WO2024203822A1 - 転写フィルム、積層体の製造方法、積層体 - Google Patents

転写フィルム、積層体の製造方法、積層体 Download PDF

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Publication number
WO2024203822A1
WO2024203822A1 PCT/JP2024/011246 JP2024011246W WO2024203822A1 WO 2024203822 A1 WO2024203822 A1 WO 2024203822A1 JP 2024011246 W JP2024011246 W JP 2024011246W WO 2024203822 A1 WO2024203822 A1 WO 2024203822A1
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Prior art keywords
resin
containing layer
mass
transfer film
compound
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PCT/JP2024/011246
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English (en)
French (fr)
Japanese (ja)
Inventor
圭吾 山口
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Fujifilm Corp
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Fujifilm Corp
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Priority to KR1020257025074A priority Critical patent/KR20250130350A/ko
Priority to JP2025510703A priority patent/JPWO2024203822A1/ja
Publication of WO2024203822A1 publication Critical patent/WO2024203822A1/ja
Anticipated expiration legal-status Critical
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/025—Electric or magnetic properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/027—Thermal properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/06—Interconnection of layers permitting easy separation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/12—Esters; Ether-esters of cyclic polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
    • H05K1/0373—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement containing additives, e.g. fillers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/005—Additives being defined by their particle size in general

Definitions

  • the present invention relates to a transfer film, a method for manufacturing a laminate, and a laminate.
  • a touch panel such as a capacitive input device (for example, an organic electroluminescence (EL) display device or a liquid crystal display device), an electrode pattern corresponding to the sensor of the visual recognition area, and conductive patterns such as wiring for the peripheral wiring portion and the extraction wiring portion are provided inside the touch panel.
  • a capacitive input device for example, an organic electroluminescence (EL) display device or a liquid crystal display device
  • a electrode pattern corresponding to the sensor of the visual recognition area for example, an organic electroluminescence (EL) display device or a liquid crystal display device
  • conductive patterns such as wiring for the peripheral wiring portion and the extraction wiring portion are provided inside the touch panel.
  • Patent Document 1 discloses a resin composition with a specific composition.
  • a method of forming a pattern using a transfer film that is constructed by arranging a temporary support and a resin-containing layer formed from a resin composition on the temporary support is also widely known, as this method requires fewer steps to obtain the desired pattern shape.
  • the present inventors have produced a transfer film using the resin composition described in Patent Document 1 and have found that there is room for further improvement in the step-following property when the film is attached to an object to be attached.
  • excellent step-following property 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 unlikely to be generated between the object to be attached and the resin-containing layer.
  • the object to be attached is a substrate having a step such as wiring, the performance of being able to attach the object to be attached and the resin-containing layer of the transfer film while suppressing the inclusion of air bubbles due to the step of the object to be attached.
  • the transfer film may be stored for a certain period of time and then used for lamination, and it is required to have excellent step-following property when attached to the object to be attached after storage.
  • 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 specified treatment including a heat treatment (hereinafter, the resin-containing layer that has been transferred and subjected to a specified treatment including a heat treatment is also referred to as a "cured film").
  • the present invention aims to provide a transfer film comprising a temporary support and a resin-containing layer, which has excellent step-following properties when the resin-containing layer is attached to an object after storage, has excellent peelability of the temporary support, and has a small linear expansion coefficient of the resin-containing layer that has been transferred and subjected to a specified treatment including a heat treatment.
  • Another object of the present invention is to provide a method for producing a laminate using the transfer film, and to provide the laminate.
  • a transfer film having a temporary support and a 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;
  • 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.
  • 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, polyphenyl
  • a transfer film comprising a temporary support and a resin-containing layer, which has excellent step-following properties when the resin-containing layer is attached to an object to be attached after storage, has excellent peelability of the temporary support, and has a small linear expansion coefficient of the resin-containing layer that has been transferred and subjected to a specified treatment including a heat treatment. Further, it is possible to provide a method for producing a laminate using the above-mentioned transfer film, and the laminate.
  • FIG. 2 is a schematic diagram showing an example of a layer structure of a transfer film.
  • FIG. 2 is a diagram (nomograph) explaining a method for measuring the boiling point of compound Y.
  • a numerical range expressed using “to” means a range that includes the numerical values before and after "to” as the lower and upper limits.
  • 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 a certain stepwise manner.
  • the upper limit or lower limit described in a certain numerical range may be replaced with a value shown in the examples.
  • process in this specification does not only refer to an independent process, but also includes processes that cannot be clearly distinguished from other processes, as long as the intended purpose of the process is achieved.
  • the temperature condition may be 25°C.
  • the temperature when performing each of the above steps may be 25°C unless otherwise specified.
  • the term "transparent" means that the average transmittance of visible light having a wavelength 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.
  • active light rays or “radiation” refers to, for example, the bright line spectrum of a mercury lamp, such as g-line, h-line, and i-line, far ultraviolet light represented by an excimer laser, extreme ultraviolet light (EUV light), X-rays, and electron beams (EB).
  • EUV light extreme ultraviolet light
  • X-rays and electron beams (EB).
  • EB electron beams
  • light refers to active light rays or radiation.
  • exposure includes not only exposure to mercury lamps, far ultraviolet rays such as those from excimer lasers, extreme ultraviolet rays, X-rays, and EUV light, but also drawing with particle beams such as electron beams and ion beams.
  • the content ratio of each repeating unit in a polymer is a molar ratio.
  • the refractive index is a value measured by an ellipsometer at a wavelength of 550 nm.
  • the molecular weight is the weight average molecular weight (Mw).
  • Mw weight average molecular weight
  • Mn number average molecular weight
  • (meth)acrylic acid is a concept that includes both acrylic acid and methacrylic acid
  • (meth)acryloyl group is a concept that includes both acryloyl group and methacryloyl group
  • (meth)acrylate is a concept that includes both acrylate and methacrylate.
  • water-soluble means that the solubility in 100 g of water at pH 7.0 and a liquid temperature of 22°C is 0.1 g or more.
  • solid content of a composition refers to the components that form a composition layer formed using the composition.
  • a solvent e.g., an organic solvent and water
  • liquid components are also considered to be solids if they form a composition layer.
  • the layer thickness is the average thickness measured using a scanning electron microscope (SEM) for thicknesses of 0.5 ⁇ m or more, and the average thickness measured using a transmission electron microscope (TEM) for thicknesses of less than 0.5 ⁇ m.
  • SEM scanning electron microscope
  • TEM transmission electron microscope
  • boiling point means the boiling point under normal pressure (1 atmosphere, 760 mmHg).
  • the transfer film of the present invention is 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;
  • the mass ratio of the content of the compound Y to the content of the resin X (hereinafter also referred to as the "specific mass ratio") is 0.20 to 2.00.
  • the transfer film having the above-described configuration has excellent step-following properties when the resin-containing layer is attached to an object to be attached after storage, has excellent peelability of the temporary support, and has a small linear expansion coefficient of the resin-containing layer (cured film) that has been transferred and subjected to a specified treatment including a heat treatment.
  • a specified treatment including a heat treatment.
  • the present inventors speculate as follows.
  • the compound Y functions as a component for ensuring plasticity in the resin-containing layer, and is removed by volatilization by heat treatment, and is unlikely to remain in the cured film system.
  • the transfer film when the resin-containing layer of the transfer film is laminated to a substrate due to the above-mentioned action of the compound Y, the transfer film has excellent step conformability due to the plasticizing effect of the compound Y, and the cured film formed by the resin-containing layer of the transfer film is subjected to a predetermined treatment including heat treatment to reduce the content of the compound Y, so that the thermal expansion coefficient can be suppressed to a low level.
  • the resin-containing layer of the transfer film contains the compound Y and the specific mass ratio of the resin X to the compound Y is 0.20 to 2.00, it is presumed that the transfer film has excellent levels of good step conformability when the resin-containing layer is attached to an object to be attached after storage, good peelability of the temporary support, and a low linear expansion coefficient of the cured film.
  • the compound Y is unlikely to volatilize due to the action of the environment during storage of the transfer film, mainly due to the molecular weight and boiling point being equal to or higher than a predetermined value, and therefore contributes to the improvement of good step-following property when pasting to a pasting target after storage.
  • the compound Y is unlikely to remain in the system of the cured film formed by the resin-containing layer, mainly due to the molecular weight and boiling point being equal to or lower than a predetermined value and the fact that it does not have a crosslinkable group, and the thermal expansion coefficient of the cured film is suppressed to a low value.
  • the term "the effect of the present invention is superior” may refer to superior conformability to unevenness when the transfer film is applied to an object after storage, superior peelability of the temporary support, and/or a smaller linear expansion coefficient of the resin-containing layer (cured film) that has been transferred and subjected to a specified treatment including a heat treatment.
  • the transfer film has a temporary support and a resin-containing layer disposed on the temporary support.
  • the transfer film may include layers other than the resin-containing layer on the temporary support.
  • the resin-containing layer disposed on the temporary support and the other layers optionally included therein may be collectively referred to as "composition layer”.
  • the transfer film may have a protective film (hereinafter, also referred to as a "cover film”) on the composition layer.
  • FIG. 1 is a schematic cross-sectional view 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. 1 has a cover film 16, the transfer film may have no cover film 16. As described later, 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.
  • the transfer film has a temporary support.
  • the temporary support is a member that supports the composition layer, and is ultimately removed by a peeling treatment.
  • 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 has flexibility and does not significantly deform, shrink, or stretch under pressure or under pressure and heat. Examples of the film include polyethylene terephthalate film (e.g., biaxially stretched polyethylene terephthalate film, etc.), polymethyl methacrylate film, cellulose triacetate film, polystyrene film, polyimide film, and polycarbonate film, and polyethylene terephthalate film is preferred.
  • the temporary support is preferably free of deformation such as wrinkles and scratches.
  • the temporary support is preferably highly transparent, because it can be pattern-exposed through the temporary support.
  • the transmittance at wavelengths of 313 nm, 365 nm, 405 nm, and 436 nm is preferably 60% or more, more preferably 70% or more, even more preferably 80% or more, and most preferably 90% or more.
  • the upper limit is preferably less than 100%.
  • Preferred values of the transmittance at each of the above wavelengths include, for example, 87%, 92%, and 98%.
  • the haze of the temporary support is preferably small.
  • the haze value of the temporary support is preferably 2% or less, more preferably 0.5% or less, and even more preferably 0.1% or less.
  • the lower limit is preferably 0% or more.
  • the number of fine particles, foreign matter, and defects contained in the temporary support is small.
  • the number of fine particles, foreign matter, and defects having a diameter of 1 ⁇ m or more in the temporary support is preferably 50 pieces/10 mm2 or less, more preferably 10 pieces/10 mm2 or less , even more preferably 3 pieces/10 mm2 or less , and particularly preferably 0 pieces/10 mm2 .
  • the thickness of the temporary support is preferably from 5 to 200 ⁇ m, and from the viewpoints of ease of handling and versatility, it is more preferably from 5 to 150 ⁇ m, further preferably from 5 to 50 ⁇ m, and particularly preferably from 5 to 35 ⁇ m.
  • the thickness of the temporary support can be calculated as the average value of any five points measured by cross-sectional observation using a SEM (scanning electron microscope).
  • the surface of the temporary support which comes into contact with the composition layer may be surface-modified by UV irradiation, corona discharge, plasma, or the like.
  • the exposure dose of UV irradiation is preferably 10 to 2000 mJ/ cm2 , more preferably 50 to 1000 mJ/ cm2 .
  • Examples of light sources for UV irradiation include low-pressure mercury lamps, high-pressure mercury lamps, extra-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 power and illuminance can be adjusted as appropriate.
  • Examples of the temporary support include a biaxially oriented polyethylene terephthalate film having a thickness of 16 ⁇ m, a biaxially oriented polyethylene terephthalate film having a thickness of 12 ⁇ m, and a biaxially oriented polyethylene terephthalate film having a thickness of 9 ⁇ m.
  • the temporary support may be a recycled product.
  • a recycled product may be a product obtained by cleaning and chipping a used film or the like, and forming the obtained material into a film.
  • a commercially available recycled product may be the Ecouse series (manufactured by Toray Industries, Inc.).
  • 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 ⁇ m.
  • the thickness of the lubricant layer is preferably 0.05 to 1.0 ⁇ m.
  • Examples of commercially available temporary supports include 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.).
  • the resin-containing layer contains a 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 further preferably a (meth)acryloyl group.
  • the resin may be either an unmodified product or a modified product.
  • an epoxy resin is a resin having an epoxy group, and may further have a functional group other than the epoxy group and a structure containing the functional group.
  • Resin X examples include known resins.
  • Resin X is preferably 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, polyethersulfones, polyarylates, polyetherimides, polybenzimidazoles, polyphenylsulfones, polycarbonates, acrylonitrile-butadiene-styrene resins (ABS resins), polyphenylene sulfide, polycyclopentadiene, polyesters, and organosilicon compounds, more preferably 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, still more preferably at least one selected from the group consist
  • the phenolic resin is a resin having a phenolic hydroxyl group.
  • examples of the phenol resin include phenol novolac resin, cresol novolac resin, biphenyl aralkyl type phenol resin, naphthol aralkyl resin, and naphthol novolac resin.
  • 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-
  • phenol resins examples include those described in JP-A-2021-157174. Further, examples of the phenolic resin include phenolic hardeners such as EPICLON series, EXB9451, EXB9460, EXB9460S, and HPC8000-65T (manufactured by DIC Corporation).
  • the epoxy resin is a resin having an epoxy group.
  • 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 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, cyclohexane dimethanol type epoxy resins, naphthylene ether type epoxy resins,
  • 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.
  • liquid epoxy resin an epoxy resin that is liquid at a temperature of 20°C
  • solid epoxy resin an epoxy resin that is solid at a temperature of 20°C
  • liquid epoxy resin bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, or naphthalene type epoxy resin is preferred, and bisphenol A type epoxy resin, bisphenol F type epoxy resin, or naphthalene type epoxy resin is more preferred.
  • liquid epoxy resins examples include HP4032, HP4032D, EXA4032SS, and HP4032SS (naphthalene type epoxy resins) manufactured by DIC Corporation; jER828EL (bisphenol A type epoxy resin), jER807 (bisphenol F type epoxy resin), and jER152 (phenol novolac type epoxy resin) manufactured by Mitsubishi Chemical Corporation; ZX1059 (a mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin) manufactured by Nippon Steel Chemical & Material Co., Ltd.
  • HP4032SS or ZX1059 is preferred.
  • solid epoxy resin tetrafunctional naphthalene type epoxy resin, cresol novolac type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol epoxy resin, naphthol novolac epoxy resin, biphenyl type epoxy resin, or naphthylene ether type epoxy resin is preferable, tetrafunctional naphthalene type epoxy resin, biphenyl type epoxy resin, or naphthylene ether type epoxy resin is more preferable, and biphenyl type epoxy resin is further preferable.
  • solid epoxy resins examples include HP-4700, HP-4710 (tetrafunctional naphthalene type epoxy resin), 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.
  • epoxy resins examples 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 & Material Co., Ltd.; YX4000H, YL6121 (biphenyl type epoxy resin), and YX4000HK (bixylenol type epoxy resin), manufactured by Mitsubishi Chemical Corporation.
  • the solid epoxy resin YX4000HK, NC3000L, or HP7200H is preferable.
  • 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.
  • ether bonds are directly bonded to at least three positions, i.e., the ipso-, ortho- and para-positions, of the benzene ring.
  • the polyphenylene ether resin having a branched structure can be obtained, for example, by polymerizing two or more kinds of phenol compounds.
  • the above-mentioned phenol compound is preferably a phenol compound having hydrogen atoms at the ortho and para positions and having a polymerizable group, or a mixture of a phenol compound having hydrogen atoms at the ortho and para positions and no polymerizable group and a phenol compound having no hydrogen atom at the ortho position, a hydrogen atom at the para position and having a polymerizable group.
  • 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.
  • the phenol compound is preferably 2,6-dimethylphenol or 2-allylphenol.
  • the polyphenylene ether resin also preferably has a polymerizable group.
  • the polymerizable group is preferably an ethylenically unsaturated group, more preferably a vinylphenyl group or a (meth)acryloyl group.
  • the resin-containing layer preferably contains a maleimide compound, which will be described later, that reacts with the polyphenylene ether resin to obtain a modified polyphenylene ether.
  • modified polyphenylene ethers include resins obtained by curing the resin compositions described in WO 2022/102756.
  • 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.
  • polyphenylene ether resins include those described in JP-A-2022-157695.
  • the silicone resin is a resin having an organosiloxane structure.
  • the silicone resin include curable silicone resins, silicone graft resins, and modified silicone resins such as alkyl-modified silicone resins, with curable silicone resins being preferred.
  • the curable silicone resin include an addition reaction type silicone resin, a condensation reaction type silicone resin, and an ultraviolet or electron beam curable silicone resin.
  • ultraviolet-curable silicone resins include those that utilize the same radical reaction as silicone rubber crosslinking, those that introduce unsaturated groups to cause photocuring, those that use ultraviolet light or electron beams to decompose onium salts to generate strong acids and cleave epoxy groups to cause crosslinking, and those that crosslink by addition reaction of thiols to vinyl siloxanes.
  • Specific examples include acrylate-modified polydimethylsiloxanes and glycidoxy-modified polydimethylsiloxanes.
  • 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.
  • the silicone resin preferably has 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 further preferably a benzene ring.
  • 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, for example, a polymerizable group contained in the resin.
  • the organosilicon compound may, for example, be a compound having a silyl group, and 1,4-bis(dimethylsilyl)benzene or trivinylphenylsilane is preferred.
  • the reaction temperature is preferably from 100 to 200° C., and the reaction time is preferably from 1 to 10 hours.
  • silicone resins examples include resins obtained from organosiloxanes and curable compositions described in JP 2020-026502 A.
  • the cage polysilsesquioxane may be any of a T8 polysilsesquioxane consisting of eight structural units T3 described below, a T10 polysilsesquioxane consisting of ten structural units T3 described below, and a T12 polysilsesquioxane consisting of twelve structural units T3 described below. It is also preferable that the polysilsesquioxane 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).
  • 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.
  • X 1 's each independently represent a hydrogen atom or an alkyl group.
  • multiple R 1 's may be the same or different.
  • the polysilsesquioxane may be a copolymer containing multiple structural units having different R 1 's.
  • the chain-like aliphatic hydrocarbon group and aromatic hydrocarbon group may further have a substituent such as a halogen atom, an alkyl group, an alkoxy group, an aryl group, or a polymerizable group-containing group (for example, a group represented by -L P -P, where L 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 combining these), and P represents a polymerizable group (examples include the above-mentioned polymerizable groups).
  • the alkyl group represented by X1 preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, further preferably 1 to 4 carbon atoms, and particularly preferably 1 to 3 carbon atoms.
  • the polysilsesquioxane preferably contains a structural unit selected from structural units T2 and T3.
  • the total content of the structural units selected from structural units T2 and T3 is preferably 50 to 70 mol % or more, and more preferably 70 to 100 mol % or more, based on the total of all structural units of the polysilsesquioxane.
  • the content of each of the structural units can be calculated, for example, from the peak position and peak area ratio in 29Si -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%, based on the total of all structural units of the polysilsesquioxane. It is also preferable that the polysilsesquioxane contains a structural unit having a chain-like hydrocarbon group.
  • the content of the structural unit having a chain-like hydrocarbon group is preferably 10 to 90 mol%, more preferably 30 to 70 mol%, and even more preferably 40 to 60 mol%, based on the total of all structural units of the polysilsesquioxane.
  • 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.
  • the benzocyclobutene resin is a resin having a benzocyclobutene ring.
  • Benzocyclobutene resins include, for example, divinylsiloxane-bisbenzocyclobutene resins (eg, CYCLOTENE resins, manufactured by The Dow Chemical Company).
  • alkyl (meth)acrylate is methyl (meth)acrylate.
  • the total content of the 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, and the upper limit is preferably 100% by mass or less, more preferably 90% by mass or less.
  • 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.
  • 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 further preferably a benzene ring.
  • repeating unit having an aromatic ring examples 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 the (meth)acrylate having an aromatic ring include benzyl (meth)acrylate, phenethyl (meth)acrylate, and phenoxyethyl (meth)acrylate.
  • Styrene and polymerizable styrene derivatives include, for example, styrene, methylstyrene, vinyltoluene, tert-butoxystyrene, acetoxystyrene, styrene dimer, and styrene trimer.
  • 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.
  • 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 repeating units having an alicyclic ring are derived include dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, and cyclohexyl (meth)acrylate.
  • a liquid crystal polymer is a resin that exhibits liquid crystallinity.
  • the liquid crystal polymer is preferably a thermotropic liquid crystal polymer, which means a polymer that exhibits liquid crystallinity within a certain 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 amide bonds are introduced into thermoplastic liquid crystal polyesters.
  • 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 further preferably a benzene ring.
  • the monomer from which the repeating unit having an aromatic ring is derived is preferably p-hydroxybenzoic acid, 4,4'-dihydroxybiphenyl, hydroquinone, terephthalic acid, or isophthalic acid.
  • the liquid crystal polymer preferably contains two or more repeating units derived from a compound selected from p-hydroxybenzoic acid, 4,4'-dihydroxybiphenyl, hydroquinone, terephthalic acid, and isophthalic acid, and more preferably contains four or five repeating units derived from the above compounds.
  • the liquid crystal polymer may 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,
  • liquid crystal polymers examples include those described in JP 2006-299254 A and WO 2015/064437 A.
  • polyethersulfone examples include known resins.
  • organosilicon compound examples include compounds having a silyl group, and 1,4-bis(dimethylsilyl)benzene, trivinylphenylsilane, or a compound represented by the following formula (SiA) are preferred.
  • the organosilicon compound preferably further has a polymerizable group.
  • the polymerizable group examples include the polymerizable group contained in the resin.
  • * indicates the bonding position of each structural unit.
  • Examples of the compound represented by formula (SiA) include components (a) to (e) which are components constituting the organosilicon compound represented by J-3 in the examples described later.
  • the organosilicon compound is also preferably used in combination with a silicone resin and a hydrosilation agent.
  • resin X examples include known resins other than the various resins mentioned above.
  • the weight average molecular weight (Mw) of the resin X is, for example, preferably from 2,000 to 500,000, and more preferably from 5,000 to 100,000.
  • the number average molecular weight (Mn) of the resin X is, for example, preferably 800 to 250,000, and more preferably 2,000 to 50,000.
  • the dispersity (Mw/Mn) of the resin X is, for example, preferably from 1.0 to 3.5, and more preferably from 2.0 to 3.0.
  • Resin X may be used alone or in combination of two or more kinds.
  • the content of resin X is preferably 5.0% by mass or more, more preferably 10.0% by mass or more, based on 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, based on the total mass of the resin-containing layer.
  • the upper limit of the content of resin X based on the total mass of the resin-containing layer is preferably 50.0% by mass or less, more preferably 30.0% by mass or less.
  • the resin-containing layer contains a compound Y.
  • Compound Y is a compound having a molecular weight of 200 to 1000, a boiling point of 230 to 500° C., and having no crosslinkable groups.
  • crosslinkable group refers to a group that can undergo a reaction under certain conditions to form a crosslinked structure, and specific examples thereof include an ethylenically unsaturated group, a cyclic ether group, and a silane coupling group.
  • the boiling point of the compound Y is intended to be a value determined by the following measurement method.
  • the gas temperature at the point when the evaporated gas starts to condense is defined as the boiling point (measured from 23° C. to 300° C., temperature rise rate 1° C./min).
  • the distillation is carried out using a Liebig condenser, and if distillation does not start at 300°C under normal pressure, distillation is carried out under reduced pressure.
  • the same distillation is carried out at pressures of 100 mmHg, 50 mmHg, and 5 mmHg in that order (23°C to 300°C, and if distillation does not start at 300°C, the next pressure is used).
  • the boiling point at normal pressure is calculated using the nomograph shown in Figure 2 (source: Science of Petroleum, Vol.II. p.1281 (1938)) from the temperature and pressure at which the evaporated gas begins to condense. If distillation does not start at 300°C under 5 mmHg, the boiling point at normal pressure is considered to be greater than 500°C.
  • the method of using the nomograph is well known. Specifically, a straight line is drawn between the boiling point of the reduced pressure on line A and the degree of reduced pressure on line C (step 1), and the value at the intersection of the line drawn in step 1 and line B is read (step 2), and this is considered to be the boiling point at normal pressure.
  • the lower limit of the molecular weight of compound Y is preferably 250 or more, and more preferably 300 or more.
  • the upper limit is preferably 800 or less, and more preferably 600 or less.
  • the lower limit of the boiling point of compound Y is preferably 250° C. or more, more preferably 280° C. or more, even more preferably 300° C. or more, and particularly preferably 350° C. or more.
  • the upper limit is preferably 480° C. or less, more preferably 450° C. or less.
  • the above molecular weight of compound Y refers to the weight average molecular weight.
  • 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 by a B-type viscometer.
  • 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.
  • phosphate esters examples include triamyl phosphate and tris(2-butoxyethyl) phosphate.
  • polycarboxylic acid esters examples include aliphatic dicarboxylic acid esters (e.g., adipic acid esters, azelaic acid esters, and sebacic acid esters); aromatic dicarboxylic acid esters (e.g., phthalic acid esters); trimellitic acid esters; and citrate esters (e.g., tributyl acetyl citrate).
  • aliphatic dicarboxylic acid esters e.g., adipic acid esters, azelaic acid esters, and sebacic acid esters
  • aromatic dicarboxylic acid esters e.g., phthalic acid esters
  • trimellitic acid esters e.g., trimellitic acid esters
  • citrate esters e.g., tributyl acetyl citrate
  • polyvalent carboxylates include ethyl phthalyl ethyl glycolate, dihexyl phthalate, tributyl o-acetylcitrate, 2-ethylhexyl benzyl phthalate, bis(2-ethylhexyl) isophthalate, tris(2-ethylhexyl) trimellitate, and bis(2-butoxyethyl) adipate.
  • the polyether esters are preferably organic acid esters of polyalkylene glycol.
  • organic acids include monocarboxylic acids (e.g., butanoic acid, isobutanoic acid, 2-ethylbutyric acid, 2-ethylhexyl acid, and decanoic acid).
  • polyether esters include triethylene glycol bis 2-ethylhexanoate.
  • alkylene glycol monoalkyl ethers and alkylene glycol dialkyl ethers include, for example, 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.
  • mPEG6-OH hexaethylene glycol monomethyl ether
  • pentaethylene glycol monomethyl ether tetraethylene glycol monomethyl ether
  • heptaethylene glycol monomethyl ether octaethylene glycol monomethyl ether
  • nonaethylene glycol monomethyl ether pentaethylene glycol dimethyl ether
  • the 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% by mass or more, more preferably 3.0% by mass or more, even more preferably 5.0% by mass or more, particularly preferably more than 5.0% by mass, and most preferably 10.0% by mass or more, based on the total mass of the resin-containing layer.
  • the upper limit is preferably 75.0% by mass or less, more preferably 70.0% by mass or less, and even more preferably 60.0% by mass or less.
  • 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, and more preferably 1.40 or less.
  • the resin-containing layer also preferably contains a filler.
  • the average particle size 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 size of the filler is also preferably 5 to 100 nm.
  • the average particle size of the filler is calculated by the following particle size measurement method.
  • Particle size measurement method A rectangular region of 3 ⁇ m ⁇ 10 ⁇ m in a cross section along the normal direction of the surface of the resin-containing layer is observed with a scanning electron microscope, and the operation of measuring the long diameters of all fillers observed in the above region is performed at five different points in the resin-containing layer, and the average value of the long diameters of all fillers measured in each operation is regarded as the average particle size of the filler.
  • a cross section along the normal direction of the surface of the resin-containing layer (the surface opposite to the temporary support side) is cut out, and a rectangular area of 3 ⁇ m ⁇ 10 ⁇ m on the cross section is observed with a scanning electron microscope, and the major axis of all fillers observed within the area is measured.
  • a scanning electron microscope S-4800 manufactured by Hitachi High-Tech Corporation is used. The magnification during observation is 50,000 times.
  • the above operation is carried out at five different locations in the resin-containing layer, and the average value (arithmetic mean value) of the major axis lengths of all the fillers measured in each operation is defined as the average particle size of the filler.
  • the above-mentioned major axis refers to the length of the longest line segment among the line segments connecting any two points on the contour line of the outer shape of the filler in the observed image. Furthermore, when the filler particles are aggregated to form aggregates in the observed image, the major axis of each filler particle that constitutes the aggregate is measured.
  • filler examples include organic fillers and inorganic fillers, with inorganic fillers being preferred.
  • 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).
  • the shape of the filler may be either spherical or non-spherical (eg, crushed or fibrous), with spherical being preferred.
  • the filler may be surface-treated.
  • the surface treatment include a treatment for introducing a functional group and a treatment using a known surface modifier.
  • the functional group include a polymerizable group (e.g., a polymerizable group of a polymerizable compound described later) and a hydrophobic group.
  • the surface modifier include known surface modifiers such as silane coupling agents, titanate coupling agents, and silazane compounds.
  • Fillers include, for example, Seahoster KE-S30 (manufactured by Nippon Shokubai Co., Ltd., silicon dioxide, solids concentration 100% by mass), NHM-3N (manufactured by Tokuyama Corporation, silicon dioxide, solids concentration 100% by mass), YA050C-MJE (manufactured by Admatechs Co., Ltd., silicon dioxide, MEK slurry with a solids 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, silicon dioxide), and MEK-AC-514.
  • Seahoster KE-S30 manufactured by Nippon Shokubai Co., Ltd., silicon dioxide, solids concentration 100% by mass
  • NHM-3N manufactured by Tokuyama Corporation, silicon dioxide, solids concentration 100% by mass
  • YA050C-MJE manufactured by Admate
  • 0Z (Nissan Chemical Industries, silicon dioxide), MEK-EC-2430Z (Nissan Chemical Industries, solids concentration 30% by mass), barium sulfate (Nihon Solvay, solids concentration 100% by mass), NHM-5N (Tokuyama Corporation, silicon dioxide, solids concentration 100% by mass), Y50SP-AM1 (Admatechs, silicon dioxide, MEK slurry with a solids concentration of 50% by mass), and Y50SZ-AM1 (Admatechs, silicon dioxide, MEK slurry with a solids concentration of 50% by mass).
  • the refractive index of the filler is preferably from 0.5 to 3.0, and more preferably from 1.2 to 1.8.
  • the refractive index can be measured by the method described above.
  • the fillers may be used alone or in combination of two or more.
  • the content of the filler is preferably 20.0% by mass or more, more preferably 30.0% by mass or more, even more preferably 40.0% by mass or more, and particularly preferably 50.0% by mass or more, based on the total mass of the resin-containing layer.
  • the upper limit is preferably 90.0% by mass or less, and more preferably 80.0% by mass or less.
  • the resin-containing layer may contain a polymerizable compound.
  • the polymerizable compound is a compound different from the above-mentioned various components.
  • the resin-containing layer preferably further contains a photopolymerization initiator described below.
  • the polymerizable compound is a compound having one or more polymerizable groups in one molecule.
  • a compound having an ethylenically unsaturated group is preferable, a compound having a (meth)acryloyl group, a vinyl group, or a styryl group is more preferable, and a compound having a (meth)acryloyl group is even more preferable.
  • the number of polymerizable groups that the polymerizable compound has is preferably 1 or 2 or more, more preferably 2 to 10, and even more preferably 2 to 6.
  • 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 tri- or higher functional polymerizable compound.
  • 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.
  • 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 Co.,
  • tri- or higher functional polymerizable compounds examples include dipentaerythritol (tri/tetra/penta/hexa)(meth)acrylate, pentaerythritol (tri/tetra)(meth)acrylate, trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, isocyanuric acid (meth)acrylate, and (meth)acrylate compounds having a glycerin tri(meth)acrylate skeleton.
  • (tri/tetra/penta/hexa)(meth)acrylate is a concept that encompasses tri(meth)acrylate, tetra(meth)acrylate, penta(meth)acrylate, and hexa(meth)acrylate
  • (tri/tetra)(meth)acrylate” is a concept that encompasses tri(meth)acrylate and tetra(meth)acrylate.
  • polymerizable compounds examples 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.).
  • 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, more preferably 8 or more.
  • the upper limit is preferably 20 or less.
  • trifunctional or higher urethane (meth)acrylates examples 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.).
  • the polymerizable compounds may be used alone or in combination of two or more.
  • the content of the polymerizable compound is preferably 30.0% by mass or less, more preferably 25.0% by mass or less, and even more preferably 20.0% by mass or less, based on the total mass of the resin-containing layer.
  • the lower limit is preferably 1.0% by mass or more.
  • the resin-containing layer may contain a photopolymerization initiator.
  • the photopolymerization initiator include a photoradical polymerization initiator, a photocationic polymerization initiator, and a photoanionic polymerization initiator, and a photoradical polymerization initiator is preferable.
  • the photopolymerization initiator examples include oxime ester compounds (photopolymerization initiators having an oxime ester structure), aminoacetophenone compounds (photopolymerization initiators having an aminoacetophenone structure), hydroxyacetophenone compounds (photopolymerization initiators having a hydroxyacetophenone structure), acylphosphine oxide compounds (photopolymerization initiators having an acylphosphine oxide structure), and bistriphenylimidazole compounds (photopolymerization initiators having a bistriphenylimidazole structure).
  • an oxime ester compound or an aminoacetophenone compound is preferable, and an oxime ester compound is more preferable.
  • oxime ester compounds include 1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2-(O-benzoyloxime)] (product name: IRGACURE OXE-01, manufactured by BASF), ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime) (product name: IRGACURE OXE-02, manufactured by BASF), [ 8-[5-(2,4,6-trimethylphenyl)-11-(2-ethylhexyl)-11H-benzo[a]carbazoyl][2-(2,2,3,3-tetrafluoropropoxy)phenyl]methanone-(O-acetyloxime) (trade name: IRGACURE OXE-03, manufactured by BASF Corporation), 1-[4-[4-(2-benzofuranylcarbonyl)phenyl]thio]phenyl
  • 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.).
  • photopolymerization initiators 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 1 173), 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 H), and bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (trade name: Omnirad 819) are also included.
  • photopolymerization initiators include those described in paragraphs 0031 to 0042 of JP2011-095716A and paragraphs 0064 to 0081 of JP2015-014783A.
  • 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.
  • the resin-containing layer may contain a photoacid generator.
  • the photoacid generator is a compound that generates an acid when exposed to light (eg, exposure light).
  • photoacid generators include ionic photoacid generators and non-ionic photoacid generators.
  • the ionic photoacid generator include a compound having a sulfonium structure, an onium salt compound having a diaryliodonium or triarylsulfonium structure, and an ammonium salt compound having a quaternary ammonium structure.
  • Examples of the ionic photoacid generator include the ionic photoacid generators described in paragraphs 0114 to 0133 of JP2014-085643A.
  • nonionic photoacid generators examples include trichloromethyl-s-triazine and its derivatives (trichloromethyl-s-triazine 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 the compounds described in paragraphs 0083 to 0088 of JP 2011-221494 A.
  • Examples of oxime sulfonate compounds include the compounds described in paragraphs 0084 to 0088 of WO 2018/179640 A.
  • the photoacid generators may be used alone or in combination of two or more.
  • the content of the photoacid generator is preferably from 0.1 to 10.0% by mass, and more preferably from 0.5 to 5.0% by mass, based on the total mass of the resin-containing layer.
  • the resin-containing layer may contain a surfactant.
  • the surfactant include those described in paragraph 0017 of Japanese Patent No. 04502784 and paragraphs 0060 to 0071 of JP-A-2009-237362.
  • the surfactant examples include a hydrocarbon surfactant, a fluorine surfactant, and a silicone surfactant. From the viewpoint of improving environmental compatibility, it is preferable that the surfactant does not contain a fluorine atom.
  • the surfactant is preferably a hydrocarbon surfactant or a silicone surfactant.
  • 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.
  • fluorosurfactants include acrylic compounds that have a molecular structure containing a functional group having a fluorine atom, and when heat is applied, the functional group having the fluorine atom is cleaved and the fluorine atom is volatilized.
  • fluorosurfactants include the Megafac DS series (manufactured by DIC Corporation, Chemical Daily (February 22, 2016), Nikkei Business Daily (February 23, 2016), Megafac DS-21, etc.).
  • the fluorosurfactant may be a polymer of a fluorine atom-containing vinyl ether compound having a fluorinated alkyl group or a fluorinated alkylene ether group and a hydrophilic vinyl ether compound.
  • the fluorosurfactant may be a block polymer.
  • the fluorine-based surfactant may 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).
  • examples of the fluorine-based surfactant include fluorine-containing polymers having a group having an ethylenically unsaturated group in the side chain, specifically, Megafac RS-101, RS-102, RS-718K, and RS-72-K (all manufactured by DIC Corporation).
  • fluorosurfactants from the viewpoint of improving environmental compatibility, surfactants derived from alternative materials to compounds having a linear perfluoroalkyl group with seven or more carbon atoms, such as perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic acid (PFOS), are preferred.
  • PFOA perfluorooctanoic acid
  • PFOS perfluorooctanesulfonic acid
  • 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.
  • glycerol trimethylolpropane
  • trimethylolethane trimethylolethane
  • propoxylates e.g., glycerol propoxylate and glycerol ethoxylate
  • polyoxyethylene lauryl ether polyoxyethylene stearyl ether
  • polyoxyethylene oleyl ether polyoxyethylene octylphenyl
  • hydrocarbon surfactants examples 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 Corporation); 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 Co., Ltd.); Olfine E1010, Surfynol 104, 400, and 440 (manufactured by Nissin Chemical Industry Co., Ltd.).
  • silicone surfactants include linear polymers consisting of siloxane bonds, modified siloxane polymers with organic groups introduced into the side chains and/or ends, and polymers having repeating units with hydrophilic groups in the side chains and repeating units with groups with siloxane bonds in the side chains.
  • silicone surfactants polymers having repeating units with hydrophilic groups in the side chains and repeating units with groups with siloxane bonds in the side chains are preferred.
  • the above polymers may be either random copolymers or block copolymers.
  • the repeating unit having a group with a siloxane bond in the side chain is preferably a repeating unit represented by formula (SX1) or a repeating unit represented by formula (SX2).
  • each R independently represents an alkyl group having 1 to 3 carbon atoms
  • R1 represents a hydrogen atom or a methyl group
  • L1 represents a single bond or a divalent organic group.
  • the R's may be the same or different.
  • R 1 represents a hydrogen atom or a methyl group.
  • R 2 represents an alkylene group having 1 to 10 carbon atoms.
  • R 3 represents an alkyl group having 1 to 4 carbon atoms.
  • n represents an integer of 5 to 50.
  • the repeating unit having a hydrophilic group in the side chain is preferably a repeating unit represented by formula (SX3).
  • R4 and R5 each independently represent a hydrogen atom or a methyl group, n represents an integer of 1 to 4, and m represents an integer of 1 to 100.
  • 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-22-49 52, X-22-4272, X-22-6266, KF-351A, K354L, KF-355A, KF-945, KF-640, KF-642, KF-643, 01KP-103, KP-104, KP-105, KP-106, KP-109, KP-109, KP-112, KP-120, KP-12 1, KP-124, KP-125, KP-301, K
  • Surfactants also include nonionic surfactants.
  • the surfactants may be used alone or in combination of two or more.
  • the content of the surfactant is preferably from 0.01 to 3.0% by mass, more preferably from 0.01 to 1.0% by mass, and further preferably from 0.05 to 0.8% by mass, based on the total mass of the resin-containing layer.
  • the resin-containing layer may contain a hardener.
  • the curing agent is not particularly limited as long as it is a compound that promotes the curing of various components contained in the resin-containing layer.
  • the hardener include cyanate ester hardeners and benzoxazine hardeners.
  • the cyanate ester hardeners and benzoxazine hardeners include those described in JP-A-2020-154325 and JP-A-2004-277460.
  • the resin-containing layer may contain other additives in addition to the various components described above.
  • other additives include heterocyclic compounds (e.g., compounds such as triazole, tetrazole, and benzotriazole, and derivatives thereof, as well as rust inhibitors), aliphatic thiol compounds, thermal crosslinking compounds, polymerization inhibitors, hydrogen donor compounds, impurities, plasticizers, sensitizers, alkoxysilane compounds, maleimide compounds, and hydrosilylation agents.
  • heterocyclic compound, the aliphatic thiol compound, the thermal crosslinking compound, the polymerization inhibitor, and the hydrogen donor compound include various components described in WO 2022/039027.
  • Examples of the plasticizer, sensitizer, and alkoxysilane compound include those described in paragraphs 0097 to 0119 of WO 2018/179640.
  • Examples of the maleimide compound (a compound having a maleimide ring) include known maleimide compounds and the maleimide compounds described in WO 2022/102756.
  • Examples of hydrosilylation agents include platinum-based catalysts such as carbon powder carrying platinum metal, 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 catalysts and rhodium catalysts.
  • the hydrosilylation agent is preferably used as a curing agent for the organosilicon compound.
  • the resin-containing layer may contain impurities.
  • impurities include sodium, potassium, magnesium, calcium, iron, manganese, copper, aluminum, titanium, chromium, cobalt, nickel, zinc, tin, halogens, and ions thereof. Since halide ions, sodium ions, and potassium ions are easily mixed in as impurities, it is preferable to set the contents to the following values.
  • the content of impurities is preferably 80 ppm by mass or less, more preferably 10 ppm by mass or less, and even more preferably 2 ppm by mass or less, based on the total mass of the resin-containing layer.
  • the lower limit is often 0 ppb by mass or more, but may be 1 ppb by mass or more, or 0.1 ppm by mass or more, based on the total mass of the resin-containing layer.
  • the amounts of impurities in the composition include a chloride ion concentration of 1.5 ppm by mass, a bromide ion concentration of 0.5 ppm by mass, a sodium ion concentration of 1.5 ppm by mass, and an iron ion concentration of 0.3 ppm by mass, relative to the total solid content of the composition.
  • 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 inclusion of impurities when forming the resin-containing layer.
  • the content of impurities can be quantified by known methods such as ICP (Inductively Coupled Plasma) emission spectroscopy, atomic absorption spectroscopy, and ion chromatography.
  • ICP Inductively Coupled Plasma
  • the content of compounds such as benzene, formaldehyde, trichloroethylene, 1,3-butadiene, carbon tetrachloride, chloroform, N,N-dimethylformamide, N,N-dimethylacetamide, and hexane is preferably small.
  • the content of each of these compounds is preferably 100 mass ppm or less, more preferably 20 mass ppm or less, and even more preferably 4 mass ppm or less, relative to the total mass of the resin-containing layer.
  • the lower limit may be 10 mass ppb or more, or 100 mass ppb or more, relative to the total mass of the resin-containing layer.
  • the content of these compounds can be adjusted in the same manner as for the above-mentioned impurities, and the content of these compounds can be quantified by known measurement methods.
  • the water 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, 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 more preferably 0.1% by mass or more.
  • Specific examples of the water 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.
  • 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, and improving lamination properties.
  • 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.
  • the lower limit of the average thickness of the resin-containing layer is preferably 0.5 ⁇ m or more, more preferably 1.0 ⁇ m or more, even more preferably 3.0 ⁇ m or more, and particularly preferably 5.0 ⁇ m or more.
  • the upper limit is preferably 40 ⁇ m or less, more preferably 25 ⁇ m or less, even more preferably 20 ⁇ m or less, and particularly preferably 19 ⁇ m or less.
  • the average thickness of the resin-containing layer is 40 ⁇ m or less, it is preferable in terms of excellent pattern resolution, and when the average thickness of the resin-containing layer is 0.5 ⁇ m or more, it is preferable in terms of excellent reliability.
  • the resin-containing layer 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.
  • the weight loss rate of the resin-containing layer when heated at 300° C. for 3 hours is preferably 10.0% by mass or more, and 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 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.
  • An evaluation sample (Sample A) is prepared by overlapping resin-containing layers of the transfer film to form a free-standing film.
  • the following describes, for example, the case where sample A is produced using five transfer films. First, two transfer films from which the protective film has been peeled off are laminated 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.
  • the transfer film from which the protective film has been peeled off is laminated 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.
  • the laminate 1 is separately produced, and the resin-containing layer of the laminate 1 and the resin-containing layer of the laminate 2 are laminated together so that the resin-containing layers face each other to obtain a laminate 3 (temporary support/five resin-containing layers/temporary support).
  • the two temporary supports are peeled off from the laminate 3 to obtain sample A.
  • 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 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 the range of room temperature to 300° C. (under a nitrogen atmosphere, heating rate of 10° C./min, and holding at 300° C. for 3 hours).
  • the TG-DTA device for example, "TG/DTA6200" manufactured by Seiko Instruments can be used.
  • Requirement 2 It is preferable that the resin-containing layer satisfies the following requirement 2.
  • Requirement 2 The content of compound Y in the resin-containing layer is more than 5.0 mass% based on 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 mass% or less based on the total mass of the resin-containing layer.
  • the content of compound Y when the resin-containing layer is heated at 300° C. for 3 hours 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, based on the total mass of the resin-containing layer after heating.
  • the lower limit is preferably 0% by 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.
  • 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).
  • the "content (mass %) of compound Y in the resin-containing layer after the resin-containing layer is heated at 300° C. for 3 hours” can be measured based on 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 in 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 the resin-containing layer is heated at 300° C.
  • the solvent used for extracting the compound Y is preferably a solvent capable of dissolving 5% by mass or more of the compound Y, and for example, tetrahydrofuran (THF) is preferable.
  • sample A is prepared in the same manner as described in (Preparation of evaluation sample (sample A)) of ⁇ Requirement 1>. Next, 50 mg of sample A is immersed in 5 ml of the solvent for 48 hours to extract the components in sample A into the solvent.
  • 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 the compound Y is preferably a solvent capable of dissolving 5% by mass or more of the compound Y, and for example, tetrahydrofuran (THF) is preferable.
  • the content (mass %) of compound Y in the resin-containing layer is calculated by ⁇ (content of compound Y in resin-containing layer/mass of sample A) ⁇ 100 ⁇ .
  • GC-MS measurement conditions Apparatus: Shimadzu Corporation "2010-Ultra"
  • the resin-containing layer preferably satisfies the following requirement 3 and/or requirement 4.
  • 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.].
  • Requirement 4 The glass transition temperature Y [° C.] after heating the resin-containing layer at 300° C. for 3 hours satisfies formula (2).
  • 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.
  • 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.
  • the evaluation sample (sample A) is prepared by the same method as the procedure explained in (Preparation of evaluation sample (sample A)) of ⁇ Requirement 1>.
  • the prepared Sample A (freestanding film) is cut into a rectangular shape (19 mm ⁇ 5 mm), and the glass transition temperature is measured using a TMA (thermomechanical analyzer, “TMA450EM” manufactured by TA Instruments).
  • 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 the 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.
  • 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). Next, the prepared Sample B (freestanding film) is cut into a strip (19 mm ⁇ 5 mm), and the glass transition temperature is measured using a TMA (thermomechanical analyzer, “TMA450EM” manufactured by TA Instruments).
  • 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 the 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 (Y [° C.]) of the resin-containing layer when heated at 300° C. for 3 hours.
  • the linear expansion coefficient of the cured film of the resin-containing layer is preferably 150 ppm/K or less, and more preferably 35 ppm/K or less.
  • the lower limit is preferably 0 ppm/K or more.
  • the linear expansion coefficient of the cured film of the resin-containing layer can be measured by the following procedure.
  • Example B A sample A similar to that described in (Preparation of Evaluation Sample (Sample A)) of Requirement 1 is prepared. Next, an evaluation sample (Sample B) is prepared by either Method X or Method Y using the prepared sample A.
  • Sample B is prepared according to Method X below.
  • Method X Sample A was exposed to light (exposure conditions: high pressure mercury lamp, cumulative illuminance of 100 mJ/cm 2 measured with a 365 nm wavelength illuminometer) and then heated in an oven (220° C., 5 hours) to obtain Sample B.
  • sample B is prepared according to method Y below.
  • Method Y Sample A was subjected to a heat treatment in an oven (220° C., 5 hours) to obtain Sample B.
  • CTE coefficient of linear expansion
  • Sample B freestanding film prepared by method X or method Y is cut into a rectangular shape (19 mm x 5 mm), and the linear expansion coefficient is measured using a TMA (thermomechanical analyzer, "TMA450EM” manufactured by TA Instruments).
  • TMA thermomechanical analyzer
  • 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 linear expansion coefficient is the value (ppm/K) in the range of 50° C. to 150° C. during temperature rise, and the average value of three measurements is regarded as the linear expansion coefficient of the cured film of the resin-containing 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.
  • the transfer film may have a cover film (protective film).
  • the number of fish eyes having a diameter of 80 ⁇ m or more contained in the cover film is preferably 5 or less per square meter.
  • Fish eyes are foreign matter, unmelted matter, and/or oxidized deterioration products of the material that are 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.
  • the number of particles having a diameter of 3 ⁇ m or more contained in the cover film is preferably 30 pieces/mm2 or less , more preferably 10 pieces/mm2 or less , and even more preferably 5 pieces/mm2 or less . This makes it possible to suppress defects caused by unevenness due to the particles contained in the cover film being transferred to the composition layer.
  • the arithmetic mean roughness Ra of the surface of the cover film is preferably 0.01 ⁇ m or more, more preferably 0.02 ⁇ m or more, and even more preferably 0.03 ⁇ m 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. Furthermore, from the viewpoint of suppressing defects during transfer, Ra is preferably less than 0.50 ⁇ m, more preferably 0.40 ⁇ m or less, and even more preferably 0.30 ⁇ m or less.
  • cover film examples include a polyethylene terephthalate film, a polypropylene film, a polystyrene film, and a polycarbonate film.
  • cover film examples include those described in paragraphs 0083 to 0087 and 0093 of JP-A No. 2006-259138.
  • cover films examples 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.
  • a recycled product may be a product obtained by cleaning and chipping a used film, and then forming the obtained material into a film.
  • a commercially available recycled product may be the Ecouse series (manufactured by Toray Industries, Inc.).
  • the transfer film may include other layers in addition to the layers described above.
  • the other layers include, for example, a high refractive index layer.
  • high refractive index layers include those described in paragraphs 0168 to 0188 of WO 2021/187549, the contents of which are incorporated herein by reference.
  • the transfer film can be produced by a known production method.
  • a resin composition is preferably applied onto a temporary support to form a resin-containing layer.
  • a method for manufacturing the transfer film 100 shown in FIG. 1 includes a method including 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, a cover film is pressed onto the resin-containing layer of the transfer film produced by the above-mentioned production method to produce the transfer film 100 shown in Fig. 1.
  • the transfer film 100 shown in Fig. 1 may be wound up after production and stored as a roll of the transfer film 100.
  • the transfer film 100 in the roll form can be provided in that form for the lamination step with a substrate in a roll-to-roll system described later.
  • the transfer film may have an intermediate layer and/or a thermoplastic resin layer between the temporary support and the resin-containing layer.
  • the composition for forming an intermediate layer the method for forming an intermediate layer, the composition for forming a thermoplastic resin layer, and the method for forming a 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.
  • the resin-containing layer can be formed by a known method, for example, a method of forming the layer by applying and drying a resin composition.
  • the various components that can be contained in the resin composition have the same meanings as the various components that can be contained in the resin-containing layer described above, and preferred embodiments are also the same.
  • the preferred range of the content of each component in the resin composition is the same as the preferred range obtained by replacing the above “content (mass%) of each component relative to the total mass of the resin-containing layer" with “content (mass%) of each component relative to the total solid content of the resin composition.”
  • the description "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.”
  • the resin composition preferably contains a solvent in order to improve the coating property.
  • the solvent is not particularly limited as long as it can dissolve or disperse various components that may be contained in the resin composition.
  • the solvent 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.
  • alcohol solvents e.g., methanol and ethanol
  • ketone solvents e.g., acetone and methyl ethyl ketone
  • aromatic hydrocarbon solvents
  • the solvent may be used alone or in combination of two or more.
  • the content of the solvent is preferably from 50 to 1,900 parts by mass, more preferably from 100 to 1,200 parts by mass, and even more preferably from 100 to 900 parts by mass, relative to 100 parts by mass of the total solid content of the composition.
  • Coating methods include, for example, slit coating, spin coating, curtain coating, and inkjet coating.
  • the resin pattern obtained from the resin-containing layer formed using the transfer film can be used for various applications, such as an electrode protective film, an insulating film, a planarizing film, an overcoat film, a hard coat film, a passivation film, a partition wall, a spacer, a microlens, an optical filter, an anti-reflection film, an etching resist, and a plating member.
  • examples of the material include protective films or insulating films for touch panel electrodes, protective films or insulating films for printed wiring boards, protective films or insulating films for TFT substrates, interlayer insulating films in build-up substrates for semiconductor packages, organic interposers, color filters, overcoat films for color filters, and etching resists for wiring formation.
  • the method for producing the laminate is not particularly limited as long as it is a method using the above-mentioned transfer film.
  • Examples of the method for producing the laminate include known methods such as a method for producing a build-up substrate, and a method including steps Z1 to Z3 is preferable, and a method including steps Z1 to Z4 is more preferable.
  • Step Z1 forming a resin-containing layer on a substrate using the above-mentioned transfer film
  • 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 by step Z3.
  • the method for producing a laminate includes steps Z1 to Z4, and further includes step Z5 of forming a resin-containing layer on the laminate produced by step Z4 using a transfer film, and preferably comprises repeatedly carrying out steps Z2 to Z5.
  • 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 to the temporary support is brought into contact with the substrate, and the transfer film and the substrate are laminated together. In addition, when the transfer film has a cover film, it is preferable that the step Z1 is performed after peeling off the cover film from the transfer film. Examples of methods for attaching the transfer film include known transfer and lamination methods. A preferred method is to place a substrate on the surface of the resin-containing layer and apply pressure and heat with a roll or the like. The lamination method may be carried out using a known laminator such as a vacuum laminator or an autocut laminator. The lamination temperature is not particularly limited, but is preferably from 70 to 130°C.
  • the substrate examples 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 a light-transmitting substrate such as a glass substrate, and may be, for example, reinforced glass such as Gorilla Glass manufactured by Corning Inc. Examples of materials contained in the substrate include materials described in JP-A-2010-086684, JP-A-2010-152809, and JP-A-2010-257492.
  • the resin substrate is preferably a resin film having small optical distortion and/or high transparency, and specific examples thereof include polyester, polyethylene terephthalate (PET), polyethylene naphthalate, polycarbonate, triacetyl cellulose, cycloolefin polymer, and polyimide.
  • a resin substrate having a conductive layer is preferable, and a resin film having a conductive layer is more preferable, in that it can be produced by a roll-to-roll process.
  • the substrate having a conductive layer may be a laminate obtained by the above-mentioned method for producing a laminate.
  • the conductive layer may be, for example, a known conductive layer used for circuit wiring or touch panel wiring.
  • a metal layer e.g., metal foil, etc.
  • a conductive metal oxide layer e.g., graphene layer
  • a carbon nanotube layer e.g., graphene layer
  • a conductive polymer layer e.g., polystyrene layer
  • a metal layer is more preferred
  • a copper layer or a silver layer is even more preferred.
  • the conductive layer may be one or two 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 elemental metals and conductive metal oxides.
  • Examples of elemental metals include Al, Zn, Cu, Fe, Ni, Cr, Mo, Ag, and Au.
  • conductive metal oxides include ITO (indium tin oxide), IZO (indium zinc oxide), and SiO 2. Conductive means that the volume resistivity is less than 1 ⁇ 10 6 ⁇ cm, and preferably the volume resistivity is less than 1 ⁇ 10 4 ⁇ cm.
  • the conductive layer may be in a pattern.
  • methods for producing a patterned conductive layer include subtractive methods and additive methods such as etching.
  • Examples of the etching method include the wet etching method described in paragraphs 0048 to 0054 of JP 2010-152155 A and known dry etching methods such as plasma etching.
  • the etching method may also be a method using an etching resist.
  • 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.
  • Methods for forming a pattern having vias include, for example, methods using a drill, a laser, and plasma.
  • the method for forming a pattern having vias preferably includes a step of exposing the resin-containing layer to a pattern, 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 an opening region in the pattern (a region where the resist film is not arranged).
  • the resin-containing layer may be exposed from the side opposite to the substrate, or from the substrate side of the resin-containing layer.
  • the light source used for exposure may be any light source that irradiates light in a wavelength range to which various photosensitive components in the resin-containing layer (e.g., a resin, a polymerizable compound, a photopolymerization initiator, a photoacid generator, etc.) are sensitive (e.g., light in a wavelength range of 254 nm, 313 nm, 365 nm, 405 nm, etc.).
  • various photosensitive components in the resin-containing layer e.g., a resin, a polymerizable compound, a photopolymerization initiator, a photoacid generator, etc.
  • Specific examples include ultra-high pressure mercury lamps, high pressure mercury lamps, metal halide lamps, and LEDs (Light Emitting Diodes).
  • the exposure dose is preferably from 5 to 200 mJ/ cm2 , and more preferably from 10 to 200 mJ/ cm2 .
  • 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.
  • the pattern exposure may be exposure through a mask or direct exposure using a laser or the like.
  • the mask include a quartz mask, a soda lime glass mask, and a film mask.
  • the quartz mask is preferred because of its excellent dimensional accuracy, and the film mask is preferred because it can be easily made large in size.
  • the material of the film mask is preferably a polyester film, more preferably a polyethylene terephthalate film, for example, XPR-7S SG (manufactured by Fujifilm Global Graphic Systems Co., Ltd.).
  • the pattern having vias may be either through holes or via holes.
  • the shape of the via in the pattern can be, for example, a rectangle, a trapezoid, or an inverted trapezoid in cross-sectional shape; and a circle or a rectangle in front shape (the shape of the via when observed from a direction in which the via bottom is visible).
  • An inverted trapezoid is preferred as the cross-sectional shape because it increases the adhesion of plated copper to the via wall surface.
  • the via size (diameter) is preferably 300 ⁇ m or less, more preferably 100 ⁇ m or less, further preferably 50 ⁇ m or less, and particularly preferably 5 ⁇ m or less.
  • the lower limit is preferably 1 ⁇ m or more.
  • the number of the vias may be one or more, and is preferably two or more.
  • Step Z3 is a step of subjecting the pattern to a heat treatment.
  • compound Y contained in the resin-containing layer in the pattern obtained in step Z2 can be removed from the system.
  • the resin-containing layer in the pattern obtained in step Z2 is a thermosetting resin-containing layer
  • the thermal curing of the resin-containing layer progresses and compound Y can be removed from the resin-containing layer.
  • the heating temperature is preferably set to the boiling point of compound Y or higher.
  • the heating temperature is preferably 100 to 300° C., and the heating time is preferably 10 minutes to 10 hours.
  • Step Z4 is a step of forming a circuit pattern on the pattern.
  • a semi-additive process is preferred because it allows the formation of fine wiring.
  • a seed layer is first formed by electroless copper plating using a palladium catalyst or the like on the via bottoms, via wall surfaces, and the entire surface of a pattern having vias.
  • the seed layer is for forming a power supply layer for electrolytic copper plating, and the thickness of the seed layer is preferably 0.1 to 2.0 ⁇ m.
  • the electroless copper plating process is carried out by reacting copper ions with a reducing agent to deposit metallic copper on the surface of a pattern having vias. Examples of the electroless plating process and the electrolytic plating process include known plating processes.
  • the catalyst for the electroless plating process is preferably a palladium-tin mixed catalyst.
  • the average primary particle size of the mixed catalyst is preferably 10 nm or less.
  • the plating solution for the electroless plating process preferably contains hypophosphorous acid (reducing agent).
  • Examples of electroless copper plating solutions include "MSK-DK” manufactured by Atotech Japan and “ThruCup (registered trademark) PEA ver. 4" series manufactured by Uemura Kogyo Co., Ltd.
  • the method for producing the laminate may include a roughening step of roughening the pattern having the vias.
  • the roughening step is preferably performed after the step Z3 and before the step Z4.
  • the roughening step may be, for example, a known desmear treatment, and is preferably a treatment in which a roughening liquid is brought into contact with the surface.
  • the roughening liquid examples include a roughening liquid containing chromium and sulfuric acid, a roughening liquid containing an alkaline permanganate (e.g., a sodium permanganate roughening liquid), and a roughening liquid containing sodium fluoride, chromium, and sulfuric acid.
  • a roughening liquid containing chromium and sulfuric acid examples include a roughening liquid containing chromium and sulfuric acid, a roughening liquid containing an alkaline permanganate (e.g., a sodium permanganate roughening liquid), and a roughening liquid containing sodium fluoride, chromium, and sulfuric acid.
  • the heating temperature is preferably 150 to 240° C., and the heating time is preferably 15 to 500 minutes.
  • the laminate is a laminate obtained by the above-mentioned method for producing a laminate.
  • 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, including various semiconductor devices such as semiconductor packages used in electrical products (e.g., computers, mobile phones, digital cameras, televisions, etc.) and vehicles (e.g., motorcycles, automobiles, trains, ships, aircraft, etc.).
  • a mixture was prepared by mixing various components in the amounts (solid content amounts) shown in the "Resin-containing layer” column in the table. The mixture was then diluted with a mixed solvent containing 25% by mass of MEK (methyl ethyl ketone) and 75% by mass of NMP (N-methylpyrrolidone) to a solid content of 30% by mass.
  • MEK methyl ethyl ketone
  • NMP N-methylpyrrolidone
  • ⁇ resin ⁇ A-1 Phenol resin, TR4020G, manufactured by Asahi Organic Chemicals Co., Ltd.
  • A-2 Epoxy resin, ZX1059 (mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin (1:1)), manufactured by Nippon Steel Chemical & Material Co., Ltd.
  • A-3 Polyphenylene ether resin having a branched structure, synthesized by the following method.
  • 1.3 g of di- ⁇ -hydroxo-bis[(N,N,N',N'-tetramethylethylenediamine)copper(II)] chloride (Cu/TMEDA) and 1.59 mL of tetramethylethylenediamine (TMEDA) were added and thoroughly dissolved, and 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.
  • A-4 Silicone resin, organopolysiloxane having 0.23 moles of vinyl groups per 100 g and a viscosity of 2,000 mPa ⁇ s, represented by the 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
  • ⁇ A-5 Benzocyclobutene resin, cyclotene resin XUR-JW-1148-200201415-47, manufactured by The Dow Chemical Company
  • a mixture was prepared by placing 1-methoxy-2-acetoxypropane (PGMEA, 60 parts) and propylene glycol monomethyl ether (PGME, 240 parts by mass) in a 2000 mL flask. The mixture was heated to 90° C. while being stirred at a stirring speed of 250 rpm.
  • PGMEA 1-methoxy-2-acetoxypropane
  • PGME propylene glycol monomethyl ether
  • V-601 (dimethyl 2,2'-azobis(2-methylpropionate), 9.637 parts by mass) was dissolved in PGMEA (136.56 parts by mass) to obtain the dropping liquid (2).
  • the dropping liquid (1) and the dropping liquid (2) were simultaneously dropped over 3 hours into a 2000 mL flask containing the above mixed liquid heated to 90° C.
  • V-601 (2.401 parts by mass) was added to the flask three times every hour. Then, the mixture was stirred at 90° C. for another 3 hours. Then, the reaction liquid obtained in the flask was diluted with PGMEA to obtain a solution containing Resin A-6 (solid concentration 36.3% by mass).
  • a dropping liquid (1) methyl methacrylate (40 parts by mass), dicyclopentanyl methacrylate (40 parts by mass), and methacrylic acid (20 parts by mass) were mixed and diluted with PGMEA (60 parts) to obtain a dropping liquid (1).
  • PGMEA g., 1,3-azobis(2-methylpropionate), 9.637 parts by mass
  • PGMEA 136.56 parts by mass
  • A-8 Liquid crystal polymer (liquid crystal polyester), synthesized by the following method.
  • a 2.5L reaction vessel equipped with a stirring blade and a distillation tube 435g of p-hydroxybenzoic acid, 164g of 4,4'-dihydroxybiphenyl, 44g of hydroquinone, 146g of terephthalic acid, 78g of isophthalic acid, and 684g of acetic anhydride were charged, and the mixture was reacted at 150°C for 2.5 hours while stirring under a nitrogen gas atmosphere, and then heated to 300°C in 3.5 hours. Thereafter, the polymerization temperature was maintained at 300°C, the pressure was reduced to 1.0mmHg in 1.0 hour, and the reaction was continued for another 2 hours. Next, the inside of the reaction vessel was pressurized to 0.12MPa, and Resin A-8 was discharged into a strand-like material to obtain Resin A-8.
  • A-10 Silsesquioxane resin with the following structure, synthesized using the following method.
  • Polysilsesquioxane A-10 had an Mw of 43,700 and an Mn of 8,900, and contained a cage-type polysilsesquioxane.
  • 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 solid content 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.
  • the components (a) to (e) are shown below.
  • 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
  • ⁇ Comparative Compound Y> 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.
  • NHM-5N Silicon dioxide (spherical silica), surface-treated product, manufactured by Tokuyama Corporation
  • NP-5N Silicon dioxide (spherical silica), surface-treated product, manufactured by Tokuyama Corporation
  • 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 JP2020-026502A J-5: "MIR-500-60T”: isopropylidene group-containing maleimide compound, toluene solution
  • the transfer film from which the protective film had been peeled off was laminated to the laminate 1 so that the resin-containing layer of the transfer film faced the resin-containing layer of the laminate 1, and then one of the two temporary supports was peeled off to obtain a laminate 2 having a temporary support and three resin-containing layers.
  • the laminate 1 was separately produced, and the resin-containing layer of the laminate 1 and the resin-containing layer of the laminate 2 produced above were laminated together so that the resin-containing layers faced each other, to obtain a laminate 3 (temporary support/five resin-containing layers/temporary support).
  • the two temporary supports were peeled off from the laminate 3 to obtain sample A.
  • Sample A was prepared in the same manner as in the procedure shown 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]. Next, the prepared Sample A was heated at 300° C. for 3 hours in 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 to extract the components in sample B into THF.
  • THF tetrahydrofuran
  • Sample A was prepared in the same manner as shown 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 self-supporting film
  • the glass transition temperature was measured using a TMA (thermomechanical analyzer, "TMA450EM” manufactured by TA Instruments).
  • 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 the 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.
  • ⁇ Measurement 4 Measurement of glass transition temperature (Y [°C]) of resin-containing layer when heated at 300°C for 3 hours> Sample A was prepared in the same manner as in the procedure shown 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 was heated at 300° C. for 3 hours in a nitrogen atmosphere to prepare an evaluation sample (Sample B).
  • the prepared sample B (self-supporting 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).
  • TMA thermomechanical analyzer
  • 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.
  • the obtained values were then classified according to the following criteria. The results are shown in Table 1. (standard) "A”: Y ⁇ 150 "B”: Y ⁇ 150
  • step conformability (after storage, 3 ⁇ m)>
  • the transfer film was stored under conditions of 40° C. and 50% RH for 120 days.
  • 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.
  • Method X Sample A was subjected to an exposure treatment (exposure conditions: high-pressure mercury lamp, cumulative illuminance measured with a 365 nm wavelength illuminometer of 100 mJ/cm 2 ) and then a heat treatment in an oven (220° C., 5 hours) to produce Sample B.
  • Sample B was prepared according to Method Y below.
  • Method Y Sample B was produced by subjecting Sample A to a heat treatment in an oven (220° C., 5 hours).
  • Sample B (self-supporting film) prepared by method X or method Y was cut into a rectangular shape (19 mm x 5 mm), and the linear expansion coefficient was measured using a TMA (thermomechanical analyzer, "TMA450EM” manufactured by TA Instruments). The measurement conditions were a heating rate of 10°C/min, a chuck distance of 16 mm, and a load of 49 mN. The measurement was performed in a temperature range of -60°C to 350°C. The linear expansion coefficient was determined as a value (ppm/K) in the range of 50°C to 150°C during heating, and was calculated as the average value of three measurements.
  • TMA thermomechanical analyzer
  • CTE Evaluation Criteria
  • Table 1 is shown below.
  • Table 1 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 the 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, the measurement, and the evaluation are shown in that order).
  • the column “B/A (mass ratio)” indicates the mass ratio calculated by "content of compound Y and comparative compound RY (B)" / "content of
  • the transfer film of the embodiment has excellent conformability to unevenness when the resin-containing layer is attached to an object after storage, has excellent peelability from the temporary support, and has a small coefficient of linear expansion (CTE) of the resin-containing layer that has been transferred and subjected to a specified treatment, including a heat treatment.
  • CTE coefficient of linear expansion
  • 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 was formed, and a resin-containing layer was formed on both sides of the glass epoxy substrate.
  • a vacuum laminator was used for this.
  • the lamination was performed using a vacuum laminator manufactured by MCK Corporation under the following conditions: substrate temperature: 40°C, rubber roller temperature: 100°C, linear pressure: 3 N/cm, and conveying speed: 2 m/min.
  • a pattern having a via with a diameter of ⁇ 60 ⁇ m was formed at a predetermined position on the resin-containing layer, and then the layer was heated.
  • the residue was removed using a sodium permanganate aqueous solution as a roughening solution, and electroless plating was performed.
  • a resist pattern was formed at a predetermined position using a known dry film resist, and electrolytic plating was performed.
  • the resist pattern was peeled off using a peeling solution.
  • a seed layer etching process was performed, followed by a heat treatment (200° C., 1 hour) to form copper wiring on the cured film.
  • the above steps from lamination to heat treatment were repeated three times, and finally a solder resist was formed as the outermost layer, and a semiconductor element was sealed and mounted to produce a semiconductor package.
  • the obtained semiconductor package was mounted at a predetermined position on a printed wiring board to obtain a semiconductor package substrate. It was confirmed that the obtained semiconductor package substrate operated normally.

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