilm Global Graphic Systems Co., Ltd.) can be mentioned.

[0234] [Step 4] Step 4 is a step of removing the water-soluble resin layer and the unexposed photosensitive composition layer from the pattern-exposed laminate obtained in step 3 to form a pattern having vias.

[0235] The water-soluble resin layer and the photosensitive composition layer can be removed by known methods, such as a method using a developer. Examples of methods for removing the water-soluble resin layer include removal using water or an alkaline developer. Examples of methods for removing the unexposed photosensitive composition layer include removal using an alkaline developer or an organic solvent developer. The removal of the water-soluble resin layer and the unexposed photosensitive composition layer may be performed sequentially or simultaneously, depending on the composition of each layer. For example, the water-soluble resin layer may be removed using an alkaline developer, and then the unexposed photosensitive composition layer may be removed using an organic solvent developer, or the water-soluble resin layer and the unexposed photosensitive composition layer may be removed at the same time using an alkaline developer.

[0236] The alkaline developer is preferably an aqueous alkaline solution. The aqueous alkaline solution preferably contains a compound having a pKa of 7 to 13 at a concentration of 0.05 to 5 mol / L. The water content in the alkaline developer is preferably 50% by mass or more, more preferably 60% by mass or more, even more preferably 85% by mass or more, particularly preferably 90% by mass or more, and most preferably 95% by mass or more, based on the total mass of the alkaline developer. The upper limit is preferably less than 100% by mass, based on the total mass of the alkaline developer. Examples of alkaline developers include aqueous sodium carbonate solutions, aqueous potassium carbonate solutions, aqueous sodium hydroxide solutions, aqueous potassium hydroxide solutions, and aqueous tetramethylammonium hydroxide (TMAH) solutions. Examples of the concentration of the alkaline component constituting the alkaline developer include 0.1% by mass aqueous solutions, 1.0% by mass aqueous solutions, and 2.38% by mass aqueous solutions. The alkaline developer may also contain a water-soluble organic solvent, a surfactant, and the like. Examples of the alkaline developer include the developer described in paragraph 0194 of WO 2015 / 093271.

[0237] Examples of organic solvent developers include developers containing organic solvents such as ketone solvents, ester solvents, alcohol solvents, amide solvents, ether solvents, and hydrocarbon solvents. Cyclopentanone or propylene glycol monomethyl ether acetate is preferred as the organic solvent developer. In the organic solvent developer, a mixture of multiple organic solvents may be used, or the organic solvent may be mixed with an organic solvent other than those mentioned above or with water. The water content of the organic solvent developer is preferably less than 10% by mass, based on the total mass of the organic solvent developer, and more preferably substantially free of water. The organic solvent content of the organic solvent developer is preferably 50% by mass or more, more preferably 60% by mass or more, even more preferably 85% by mass or more, particularly preferably 90% by mass or more, and most preferably 95% by mass or more, based on the total mass of the organic solvent developer. The upper limit is preferably 100% by mass or less, based on the total mass of the organic solvent developer.

[0238] As a removal method using a developer, a known development method can be used. Examples include puddle development, shower development, spin development, and dip development. In shower development, unnecessary portions can be removed by spraying a developer onto the composition layer after exposure. It is also preferable to spray a detergent or the like onto the composition layer by showering and then remove development residues by scrubbing with a brush or the like after development. The temperature of the developer is preferably 20 to 40°C.

[0239] The pattern having vias may be formed only in the photosensitive composition layer, or may be formed in both the photosensitive composition layer and the substrate. The pattern having vias may be either a through hole or a via hole. Examples of the shape of the via include a square, trapezoid, and inverted trapezoid cross-sectional shape; and a circle and a square front shape (the shape when the via is observed from the direction in which the via bottom is visible). In order to improve the adhesion of plated copper to the via wall surface, an inverted trapezoid cross-sectional shape is preferred. The via size (diameter) is preferably 300 μm or less, more preferably 100 μm or less, even more preferably 50 μm or less, and particularly preferably 5 μm or less. The lower limit is preferably 1 μm or more. The number of vias may be 1 or more, and preferably 2 or more.

[0240] [Step 5] The pattern forming method of the present invention also preferably includes, after step 4, step 5 of subjecting the pattern obtained in step 4 to at least one of heating and exposure. Step 5 promotes the reaction of the resin precursor in the photosensitive composition layer (e.g., a ring-closing reaction of a polyimide precursor and a polybenzoxazole precursor), allowing the formation of a resin. Step 5 is preferably a step of at least heating.

[0241] The temperature and time of the heat treatment can be appropriately selected depending on the type of resin and its precursor. The heat treatment temperature is preferably 120 to 400°C, more preferably 150 to 400°C, and even more preferably 180 to 350°C. The heat treatment time is preferably 1 to 24 hours, more preferably 1 to 12 hours, and even more preferably 1 to 9 hours. The heat treatment may be performed in either an air environment or a nitrogen-substituted environment. The atmospheric pressure in the heat treatment environment is preferably 8.1 kPa or more, more preferably 50.66 kPa or more. The upper limit is preferably 121.6 kPa or less, more preferably 111.46 kPa or less, and even more preferably 101.3 kPa or less.

[0242] The light source and exposure dose for the exposure treatment can be appropriately selected depending on the type of photosensitive component in the photosensitive composition layer. Examples of light sources include ultra-high pressure mercury lamps, high pressure mercury lamps, metal halide lamps, and LEDs (Light Emitting Diodes). The exposure dose is 5 to 2000 mJ / cm. ２ is preferred, and 10 to 2000 mJ / cm ２ is more preferred.

[0243] [Other Steps] The pattern formation method may include other steps in addition to those described above. Examples of other steps include the following steps.

[0244] <Cover Film Peeling Step> When the transfer film has a cover film in the pattern forming method, it is preferable to include a step of peeling off the cover film from the transfer film. As the method for peeling off the cover film, a known method can be applied.

[0245] <Step of Reducing Visible Light Reflectance> When the substrate is a substrate having a conductive layer, the pattern formation method may further include a step of performing a treatment to reduce the visible light reflectance of the conductive layer. When the substrate is a substrate having multiple conductive layers, the treatment to reduce the visible light reflectance may be performed on some or all of the conductive layers. An example of a treatment to reduce the visible light reflectance is oxidation treatment. For example, copper can be oxidized to copper oxide, thereby blackening the conductive layer, thereby reducing the visible light reflectance of the conductive layer. Suitable embodiments of the treatment to reduce the visible light reflectance include those described in paragraphs

[0017] to

[0025] of JP 2014-150118 A and paragraphs

[0041] ,

[0042] ,

[0048] , and

[0058] of JP 2013-206315 A, the contents of which are incorporated herein by reference.

[0246] <Etching Step> When the base material is a substrate having a conductive layer, the pattern formation method may include a step (etching step) of etching the conductive layer in an area where the formed pattern (film) is not disposed, using the formed pattern (film) as an etching resist film. Examples of the etching method include the wet etching method described in paragraphs 0048 to 0054 of JP 2010-152155 A and known dry etching methods such as plasma etching.

[0247] The pattern formation method preferably uses a substrate having a plurality of conductive layers on both surfaces, and sequentially or simultaneously forms patterns on the conductive layers formed on both surfaces. With this configuration, a first conductive pattern can be formed on one surface of the substrate, and a second conductive pattern can be formed on the other surface. Formation may also be performed from both sides of the substrate using a roll-to-roll method. The pattern formation method is also preferably used in a method for producing a patterned laminate. The method for producing a patterned laminate is not particularly limited as long as it includes the above-mentioned pattern formation method.

[0248] [Laminate] The laminate is a laminate having a pattern obtained by the above-described pattern forming method. The laminate includes, for example, a substrate and a pattern having vias formed by an exposed photosensitive composition layer. The laminate may further include at least one of a wiring layer and an insulating layer. The laminate also preferably includes, in this order, a wiring layer and an insulating layer on the surface of the pattern opposite the substrate side. The film formed by the transfer pattern of the present invention has excellent adhesion to the layer laminated on the surface opposite the substrate side, and in the above-described embodiment, migration in the wiring layer can be more effectively suppressed. The insulating layer may be a layer formed by the transfer film of the present invention. The method for forming the wiring layer and insulating layer is not particularly limited, and known methods can be used. For example, the same method as in step Z6 described below can be used as the method for forming the wiring layer. For example, a method of applying and curing an insulating layer-forming composition, a method using a transfer film, and the pattern forming method of the present invention can be used as the method for forming the insulating layer.

[0249] The laminate is used in, for example, semiconductor devices, including various semiconductor devices such as semiconductor packages used in electrical appliances (e.g., computers, mobile phones, digital cameras, televisions, etc.) and vehicles (e.g., motorcycles, automobiles, trains, ships, aircraft, etc.).

[0250] [Method for Manufacturing a Semiconductor Package] The above-described pattern forming method can be suitably applied as a method for manufacturing a semiconductor package. Examples of methods for manufacturing a semiconductor package include known manufacturing methods such as a method for manufacturing a build-up substrate. Specifically, examples include a manufacturing method having steps Z1 to Z6 in this order. Step Z1: a step of laminating a transfer film and a substrate onto a substrate having a conductive layer so that the photosensitive composition layer of the transfer film faces the substrate. Step Z2: a step of removing the temporary support from the laminate obtained in step Z1. Step Z3: a step of pattern-exposing the photosensitive composition layer from the water-soluble resin layer side of the laminate from which the temporary support has been removed. Step Z4: a step of removing the water-soluble resin layer and the unexposed photosensitive composition layer from the pattern-exposed laminate to form a pattern having vias. Step Z5: a step of subjecting the obtained pattern to at least one of heating and exposure. Step Z6: a step of forming a circuit pattern on the pattern.

[0251] The steps Z1 to Z5 include the steps 1 to 5 described above, respectively.

[0252] [Step Z6] Step Z6 is a step of forming a circuit pattern on the pattern. A semi-additive process is preferred as a method for forming a circuit pattern because it allows for the formation of fine wiring. Examples of semi-additive processes include the following: First, after Step Z4 or Step Z5, electroless copper plating is performed on the via bottom, via wall, and the entire surface of the pattern using a palladium catalyst or the like to form a seed layer. The seed layer is used to form a power supply layer for electrolytic copper plating, and the seed layer thickness is preferably 0.1 to 2.0 μm. A seed layer thickness of 0.1 μm or more tends to suppress a decrease in connection insulation reliability during electrolytic copper plating. A seed layer thickness of 2.0 μm or less tends to eliminate the need for a large etching amount when flash etching the seed layer between wirings, and tends to suppress damage to the wiring during etching. Electroless copper plating is performed by depositing metallic copper on the surface of a pattern having vias through a reaction between copper ions and a reducing agent. Examples of electroless plating methods and electrolytic plating methods include known plating methods. The catalyst used in the electroless plating process is preferably a palladium-tin mixed catalyst. The average primary particle size of the mixed catalyst is preferably 10 nm or less. The plating composition used in the electroless plating process preferably contains hypophosphorous acid as a reducing agent. Commercially available electroless copper plating solutions include, for example, "MSK-DK" manufactured by Atotech Japan and the "Sulcup (registered trademark) PEA ver. 4" series manufactured by Uemura Kogyo Co., Ltd.

[0253] After electroless copper plating, it is also preferable to thermocompress the surface of the photosensitive composition layer of the transfer film opposite the temporary support onto the electroless copper plating using a roll laminator. The thickness of the photosensitive composition layer is preferably 5 to 30 μm, since it can be made greater than the wiring height after electrocopper plating. After thermocompression bonding of the transfer film, the photosensitive composition layer is exposed, for example, through a mask on which the desired wiring pattern is drawn. Examples of the exposure method include the exposure method in step 3. The temporary support may be peeled off either before or after exposure. After exposure, the water-soluble resin layer and the exposed photosensitive composition layer are developed using a developer to form a pattern. After forming the pattern, development residues may be removed using plasma or the like. After development, electrocopper plating is performed to form a copper circuit layer and via filling. After electrocopper plating, the pattern is peeled off using an alkaline aqueous solution or an amine-based stripper. After peeling the pattern, the seed layer between the wiring is removed (flash etching). Flash etching is performed using an oxidizing solution containing, for example, sulfuric acid and an acidic solution such as hydrogen peroxide. Examples of oxidizing solutions include "SAC" manufactured by JCU Corporation and "CPE-800" manufactured by Mitsubishi Gas Chemical Company, Inc. After flash etching, palladium and other materials adhering to the portions between the wirings are removed as necessary. Palladium can be removed using an acidic solution such as nitric acid and hydrochloric acid.

[0254] After the pattern is removed or after the flash etching step, a post-baking treatment is preferably performed. The post-baking treatment sufficiently cures any unreacted thermosetting components, thereby improving the electrical insulation reliability, curing characteristics, and adhesive strength with plated copper. The preferred thermosetting conditions are a curing temperature of 150 to 240°C and a curing time of 15 to 500 minutes.

[0255] The method for manufacturing a semiconductor package may include a roughening step of roughening a pattern having vias. The roughening step is preferably performed after step Z5 and before step Z6. By performing the roughening step, the pattern surface can be roughened to improve adhesion with the circuit wiring. Smears can also be removed at the same time. Examples of the roughening step include known desmearing treatments, and treatments involving contact with a roughening liquid are preferred. Examples of roughening liquids include roughening liquids containing chromium and sulfuric acid, roughening liquids containing alkaline permanganate (e.g., sodium permanganate roughening liquid, etc.), and roughening liquids containing sodium fluoride, chromium, and sulfuric acid.

[0256] The above-described steps are repeated depending on the number of layers required to manufacture a semiconductor package. It is preferable to form a solder resist on the outermost layer.

[0257] [Semiconductor Package] The transfer film described above is suitable for use in the manufacture of a semiconductor package. The semiconductor package is not particularly limited as long as it includes a layer formed from the transfer film, and preferably includes the laminate described above, and is more preferably manufactured by the semiconductor package manufacturing method described above. In the semiconductor package, the layer formed from the transfer film may be used as an insulating film, or may be used as an organic interposer or insulating film in a so-called build-up substrate.

[0258] The present invention will be described in more detail below based on examples. The materials, amounts used, ratios, processing details, processing procedures, etc. shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be interpreted as being limited by the examples shown below. In the following examples, "%" means "% by mass" unless otherwise specified.

[0259] [Preparation of composition for forming water-soluble resin layer] The components were mixed to obtain the blending amounts (blending amounts in terms of solid content ratio) shown in Table 1 below, and the mixture was diluted to a solid content concentration of 5% using a mixed solvent of ion-exchanged water / methanol (manufactured by Mitsubishi Gas Chemical Company, Inc.) = 40 / 60 (mass ratio) as the solvent. Various components contained in the water-soluble resin layer are shown below.

[0260] [Water-soluble resin] PVA: Polyvinyl alcohol, Kuraray Poval PVA-205, manufactured by Kuraray Co., Ltd. PVP: Polyvinylpyrrolidone, Polyvinylpyrrolidone K-30, manufactured by Nippon Shokubai Co., Ltd. HPMC: Hydroxypropyl methylcellulose, Metrose 60SH-03, manufactured by Shin-Etsu Chemical Co., Ltd.

[0261] [Surfactants] Surfactant A: Silicone surfactant, BYK-345, manufactured by BYK Japan Surfactant B: Silicone surfactant, BYK-348, manufactured by BYK Japan Surfactant C: Silicone surfactant, EXP. S-506, manufactured by DIC Surfactant D: Fluorine-based surfactant, Megafac (registered trademark) F-444, manufactured by DIC

[0262]

[0263] [Preparation of composition for forming photosensitive composition layer] Various components were mixed to prepare a mixture in the amounts (solid content ratio) shown in Table 2 below. Next, the mixture was diluted with a mixed solvent containing 25% by mass of MEK (methyl ethyl ketone) and 75% by mass of NMP (N-methylpyrrolidone) to a solid content of 30% by mass. The various components contained in the composition for forming photosensitive composition layer are shown below.

[0264] The various components contained in the composition are listed below.

[0265] [Resins (specific compounds or comparative compounds)] Resin A: polyimide precursor, resin synthesized by the synthesis method for resin A described later Resin B: polyimide precursor, resin synthesized by the synthesis method for resin B described later Resin C: polyphenylene ether resin having a branched structure, resin synthesized by the synthesis method for resin C described later Resin D: phenolic resin, TR4020G, manufactured by Asahi Organic Chemicals Co., Ltd. Resin E: epoxy resin, ZX1059 (mixture of bisphenol A epoxy resin and bisphenol F epoxy resin (1:1)), manufactured by Nippon Steel Chemical & Material Co., Ltd. Resin Z: acrylic resin, styrene / acrylic acid = 71% by mass / 29% by mass, resin synthesized by the synthesis method for resin Z described later

[0266]

[0267] <Method for Synthesizing Resin A> 4,4'-oxydiphthalic anhydride (dried at 140°C for 12 hours, 20.0 g, 64.5 mmol), 2-hydroxyethyl methacrylate (16.8 g, 129 mmol), hydroquinone (0.05 g), pyridine (20.4 g, 258 mmol), and diethylene glycol dimethyl ether (100 g) were mixed and stirred at 60°C for 18 hours to obtain a reaction mixture (a diester of 4,4'-oxydiphthalic acid and 2-hydroxyethyl methacrylate). Next, the obtained diester was treated with thionyl chloride (SOCl ２ ) to obtain a reaction mixture. Next, a solution of 4,4'-diaminodiphenyl ether (11.08 g, 58.7 mmol) dissolved in N-methylpyrrolidone (100 mL) was added dropwise to the reaction mixture over 20 minutes at -5 to 0°C. After reacting the reaction mixture at 0°C for 1 hour, ethanol (70 g) was added and the mixture was stirred at room temperature for 1 day. The resulting reaction solution was added to water (5 L) and stirred at 5,000 rpm for 15 minutes to obtain a precipitate, which was a crude polymer. The precipitate collected by filtration from the mixture was stirred in water (3 L) for 30 minutes and collected by filtration again. The resulting precipitate was dried under reduced pressure at 45°C for 3 days to obtain Resin A, a polyimide precursor. Resin A had a weight-average molecular weight (Mw) of 18,000.

[0268] <Method for synthesizing resin B> 4,4'-oxydiphthalic dianhydride (77.6 g) and diphenyl-3,3',4,4'-tetracarboxylic dianhydride (73.6 g) were placed in a 2 L separable flask, 2-hydroxyethyl methacrylate (134.0 g) and γ-butyrolactone (400 mL) were added, and pyridine (79.1 g) was added while stirring at room temperature to obtain a reaction mixture. After the heat generated by the reaction had ceased, the mixture was allowed to cool to room temperature and allowed to stand for an additional 16 hours. Next, a solution of dicyclohexylcarbodiimide (DCC, 206.3 g) dissolved in γ-butyrolactone (180 mL) was added to the reaction mixture over 40 minutes while stirring under ice cooling. Next, a suspension of 4,4'-oxydianiline (ODA, Mw = 200.24, 93.0 g) in γ-butyrolactone (350 mL) was added over 60 minutes with stirring. After further stirring at room temperature for 2 hours, ethanol (30 mL) was added and stirred for 1 hour, followed by the addition of γ-butyrolactone (400 mL). The precipitate formed in the reaction mixture was removed by filtration to obtain a reaction solution. The resulting reaction solution was added to ethyl alcohol (3 L) to obtain a crude polymer precipitate. The resulting crude polymer was collected by filtration and dissolved in tetrahydrofuran (1.5 L) to obtain a crude polymer solution. The resulting crude polymer solution was purified using an anion exchange resin (Amberlyst TM15, manufactured by Organo Corporation) to obtain a polymer solution. The resulting polymer solution was added dropwise to water (28 L) to precipitate the polymer, and the resulting precipitate was collected by filtration and dried under vacuum to obtain Resin B, a powdered polyimide precursor. The weight average molecular weight (Mw) of Resin B was 22,000. The imide group content of the polyimide obtained from Resin B was 27.4 mass % per repeating unit.

[0269] <Method for Synthesizing Resin C> 1.3 g of di-μ-hydroxo-bis[(N,N,N',N'-tetramethylethylenediamine)copper(II)] chloride (Cu / TMEDA) and 1.59 mL of tetramethylethylenediamine (TMEDA) were added to a two-necked recovery flask and thoroughly dissolved. Oxygen was supplied at 10 mL / min. 52.5 g of 2,6-dimethylphenol and 6.5 g of 2-allylphenol were dissolved in 0.75 L of toluene to prepare a raw material solution. This raw material solution was added dropwise to the recovery flask and reacted at 45°C for 5 hours while stirring at a rotation speed of 600 rpm. After completion of the reaction, the resulting mixture was reprecipitated in a mixture of 10 L of methanol and 11 mL of concentrated hydrochloric acid, filtered, and dried at 70°C for 24 hours to obtain Resin C. Resin C had a number average molecular weight of 25,000 and a weight average molecular weight of 66,000.

[0270] <Method for synthesizing resin Z> 1-methoxy-2-acetoxypropane (PGMEA, 60 parts) and propylene glycol monomethyl ether (PGME, 240 parts by mass) were placed in a flask to prepare a mixed solution. The resulting mixed solution was heated to 90°C while stirring at a stirring speed of 250 rpm. Styrene (71 parts by mass) and acrylic acid (29 parts by mass) were mixed and diluted with PGMEA (60 parts by mass) to obtain a dropping solution (1). V-601 (dimethyl 2,2'-azobis(2-methylpropionate), 9.637 parts by mass) was dissolved in PGMEA (136.56 parts by mass) to obtain a dropping solution (2). Next, dropping solutions (1) and (2) were simultaneously added dropwise over 3 hours to a flask containing the above mixed solution heated to 90°C. After the dropwise addition was completed, V-601 (2.401 parts by mass) was added to the flask three times at one-hour intervals. The mixture was then stirred at 90°C for an additional 3 hours. The resulting reaction solution was then diluted with PGMEA to obtain a solution containing Resin Z (solid concentration: 36.3% by mass).

[0271] [Polymerizable Compounds] D-1: Compound having the following structure

[0272]

[0273] DPHA: dipentaerythritol hexaacrylate, manufactured by Tokyo Chemical Industry Co., Ltd. SR205NS: bifunctional polymerizable compound, manufactured by Sartomer Co., Ltd. SR209: bifunctional polymerizable compound, manufactured by Sartomer Co., Ltd.

[0274] [Photopolymerization initiator] Oxe-01: Irgacure OXE-01, manufactured by BASF

[0275] [Filler] NHM-5N: silicon dioxide, surface-treated, average particle size 100 nm, manufactured by Tokuyama Corporation YA050C-MJE: spherical silica slurry, surface-treated, average particle size 50 nm, solid content concentration 50 mass % MEK slurry, manufactured by Admatechs Co., Ltd.

[0276] [Other additives] C-1: Thermal base generator, compound having the following structure

[0277]

[0278] EPEG: plasticizer, ethyl phthalyl ethyl glycolate, manufactured by Tokyo Chemical Industry Co., Ltd. HAT: rust inhibitor, 5-amino-1H-tetrazole Z-1: jer828: bisphenol A type epoxy resin, manufactured by Mitsubishi Chemical Corporation Z-2: HPC8000-65T: dicyclopentadiene type diphenol compound (polycyclopentadiene type diphenol compound) type active ester curing agent, toluene solution with solid content concentration of 65 mass%, manufactured by DIC Corporation S-506: silicone-based surfactant, manufactured by DIC Corporation F-551A: fluorine-based surfactant, manufactured by DIC Corporation

[0279] [Preparation of Transfer Film] The prepared water-soluble resin layer-forming composition was applied to a temporary support (QS62, manufactured by Toray Industries, Inc., 31 μm thick PET film) and dried at 100° C. to form a water-soluble resin layer as shown in Table 2 below. The coating amount was adjusted so that the film thickness after drying would be the value shown in Table 2. The prepared photosensitive composition layer-forming composition was applied to the formed water-soluble resin layer and dried at 100° C. to form a photosensitive composition layer. The coating amount was adjusted so that the film thickness after drying would be the value shown in Table 2. Next, a protective film (manufactured by Oji F-Tex Co., Ltd., polypropylene film, FG-201, thickness 30 μm) was laminated to the surface of the photosensitive composition layer opposite the water-soluble resin layer side, thereby obtaining transfer films for each of the Examples and Comparative Examples.

[0280] [Calculation of Surface Free Energy] The surface free energy was calculated according to the procedure shown below. A copper-clad polyimide film (Metalloyal, manufactured by Toray Industries, Inc.) was used as the substrate, and the transfer film of each Example or Comparative Example was laminated onto the substrate so that the photosensitive composition layer faced the substrate, thereby obtaining a laminate having the substrate, photosensitive composition layer, water-soluble resin layer, and temporary support in this order. The lamination was performed using a vacuum laminator manufactured by MCK Corporation under conditions of a substrate temperature of 50°C, a rubber roller temperature of 100°C, a linear pressure of 3 N / cm, and a conveying speed of 1 m / min. The temporary support was peeled off from the obtained laminate, and the exposed water-soluble resin layer side was exposed to light (high-pressure mercury lamp, integrated illuminance of 1000 mJ / cm measured with an illuminometer at a wavelength of 365 nm). ２ After the exposure, the water-soluble resin layer was removed by immersion in a 1% aqueous solution of sodium carbonate for 60 seconds. The resulting laminate was heated at 200°C for 1.5 hours in an oven adjusted under a nitrogen atmosphere to form a cured layer, thereby preparing a sample for evaluation.

[0281] The contact angles of pure water and methylene iodide were measured for the surface of the cured layer of the obtained evaluation sample opposite the substrate side using a contact angle meter CA-A (manufactured by Kyowa Interface Science Co., Ltd.). The contact angles were measured three times at different locations, and the average value was used. From the obtained contact angles, the surface free energy and the polar component of the surface free energy were calculated according to the Owens and Wendt method described above.

[0282] [Evaluation] Using the resulting transfer films of each Example and Comparative Example, the pattern formability and film loss, as well as the heat resistance, dielectric properties, insulating film adhesion, and migration suppression properties of the resulting films were evaluated.

[0283] [Heat Resistance] The evaluation sample obtained in the above [Surface Free Energy Measurement] was immersed in 2M hydrochloric acid for 8 hours for a peeling treatment, rinsed (in pure water at room temperature for 1 hour), and then peeled off from the substrate to obtain a free-standing film derived from the photosensitive composition layer. If the free-standing film could not be peeled off by the above peeling treatment, it was further immersed in 2M hydrochloric acid for about 1 week for peeling. The obtained free-standing film was cut into strips. The produced free-standing film was cut into strips (19 mm x 5 mm) and the linear expansion coefficient was measured using a TMA (thermomechanical analyzer, "TMA450EM" manufactured by TA Instruments). The measurement conditions were a heating rate of 10°C / min, a chuck distance of 10 mm, and a load of 40 mN. The linear expansion coefficient was measured as a value (ppm / K) in the temperature range of 50°C to 150°C during heating, and was calculated as the average of three measurements. From the obtained linear expansion coefficient, heat resistance was evaluated according to the following evaluation criteria.

[0284] <Evaluation criteria> A: Linear expansion coefficient is 25 ppm / K or less B: Linear expansion coefficient is more than 25 ppm / K and less than 60 ppm / K C: Linear expansion coefficient is more than 60 ppm / K

[0285] [Dielectric Properties] A free-standing film derived from the photosensitive composition layer was obtained using the same procedure as in the evaluation of [Heat Resistance] described above. The obtained free-standing film was cut into a size of 2 cm x 3 cm, and the relative dielectric constant was measured using a 28 GHz split cylinder resonator (manufactured by Kanto Electronics Application Development Co., Ltd.). Three samples were measured, and the average value was used. From the obtained relative dielectric constant, the dielectric properties were evaluated according to the following evaluation criteria.

[0286] <Evaluation criteria> A: Relative dielectric constant is 2.9 or less B: Relative dielectric constant is more than 2.9 and less than 3.5 C: Relative dielectric constant is more than 3.5

[0287] [Insulating Film Adhesion] The insulating film adhesion, which is the adhesion between a cured layer formed from a photosensitive composition layer and an insulating film formed on the cured layer, was evaluated according to the following procedure. The photosensitive composition layer of the prepared transfer film was laminated on the surface of the cured layer of the evaluation sample obtained in the above-mentioned [Measurement of Surface Free Energy] so that the photosensitive composition layer faced the cured layer, thereby obtaining a laminate having, in this order, a substrate, a cured layer, a photosensitive composition layer, a water-soluble resin layer, and a temporary support. The lamination was performed using a vacuum laminator manufactured by MCK Corporation under conditions of a nip pressure of 0.6 MPa, a rubber roller temperature of 100°C, and a conveying speed of 1 m / min. The temporary support was peeled off from the obtained laminate, and the exposed water-soluble resin layer side was exposed to light (high-pressure mercury lamp, integrated illuminance of 1000 mJ / cm measured with an illuminometer at a wavelength of 365 nm). ２ After the exposure, the water-soluble resin layer was removed by immersion in a 1% aqueous solution of sodium carbonate for 60 seconds. The obtained laminate was heated at 200°C for 1.5 hours in an oven adjusted under a nitrogen atmosphere to prepare a sample for adhesion evaluation having a substrate, a cured layer, and a cured layer (insulating film) in this order.

[0288] Using the obtained adhesion evaluation sample, a cross-cut test (JIS K 5600) was performed according to the following procedure. Six incisions were made at 1 mm intervals on the surface of the adhesion evaluation sample opposite the substrate side, and then six more incisions were made at 1 mm intervals perpendicular to the first incisions, forming a checkerboard pattern of 25 1 mm square incisions. Next, tape (CT-24 manufactured by Nichiban, adhesive strength >4 N / cm) was applied to the checkerboard incisions, and the degree of peeling of the cured layer on the outermost surface when peeled was confirmed. The insulating film adhesion was evaluated from the degree of peeling according to the following evaluation criteria.

[0289] <Evaluation criteria> A: The number of squares in which more than half of the area was peeled off was 10 or less. B: The number of squares in which more than half of the area was peeled off was more than 10, or the transfer film could not be laminated and a sample for adhesion evaluation could not be prepared.

[0290] [Pattern Formability] The pattern formability of the photosensitive composition layer was evaluated according to the following procedure. A copper-clad polyimide film (Metalloyal, manufactured by Toray Industries, Inc.) was used as a substrate, and a transfer film was laminated on the substrate so that the substrate and the photosensitive composition layer faced each other, to obtain a laminate having the substrate, the photosensitive composition layer, the water-soluble resin layer, and the temporary support in this order. The lamination was performed using a vacuum laminator manufactured by MCK Corporation under conditions of a nip pressure of 0.6 MPa, a rubber roller temperature of 100°C, and a conveying speed of 1 m / min. The temporary support was peeled off from the obtained laminate. The exposed water-soluble resin layer side was exposed to light through a mask having five sets of patterns with L / S = 5 / 5, 10 / 10, 15 / 15, 20 / 20, 25 / 25, and 30 / 30 (μm / μm) (high-pressure mercury lamp, cumulative illuminance of 100 mJ / cm measured with an illuminometer at a wavelength of 365 nm). ２ After the exposure, the substrate was immersed in a 1% aqueous solution of sodium carbonate for 60 seconds to remove the water-soluble resin layer, and then immersed in cyclopentanone for 120 seconds and then in PGMEA for 30 seconds to remove the unexposed portions of the photosensitive composition layer, thereby forming a pattern. In Comparative Example 2, after the exposure, the substrate was immersed in a 1% aqueous solution of sodium carbonate for 60 seconds to remove the water-soluble resin layer and the unexposed portions of the photosensitive composition layer, thereby forming a pattern, and the cross-sectional shape of the pattern was confirmed.

[0291] The cross-sectional shapes of five patterns having an L / S size identical to the film thickness of the photosensitive composition layer before exposure (aspect ratio 1:1 (=film thickness of the photosensitive composition layer before exposure: L / S size), for example, when the film thickness before exposure is 10 μm, a pattern having an L / S=10 / 10 (μm / μm)) were observed using a scanning electron microscope (S-4800, manufactured by Hitachi, Ltd.). From the state of the observed pattern, the pattern formability was evaluated according to the following evaluation criteria.

[0292] <Evaluation criteria> A: Defects were confirmed in one or less patterns B: Defects were confirmed in two or more patterns

[0293] [Film Loss] Film loss was evaluated based on the film thickness of the pattern observed in the evaluation of [Pattern Formability] above and the film thickness before exposure, according to the following evaluation criteria: Film loss is a property indicating the degree of reduction in the film thickness of the formed pattern relative to the film thickness of the photosensitive composition layer formed by the transfer film before exposure, and small film loss is preferred.

[0294] <Evaluation Criteria> A: The film thickness of the pattern is 80% or more of the film thickness before exposure. B: The film thickness of the pattern is less than 80% of the film thickness before exposure.

[0295] [Migration suppression] Cu / Ti sputtering was performed on the surface of the cured layer of the evaluation sample obtained in the above [Surface free energy measurement] to form a 0.2 μm thick seed layer. A resist layer was formed on the seed layer, followed by pattern exposure and development to form a resist pattern with L / S = 10 / 10 (μm / μm). Next, electrolytic plating was performed using a copper sulfate aqueous solution, and then the resist was stripped by immersion in a 3% sodium hydroxide aqueous solution. The exposed seed layer was then removed by immersion in an aqueous solution containing 0.1% sulfuric acid and 0.1% hydrogen peroxide. This resulted in a laminate having a comb-shaped copper pattern with L / S = 10 / 10 μm formed on the surface of the cured layer. The total film thickness of the copper pattern and seed layer was 1 μm.

[0296] A transfer film was laminated onto the surface of the obtained laminate on which the copper pattern was formed so that it faced the photosensitive composition layer, and a cured layer was formed in the same manner as in the above-mentioned [Measurement of surface free energy] to prepare a sample for migration evaluation. Note that, for the voltage application portion of the copper pattern, Kapton tape was attached for protection before laminating the transfer film, and the Kapton tape was removed together with the photosensitive composition layer to prevent the formation of a cured layer.

[0297] Ten samples for each of the migration evaluation samples were prepared and placed in a chamber at 130°C and 80% RH (relative humidity) using a HAST tester with a voltage of 3.0 V applied for 168 hours. The migration suppression ability was evaluated based on the number of samples that showed migration when the initial resistance value measured at room temperature was 1 × 10１４ Ω or more in samples, 1 × 10 ３ When the resistance drops to Ω or less, it is counted as the occurrence of migration. In practical terms, it is preferable that the migration suppression ability be rated A or higher.

[0298] <Evaluation criteria> A: Migration occurred in 2 or less samples B: Migration occurred in 3 to 5 samples C: Migration occurred in 6 to 10 samples

[0299] [Results] Tables 2 to 4 show the configuration and evaluation results of each transfer film. In the tables, "amount" represents the content (mass %) relative to the total solid content of the photosensitive composition layer. Table 3 is a continuation of Table 2. For example, the transfer film of Example 1 has a water-soluble resin layer of Type 1, and the photosensitive composition layer contains Resin A, Oxe-01, C-1, EPEG, HAT, and S-506, and the above-mentioned surface free energy is 40 mJ / m ２ and the polar component of the surface free energy is 10 mJ / m ２ is.

[0300]

[0301]

[0302]

[0303] From the results shown in the table, it was confirmed that the transfer film of the present invention can form a film that contributes to suppressing migration between wirings.

[0304] It was confirmed that when the photosensitive composition layer contains a filler, the heat resistance is superior (e.g., comparison between Examples 1 to 8). It was confirmed that when the filler content is 60.0 mass or less, the dielectric properties are superior (e.g., comparison between Example 4 and Examples 9 to 12).

[0305] Examples 53 to 56 Transfer films were prepared in the same manner as in Example 1, except that the various components were mixed in the amounts (amounts based on solid content) shown in Tables 5 and 6 below. Following the same procedures as in Example 1, the pattern formability and film loss, as well as the heat resistance, dielectric properties, insulating film adhesion, and migration suppression properties of the resulting films, were evaluated. Furthermore, the fine pattern formability was evaluated according to the following procedures.

[0306] Details of the photopolymerization initiator, chain transfer agent, polymerization inhibitor, and sensitizer used in Examples 54 to 56 are shown below: B-1: TR-HABI 101, manufactured by Tronly B-2: TR-HABI 103, manufactured by Tronly B-3: TR-HABI 107, manufactured by Tronly E-1: Chain transfer agent, the following compound

[0307]

[0308] MEHQ: polymerization inhibitor, 4-methoxyphenol EAB-F: sensitizer, 4,4'-bis(diethylamino)benzophenone

[0309] [Fine Pattern Formability] In the evaluation method for [Pattern Formability] described above, the cross-sectional shapes of five patterns in which the aspect ratio of the L / S size to the film thickness of the photosensitive composition layer before exposure (film thickness of the photosensitive composition layer before exposure: L / S size) was 10:3.5 (for example, a pattern in which L / S = 3.5 / 3.5 (μm / μm) when the film thickness before exposure was 10 μm) were observed using a scanning electron microscope (S-4800, manufactured by Hitachi, Ltd.). From the state of the observed pattern, the fine pattern formability was evaluated according to the following evaluation criteria.

[0310] <Evaluation criteria> A: Defects were confirmed in one or less patterns B: Defects were confirmed in two or more patterns

[0311] The composition and evaluation results of each transfer film are shown in Tables 5 to 7. In the tables, the meaning of "amount" is the same as in Tables 2 to 4. Table 6 is a continuation of Table 5.

[0312]

[0313]

[0314] A comparison of Examples 53 to 56 confirmed that when the photopolymerization initiator contained a compound represented by formula (P1), the fine pattern formability was superior. A comparison of Examples 53 to 56 confirmed that when the photosensitive composition layer contained a chain transfer agent, the fine pattern formability was superior. A comparison of Examples 53 to 56 confirmed that when the photosensitive composition layer contained a polymerization inhibitor, the fine pattern formability was superior. A comparison of Examples 53 to 56 confirmed that when the photosensitive composition layer contained a sensitizer, the fine pattern formability was superior.

[0315] [Manufacturing of Semiconductor Package] The transfer film of each example was laminated on both sides of a glass epoxy substrate (CCL-EL190T, thickness 1.0 mm, manufactured by Mitsubishi Gas Chemical Co., Ltd.) on which a circuit pattern had been formed. Lamination was performed using a vacuum laminator manufactured by MCK Corporation under conditions of a substrate temperature of 50°C, a rubber roller temperature of 100°C, a linear pressure of 3 N / cm, and a conveying speed of 1 m / min. The temporary support was peeled off from the obtained laminate, and the water-soluble resin layer side was subjected to pattern exposure (high-pressure mercury lamp, cumulative illuminance of 500 mJ / cm measured with an illuminometer at a wavelength of 365 nm) through a mask having a Φ100 μm light-shielding portion. ２) was applied. After exposure, the substrate was immersed in a 1% aqueous solution of sodium carbonate for 60 seconds to remove the water-soluble resin layer, then immersed in cyclopentanone for 120 seconds, and then in PGMEA for 30 seconds to remove the unexposed portions of the photosensitive composition layer, forming a pattern with vias of 100 μm in diameter. The pattern was then subjected to a heat treatment (200°C for 90 minutes), after which the residue was removed using a sodium permanganate aqueous solution as a roughening solution, and electroless plating was performed. Next, a resist pattern was formed in a predetermined position using a known dry film resist, and electrolytic plating was performed. The resist pattern was then peeled off using a stripping solution. Finally, a seed layer etching process was performed to form copper wiring on the cured layer. The above steps from lamination to heat treatment were performed a total of three times. Finally, a solder resist was formed as the outermost layer, and a semiconductor element was sealed and mounted to produce a semiconductor package. The resulting semiconductor package was mounted in a predetermined position on a printed wiring board to obtain a semiconductor package substrate. The resulting semiconductor package substrate was confirmed to operate normally.

[0316] 12: Temporary support 14: Water-soluble resin layer 16: Photosensitive composition layer 100: Transfer film

Claims

1. A transfer film comprising, in this order, a temporary support, a water-soluble resin layer, and a photosensitive composition layer, wherein the photosensitive composition layer contains at least one specific compound selected from the group consisting of polyimide precursors, polyimides, polybenzoxazole precursors, polybenzoxazole, phenolic resins, epoxy resins, polyphenylene ether resins, silicone resins, benzocyclobutene resins, fluorene resins, liquid crystal polymers, polyethersulfones, polyarylates, polyetherimides, polybenzimidazoles, polyphenylsulfones, polycarbonates, acrylonitrile-butadiene-styrene copolymer resins, and polyphenylene sulfides.

2. The transfer film according to claim 1, wherein the photosensitive composition layer contains a photopolymerization initiator.

3. The surface free energy measured by measurement X is 40 mJ / m ２ Measurement X: The temporary support is peeled off from a laminate obtained by laminating the transfer film and the substrate so that the photosensitive composition layer of the transfer film faces the substrate, the entire surface of the photosensitive composition layer is exposed from the exposed water-soluble resin layer side, the water-soluble resin layer is removed, and the exposed photosensitive composition layer is heated at 200° C. for 1.5 hours in a nitrogen atmosphere to obtain a cured layer, and the surface free energy of the surface opposite to the substrate side is measured.

4. The polar component of the surface free energy is 10 mJ / m ２ The transfer film according to claim 3 .

5. The transfer film according to claim 1, which satisfies at least one of the following requirements 1 and 2. Requirement 1: The specific compound has an ethylenically unsaturated double bond. Requirement 2: The photosensitive composition layer contains a compound having an ethylenically unsaturated double bond.

6. The transfer film according to claim 5, wherein the compound having an ethylenically unsaturated double bond has a molecular weight of 800 or less.

7. The transfer film according to claim 1, wherein the specific compound comprises at least one selected from the group consisting of a polyimide precursor, a polyimide, a polybenzoxazole precursor, and a polybenzoxazole.

8. The transfer film according to claim 2, wherein the photopolymerization initiator comprises a compound represented by formula (P1). In formula (P1), R each independently represents a substituent, and n each independently represents an integer of 0 to 5.

9. The transfer film according to claim 8, wherein the photosensitive composition layer contains a chain transfer agent.

10. The transfer film according to claim 1, wherein the photosensitive composition layer contains a filler.

11. The transfer film according to claim 10, wherein the filler comprises at least one selected from the group consisting of silicon dioxide, boron nitride, barium sulfate, and silicates.

12. The transfer film according to claim 10, wherein the average particle size of the filler is 300 nm or less.

13. The transfer film according to claim 10, wherein the average particle size of the filler is 150 nm or less.

14. The transfer film according to claim 10, wherein the content of the filler is 30.0 mass % or more based on the total mass of the photosensitive composition layer.

15. The transfer film according to claim 10, wherein the content of the filler is 90.0 mass % or less based on the total mass of the photosensitive composition layer.

16. The transfer film according to claim 1, wherein the photosensitive composition layer has a thickness of 3 to 30 μm.

17. The transfer film according to claim 1, wherein the water-soluble resin layer has a thickness of 5 μm or less.

18. The transfer film according to claim 1, wherein the water-soluble resin layer contains polyvinyl alcohol.

19. The transfer film according to claim 18, wherein the content of the polyvinyl alcohol is 15.0 to 90.0 mass % based on the total mass of the water-soluble resin layer.

20. The transfer film according to claim 1, wherein the water-soluble resin layer comprises hydroxypropyl methylcellulose.

21. The transfer film according to claim 1, which is used to form an insulating film.

22. A pattern forming method comprising: step 1 of obtaining a laminate by laminating a transfer film and a substrate so that the photosensitive composition layer of the transfer film according to any one of claims 1 to 21 faces the substrate; step 2 of removing the temporary support from the laminate obtained in step 1; step 3 of pattern-exposing the photosensitive composition layer from the water-soluble resin layer side of the laminate from which the temporary support has been removed in step 2; and step 4 of removing the water-soluble resin layer and the unexposed photosensitive composition layer from the pattern-exposed laminate to form a pattern having vias.

23. A laminate comprising a pattern formed by the pattern forming method according to claim 22.

24. A semiconductor package comprising the laminate of claim 23.

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