Transfer film, laminate production method, and laminate

Abstract

A first problem addressed by the present invention is to provide a transfer film comprising a temporary support and a resin-containing layer, said transfer film having excellent conformability to a level difference when the resin-containing layer is bonded to a bonding target after storage, exhibiting excellent releasability of the temporary support, and exhibiting a small linear expansion coefficient of the resin-containing layer when the resin-containing layer has been transferred and subjected to a prescribed treatment including a heat treatment. A second problem addressed by the present invention is to provide a laminate production method and a laminate which use the transfer film.　A transfer film according to the present invention comprises a temporary support and a resin-containing layer, wherein the resin-containing layer contains a resin X and a compound Y, the compound Y has a molecular weight of 200-1000 and a boiling point of 230-500°C and does not have a crosslinkable group, and the mass ratio of the content of the compound Y to the content of the resin X is 0.20-2.00.

Description

Transfer film, laminate manufacturing method, and laminate

[0001] The present invention relates to a transfer film, a method for manufacturing a laminate, and a laminate.

[0002] In a display device equipped with a touch panel such as a capacitance-type input device (for example, an organic electroluminescence (EL) display device or a liquid crystal display device), conductive patterns such as an electrode pattern corresponding to a sensor in the visible area, and wiring for the peripheral wiring portion and the extraction wiring portion are provided inside the touch panel.

[0003] Generally, a resin composition is used to form a pattern, and for example, Patent Document 1 discloses a resin composition having a predetermined composition.

[0004] Japanese Patent Application Laid-Open No. 2021-148891

[0005] Incidentally, as a method for forming a pattern, a method using a transfer film constructed by arranging a temporary support and a resin-containing layer formed using a resin composition on this temporary support is also widely known, because it requires fewer steps to obtain the required pattern shape.

[0006] The present inventors prepared and examined transfer films using the resin composition described in Patent Document 1 and found that there is room for further improvement in the step-following ability when the film is attached to an object to be attached. Here, "excellent step-following ability when attached to an object to be attached" specifically means that when the resin-containing layer of the transfer film is attached (laminated) to the object to be attached, air bubbles are less likely to form between the object to be attached and the resin-containing layer. In other words, for example, when the object to be attached is a substrate having steps such as wiring, this refers to the ability to attach the resin-containing layer of the transfer film to the object to be attached while suppressing the inclusion of air bubbles due to the steps of the object to be attached. In particular, transfer films are sometimes stored for a certain period of time before lamination, and therefore excellent step-following ability is required when the film is attached to the object to be attached after storage. Furthermore, as basic performance, the transfer film is required to have excellent peelability from the temporary support and a small linear expansion coefficient of the resin-containing layer that has been transferred and subjected to a predetermined treatment including a heat treatment (hereinafter, the resin-containing layer that has been transferred and subjected to a predetermined treatment including a heat treatment is also referred to as a "cured film").

[0007] Therefore, an object of the present invention is to provide a transfer film including a temporary support and a resin-containing layer, which has excellent conformability to unevenness when the resin-containing layer is attached to an object after storage, excellent releasability of the temporary support, and a small linear expansion coefficient of the resin-containing layer that has been transferred and subjected to a predetermined treatment including a heat treatment. Another object of the present invention is to provide a method for producing a laminate using the above transfer film, and a laminate.

[0008] As a result of extensive research into solving the above problems, the present inventors have found that the above problems can be solved by the following configuration, and have completed the present invention.

[0009] [1] A transfer film having a temporary support and a resin-containing layer, wherein the resin-containing layer contains a resin X and a compound Y, the compound Y having a molecular weight of 200 to 1000, a boiling point of 230 to 500°C, and no crosslinkable group, and wherein the mass ratio of the content of the compound Y to the content of the resin X is 0.20 to 2.00. [2] The transfer film according to [1], wherein the resin-containing layer satisfies Requirement 1 described below. [3] The transfer film according to [1] or [2], wherein the resin-containing layer satisfies Requirement 2 described below. [4] The transfer film according to any one of [1] to [3], wherein the resin-containing layer satisfies Requirement 3 described below. [5] The transfer film according to any one of [1] to [4], wherein the resin-containing layer satisfies Requirement 4 described below. [6] The transfer film according to any one of [1] to [5], wherein the content of the resin X is 10.0 to 90.0 mass% relative to the total mass of the resin-containing layer, and the content of the compound Y is 5.0 to 70.0 mass% relative to the total mass of the resin-containing layer. [7] The transfer film according to any one of [1] to [6], wherein the resin X comprises at least one selected from the group consisting of a phenolic resin, an epoxy resin, a polyphenylene ether resin, a silicone resin, a benzocyclobutene resin, a fluorene resin, an acrylic resin, a methacrylic resin, a liquid crystal polymer, polyethersulfone, polyarylate, polyetherimide, polybenzimidazole, polyphenylsulfone, polycarbonate, an acrylonitrile-butadiene-styrene resin, polyphenylene sulfide, polycyclopentadiene, a polyester, and an organosilicon compound. [8] The transfer film according to any one of [1] to [7], wherein the resin-containing layer further comprises a filler. [9] The transfer film according to [8], wherein the filler has an average particle size of 300 nm or less.

[10] The transfer film according to [8] or [9], wherein the content of the filler is 50.0 to 90.0 mass % relative to the total mass of the resin-containing layer.

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

[10] , wherein the resin-containing layer further contains a photopolymerization initiator.

[12] A method for producing a laminate, comprising the steps of: forming a resin-containing layer on a substrate using the transfer film according to any one of [1] to

[11] ; forming a pattern having vias in the resin-containing layer; and heat-treating the pattern.

[13] A laminate produced by the method for producing a laminate according to

[12] .

[0010] According to the present invention, there is provided a transfer film including a temporary support and a resin-containing layer, which has excellent conformability to unevenness when the resin-containing layer is attached to an object to be attached after storage, excellent releasability of the temporary support, and a small linear expansion coefficient of the resin-containing layer that has been transferred and subjected to a predetermined treatment including a heat treatment. Furthermore, there is also provided a method for producing a laminate using the above transfer film, and a laminate.

[0011] 1 is a schematic diagram showing an example of a layer structure of a transfer film. FIG. 2 is a diagram (nomograph) illustrating a method for measuring the boiling point of compound Y.

[0012] The present invention will be described in detail below. In this specification, a numerical range expressed using "to" means a range that includes the numerical values ​​before and after "to" as the lower and upper limits. In addition, in the numerical ranges described in stages in this specification, the upper limit or lower limit described in a certain numerical range may be replaced with the upper limit or lower limit of another numerical range described in stages. In addition, in the numerical ranges described in this specification, the upper limit or lower limit described in a certain numerical range may be replaced with a value shown in the examples.

[0013] Furthermore, the term "process" in this specification does not only refer to an independent process, but also includes a process that cannot be clearly distinguished from other processes as long as the intended purpose of the process 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, "actinic rays" or "radiation" means, for example, the bright line spectrum of a mercury lamp, such as g-line, h-line, and i-line, far ultraviolet light typified by excimer lasers, extreme ultraviolet light (EUV light), X-rays, and electron beams (EB). In addition, in the present invention, light means actinic rays or radiation.

[0017] 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.

[0018] In this specification, unless otherwise specified, the content ratio of each repeating unit of a polymer is a molar ratio. Furthermore, in this specification, unless otherwise specified, the refractive index is a value measured by an ellipsometer at a wavelength of 550 nm.

[0019] In this specification, unless otherwise specified, when a molecular weight distribution exists, the molecular weight 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 ​​determined by gel permeation chromatography (GPC) in terms of polystyrene.

[0020] 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, and "(meth)acrylate" is a concept that encompasses both acrylate and methacrylate.

[0021] In this specification, "water-soluble" means that the solubility in 100 g of water at a liquid temperature of 22°C and a pH of 7.0 is 0.1 g or more.

[0022] In this specification, the "solid content" of a composition refers to components that form a composition layer formed using the composition. Typically, when the composition contains a solvent (e.g., an organic solvent and water), it refers to all components excluding the solvent. Furthermore, liquid components that form a composition layer are also considered to be solid content.

[0023] 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.

[0024] In this specification, unless otherwise specified, the boiling point means the boiling point under normal pressure (1 atmosphere, 760 mmHg).

[0025] [Transfer Film] The transfer film of the present invention is a transfer film having a temporary support and a resin-containing layer, wherein the resin-containing layer contains a resin X and a compound Y, the compound Y has a molecular weight of 200 to 1000, a boiling point of 230 to 500°C, and is a compound having no crosslinkable group, and the mass ratio of the content of the compound Y to the content of the resin X (hereinafter also referred to as "specific mass ratio") is 0.20 to 2.00.

[0026] The transfer film having the above configuration has excellent step-conforming properties when the resin-containing layer is laminated to a substrate after storage, excellent releasability of the temporary support, and a low linear expansion coefficient of the resin-containing layer (cured film) that has been transferred and subjected to a predetermined treatment, including a heat treatment. The detailed mechanism of action of the transfer film is unclear, but the inventor speculates as follows: When the resin-containing layer of the transfer film is laminated to a substrate to form a cured film, compound Y functions as a component to ensure plasticity in the resin-containing layer, and is removed by volatilization when subjected to a heat treatment, making it difficult to remain in the cured film system. In other words, due to the above action of compound Y, when the resin-containing layer of the transfer film is laminated to a substrate, the transfer film has excellent step-conforming properties due to the plasticizing effect of compound Y. Furthermore, the cured film formed by the resin-containing layer of the transfer film is subjected to a predetermined treatment, including a heat treatment, to reduce the content of compound Y, thereby suppressing the thermal expansion coefficient.

[0027] In particular, the transfer film contains the compound Y in the resin-containing layer, and the specific mass ratio of resin X to compound Y is 0.20 to 2.00. This is believed to result in excellent levels of conformability when the resin-containing layer is laminated to a substrate after storage, good releasability of the temporary support, and a low linear expansion coefficient of the cured film. Compound Y is unlikely to volatilize due to environmental influences during storage of the transfer film, primarily due to its molecular weight and boiling point being equal to or greater than a predetermined value. This is believed to contribute to the improvement of conformability when the transfer film is laminated to a substrate after storage. Meanwhile, compound Y is unlikely to remain in the system of the cured film formed by the resin-containing layer, primarily due to its molecular weight and boiling point being equal to or less than a predetermined value and the absence of a crosslinkable group, which is believed to result in the cured film having a low thermal expansion coefficient.

[0028] Hereinafter, "the effect of the present invention is better" may also mean that the transfer film has better conformability to unevenness when it is attached to an object to be attached after storage, that the temporary support has better peelability, and / or that the linear expansion coefficient of the resin-containing layer (cured film) that has been transferred and subjected to a predetermined treatment including a heat treatment is smaller.

[0029] The transfer film will be described below. The transfer film has a temporary support and a resin-containing layer disposed on the temporary support. The transfer film may include other layers on the temporary support in addition to the resin-containing layer. Hereinafter, the resin-containing layer disposed on the temporary support and other layers optionally included may be collectively referred to as the "composition layer." The transfer film may also have a configuration having a protective film (hereinafter also referred to as a "cover film") on the composition layer.

[0030] 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 resin-containing layer 14, and a cover film 16 are laminated in this order. Although the transfer film 100 shown in FIG. 1 has the cover film 16, the transfer film may have no cover film 16. Furthermore, as described below, the transfer film may further have an intermediate layer and / or a thermoplastic resin layer. Each component of the transfer film will be described in detail below.

[0031] [Temporary Support] The transfer film has a temporary support, which is a member that supports the composition layer and is ultimately removed by a peeling treatment.

[0032] 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 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.

[0033] The temporary support preferably has high transparency in order to allow pattern exposure through the temporary support. 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%. In terms of the pattern formability during pattern exposure through the temporary support and the transparency of the temporary support, 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. In terms of the pattern formability during pattern exposure through the temporary support and the transparency of the temporary support, the number of fine particles, foreign matter, and defects contained in the temporary support is preferably small. The number of particles, foreign matter, and defects with a diameter of 1 μm or more on the temporary support is 50 / 10 mm. ２ Preferably, 10 pieces / 10 mm or less ２ More preferably, 3 pieces / 10 mm or less ２ More preferably, 0 pieces / 10 mm or less ２ is particularly preferred.

[0034] 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).

[0035] In order to improve the adhesion between the temporary support and the composition layer, the surface of the temporary support that comes into contact with the composition layer may be surface-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 ２Examples 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.

[0036] 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.).

[0037] Examples of temporary supports 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.

[0038] The temporary support may have a layer containing fine particles (lubricant layer) on one or both sides of the temporary support in order to provide 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.).

[0039] [Resin-Containing Layer] First, various components contained in the resin-containing layer will be described below.

[0040] <Resin X> The resin-containing layer contains resin X. Resin X is different from the various components described below. Resin X may be either a thermoplastic resin or a thermosetting resin. Resin X may have a polymerizable group. The polymerizable group is preferably an ethylenically unsaturated group, more preferably a (meth)acryloyl group, a vinyl group, or a styryl group, and even more preferably a (meth)acryloyl group. Unless otherwise specified, the resin may be either an unmodified product or a modified product. For example, an epoxy resin is a resin having an epoxy group, and may further have a functional group other than an epoxy group and a structure containing that functional group.

[0041] Examples of resin X include known resins. Resin X preferably comprises at least one selected from the group consisting of phenolic resins, epoxy resins, polyphenylene ether resins, silicone resins, benzocyclobutene resins, fluorene resins, (meth)acrylic resins, liquid crystal polymers, polyethersulfone, polyarylate, polyetherimide, polybenzimidazole, polyphenylsulfone, polycarbonate, acrylonitrile-butadiene-styrene resin (ABS resin), polyphenylene sulfide, polycyclopentadiene, polyester, and organosilicon compounds, more preferably comprises at least one selected from the group consisting of phenolic resins, epoxy resins, polyphenylene ether resins, silicone resins, benzocyclobutene resins, fluorene resins, (meth)acrylic resins, and liquid crystal polymers, more preferably comprises at least one selected from the group consisting of phenolic resins, epoxy resins, polyphenylene ether resins, silicone resins, benzocyclobutene resins, (meth)acrylic resins, and liquid crystal polymers, and particularly preferably comprises at least one selected from the group consisting of phenolic resins and epoxy resins.

[0042] Phenolic resins are resins having phenolic hydroxyl groups. Examples of phenolic resins include phenol novolac resins, cresol novolac resins, biphenyl aralkyl phenolic resins, naphthol aralkyl resins, and naphthol novolac resins. Examples of phenolic resins 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 W. Phenolite series such as R-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 C-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, B isP-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 phenolic resins 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 phenolic resins include those 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).

[0043] 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.

[0044] The epoxy resin preferably 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"), in terms of excellent flexibility and improved breaking strength of the resulting cured film.

[0045] 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.

[0046] As the solid epoxy resin, a tetrafunctional naphthalene type epoxy resin, a cresol novolac type epoxy resin, a dicyclopentadiene type epoxy resin, a trisphenol epoxy resin, a naphthol novolac epoxy resin, a biphenyl type epoxy resin, or a naphthylene ether type epoxy resin is preferred, a tetrafunctional naphthalene type epoxy resin, a biphenyl type epoxy resin, or a naphthylene ether type epoxy resin is more preferred, and a 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-type epoxy resin), manufactured by Nippon Kayaku Co., Ltd.; ESN475 (naphthol novolac-type epoxy resin) and ESN485 (naphthol novolac-type epoxy resin), manufactured by Nippon Steel Chemical & Materials Co., Ltd.; YX4000H, YL6121 (biphenyl-type epoxy resin), and YX4000HK (bixylenol-type epoxy resin), manufactured by Mitsubishi Chemical Corporation. Preferred solid epoxy resins include YX4000HK, NC3000L, and HP7200H.

[0047] 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 preferably has a branched structure. In the polyphenylene ether resin having a branched structure, it is preferable that ether bonds are directly bonded to at least three positions, i.e., the ipso, ortho, and para positions, of at least one benzene ring constituting the polyphenylene ether resin.

[0048] 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.

[0049] 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.

[0050] It is also preferable that the polyphenylene ether resin has a polymerizable group. As the polymerizable group, an ethylenically unsaturated group is preferable, and a vinylphenyl group or a (meth)acryloyl group is preferable. Furthermore, when the polyphenylene ether resin has a polymerizable group, it is preferable that the resin-containing layer contains a maleimide compound described later. 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 a resin composition described in WO 2022 / 102756 can be mentioned.

[0051] 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.

[0052] The silicone resin is a resin having an organosiloxane structure. Examples of the silicone resin include curable silicone resins, silicone graft resins, and modified silicone resins such as alkyl-modified silicone resins, and curable silicone resins are preferred. Examples of the curable silicone resin include addition reaction silicone resins, condensation reaction silicone resins, and ultraviolet or electron beam curable silicone resins.

[0053] 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.

[0054] 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.

[0055] 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.

[0056] Examples of silicone resins include resins obtained from organosiloxanes and curable compositions described in JP-A-2020-026502.

[0057] The silicone resin also includes polysilsesquioxane. In this specification, polysilsesquioxane refers to a polymer having a structural unit in which one silicon atom is bonded to one organic group and three oxygen atoms. The skeleton structure of the polysilsesquioxane is not particularly limited, but a cage polysilsesquioxane is preferred. The cage polysilsesquioxane may be either a complete or incomplete type. In addition, the cage polysilsesquioxane may be a T3 consisting of eight structural units T3, which will be described later. ８ Polysilsesquioxane, T consisting of 10 constitutional units T3 described below １０ T consisting of polysilsesquioxane and 12 of the structural units T3 described below １２ The polysilsesquioxane may be any of the polysilsesquioxanes. The polysilsesquioxane preferably has a polymerizable group (for example, a polymerizable group having an ethylenically unsaturated double bond, such as a vinyl group, a styryl group, or a (meth)acryloyl group). The polysilsesquioxane preferably has a chain (straight chain or branched chain) hydrocarbon group. Examples of the chain hydrocarbon group include an alkyl group, an alkenyl group, and an alkynyl group, with an alkyl group being preferred. The chain hydrocarbon group preferably has 1 to 20 carbon atoms, more preferably 2 to 15, and even more preferably 4 to 12 carbon atoms.

[0058] The polysilsesquioxane preferably contains a structural unit selected from the structural unit T1 represented by formula (T1), the structural unit T2 represented by formula (T2), and the structural unit T3 represented by formula (T3), more preferably contains a structural unit selected from the structural unit T2 and the structural unit T3, and even more preferably contains the structural unit T3. The structural units T1 to T3 belong to the so-called T units. Formula (T1): R １ -Si(OX １ ) ２ O １／２ Formula (T2): R １ -Si(OX １ ) O２／２ Formula (T3): R １ -SiO ３／２ In formulas (T1) to (T3), R １ Each of X independently represents a monovalent organic group. １ Each independently represents a hydrogen atom or an alkyl group. １ may be the same or different. In other words, the polysilsesquioxane may contain different R １ The copolymer may be a copolymer containing a plurality of structural units having the following structure:

[0059] R １ Examples of the monovalent organic group represented by the formula (I) include a chain aliphatic hydrocarbon group (preferably linear) and an aromatic hydrocarbon group. The aliphatic hydrocarbon group preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and even more preferably 3 to 12 carbon atoms. The aromatic hydrocarbon group preferably has 4 to 20 carbon atoms, more preferably 5 to 12 carbon atoms, and even more preferably 5 to 6 carbon atoms. The chain aliphatic hydrocarbon group and aromatic hydrocarbon group may further contain a halogen atom, an alkyl group, an alkoxy group, an aryl group, and a polymerizable group-containing group (for example, -L Ｐ A group represented by -P. Ｐ represents a single bond or a divalent linking group (examples include a divalent aliphatic hydrocarbon group having 1 to 6 carbon atoms, -O-, or a group formed by combining these), and P may have a substituent such as a polymerizable group (examples include the above-mentioned polymerizable groups). X １ The alkyl group represented by the formula (I) preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 4 carbon atoms, and particularly preferably 1 to 3 carbon atoms.

[0060] The polysilsesquioxane preferably contains a structural unit selected from structural unit T2 and structural unit T3. The total content of the structural units selected from structural unit T2 and structural unit T3 is preferably 50 to 70 mol % or more, and more preferably 70 to 100 mol % or more, relative to the total of all structural units of the polysilsesquioxane. The content of each of the above structural units may be, for example, ２９It can be calculated from the peak positions and peak area ratios in Si-NMR spectrum measurement. It is also preferable that the polysilsesquioxane contains a structural unit having a polymerizable group. The content of the structural unit having a polymerizable group is preferably 10 to 90 mol%, more preferably 30 to 70 mol%, and even more preferably 40 to 60 mol%, relative to the total of all structural units of the polysilsesquioxane. It is also preferable that the polysilsesquioxane contains a structural unit having a chain hydrocarbon group. The content of the structural unit having a chain hydrocarbon group is preferably 10 to 90 mol%, more preferably 30 to 70 mol%, and even more preferably 40 to 60 mol%, relative to the total of all structural units of the polysilsesquioxane.

[0061] The weight average molecular weight (Mw) of the polysilsesquioxane is preferably 3,000 to 100,000, and more preferably 5,000 to 50,000. The number average molecular weight (Mn) of the polysilsesquioxane is preferably 1,000 to 10,000, and more preferably 2,500 to 7,000.

[0062] Benzocyclobutene resins are resins having a benzocyclobutene ring, such as divinylsiloxane-bisbenzocyclobutene resins (e.g., CYCLOTENE resins, manufactured by The Dow Chemical Company).

[0063] The (meth)acrylic resin is a resin having repeating units derived from a compound selected from (meth)acrylic acid and (meth)acrylic acid esters. Examples of repeating units derived from (meth)acrylic acid esters include repeating units derived from (meth)acrylic acid alkyl esters. The number of carbon atoms in the alkyl group (-COOR, the alkyl group in the R moiety) constituting the (meth)acrylic acid alkyl ester is preferably 1 to 50, more preferably 1 to 10, and even more preferably 1 to 6. The alkyl group may be linear, branched, or cyclic. Examples of (meth)acrylic acid alkyl esters include methyl (meth)acrylate. The total content of repeating units derived from (meth)acrylic acid and (meth)acrylic acid esters is preferably 20% by mass or more, more preferably 50% by mass or more, based on the total repeating units of the (meth)acrylic resin. The upper limit is preferably 100% by mass or less, more preferably 90% by mass or less.

[0064] The (meth)acrylic resin may have a repeating unit having an aromatic ring. The repeating unit having an aromatic ring may be a repeating unit derived from a (meth)acrylic acid ester. In other words, the repeating unit having an aromatic ring may be a repeating unit derived from a (meth)acrylic acid ester having an aromatic ring group. 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. Examples of repeating units having an aromatic ring include a repeating unit derived from a (meth)acrylate having an aromatic ring, a repeating unit derived from styrene, and a repeating unit derived from a polymerizable styrene derivative. Examples of (meth)acrylates having an aromatic ring include benzyl (meth)acrylate, phenethyl (meth)acrylate, and phenoxyethyl (meth)acrylate. Examples of styrene and polymerizable styrene derivatives include styrene, methylstyrene, vinyltoluene, tert-butoxystyrene, acetoxystyrene, styrene dimer, and styrene trimer.

[0065] The (meth)acrylic resin may have a repeating unit having an alicyclic group. The repeating unit having an alicyclic group may be a repeating unit derived from a (meth)acrylic acid ester. In other words, the repeating unit having an alicyclic group may be a repeating unit derived from a (meth)acrylic acid ester having an alicyclic group. The alicyclic ring may be either a monocyclic ring or a polycyclic ring. Examples of the alicyclic ring include a dicyclopentanyl ring, a dicyclopentenyl ring, an isobornyl ring, an adamantane ring, and a cyclohexyl ring. Examples of monomers from which the repeating unit having an alicyclic ring is derived include dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, and cyclohexyl (meth)acrylate.

[0066] 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 polyester amides in which an amide bond is introduced into a thermoplastic liquid crystal polyester.

[0067] 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 compounds 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.

[0068] The liquid crystal polymer may contain repeating units derived from compounds other than the above compounds. Other compounds include, for example, aromatic dicarboxylic acids such as 2,6-naphthalenedicarboxylic acid, 4,4'-diphenyldicarboxylic acid, 1,2-bis(phenoxy)ethane-4,4'-dicarboxylic acid, 1,2-bis(2-chlorophenoxy)ethane-4,4'-dicarboxylic acid, 4,4'-diphenyletherdicarboxylic acid, 3,3'-diphenyldicarboxylic acid, and 2,2'-diphenyldicarboxylic acid; aliphatic dicarboxylic acids such as adipic acid, azelaic acid, sebacic acid, and dodecanedioic acid; alicyclic dicarboxylic acids such as hexahydroterephthalic acid; 3,3',5,5'-tetramethyl-4,4'-dihydroxybiphenyl, t-butylhydroquinone, phenylhydroquinone, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2,2-bis(4-hydroxyphenyl)propane, 4,4'-dihydroxydiphenyl ether, chloro ... aromatic diols such as hydroquinone, 3,4'-dihydroxybiphenyl, 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxybenzophenone, and 3,4'-dihydroxybiphenyl; aliphatic and alicyclic diols such as ethylene glycol, propylene glycol, 1,4-butanediol, cyclohexanedimethanol, 1,6-hexanediol, neopentyl glycol, and 1,4-cyclohexanediol; aromatic hydroxycarboxylic acids such as 6-hydroxy-2-naphthoic acid and m-hydroxybenzoic acid; aromatic aminocarboxylic acids such as p-aminobenzoic acid and 6-amino-2-naphthoic acid; aromatic diamines such as 1,4-phenylenediamine, 4,4'-diaminobiphenyl, and 2,6-diaminonaphthalene; and aromatic hydroxylamines such as p-aminophenol.

[0069] Examples of the liquid crystal polymer include the liquid crystal polymers described in JP 2006-299254 A and WO 2015 / 064437 A.

[0070] Examples of polyethersulfone, polyarylate, polyetherimide, polybenzimidazole, polyphenylsulfone, polycarbonate, acrylonitrile-butadiene-styrene resin, polyphenylene sulfide, polycyclopentadiene, and polyester include known resins.

[0071] Examples of organosilicon compounds include compounds having a silyl group, and 1,4-bis(dimethylsilyl)benzene, trivinylphenylsilane, or a compound represented by the following formula (SiA) are preferred. It is also preferable that the organosilicon compound further has a polymerizable group. Examples of the polymerizable group include polymerizable groups contained in the resin. In formula (SiA), * indicates the bonding position of each structural unit. Examples of compounds represented by formula (SiA) include components (a) to (e), which are components constituting the organosilicon compound represented by J-3 in the examples described below. It is also preferable that the organosilicon compound is used together with a silicone resin and a hydrosilylation agent.

[0072]

[0073] Examples of the resin X include known resins other than the various resins mentioned above.

[0074] The weight average molecular weight (Mw) of resin X is, for example, preferably 2,000 to 500,000, and more preferably 5,000 to 100,000. The number average molecular weight (Mn) of resin X is, for example, preferably 800 to 250,000, and more preferably 2,000 to 50,000. The dispersity (Mw / Mn) of resin X is, for example, preferably 1.0 to 3.5, and more preferably 2.0 to 3.0.

[0075] Resin X may be used alone or in combination of two or more. The content of resin X is preferably 5.0% by mass or more, more preferably 10.0% by mass or more, relative to the total mass of the resin-containing layer. The upper limit is preferably 90.0% by mass or less, more preferably 80.0% by mass or less, even more preferably 70.0% by mass or less, and most preferably 65.0% by mass or less, relative to the total mass of the resin-containing layer. When the resin-containing layer contains a filler described below, the upper limit of the content of resin X relative to the total mass of the resin-containing layer is preferably 50.0% by mass or less, more preferably 30.0% by mass or less.

[0076] <Compound Y> The resin-containing layer contains compound Y. Compound Y is a compound having a molecular weight of 200 to 1000, a boiling point of 230 to 500°C, and no crosslinkable group. Here, the term "crosslinkable group" refers to a group that can undergo a reaction under specific conditions to form a crosslinked structure, and specific examples include an ethylenically unsaturated group, a cyclic ether group, and a silane coupling group.

[0077] In this specification, the boiling point of compound Y refers to a value determined by the following measurement method. When compound Y is distilled under atmospheric pressure (760 mmHg), the boiling point is the gas temperature at which condensation of the evaporated gas begins (measurements are made from 23°C to 300°C, with a temperature increase rate of 1°C / min). Distillation is carried out using a Liebig condenser, and if distillation does not begin at 300°C under atmospheric pressure, distillation is carried out under reduced pressure. Similar distillation is carried out at pressures of 100 mmHg, 50 mmHg, and 5 mmHg in this order (23°C to 300°C, and if distillation does not begin at 300°C, the next pressure is used). The boiling point at atmospheric pressure is determined from the temperature and pressure at which condensation of the evaporated gas begins using the nomograph shown in Figure 2 (source: Science of Petroleum, Vol. II, p. 1281 (1938)). This is taken as the boiling point (calculated value). If distillation does not begin at 300°C under 5 mmHg, the boiling point at normal pressure is considered to be greater than 500°C. The method of using a nomograph is well known. Specifically, a straight line is 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 is read (Procedure 2), and this value is considered to be the boiling point at normal pressure.

[0078] The lower limit of the molecular weight of compound Y is preferably 250 or more, more preferably 300 or more, and the upper limit is preferably 800 or less, more preferably 600 or less.

[0079] The lower limit of the boiling point of compound Y is preferably 250° C. or higher, more preferably 280° C. or higher, even more preferably 300° C. or higher, and particularly preferably 350° C. or higher. The upper limit is preferably 480° C. or lower, more preferably 450° C. or lower. When compound Y has a molecular weight distribution, the above molecular weight of compound Y refers to the weight average molecular weight.

[0080] The viscosity of compound Y at 25°C is preferably 500 mPa s or less, more preferably 300 mPa s or less, and even more preferably 100 mPa s or less. The lower limit is preferably 0.01 mPa s or more, more preferably 0.05 mPa s or more, and even more preferably 0.1 mPa s or more. The viscosity can be measured using a B-type viscometer.

[0081] Compound Y is not particularly limited, but is preferably selected from compounds such as phosphate esters, polycarboxylic acid esters, polyether esters, alkylene glycol monoalkyl ethers, alkylene glycol dialkyl ethers, and benzyl benzoate.

[0082] Examples of phosphate esters include triamyl phosphate and tris(2-butoxyethyl) phosphate.

[0083] 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 acetylcitrate). Specific examples of polycarboxylic acid esters include ethyl phthalyl ethyl glycolate, dihexyl phthalate, tributyl o-acetylcitrate, benzyl 2-ethylhexyl phthalate, bis(2-ethylhexyl) isophthalate, tris(2-ethylhexyl) trimellitate, and bis(2-butoxyethyl) adipate.

[0084] The polyether esters are preferably organic acid esters of polyalkylene glycol. Examples of the organic acid 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.

[0085] Specific 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.

[0086] Compound Y may be used alone or in combination of two or more. The lower limit of the content of compound Y is preferably 1.0 mass% or more, more preferably 3.0 mass% or more, even more preferably 5.0 mass% or more, particularly preferably more than 5.0 mass%, and most preferably 10.0 mass% or more, based on the total mass of the resin-containing layer. The upper limit is preferably 75.0 mass% or less, more preferably 70.0 mass% or less, and even more preferably 60.0 mass% or less.

[0087] In the resin-containing layer, the mass ratio (specific mass ratio) of the content of compound Y to the content of resin X is 0.20 to 2.00. The lower limit of the specific mass ratio is preferably 0.25 or more, more preferably 0.30 or more, even more preferably 0.40 or more, and particularly preferably 0.50 or more. The upper limit of the specific mass ratio is preferably 1.80 or less, more preferably 1.40 or less.

[0088] <Filler> The resin-containing layer preferably contains a filler. The average particle diameter of the filler is preferably 300 nm or less, more preferably 200 nm or less, and even more preferably 100 nm or less. The lower limit is preferably more than 0 nm, more preferably 5 nm or more, and even more preferably 10 nm or more. The average particle diameter of the filler is also preferably 5 to 100 nm. The average particle diameter of the filler is 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 resin-containing layer taken along the normal direction to the surface of the resin-containing layer 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 resin-containing layer. The average value of the major axes of all fillers measured in each operation is defined as the average particle diameter of the filler.

[0089] The procedure for the particle size measurement method is described in detail below. A cross section along the normal direction of the surface of the resin-containing layer (the surface opposite the temporary support side) is cut out, and a rectangular region of 3 μm × 10 μm on the cross section is observed with a scanning electron microscope. The major axis of all fillers observed within the region is measured. A Hitachi High-Tech S-4800 scanning electron microscope is used as the scanning electron microscope. The magnification for observation is 50,000 times. The above procedure is performed at five different locations on the resin-containing layer, and the average (arithmetic mean) of the major axes of all fillers measured in each procedure is taken as the average particle size of the filler. The major axis 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, if the filler aggregates to form aggregates in the observed image, the major axis of each filler constituting the aggregate is measured.

[0090] 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 chion-doped 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).

[0091] 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 modifiers. Examples of the functional groups include polymerizable groups (e.g., polymerizable groups contained in polymerizable compounds described below) and hydrophobic groups. Examples of surface modifiers include known surface modifiers such as silane coupling agents, titanate coupling agents, and silazane compounds.

[0092] Examples of fillers include Seahoster KE-S30 (manufactured by Nippon Shokubai Co., Ltd., silicon dioxide, solid content concentration 100% by mass), NHM-3N (manufactured by Tokuyama Corporation, silicon dioxide, solid content concentration 100% by mass), YA050C-MJE (manufactured by Admatechs Co., Ltd., silicon dioxide, MEK slurry with a solid content concentration of 50% by mass), SFP-20M (manufactured by Denka Co., Ltd., silicon dioxide), PMA-ST (manufactured by Nissan Chemical Industries, Ltd., silicon dioxide), MEK-ST-L (manufactured by Nissan Chemical Industries, Ltd., silicon dioxide), and MEK-AC-5140. Z (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), NHM-5N (manufactured by Tokuyama Corporation, silicon dioxide, 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).

[0093] The refractive index of the filler is preferably 0.5 to 3.0, more preferably 1.2 to 1.8. The refractive index can be measured by the method described above.

[0094] The filler may be used alone or in combination of two or more. When the resin-containing layer contains a filler, the content of the filler is preferably 20.0 mass% or more, more preferably 30.0 mass% or more, still more preferably 40.0 mass% or more, and particularly preferably 50.0 mass% or more, based on the total mass of the resin-containing layer. The upper limit is preferably 90.0 mass% or less, more preferably 80.0 mass% or less.

[0095] <Polymerizable Compound> The resin-containing layer may contain a polymerizable compound. The polymerizable compound is a compound different from the various components described above. When the resin-containing layer contains a polymerizable compound (preferably a compound having an ethylenically unsaturated group), it is preferable that the resin-containing layer further contains a photopolymerization initiator, which will be described later.

[0096] The polymerizable compound is a compound having one or more polymerizable groups in one molecule. As the polymerizable compound, a compound having an ethylenically unsaturated group is preferred, a compound having a (meth)acryloyl group, a vinyl group, or a styryl group is more preferred, and a compound having a (meth)acryloyl group is even more preferred.

[0097] The number of polymerizable groups in the polymerizable compound is preferably 1 or 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 polymerizable group in one molecule (hereinafter also referred to as a "monofunctional polymerizable compound"), a polymerizable compound having two polymerizable groups in one molecule (hereinafter also referred to as a "bifunctional polymerizable compound"), and a polymerizable compound having three or more polymerizable groups 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.

[0098] 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.).

[0099] 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.

[0100] 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.).

[0101] 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.).

[0102] The polymerizable compound may be used alone or in combination of two or more. The content of the polymerizable compound is preferably 30.0 mass % or less, more preferably 25.0 mass % or less, and even more preferably 20.0 mass % or less, based on the total mass of the resin-containing layer. The lower limit is preferably 1.0 mass % or more.

[0103] <Photopolymerization initiator> The resin-containing layer may contain a photopolymerization initiator. Examples of the photopolymerization initiator include a photoradical polymerization initiator, a photocationic polymerization initiator, and a photoanionic polymerization initiator, and a photoradical polymerization initiator is preferred.

[0104] 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.

[0105] 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.).

[0106] Examples of aminoacetophenone compounds include 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone (trade name: Omnirad 379EG, manufactured by IGM Resins B.V.), 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one (trade name: Omnirad 907, manufactured by IGM Resins B.V.), and API-307 (1-(biphenyl-4-yl)-2-methyl-2-morpholinopropan-1-one, manufactured by Shenzhen UV-ChemTech Ltd.).

[0107] 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).

[0108] Examples of the photopolymerization initiator include the photopolymerization initiators described in paragraphs 0031 to 0042 of JP-A No. 2011-095716 and paragraphs 0064 to 0081 of JP-A No. 2015-014783.

[0109] The photopolymerization initiator may be used alone or in combination of two or more. The content of the photopolymerization initiator is preferably 10.0% by mass or less, more preferably 5.0% by mass or less, and even more preferably 1.0% by mass or less, based on the total mass of the resin-containing layer. The lower limit is preferably 0.1% by mass or more.

[0110] <Photoacid Generator> The resin-containing layer may contain a photoacid generator, which is a compound that generates an acid when exposed to light (for example, exposure light).

[0111] Examples of photoacid generators include ionic photoacid generators and nonionic photoacid generators. Examples of ionic photoacid generators include compounds having a sulfonium structure, onium salt compounds having a diaryliodonium or triarylsulfonium structure, and ammonium salt compounds having a quaternary ammonium structure. Examples of ionic photoacid generators include those described in paragraphs

[0114] to

[0133] of JP 2014-085643 A. Examples of nonionic photoacid generators include trichloromethyl-s-triazine and its derivatives (trichloromethyl-s-triazines which may have a substituent), compounds having a diazomethane structure, compounds having an imide sulfonate structure, and compounds having an oxime sulfonate structure. Examples of trichloromethyl-s-triazine and its derivatives, diazomethane compounds, and imide sulfonate compounds include those described in paragraphs

[0083] to

[0088] of JP 2011-221494 A. Furthermore, examples of the oxime sulfonate compound include the compounds described in paragraphs 0084 to 0088 of WO 2018 / 179640.

[0112] The content of the photoacid generator is preferably 0.1 to 10.0% by mass, more preferably 0.5 to 5.0% by mass, based on the total mass of the resin-containing layer.

[0113] <Surfactant> The resin-containing layer may contain a surfactant. Examples of the surfactant include those described in paragraph 0017 of Japanese Patent No. 04502784 and paragraphs 0060 to 0071 of JP-A-2009-237362.

[0114] Examples of surfactants include hydrocarbon surfactants, fluorine surfactants, and silicone surfactants. From the viewpoint of improving environmental friendliness, it is preferable that the surfactant does not contain a fluorine atom. The surfactant is preferably a hydrocarbon surfactant or a silicone surfactant. Commercially available fluorine-based surfactants include, for example, Megafac F-171, F-172, F-173, F-176, F-177, F-141, F-142, F-143, F-144, F-437, F-475, F-477, F-479, F-482, F-551-A, F-552, F-554, F-555-A, F-556, F-557, F-558, F-559, 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 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).

[0115] 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 having an ethylenically unsaturated group in the side chain, such as Megafac RS-101, RS-102, RS-718K, and RS-72-K (all manufactured by DIC Corporation).

[0116] 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.

[0117] 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 esters. Examples of hydrocarbon surfactants include 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); NCW-101, NCW-1001, and NCW-1002 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.); Paionin D-1105, D-6112, D-6112-W, and D-6315 (manufactured by Takemoto Oil & Fat Co., Ltd.); and Olfine E1010, Surfynol 104, 400, and 440 (manufactured by Nissin Chemical Industry Co., Ltd.).

[0118] 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.

[0119] The repeating unit having a group having a siloxane bond in the side chain is preferably a repeating unit represented by formula (SX1) or a repeating unit represented by formula (SX2).

[0120]

[0121] In formula (SX1), each R independently represents an alkyl group having 1 to 3 carbon atoms. １ represents a hydrogen atom or a methyl group. １ represents a single bond or a divalent organic group. When a plurality of R's are present, the R's may be the same or different.

[0122]

[0123] In formula (SX2), R １ represents a hydrogen atom or a methyl group. ２ represents an alkylene group having 1 to 10 carbon atoms. ３ represents an alkyl group having 1 to 4 carbon atoms, and n represents an integer of 5 to 50.

[0124] The repeating unit having a hydrophilic group in the side chain is preferably a repeating unit represented by formula (SX3).

[0125]

[0126] In formula (SX3), R ４ and R ５ each independently represents a hydrogen atom or a methyl group, n represents an integer of 1 to 4, and m represents an integer of 1 to 100.

[0127] Examples of silicone surfactants include EXP.S-309-2, EXP.S-315, EXP.S-503-2, and EXP.S-505-2 (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-22-6266 , KF-351A, K354L, KF-355A, KF-945, KF-640, KF-642, KF-643, X-22-6191, X-22-4515, KF-6004, KF-6001, K F-6002, KP-101KP-103, KP-104, KP-105, KP-106, KP-109, KP-109, KP-112, KP-120, KP-121, KP-124, KP-12 No. 5, 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 Perform 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).

[0128] The surfactant also includes a nonionic surfactant.

[0129] The surfactant content is preferably 0.01 to 3.0% by mass, more preferably 0.01 to 1.0% by mass, and even more preferably 0.05 to 0.8% by mass, based on the total mass of the resin-containing layer.

[0130] <Curing Agent> The resin-containing layer may contain a curing agent. The curing agent is not particularly limited as long as it is, for example, a compound that promotes the curing of various components contained in the resin-containing layer. Examples of the curing agent include cyanate ester curing agents and benzoxazine curing agents. Examples of cyanate ester curing agents and benzoxazine curing agents include those described in JP-A-2020-154325 and JP-A-2004-277460.

[0131] <Other Additives> The resin-containing layer may contain other additives in addition to the various components described above. Examples of other additives include heterocyclic compounds (e.g., compounds such as triazole, tetrazole, and benzotriazole, and derivatives thereof, as well as rust inhibitors, etc.), aliphatic thiol compounds, thermally crosslinkable compounds, polymerization inhibitors, hydrogen donor compounds, impurities, plasticizers, sensitizers, alkoxysilane compounds, maleimide compounds, and hydrosilylation agents. Examples of heterocyclic compounds, aliphatic thiol compounds, thermally crosslinkable compounds, polymerization inhibitors, and hydrogen donor compounds include the various components described in WO 2022 / 039027. Examples of plasticizers, sensitizers, and alkoxysilane compounds include those described in paragraphs 0097 to 0119 of WO 2018 / 179640. Examples of maleimide compounds (compounds having a maleimide ring) include known maleimide compounds and the maleimide compounds described in WO 2022 / 102756. Examples of hydrosilylation agents include platinum-based 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. In addition, when an organosilicon compound is used as resin X, the hydrosilylation agent is preferably used as a curing agent for the organosilicon compound.

[0132] The resin-containing layer may contain impurities, such as sodium, potassium, magnesium, calcium, iron, manganese, copper, aluminum, titanium, chromium, cobalt, nickel, zinc, tin, halogens, and ions thereof. Halide ions, sodium ions, and potassium ions are likely to be mixed in as impurities, so the following contents are preferred.

[0133] The content of impurities is preferably 80 mass ppm or less, more preferably 10 mass ppm or less, and even more preferably 2 mass ppm or less, relative to the total mass of the resin-containing layer.The lower limit is often 0 mass ppb or more, and may be 1 mass ppb or more, or even 0.1 mass ppm or more, relative to the total mass of the resin-containing layer.Specific examples of the amount of impurities in the composition include a chloride ion concentration of 1.5 mass ppm, a bromide ion concentration of 0.5 mass ppm, a sodium ion concentration of 1.5 mass ppm, and an iron ion concentration of 0.3 mass ppm, relative to the total solid content of the composition.

[0134] Methods for adjusting the impurity content include, for example, a method of using raw materials with low impurity contents as raw materials for the various components that may be contained in the resin-containing layer, a method of purifying and using the various components that may be contained in the resin-containing layer, and a method of preventing the incorporation of impurities when forming the resin-containing layer.

[0135] The content of impurities can be determined by known methods such as ICP (Inductively Coupled Plasma) emission spectroscopy, atomic absorption spectroscopy, and ion chromatography.

[0136] The resin-containing layer preferably contains a small amount of compounds such as benzene, formaldehyde, trichloroethylene, 1,3-butadiene, carbon tetrachloride, chloroform, N,N-dimethylformamide, N,N-dimethylacetamide, and hexane. Specifically, the content of each of these compounds is preferably 100 ppm by mass or less, more preferably 20 ppm by mass or less, and even more preferably 4 ppm by mass or less, relative to the total mass of the resin-containing layer. The lower limit may be 10 ppb by mass or more, or 100 ppb by mass or more, relative to the total mass of the resin-containing layer. The content of these compounds can be adjusted using the same method as for the impurities described above. Furthermore, these compounds can be quantified using known measurement methods.

[0137] From the viewpoints of improving reliability, improving the handling properties of the transfer film, and improving lamination properties, the moisture content of the resin-containing layer is preferably 3.0% by mass or less, more preferably 2.0% by mass or less, and even more preferably 1.0% by mass or less, relative to the total mass of the resin-containing layer. The lower limit is preferably 0.0001% by mass or more, more preferably 0.01% by mass or more, and even more preferably 0.1% by mass or more. Specific examples of the moisture content in the resin-containing layer include 2.5% by mass, 1.5% by mass, and 0.3% by mass, relative to the total mass of the resin-containing layer.

[0138] The amount of residual solvent in the resin-containing layer is preferably 6.0% by mass or less, more preferably 4.0% by mass or less, even more preferably 2.0% by mass or less, and particularly preferably 1.0% by mass or less, based on the total mass of the resin-containing layer, from the viewpoints of improving reliability, improving the handling properties of the transfer film, improving lamination properties, etc. The lower limit is preferably 0.0001% by mass or more, more preferably 0.01% by mass or more, and even more preferably 0.1% by mass or more.

[0139] <Thickness of Resin-Containing Layer> The lower limit of the average thickness of the resin-containing layer is preferably 0.5 μm or more, more preferably 1.0 μm or more, even more preferably 3.0 μm or more, and particularly preferably 5.0 μm or more. The upper limit is preferably 40 μm or less, more preferably 25 μm or less, even more preferably 20 μm or less, and particularly preferably 19 μm or less. When the average thickness of the resin-containing layer is 40 μm or less, it is preferable in terms of excellent pattern resolution, and when the average thickness of the resin-containing layer is 0.5 μm or more, it is preferable in terms of excellent reliability.

[0140] <Requirement 1> The resin-containing layer preferably satisfies the following requirement 1. Requirement 1: When the resin-containing layer is heated at 300°C for 3 hours, the weight loss rate of the resin-containing layer is 8.0% by mass or more. When the resin-containing layer is heated at 300°C for 3 hours, the weight loss rate of the resin-containing layer is more preferably 10.0% by mass or more, and even more preferably 12.0% by mass or more. The upper limit is preferably 50.0% by mass or less, more preferably 40.0% by mass or less, and even more preferably 30.0% by mass or less. The weight loss rate of the resin-containing layer when heated at 300°C for 3 hours can be measured by the following procedure.

[0141] (Preparation of Evaluation Sample (Sample A)) The evaluation sample (Sample A) is prepared by overlapping the resin-containing layers of the transfer films to form a free-standing film. Hereinafter, for example, a case where Sample A is prepared using five transfer films will be described. First, two transfer films from which the protective films have been peeled are bonded together so that the resin-containing layers of each transfer film face each other, and then one of the two temporary supports is peeled off to obtain a laminate 1 having a temporary support and two resin-containing layers. Next, the transfer film from which the protective film has been peeled is bonded to the laminate 1 so that the resin-containing layer of this transfer film faces the resin-containing layer of the laminate 1, and then one of the two temporary supports is peeled off to obtain a laminate 2 having a temporary support and three resin-containing layers. Then, the laminate 1 is separately prepared, and the resin-containing layer of the laminate 1 and the resin-containing layer of the laminate 2 are bonded together so that the resin-containing layers face each other to obtain a laminate 3 (temporary support / five resin-containing layers / temporary support). Finally, the two temporary supports are peeled off from the laminate 3 to obtain sample A.

[0142] (Measurement of thermal weight loss rate when the resin-containing layer is heated at 300°C for 3 hours) The thermal weight loss rate of sample A is measured using a TG-DTA device (simultaneous thermogravimetry / differential thermal analysis device), and the average value of three measurements is taken as the thermal weight loss rate when the resin-containing layer is heated at 300°C for 3 hours. The measurement is preferably carried out under the following conditions. The final thermal weight loss rate is measured in a range of room temperature to 300°C (under a nitrogen atmosphere, at a heating rate of 10°C / min, and maintained at 300°C for 3 hours). As the TG-DTA device, for example, the "TG / DTA6200" manufactured by Seiko Instruments Inc. can be used.

[0143] <Requirement 2> The resin-containing layer preferably satisfies the following requirement 2. Requirement 2: The content of compound Y in the resin-containing layer is more than 5.0% by mass relative to the total mass of the resin-containing layer, and the content of compound Y in the resin-containing layer after heating the resin-containing layer at 300°C for 3 hours is 5.0% by mass or less relative to the total mass of the resin-containing layer.

[0144] The content of compound Y when the resin-containing layer is heated at 300°C for 3 hours is preferably 3.0 mass% or less, more preferably 2.0 mass% or less, and even more preferably 1.0 mass% or less, relative to the total mass of the resin-containing layer after heating. The lower limit is preferably 0 mass%. The content of compound Y when the resin-containing layer is heated at 300°C for 3 hours can be measured by the following procedure.

[0145] (Preparation of Evaluation Sample (Sample B)) Sample A is prepared by the same method as described in (Preparation of Evaluation Sample (Sample A)) of <Requirement 1>. Next, the prepared Sample A is heated at 300°C for 3 hours in a nitrogen atmosphere to prepare an evaluation sample (Sample B).

[0146] (Measurement of the Content (% by mass) of Compound Y in the Resin-Containing Layer After Heating the Resin-Containing Layer at 300°C for 3 Hours) The "content (% by mass) of Compound Y in the Resin-Containing Layer after Heating the Resin-Containing Layer at 300°C for 3 Hours" can be measured according to the following measurement procedure. First, 50 mg of Sample B is immersed in 5 ml of a solvent for 48 hours to extract the components of Sample B into the solvent. Next, the mass of Compound Y in the extract is determined by measurement using GC-MS, and this is defined as the "content of Compound Y in the Resin-Containing Layer after Heating the Resin-Containing Layer at 300°C for 3 Hours." Next, the content (% by mass) of Compound Y in the Resin-Containing Layer after Heating the Resin-Containing Layer at 300°C for 3 Hours is determined by {(content of Compound Y in the Resin-Containing Layer after Heating the Resin-Containing Layer at 300°C for 3 Hours) / mass of Sample B) × 100}. The solvent used for extracting the compound Y is preferably a solvent capable of dissolving 5% by mass or more of the compound Y, such as tetrahydrofuran (THF).

[0147] (Measurement of the Content of Compound Y in the Resin-Containing Layer (Unheated)) When the content of compound Y is known, the "content of compound Y in the resin-containing layer" can be the known content. When the content of compound Y is unknown, sample A is prepared using the same method as described in (Preparation of Evaluation Sample (Sample A)) of <Requirement 1>. Next, 50 mg of sample A is immersed in 5 ml of solvent for 48 hours to extract the components of sample A into the solvent. Next, the mass of compound Y in the extract is determined by measurement using GC-MS, and this is defined as the "content of compound Y in the resin-containing layer." The solvent used for extracting compound Y is preferably a solvent that dissolves 5% by mass or more of compound Y, such as tetrahydrofuran (THF). Next, the content of compound Y (% by mass) in the resin-containing layer is determined by {(content of compound Y in the resin-containing layer / mass of sample A) × 100}.

[0148] In each measurement, the following conditions are preferred as the GC-MS measurement conditions. GC-MS measurement conditions: Apparatus: Shimadzu Corporation "2010-Ultra" Column: DB-5MS (30 m, 0.25 mm, 0.25 μm) Oven: 50°C (2 min) - 20°C / min - 320°C (5 min) Injection: 1 μL (300°C, 1 / 10 split) Flow rate: 130 kPa Detection: EI-MS (m / z 19-600)

[0149] <Requirements 3 and 4> The resin-containing layer preferably satisfies the following requirement 3 and / or requirement 4. Requirement 3: When the glass transition temperature of the resin-containing layer is X [°C] and the glass transition temperature of the resin-containing layer after heating at 300°C for 3 hours is Y [°C], the formula (1) is satisfied. Formula (1) Y-X≧100 Requirement 4: The glass transition temperature of the resin-containing layer after heating at 300°C for 3 hours Y [°C] satisfies the formula (2). Formula (2) Y≧150

[0150] The value of Y-X is preferably 100 or more, more preferably 120 or more, and even more preferably 150 or more. The upper limit is preferably 500 or less, more preferably 450 or less, and even more preferably 400 or less. The value of Y is preferably 150 or more, more preferably 170 or more, and even more preferably 190 or more. The upper limit is preferably 600 or less, more preferably 550 or less, and even more preferably 500 or less.

[0151] The glass transition temperature (X [°C]) of the resin-containing layer and the glass transition temperature (Y [°C]) of the resin-containing layer when heated at 300°C for 3 hours can be measured by the following procedure.

[0152] (Measurement of Glass Transition Temperature (X [°C]) of Resin-Containing Layer (Unheated)) The evaluation sample (Sample A) is prepared by the same method as described in (Preparation of Evaluation Sample (Sample A)) of <Requirement 1>. The prepared Sample A (freestanding film) is cut into a strip (19 mm x 5 mm), and the glass transition temperature is measured using a TMA (thermomechanical analyzer, "TMA450EM" manufactured by TA Instruments). The measurement conditions are a temperature rise rate of 10°C / min, a chuck distance of 16 mm, and a load of 49 mN, and the measurement is performed in a temperature range of -60°C to 350°C. The glass transition temperature is the inflection point where the slope changes, and the average value of three measurements is taken as the glass transition temperature (X [°C]) of the resin-containing layer.

[0153] (Measurement of the Glass Transition Temperature (Y [°C]) of the Resin-Containing Layer When Heated at 300°C for 3 Hours) Sample A is prepared using the same method as described in (Preparation of Evaluation Sample (Sample A)) of Requirement 1. Next, the prepared Sample A is heated at 300°C for 3 hours in a nitrogen atmosphere to prepare an evaluation sample (Sample B). Next, the prepared Sample B (freestanding film) is cut into a strip (19 mm x 5 mm), and the glass transition temperature is measured using a TMA (thermomechanical analyzer, "TMA450EM" manufactured by TA Instruments). The measurement conditions are a heating rate of 10°C / min, a chuck distance of 16 mm, and a load of 49 mN, and the measurement is performed in a temperature range of -60°C to 350°C. The glass transition temperature is defined as the inflection point where the slope changes, and the average value of three measurements is defined as the glass transition temperature (Y [°C]) of the resin-containing layer when heated at 300°C for 3 hours.

[0154] [Coefficient of linear expansion (CTE) of cured film of resin-containing layer] The coefficient of linear expansion of the cured film of the resin-containing layer is preferably 150 ppm / K or less, more preferably 35 ppm / K or less. The lower limit is preferably 0 ppm / K or more. The coefficient of linear expansion of the cured film of the resin-containing layer can be measured by the following procedure.

[0155] <Preparation of Evaluation Sample (Sample B)> Sample A is prepared in the same manner as described in (Preparation of Evaluation Sample (Sample A)) of <Requirement 1>. Next, an evaluation sample (Sample B) is prepared using the prepared Sample A by either Method X or Method Y below.

[0156] (Method (Method X) of Preparing Evaluation Sample (Sample B) When Resin-Containing Layer Contains Photopolymerization Initiator) When the resin-containing layer contains a photopolymerization initiator, Sample B is prepared according to the following Method X. Method X: Sample A is subjected to an exposure treatment (exposure conditions: high-pressure mercury lamp, cumulative illuminance measured with an illuminometer at a wavelength of 365 nm: 100 mJ / cm ２ ) and then heat-treated in an oven (220°C, 5 hours) to give sample B.

[0157] (Method (Method Y) for Preparing Evaluation Sample (Sample B) When Resin-Containing Layer Does Not Contain Photopolymerization Initiator) When the resin-containing layer does not contain a photopolymerization initiator, Sample B is prepared according to the following Method Y. Method Y: Sample A is subjected to a heat treatment in an oven (220°C, 5 hours) to prepare Sample B.

[0158] <Measurement of the coefficient of linear expansion (CTE) of the cured film of the resin-containing layer> Sample B (freestanding film) prepared by method X or method Y was cut into a strip (19 mm x 5 mm), and the coefficient of linear expansion was measured using a TMA (thermomechanical analyzer, "TMA450EM" manufactured by TA Instruments). The measurement conditions were a temperature rise rate of 10°C / min, a chuck distance of 16 mm, and a load of 49 mN, and the measurement was performed in a temperature range of -60°C to 350°C. The coefficient of linear expansion was measured as a value (ppm / K) in the range of 50°C to 150°C during temperature rise, and the average value of three measurements was taken as the coefficient of linear expansion of the cured film of the resin-containing layer.

[0159] [Intermediate layer and thermoplastic resin layer] The transfer film may have an intermediate layer and / or a thermoplastic resin layer. Examples of the intermediate layer and the thermoplastic resin layer include those described in paragraphs 0164 to 0204 of WO 2021 / 166719, the contents of which are incorporated herein by reference.

[0160] [Cover Film] The transfer film may have a cover film (protective film).

[0161] The number of fish eyes 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.

[0162] 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.

[0163] 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.

[0164] Examples of the cover film include polyethylene terephthalate film, polypropylene film, polystyrene film, and polycarbonate film, and examples of the cover film include those described in paragraphs 0083 to 0087 and 0093 of JP-A No. 2006-259138.

[0165] 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.).

[0166] [Other Layers] The transfer film may include other layers in addition to the above-described layers. Examples of other layers include a high refractive index layer. Examples of high refractive index layers include those described in paragraphs 0168 to 0188 of International Publication No. 2021 / 187549, the contents of which are incorporated herein by reference.

[0167] [Method for Producing Transfer Film] The method for producing the transfer film can be a known method, and is preferably a method for producing the transfer film in which a resin composition is applied onto a temporary support to form a resin-containing layer.

[0168] For example, a method for manufacturing the transfer film 100 shown in Fig. 1 includes a step of applying a resin composition to the surface of a temporary support to form a coating film, and then drying the coating film to form a resin-containing layer. Furthermore, the transfer film 100 shown in Fig. 1 is manufactured by pressing a cover film onto the resin-containing layer of the transfer film manufactured by the above manufacturing method. The transfer film 100 shown in Fig. 1 may also be wound up after manufacturing and stored as a roll-form transfer film 100. The roll-form transfer film 100 can be provided in its original form for the lamination step with a substrate in a roll-to-roll system described below.

[0169] As described above, the transfer film may have an intermediate layer and / or a thermoplastic resin layer between the temporary support and the resin-containing layer. Examples of the intermediate layer-forming composition, the method for forming the intermediate layer, the thermoplastic resin layer-forming composition, and the method for forming the thermoplastic resin layer are described in paragraphs 0133 to 0136 and 0143 to 0144 of International Publication No. 2021 / 033451, the contents of which are incorporated herein by reference.

[0170] <Method of Forming Resin-Containing Layer> As a method of forming the resin-containing layer, a known method can be used, and for example, a method of forming the layer by applying and drying a resin composition can be mentioned.

[0171] The various components that can be contained in the resin composition are, for example, synonymous with the various components that can be contained in the resin-containing layer described above, and the preferred embodiments are also the same. However, the preferred range of the content of the various components in the resin composition is the same as the preferred range obtained by replacing the above-mentioned "content (mass%) of the various components relative to the total mass of the resin-containing layer" with "content (mass%) of the various components relative to the total solid content of the resin composition." Specifically, the statement "The content of resin X is preferably 5.0 mass% or more relative to the total mass of the resin-containing layer" should be replaced with "The content of resin X is preferably 5.0 mass% or more relative to the total solid content of the resin composition." In addition, it is also preferable that the resin composition contains a solvent (solvent) to improve coatability.

[0172] The solvent is not particularly limited as long as it can dissolve or disperse the various components that may be contained in the resin composition. 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. 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, per 100 parts by mass of the total solids content of the composition.

[0173] Examples of coating methods include slit coating, spin coating, curtain coating, and inkjet coating.

[0174] [Uses] The resin pattern obtained from the resin-containing layer formed using the transfer film can be used in a variety of applications. For example, it can be used in 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, it can be used in 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.

[0175] [Method for Producing Laminate] The method for producing the laminate is not particularly limited as long as it is a method using the transfer film described above. Examples of methods for producing a laminate include known production methods such as production methods for build-up substrates. A production method including steps Z1 to Z3 is preferred, and a production method including steps Z1 to Z4 is more preferred. Step Z1: Forming a resin-containing layer on a substrate using the transfer film described above; Step Z2: Forming a pattern having vias in the resin-containing layer; Step Z3: Heat-treating the pattern; Step Z4: Forming a circuit pattern on the pattern formed in step Z3. Furthermore, the method for producing a laminate includes steps Z1 to Z4, and preferably further includes step Z5 of forming a resin-containing layer on the laminate produced in step Z4 using a transfer film, and steps Z2 to Z5 are repeatedly performed.

[0176] <Step Z1> Step Z1 is a step of forming a resin-containing layer on a substrate using a transfer film. It is preferable that the surface of the transfer film opposite the temporary support be brought into contact with the substrate, and the transfer film and the substrate be bonded together. When the transfer film has a cover film, step Z1 is preferably performed after peeling the cover film from the transfer film. Examples of methods for bonding the transfer film include known transfer methods and lamination methods. A preferred method involves placing a substrate on the surface of the resin-containing layer and applying pressure and heat using a roll or the like. Examples of the lamination method include known laminators such as a vacuum laminator and an auto-cut laminator. The lamination temperature is not particularly limited, but is preferably 70 to 130°C.

[0177] (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, with a substrate having a conductive layer being preferred. The substrate may be composed of a light-transmitting substrate such as a glass substrate, or may be tempered glass such as Corning Gorilla Glass. Examples of materials contained in the substrate include materials described in JP 2010-086684 A, JP 2010-152809 A, and JP 2010-257492 A. Resin substrates are preferably resin films with low optical distortion and / or high transparency. Specific examples include polyester, polyethylene terephthalate (PET), polyethylene naphthalate, polycarbonate, triacetyl cellulose, cycloolefin polymer, and polyimide.

[0178] 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, because it can be produced by a roll-to-roll process. The substrate having a conductive layer may also be a laminate obtained by the above-mentioned method for producing a laminate.

[0179] Examples of the conductive layer include known conductive layers used for 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 may also be one or more layers. The conductive layer may be used alone or in combination of two or more types. 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 ２ The conductivity is such that the volume resistivity is 1×10 ６ It means that the volume resistivity is less than 1×10４ It is preferably less than Ωcm.

[0180] 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 etching methods include wet etching methods 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.

[0181] <Step Z2> Step Z2 is a step of forming a pattern having vias in the resin-containing layer. The pattern having vias may be formed only in the resin-containing layer, or may be formed in both the resin-containing layer and the substrate. Examples of methods for forming the pattern having vias include methods using a drill, a laser, and plasma.

[0182] Furthermore, when the resin-containing layer is photosensitive, the method for forming a pattern having vias preferably includes a step of pattern-exposing the resin-containing layer, a step of developing the exposed resin-containing layer with a developer to form a pattern, and a step of etching the conductive layer in the opening regions in the pattern (regions where the resist film is not disposed). It is more preferable to include a step of curing the pattern between the pattern-forming step and the etching step. The resin-containing layer may be exposed from the side opposite the substrate, or from the substrate side of the resin-containing layer.

[0183] 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, 405 nm, etc.) to which various photosensitive components in the resin-containing layer (e.g., resin, polymerizable compound, photopolymerization initiator, photoacid generator, etc.) are sensitive. Specific examples include ultra-high pressure mercury lamps, high pressure mercury lamps, metal halide lamps, and LEDs (light-emitting diodes).

[0184] The exposure dose is 5 to 200 mJ / cm ２is preferred, and 10 to 200 mJ / cm ２ is more preferred.

[0185] In step Z2, exposure may be performed after peeling off the temporary support, or exposure may be performed through the temporary support before peeling off the temporary support, and then the temporary support may be peeled off. Patternwise exposure is preferably performed without peeling off the temporary support in order to prevent mask contamination due to contact between the resin-containing layer and the mask and to avoid the influence of foreign matter attached to the mask on the exposure. The patternwise exposure may be exposure through a mask or direct exposure using a laser or the like. 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 larger. 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.) is exemplified.

[0186] The pattern having vias may be either through holes or via holes. The shape of the vias in the pattern may be, for example, a square, trapezoid, or inverted trapezoid in cross section; or a circle or square in front view (the shape of the via when observed from the direction in which the via bottom is visible). An inverted trapezoid is preferred as the cross section because it improves the adhesion of plated copper to the via wall surface. 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 2 or more, and preferably 2 or more.

[0187] <Step Z3> Step Z3 is a step of heat-treating the pattern. By carrying out Step Z3, compound Y contained in the resin-containing layer in the pattern obtained in Step Z2 can be removed from the system. Furthermore, if the resin-containing layer in the pattern obtained in Step Z2 is a thermosetting resin-containing layer, step Z3 allows the resin-containing layer to be thermally cured and compound Y to be removed from the resin-containing layer. When carrying out the heat treatment in Step Z3, the heating temperature is preferably equal to or higher than the boiling point of compound Y. The heating temperature is preferably 100 to 300°C, and the heating time is preferably 10 minutes to 10 hours.

[0188] [Step Z4] Step Z4 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. For example, in the semi-additive process, a seed layer is first formed by electroless copper plating using a palladium catalyst or the like on the via bottoms, via walls, and the entire surface of a via-containing pattern. 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 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, thereby suppressing damage to the wiring during etching. Electroless copper plating is performed by depositing metallic copper on the surface of a via-containing pattern 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 for the electroless plating treatment is preferably a palladium-tin mixed catalyst. The average primary particle size of the mixed catalyst is preferably 10 nm or less. The plating solution for the electroless plating treatment preferably contains hypophosphorous acid (reducing agent). Examples of electroless copper plating solutions include "MSK-DK" manufactured by Atotech Japan and the "Sulcup (registered trademark) PEA ver. 4" series manufactured by Uemura Kogyo Co., Ltd.

[0189] The method for manufacturing a laminate may include a roughening step of roughening a pattern having vias. The roughening step is preferably performed after step Z3 and before step Z4. By performing the roughening step, the pattern surface can be roughened to improve adhesion to 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 the roughening liquid include a roughening liquid containing chromium and sulfuric acid, a roughening liquid containing an alkaline permanganate (e.g., a sodium permanganate roughening liquid, etc.), and a roughening liquid containing sodium fluoride, chromium, and sulfuric acid.

[0190] It is preferable to carry out a heat treatment after forming the circuit pattern, in order to improve the electrical insulation reliability, curing characteristics, and adhesive strength with plated copper. The heating temperature is preferably 150 to 240°C, and the heating time is preferably 15 to 500 minutes.

[0191] [Laminate] The laminate is a laminate obtained by the above-mentioned laminate manufacturing method. The cured 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. The laminate is used, for example, in semiconductor devices. Examples of semiconductor devices include 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.).

[0192] 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, unless otherwise specified, "parts" and "%" mean "parts by mass" and "% by mass", respectively.

[0193] [Preparation of Composition] A mixture was prepared by mixing various components in the amounts (amounts of solids) shown in the "Resin-Containing Layer" column in the table. 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 solids concentration of 30% by mass. When the silica was not in a slurry form (when it was in a powder form), the silica was dispersed in a 50% by mass MEK solution to form a slurry, and then the mixture was mixed to prepare the composition.

[0194] [Preparation of Transfer Film] The obtained composition was applied to a temporary support shown in the table and dried at 100°C to form a resin-containing layer. The resin-containing layer had a thickness shown in the table after drying. Next, a protective film (Oji F-Tex Co., Ltd., polypropylene film, FG-201, thickness 30 μm) was laminated to the side of the resin-containing layer opposite the temporary support to obtain a transfer film.

[0195] [Types of temporary supports and various components constituting the resin-containing layer] The types of temporary supports and various components contained in the resin-containing layer are shown below. [Temporary supports] PET1: 16 μm thick PET film ("Lumirror 16FB40", manufactured by Toray Industries, Inc.) PET2: 50 μm thick PET film ("Lumirror #50-T60", manufactured by Toray Industries, Inc.)

[0196] [Resins] A-1: ​​Phenolic resin, TR4020G, manufactured by Asahi Organic Chemicals Co., Ltd. A-2: Epoxy resin, ZX1059 (a mixture of bisphenol A epoxy resin and bisphenol F epoxy resin (1:1)), manufactured by Nippon Steel Chemical & Material Co., Ltd.

[0197] A-3: Polyphenylene ether resin having a branched structure, synthesized by the following method. 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 1500 mL 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 resin 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 A-3. Resin A-3 had a number average molecular weight of 25,000 and a weight average molecular weight of 66,000.

[0198] A-4: Silicone resin, average unit formula M ２ D ３ M: (CH ２ =CH)(CH ３ ) (C ６ H ５ ) SiO １／２ D: (C ６ H ５ ) ２ SiO ２／２

[0199] A-5: Benzocyclobutene resin, Cyclotene resin XUR-JW-1148-200201415-47, manufactured by The Dow Chemical Company

[0200] A-6: Acrylic resin, styrene / acrylic acid = 71% by mass / 29% by mass, synthesized by the following method. A 2000 mL flask was charged with 1-methoxy-2-acetoxypropane (PGMEA, 60 parts) and propylene glycol monomethyl ether (PGME, 240 parts by mass) to prepare a mixed solution. The resulting mixed solution was heated to 90°C while stirring at a stirring speed of 250 rpm. Dropping solution (1) was obtained by mixing styrene (71 parts by mass) and acrylic acid (29 parts by mass) and diluting with PGMEA (60 parts by mass). Dropping solution (2) was obtained by dissolving V-601 (dimethyl 2,2'-azobis(2-methylpropionate), 9.637 parts by mass) in PGMEA (136.56 parts by mass). Next, Dropping Solution (1) and Dropping Solution (2) were simultaneously added dropwise over 3 hours to a 2000 mL flask containing the mixed solution heated to 90°C. After completion of the dropwise addition, V-601 (2.401 parts by mass) was added to the flask three times every hour. The mixture was then stirred at 90°C for an additional 3 hours. The reaction solution obtained in the flask was then diluted with PGMEA to obtain a solution containing Resin A-6 (solid concentration 36.3% by mass).

[0201] A-7: Methacrylic resin, methyl methacrylate / dicyclopentanyl methacrylate / methacrylic acid = 40% by mass / 40% by mass / 20% by mass, synthesized by the following method. Resin A-7 was synthesized in the same manner as Resin A-6 described above, except that the dropping liquid (1) and dropping liquid (2) were changed, to obtain a solution containing Resin A-7 (solid content concentration 36.3% by mass). Dropping liquid (1) was obtained by mixing methyl methacrylate (40 parts by mass), dicyclopentanyl methacrylate (40 parts by mass), and methacrylic acid (20 parts by mass) and diluting with PGMEA (60 parts). Dropping liquid (2) was obtained by dissolving V-601 (dimethyl 2,2'-azobis(2-methylpropionate), 9.637 parts by mass) in PGMEA (136.56 parts by mass).

[0202] A-8: Liquid crystal polymer (liquid crystalline polyester), synthesized by the following method. A 2.5 L reaction vessel equipped with a stirring blade and a distillation tube was charged with 435 g of p-hydroxybenzoic acid, 164 g of 4,4'-dihydroxybiphenyl, 44 g of hydroquinone, 146 g of terephthalic acid, 78 g of isophthalic acid, and 684 g of acetic anhydride, and the mixture was stirred under a nitrogen gas atmosphere while reacting at 150 ° C for 2.5 hours, and then heated to 300 ° C over 3.5 hours. Thereafter, the polymerization temperature was maintained at 300 ° C, the pressure was reduced to 1.0 mmHg over 1.0 hour, and the reaction was continued for another 2 hours. Next, the reaction vessel was pressurized to 0.12 MPa, and Resin A-8 was discharged into a strand-like material to obtain Resin A-8.

[0203] A-9: Vinylbenzyl-modified polyphenylene ether resin, manufactured by Mitsubishi Gas Chemical Co., Ltd., "OPE-2St 1200" toluene solution

[0204] A-10: Silsesquioxane resin having the following structure, synthesized by the following method.

[0205]

[0206] Styrylmethoxysilane (0.15 mol), hexyltrimethoxysilane (0.15 mol), and 75.0 g of methyl isobutyl ketone were mixed in a 300 mL three-neck flask and stirred while heating at an external temperature of 80 ° C. 18.0 g of a 0.1% by mass aqueous potassium hydroxide solution was added dropwise thereto at a constant rate over 5 minutes, and the mixture was stirred and heated for 5 hours. During heating, the reaction was carried out while removing refluxed methanol from the system using a Dean-Stark apparatus. After stopping the stirring and cooling to room temperature (25 ° C) in a water bath, 150 g of methyl isobutyl ketone and 150 g of 5% by mass saline were added to extract the organic phase. The organic phase was washed once with 150 g of 5% by mass saline and twice with 150 g of pure water, successively, dried over 45 g of magnesium sulfate, and then concentrated at 50 ° C under a reduced pressure of 35 mmHg to obtain a methyl isobutyl ketone solution of polysilsesquioxane A-1. Polysilsesquioxane A-10 had an Mw of 43,700 and an Mn of 8,900, and contained a cage polysilsesquioxane. The weight-average molecular weight and number-average molecular weight of the polysilsesquioxane were determined by a GPC analyzer using a column of TSKgel Super HM-H (a trade name of Tosoh Corporation), using a solvent of PFP (pentafluorophenol) / chloroform = 1 / 2 (mass ratio) and a differential refractometer, and were converted using polystyrene as a standard substance.

[0207] J-1: Jer828: Bisphenol A type epoxy resin, manufactured by Mitsubishi Chemical Corporation. J-2: HPC8000-65T: Dicyclopentadiene type diphenol compound (polycyclopentadiene type diphenol compound) type active ester curing agent, toluene solution with a solids concentration of 65% by mass, manufactured by DIC Corporation. J-3: Organosilicon compound (silyl compound): synthesized by the following method. 700.0 g of 1,4-bis(dimethylsilyl)benzene (manufactured by Shin-Etsu Chemical Co., Ltd.) and 0.36 g of 5% by mass platinum carbon powder (manufactured by N.E. Chemcat Corporation) were added to a 2 L four-neck flask equipped with a stirrer, a condenser, a dropping funnel, and a thermometer, and the mixture was heated to 90°C using an oil bath. 149 g of trivinylphenylsilane (manufactured by Shin-Etsu Chemical Co., Ltd.) was added dropwise to the mixture. After the dropwise addition was completed, the mixture was stirred at 95°C for 4 hours. After stirring, the mixture was returned to 25°C, 8.4 g of activated carbon was added, and the mixture was stirred for 2 hours. After stirring, the mixture was filtered and concentrated under reduced pressure to obtain 500 g of a silyl compound. The silyl compound was a mixture of compounds having a structure represented by any one of formulas (a) to (e), with the ratio of each compound being (a):(b):(c):(d):(e) = 29:21:16:9:25 (mol%). Components (a) to (e) are shown below.

[0208]

[0209]

[0210]

[0211]

[0212] [Compound Y and Comparative Compound Y] <Compound Y> Y-1: Ethylphthalylethyl glycolate, manufactured by Tokyo Chemical Industry Co., Ltd. Y-2: Dihexyl phthalate, manufactured by Tokyo Chemical Industry Co., Ltd. Y-3: Tributyl o-acetylcitrate, manufactured by Tokyo Chemical Industry Co., Ltd. Y-4: Benzyl 2-ethylhexyl phthalate, manufactured by Tokyo Chemical Industry Co., Ltd. Y-5: Bis(2-ethylhexyl) isophthalate, manufactured by Tokyo Chemical Industry Co., Ltd. Y-6: Triamyl phosphate, manufactured by Tokyo Chemical Industry Co., Ltd. Y-7: Tris(2-butoxyethyl) phosphate, manufactured by Tokyo Chemical Industry Co., Ltd. Y-8: Triethylene glycol bis(2-ethylhexanoate), manufactured by Fujifilm Wako Pure Chemical Industries Co., Ltd. Y-9: Tris(2-ethylhexyl) trimellitate, manufactured by Tokyo Chemical Industry Co., Ltd. Y-10: Bis(2-butoxyethyl) adipate, manufactured by Tokyo Chemical Industry Co., Ltd. Y-11: mPEG6-OH: hexaethylene glycol monomethyl ether, manufactured by TCI

[0213] <Comparative Compound Y> RY-1: 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid, manufactured by Tokyo Chemical Industry Co., Ltd. RY-2: acetophenone, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.

[0214] [Filler] NHM-5N: Silicon dioxide (spherical silica), surface-treated, manufactured by Tokuyama Corporation NP-5N: Silicon dioxide (spherical silica), surface-treated, manufactured by Tokuyama Corporation

[0215] [Photopolymerization initiator] Oxe-01: Irgacure OXE-01, manufactured by BASF Irg379: Irgacure (Omnirad) 379EG, manufactured by IGM Resins B.V.

[0216] [Polymerizable compounds] SR205NS: the following compound, manufactured by Sartomer Corporation SR209: the following compound, manufactured by Sartomer Corporation

[0217]

[0218] [Surfactants] S-506: Silicone surfactant, manufactured by DIC Corporation F-551A: Megafac (registered trademark) F551A, fluorine-based surfactant, manufactured by DIC Corporation

[0219] [Rust inhibitor] HAT: 5-amino-1H-tetrazole ATA: 3-amino-1,2,4-triazole

[0220] [Others] J-4: Platinum catalyst: hydrosilylation agent, dilution of platinum 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex with polysiloxane (platinum content: 1% by mass), component (C) of JP 2020-026502 A J-5: "MIR-500-60T": isopropylidene group-containing maleimide compound, toluene solution

[0221] [Measurement of Average Particle Diameter] The resin-containing layer of each transfer film of each Example and Comparative Example was transferred onto a glass substrate to prepare a glass substrate with a resin-containing layer. Next, a cross section of the resin-containing layer was cut out along the normal direction to the surface, and the cross section was observed using a scanning electron microscope. The major axes of all fillers observed within a region measuring 3 μm in the longitudinal direction parallel to the thickness direction of the resin-containing layer and 10 μm in the transverse direction perpendicular to the longitudinal direction were measured. The above procedure was performed at five different locations on the resin-containing layer, and the average (arithmetic mean) of the major axes of all fillers measured in each procedure was taken as the average particle diameter of the filler. After measuring the average particle diameter of each transfer film of each Example and Comparative Example as described above, the resin-containing layer of the glass substrate with a resin-containing layer was heated at 220° C. for 5 hours, and then the average particle diameter was measured using the same procedure as described above. The average particle diameter was the same as the average particle diameter before the heat treatment.

[0222] [Measurement and Evaluation of Transfer Film] The following measurements and evaluations were carried out using each of the transfer films of the Examples and Comparative Examples.

[0223] [Measurement 1: Measurement of thermal weight loss rate when the resin-containing layer was heated at 300°C for 3 hours] <Preparation of evaluation sample (Sample A)> Five transfer films of each of the examples and comparative examples were prepared, and Sample A was prepared according to the following procedure. Two transfer films from which the protective films had been peeled were bonded together so that the resin-containing layers of each transfer film faced each other, and then one of the two temporary supports was peeled off to obtain Laminate 1 having a temporary support and two resin-containing layers. Next, the transfer film from which the protective film had been peeled off was bonded to Laminate 1 so that the resin-containing layer of this transfer film faced the resin-containing layer of Laminate 1, and then one of the two temporary supports was peeled off to obtain Laminate 2 having a temporary support and three resin-containing layers. Then, Laminate 1 was separately prepared, and the resin-containing layer of Laminate 1 and the resin-containing layer of Laminate 2 prepared above were bonded together so that the resin-containing layers faced each other, to obtain Laminate 3 (temporary support / five resin-containing layers / temporary support). Finally, the two temporary supports were peeled off from the laminate 3 to obtain a sample A.

[0224] <Measurement of Thermal Weight Loss Rate When Resin-Containing Layer is Heated at 300°C for 3 Hours> The obtained Sample A was measured using a TG-DTA device ("TG / DTA6200" manufactured by Seiko Instruments Inc.), and the average value of the thermal weight loss rate measured three times was evaluated according to the following evaluation criteria. The measurement was carried out under the conditions shown below. The final thermal weight loss rate was measured in the range from room temperature to 300°C (in a nitrogen atmosphere, at a temperature increase rate of 10°C / min, and held at 300°C for 3 hours). The results are shown in Table 1.

[0225] [Measurement 2: Measurement of the remaining amount of compound Y when the resin-containing layer was heated at 300°C for 3 hours] Sample A was prepared in the same manner as in the procedure described in <Preparation of evaluation sample (sample A)> in [Measurement 1: Measurement of the thermal weight loss rate when the resin-containing layer was heated at 300°C for 3 hours]. The prepared sample A was then heated at 300°C for 3 hours under a nitrogen atmosphere to prepare an evaluation sample (sample B). Next, 50 mg of sample B was immersed in 5 ml of tetrahydrofuran (THF) for 48 hours, thereby extracting the components in sample B into THF. Next, the mass of compound Y in the extract was determined by measurement using a gas chromatograph (GC-MS) under the following measurement conditions, and this was defined as the "content of compound Y in the resin-containing layer after heating the resin-containing layer at 300°C for 3 hours." Next, the content (mass%) of compound Y in the resin-containing layer after heating the resin-containing layer at 300°C for 3 hours was determined by {(content of compound Y in the resin-containing layer after heating the resin-containing layer at 300°C for 3 hours) / mass of sample B) × 100}.

[0226] (GC-MS measurement conditions) Apparatus: Shimadzu Corporation "2010-Ultra" Column: DB-5MS (30 m, 0.25 mm, 0.25 μm) Oven: 50°C (2 min) - 20°C / min - 320°C (5 min) Injection: 1 μL (300°C, 1 / 10 split) Flow rate: 130 kPa Detection: EI-MS (m / z 19-600) The results are shown in Table 1.

[0227] [Measurements 3 and 4: Measurement of the glass transition temperature (X [°C]) of the resin-containing layer (unheated) and the glass transition temperature (Y [°C]) of the resin-containing layer after heating at 300°C for 3 hours]

[0228] <Measurement of Glass Transition Temperature (X [°C]) of Resin-Containing Layer (Unheated)> Sample A was prepared in the same manner as in <Preparation of Evaluation Sample (Sample A)> in [Measurement 1: Measurement of Thermal Weight Loss Rate When Resin-Containing Layer is Heated at 300°C for 3 Hours]. The prepared Sample A (freestanding film) was cut into strips (19 mm x 5 mm), and the glass transition temperature was measured using a TMA (thermomechanical analyzer, "TMA450EM" manufactured by TA Instruments). The measurement conditions were a temperature rise rate of 10°C / min, a chuck distance of 16 mm, and a load of 49 mN. The measurement was performed in a temperature range of -60°C to 350°C. The glass transition temperature was determined as the inflection point where the slope changes, and was calculated as the average value of three measurements.

[0229] <Measurement 4: Measurement of the glass transition temperature (Y [°C]) of the resin-containing layer when heated at 300°C for 3 hours> Sample A was prepared in the same manner as in <Preparation of evaluation sample (Sample A)> in [Measurement 1: Measurement of the thermal weight loss rate when the resin-containing layer is heated at 300°C for 3 hours]. The prepared Sample A was heated at 300°C for 3 hours under a nitrogen atmosphere to prepare an evaluation sample (Sample B). Next, the prepared Sample B (freestanding film) was cut into a strip (19 mm x 5 mm), and the glass transition temperature 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 16 mm, and a load of 49 mN. The measurement was performed in a temperature range of -60°C to 350°C. The glass transition temperature was determined as the inflection point where the slope changes, and was calculated as the average of three measurements. The obtained values ​​were then classified based on the following criteria. The results are shown in Table 1. (Criteria) "A": Y≧150 "B": Y<150

[0230] <Measurement 3: Calculation of Y-X Value> The Y-X value was calculated using the values ​​of "glass transition temperature (X [°C]) of the resin-containing layer (unheated)" and "glass transition temperature (Y [°C]) of the resin-containing layer when heated at 300°C for 3 hours" obtained by the above measurement. The obtained values ​​were then classified based on the following criteria. The results are shown in Table 1. (Criteria) "A": Y-X≧100 "B": Y-X<100

[0231] [Evaluation 1: Evaluation of temporary support releasability] The cover film was peeled off from the transfer film (9 cm x 9 cm), and a 10 x 10 cm piece of glass (Corning Eagle XG) with a thickness of 0.1 mm was applied. ２ (Lamination conditions: rubber roller temperature (lamination temperature) 100°C, linear pressure 3 N / cm, transport speed 2 m / min.) After leaving it for 30 minutes, the temporary support was peeled off at a peel angle of 120°, and the proportion of the resin-containing layer remaining on the temporary support side was evaluated according to the following criteria.

[0232] (Evaluation criteria (removability of temporary support) "A": The resin-containing layer remaining on the temporary support accounted for less than 10% of the surface area of ​​the temporary support. "B": The resin-containing layer remaining on the temporary support accounted for 10% or more and less than 50% of the surface area of ​​the temporary support. "C": The resin-containing layer remaining on the temporary support accounted for 50% or more of the surface area of ​​the temporary support.

[0233] [Evaluation 2: Evaluation of step-conforming ability] <Evaluation of step-conforming ability (fresh, 3 μm)> A test substrate was prepared by forming a 3 μm-thick copper pattern (line / space=3 μm / 3 μm) in a comb-like pattern on a silicon wafer. The protective film was peeled off and the resin-containing layer of the transfer film was vacuum-laminated at a temperature of 100° C. and a conveying speed of 2 m / min so that it faced the surface of the test substrate on which the wiring had been formed. The area between the copper patterns after lamination was observed with an optical microscope and evaluated according to the following criteria.

[0234] (Evaluation criteria (step conformability)) "A": No air had entered between the wirings, or only a small amount of air had entered between the wirings (air bubble area was less than 10% of the area between the wirings). "B": Some air had entered between the wirings (air bubble area was 10% or more but less than 40% of the area between the wirings). "C": Air had entered between the wirings (air bubble area was 40% or more of the area between the wirings).

[0235] <Evaluation of step-conforming ability (3 μm after storage)> The transfer film was stored for 120 days under conditions of 40° C. and 50% RH. The step-conforming ability after storage was evaluated in the same manner as in <Evaluation of step-conforming ability (fresh)>, except that the transfer film after storage was used.

[0236] [Evaluation 3: Evaluation of coefficient of linear expansion (CTE) of cured film of resin-containing layer] <Preparation of evaluation sample (sample A)> Sample A shown in <Preparation of evaluation sample (sample A)> in the above-mentioned [Measurement 1: Measurement of thermal weight loss rate when resin-containing layer is heated at 300°C for 3 hours] was prepared.

[0237] <Evaluation of the coefficient of linear expansion (CTE) of the cured film of the resin-containing layer> (Preparation of evaluation sample (sample B)) <Preparation method (method X) of evaluation sample (sample B) when the resin-containing layer contains a photopolymerization initiator> When the resin-containing layer contains a photopolymerization initiator, sample B was prepared according to the following method X. Method X: Sample A was subjected to an exposure treatment (exposure conditions: high-pressure mercury lamp, cumulative illuminance measured with an illuminometer at a wavelength of 365 nm: 100 mJ / cm ２ ), and then heat treatment was performed in an oven (220°C, 5 hours) to prepare sample B.

[0238] <<Method for Preparing Evaluation Sample (Sample B) When Resin-Containing Layer Does Not Contain Photopolymerization Initiator (Method Y)>> When the resin-containing layer did not contain a photopolymerization initiator, Sample B was prepared according to the following Method Y. Method Y: Sample A was subjected to a heat treatment in an oven (220°C, 5 hours) to prepare Sample B.

[0239] (Evaluation of the coefficient of linear expansion (CTE) of the cured film of the resin-containing layer) Sample B (freestanding film) prepared by method X or method Y was cut into a strip (19 mm x 5 mm), and the coefficient of linear expansion was measured using a TMA (thermomechanical analyzer, "TMA450EM" manufactured by TA Instruments). The measurement conditions were a temperature rise rate of 10°C / min, a chuck distance of 16 mm, and a load of 49 mN. The measurement was carried out in a temperature range of -60°C to 350°C. The coefficient of linear expansion was measured as a value (ppm / K) in the range of 50°C to 150°C during temperature rise, and was calculated as the average of three measurements.

[0240] (Evaluation criteria (CTE)) "A": 35 ppm / K or less "B": More than 35 ppm / K and less than 150 ppm / K "C": More than 150 ppm / K

[0241] Table 1 is shown below. In Table 1 below, the configuration and evaluation results of each transfer film of the Examples and Comparative Examples are shown in the left column (Table 1-X1 to Table 1-X5) and the right column (Table 1-Y1 to Table 1-Y5). That is, the configuration and evaluation results of each transfer film of the Examples and Comparative Examples in Table 1 are shown by combining Examples or Comparative Examples with the same numbers in Table 1-XN (N: 1 to 5) and Table 1-YN (N: 1 to 5) (specifically, Table 1-X1 and Table 1-Y1, Table 1-X2 and Table 1-Y2, Table 1-X3 and Table 1-Y3, Table 1-X4 and Table 1-Y4, and Table 1-X5 and Table 1-Y5 are each combined, and for each Example and Comparative Example, the main configuration of the transfer film, the film thickness of the resin-containing layer, measurement, and evaluation are shown in that order). In the table, the column "B / A (mass ratio)" indicates the mass ratio calculated by "content of compound Y and comparative compound RY (B)" / "content of resin X (A)".

[0242]

[0243]

[0244]

[0245]

[0246]

[0247]

[0248]

[0249]

[0250]

[0251]

[0252] From the results shown in the table, it is clear that the transfer films of the examples have excellent step-following properties when the resin-containing layer is attached to the substrate after storage, have excellent peelability of the temporary support, and have a small coefficient of linear expansion (CTE) of the resin-containing layer that has been transferred and subjected to a specified treatment including heat treatment.

[0253] Furthermore, comparison of the Examples confirmed that when the resin-containing layer contains a filler, the linear expansion coefficient of the cured film of the resin-containing layer becomes smaller. Furthermore, comparison of the Examples confirmed that when the glass transition temperature of the resin-containing layer is 150°C or higher when heated at 300°C for 3 hours, the linear expansion coefficient of the cured film of the resin-containing layer becomes smaller (see, in particular, Examples 80 to 87). Furthermore, comparison of the Examples confirmed that when the specific content ratio (content of compound Y / content of resin X) is 0.25 to 2.00, the step-following ability is better (see, in particular, Examples 16, 17, 22, 23, 127, 128, 133, and 134).

[0254] <Resin Pattern Producibility> It was confirmed that a resin pattern could be formed using the transfer film of the example. The specific procedure was as follows.

[0255] 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, and a resin-containing layer was formed on both sides of the glass epoxy substrate. A vacuum laminator was used for this. Lamination was performed using a vacuum laminator manufactured by MCK Corporation under conditions of a substrate temperature of 40°C, a rubber roller temperature of 100°C, a linear pressure of 3 N / cm, and a conveying speed of 2 m / min. A pattern having vias with a diameter of 60 μm was formed at predetermined positions on the resin-containing layer and subjected to a heat treatment. After that, residues were removed using an aqueous sodium permanganate solution as a roughening solution, and electroless plating was performed. Next, a resist pattern was formed at predetermined positions 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 treatment was performed, followed by a heat treatment (200°C, 1 hour) to form copper wiring on the cured film. The above process from lamination to heat treatment was repeated 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.

[0256] 12: Temporary support 14: Resin-containing layer 16: Cover film 100: Transfer film

Claims

1. A transfer film having a temporary support and a resin-containing layer, the resin-containing layer contains a resin X and a compound Y, the compound Y has a molecular weight of 200 to 1000, a boiling point of 230 to 500°C, and is a compound having no crosslinkable group; A transfer film, wherein the mass ratio of the content of the compound Y to the content of the resin X is 0.20 to 2.

00.

2. The transfer film according to claim 1 , wherein the resin-containing layer satisfies requirement 1. Requirement 1: When the resin-containing layer is heated at 300° C. for 3 hours, the weight loss of the resin-containing layer is 8.0% by mass or more.

3. The transfer film according to claim 1 or 2, wherein the resin-containing layer satisfies requirement 2. Requirement 2: The content of the compound Y in the resin-containing layer is more than 5.0 mass % relative to the total mass of the resin-containing layer, and the content of the compound Y in the resin-containing layer after heating the resin-containing layer at 300°C for 3 hours is 5.0 mass % or less relative to the total mass of the resin-containing layer.

4. The transfer film according to claim 1 or 2, wherein the resin-containing layer satisfies requirement 3. Requirement 3: Formula (1) is satisfied when the glass transition temperature of the resin-containing layer is X°C and the glass transition temperature of the resin-containing layer after heating at 300°C for 3 hours is Y°C. Formula (1) Y-X≧100

5. The transfer film according to claim 1 or 2, wherein the resin-containing layer satisfies requirement 4. Requirement 4: When the glass transition temperature of the resin-containing layer after heating at 300° C. for 3 hours is defined as Y° C., the formula (2) is satisfied. Formula (2) Y≧150

6. the content of the resin X is 10.0 to 90.0% by mass relative to the total mass of the resin-containing layer, 3. The transfer film according to claim 1, wherein the content of the compound Y is 5.0 to 70.0% by mass relative to the total mass of the resin-containing layer.

7. 3. The transfer film according to claim 1, wherein the resin X comprises at least one selected from the group consisting of a phenolic resin, an epoxy resin, a polyphenylene ether resin, a silicone resin, a benzocyclobutene resin, a fluorene resin, an acrylic resin, a methacrylic resin, a liquid crystal polymer, polyethersulfone, polyarylate, polyetherimide, polybenzimidazole, polyphenylsulfone, polycarbonate, an acrylonitrile-butadiene-styrene resin, polyphenylene sulfide, polycyclopentadiene, polyester, and an organosilicon compound.

8. The transfer film according to claim 1 or 2, wherein the resin-containing layer further comprises a filler.

9. The transfer film according to claim 8 , wherein the filler has an average particle size of 300 nm or less.

10. The transfer film according to claim 8, wherein the content of the filler is 50.0 to 90.0% by mass with respect to the total mass of the resin-containing layer.

11. The transfer film according to claim 1 or 2, wherein the resin-containing layer further contains a photopolymerization initiator.

12. The transfer film described in claim 1, wherein the resin X includes at least one selected from the group consisting of phenolic resin, epoxy resin, polyphenylene ether resin, silicone resin, benzocyclobutene resin, and polyester.

13. The transfer film described in claim 1, wherein the resin X includes at least one selected from the group consisting of phenolic resin, polyphenylene ether resin, silicone resin, benzocyclobutene resin, and polyester.

14. A transfer film as described in claim 12, wherein the resin-containing layer contains the resin X and further has a filler.

15. The content of the resin X is 10.0 to 90.0 mass% with respect to the total mass of the resin-containing layer including the resin X and the compound Y, The transfer film according to claim 13, wherein the content of the compound Y is 5.0 to 70.0% by mass relative to the total mass of the resin-containing layer.

16. forming a resin-containing layer on a substrate using the transfer film according to claim 1 or 2; forming a pattern having vias in the resin-containing layer; and heat-treating the pattern.

17. A laminate produced by the method for producing a laminate according to claim 16.