WO2024024783A1 - Film de transfert, procédé de fabrication de stratifié, stratifié et procédé de fabrication de boîtier de semi-conducteur - Google Patents

Film de transfert, procédé de fabrication de stratifié, stratifié et procédé de fabrication de boîtier de semi-conducteur Download PDF

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Publication number
WO2024024783A1
WO2024024783A1 PCT/JP2023/027215 JP2023027215W WO2024024783A1 WO 2024024783 A1 WO2024024783 A1 WO 2024024783A1 JP 2023027215 W JP2023027215 W JP 2023027215W WO 2024024783 A1 WO2024024783 A1 WO 2024024783A1
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Prior art keywords
photosensitive layer
group
transfer film
compound
mass
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PCT/JP2023/027215
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English (en)
Japanese (ja)
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圭吾 山口
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富士フイルム株式会社
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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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • 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
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
    • 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
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/037—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polyamides or polyimides
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20—Exposure; Apparatus therefor
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/38—Treatment before imagewise removal, e.g. prebaking

Definitions

  • the present invention relates to a composition, a transfer film, a method for manufacturing a laminate, a laminate, and a method for manufacturing a semiconductor package.
  • a display device equipped with a touch panel such as a capacitive input device
  • the display device is, for example, an organic electroluminescence (EL) display device, a liquid crystal display device, etc.
  • an electrode pattern corresponding to a sensor in a viewing section is, peripheral wiring, etc.
  • a conductive pattern such as a wiring section and a lead-out wiring section is provided inside the touch panel.
  • Patent Document 1 discloses a photosensitive resin composition having a predetermined structure.
  • a temporary support and a photosensitive resin composition formed on the temporary support are used.
  • a method of using a transfer film configured by arranging layers is also widely known.
  • the present inventors produced a transfer film using a photosensitive resin composition such as that described in Patent Document 1, and investigated the coefficient of linear expansion of a cured product formed by the photosensitive layer of the transfer film. It has become clear that there is room for improvement (specifically, reducing the coefficient of linear expansion).
  • the basic performance of the transfer film is that it has excellent releasability of the temporary support and is also required to have excellent step followability when laminated to an object to be laminated.
  • excellent step followability when laminating to the object to be laminated specifically means that when laminating the photosensitive layer of the transfer film to the object to be laminated, This means that bubbles are unlikely to form between the compound and the photosensitive layer.
  • the object to be bonded is a base material with a step such as wiring
  • the photosensitive layer between the object and the transfer film is suppressed while suppressing the inclusion of air bubbles due to the effect of the step of the object to be bonded.
  • This refers to the ability to laminate with.
  • transfer films are sometimes used for pattern formation after being stored for a certain period of time, and there is a demand for excellent step followability when laminating them to objects to be laminated after storage.
  • the present invention provides a transfer film that has excellent step followability when laminated to an object to be laminated after storage, has excellent removability of a temporary support, and has a small linear expansion coefficient of the cured product of the photosensitive layer.
  • the task is to do so.
  • Another object of the present invention is to provide a method for manufacturing a laminate, a laminate, and a semiconductor package using the above transfer film.
  • a transfer film comprising a temporary support and a photosensitive layer
  • the photosensitive layer is a resin X selected from the group consisting of polyimide, polybenzoxazole, and precursors thereof; a photopolymerization initiator; A compound Y different from the photopolymerization initiator, The molecular weight of the compound Y is 200 to 1000, and the boiling point is 230 to 500°C, The mass ratio of the content of the compound Y to the content of the resin X is 0.40 to 1.50, When the compound Y is a polymerizable compound, the polymerizable compound has a methacryloyl group, a transfer film.
  • the compound Y contains a polymerizable compound having a methacryloyl group, and The transfer film according to any one of [1] to [4], wherein the homopolymer derived from the polymerizable compound has a decomposition temperature of 300° C. or lower.
  • the transfer film of the above compound Y The transfer film according to any one of [1] to [6], which has a viscosity at 25° C.
  • the content of the resin X is based on the total mass of the photosensitive layer,
  • it contains a filler The transfer film according to any one of [1] to [11], wherein the content of the filler is 30.0% by mass or more based on the total mass of the photosensitive layer.
  • a transfer film that has excellent step followability when laminated to an object to be laminated after storage, has excellent releasability of a temporary support, and has a small coefficient of linear expansion of the cured product of the photosensitive layer. can. Further, according to the present invention, it is possible to provide a method for manufacturing a laminate, a laminate, and a method for manufacturing a semiconductor package using the above transfer film.
  • FIG. 2 is a diagram (nomograph) illustrating a method for measuring the boiling point of compound Y.
  • a numerical range expressed using " ⁇ " means a range that includes the numerical values written before and after " ⁇ " as a lower limit value and an upper limit value.
  • the upper limit or lower limit described in a certain numerical range may be replaced with the upper or lower limit of another numerical range described in stages. good.
  • the upper limit or lower limit described in a certain numerical range may be replaced with the value shown in the Examples.
  • process in this specification refers not only to an independent process, but also to the term “process” when the intended purpose of the process is achieved, even if the process cannot be clearly distinguished from other processes. included.
  • the temperature condition may be 25°C.
  • the temperature at which each of the above steps is performed may be 25° C. unless otherwise specified.
  • transparent means that the average transmittance of visible light with a wavelength of 400 to 700 nm is 80% or more, preferably 90% or more. Further, 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 rays or “radiation” include, for example, the bright line spectrum of mercury lamps such as G-line, H-line, and I-line, deep ultraviolet rays typified by excimer lasers, extreme ultraviolet rays (EUV light), Refers to X-rays and electron beams (EB).
  • light means actinic rays or radiation.
  • Exposure refers not only to exposure to far ultraviolet rays, extreme ultraviolet rays, X-rays, and EUV light represented by mercury lamps and excimer lasers, but also to electron beams and ion beams, unless otherwise specified. Exposure also includes drawing using a particle beam such as a beam.
  • the content ratio of each repeating unit of the polymer is a molar ratio.
  • the refractive index is a value measured with an ellipsometer at a wavelength of 550 nm.
  • the molecular weight when there is a molecular weight distribution 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 and methacryloyl groups.
  • (meth)acrylate is a concept that includes both acrylate and methacrylate.
  • (poly)oxyalkylene group is a concept that includes both an oxyalkylene group and a polyoxyalkylene group.
  • 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.
  • the "solid content" of a composition refers to components that form a composition layer formed using the composition.
  • a solvent eg, an organic solvent, water, etc.
  • liquid components are also considered solid components as long as they form a composition layer.
  • the photosensitive layer of the transfer film contains a solvent (solvent) with a boiling point of 230°C or higher that can correspond to a type of compound Y
  • the compound in the photosensitive composition composition for forming the photosensitive layer
  • a solvent (solvent) with a boiling point of 230°C or higher that can fall under one type of Y is considered to be a "solid content”.
  • the thickness of a layer is an average thickness measured using a scanning electron microscope (SEM) for a thickness of 0.5 ⁇ m or more, and is 0.5 ⁇ m.
  • SEM scanning electron microscope
  • TEM transmission electron microscope
  • the above-mentioned average thickness is the average thickness obtained by preparing a section to be measured using an ultramicrotome, measuring the thickness at five arbitrary points, and calculating the arithmetic average of the thicknesses.
  • the boiling point means the boiling point under normal pressure (1 atmosphere, 760 mmHg) unless otherwise specified.
  • the transfer film of the present invention is a transfer film having a temporary support and a photosensitive layer,
  • the photosensitive layer is A resin X (hereinafter abbreviated as "resin X”) selected from the group consisting of polyimide, polybenzoxazole, and their precursors, a photopolymerization initiator; Compound Y (hereinafter abbreviated as “compound Y”) different from the photopolymerization initiator,
  • the molecular weight of the compound Y is 200 to 1000, and the boiling point is 230 to 500°C,
  • the mass ratio of the content of the compound Y to the content of the resin X (hereinafter also referred to as "specific mass ratio") is 0.40 to 1.50,
  • the compound Y is a polymerizable compound, the polymerizable compound has a methacryloyl group.
  • the transfer film having the above structure has excellent step followability when laminated to an object to be laminated after storage, excellent releasability of the temporary support, and a small coefficient of linear expansion of the cured product of the photosensitive layer.
  • the detailed mechanism of action of the transfer film is not clear, the inventors of the present invention speculate as follows.
  • Compound Y functions as a component to ensure the plasticity of the resin in the photosensitive layer, and is removed by volatilization when heat treatment is performed after development, so that it is unlikely to remain in the resin pattern system.
  • the transfer film has excellent step followability due to the plasticizing effect brought about by Compound Y when the photosensitive layer of the transfer film is laminated to the object to be laminated. It is presumed that the thermal expansion coefficient of the resin pattern formed by the film decreases as the content of compound Y decreases.
  • the transfer film has a photosensitive layer containing the compound Y, and the resin X and the compound Y are in a specific mass ratio, so that the transfer film has good step followability when laminated to an object after storage, It is presumed that the three effects of the releasability of the temporary support and the coefficient of linear expansion of the cured product of the photosensitive layer were achieved at an excellent level.
  • compounds with a molecular weight of less than 200 and/or a boiling point of less than 230°C are likely to volatilize due to the effects of the environment during storage of the transfer film. It is assumed that this will not contribute to improving the level difference followability.
  • the transfer film should have better step followability when laminated to the object to be laminated after storage, better releasability of the temporary support, and/or better linear expansion coefficient of the cured product of the photosensitive layer.
  • a smaller value may also be referred to as "the effect of the present invention is better.”
  • the transfer film has a temporary support and a photosensitive layer disposed on the temporary support.
  • the photosensitive layer of the transfer film is preferably a negative photosensitive layer.
  • the transfer film may include layers other than the photosensitive layer on the temporary support. Note that hereinafter, the photosensitive layer disposed on the temporary support and other optionally included layers may be collectively referred to as a "composition layer.” Further, the transfer film may have a structure in which a protective film (hereinafter sometimes referred to as "cover film”) is provided 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 structure in which a temporary support 12, a photosensitive layer 14, and a cover film 16 are laminated in this order.
  • the transfer film 100 shown in FIG. 1 has a cover film 16
  • the transfer film may have a form without the cover film 16.
  • the transfer film may further include an intermediate layer and/or a thermoplastic resin layer. Each member included in 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 finally removed by a peeling process.
  • the temporary support may have either a single layer structure or a multilayer structure.
  • the temporary support is preferably a film, more preferably a resin film.
  • As the temporary support it is also preferable to use a film that is flexible and does not undergo significant deformation, shrinkage, or elongation under pressure or under pressure and heat.
  • Examples of the above film include polyethylene terephthalate film (e.g., biaxially oriented polyethylene terephthalate film, etc.), polymethyl methacrylate film, cellulose triacetate film, polystyrene film, polyimide film, and polycarbonate film, with polyethylene terephthalate film being preferred.
  • the temporary support has no deformation such as wrinkles or scratches.
  • the temporary support preferably has high transparency in that pattern exposure can be performed 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 wavelengths include, for example, 87%, 92%, and 98%. In terms of pattern formation properties during pattern exposure through the temporary support and transparency of the temporary support, it is preferable that the haze of the temporary support is small.
  • 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 be as small as possible.
  • the number of fine particles, foreign matter, and defects with a diameter of 1 ⁇ m or more in the temporary support is preferably 50 pieces/10 mm 2 or less, more preferably 10 pieces/10 mm 2 or less, still more preferably 3 pieces/10 mm 2 or less, and 0 pieces/10 mm 2 or less. 10 mm 2 is particularly preferred.
  • the thickness of the temporary support is preferably 5 to 200 ⁇ m, more preferably 5 to 150 ⁇ m, even more preferably 5 to 50 ⁇ m, and particularly preferably 5 to 35 ⁇ m in terms of ease of handling and versatility.
  • the thickness of the temporary support can be calculated as the average value of five arbitrary points measured by cross-sectional observation using a SEM (scanning electron microscope).
  • the surface of the temporary support in contact with the composition layer may be surface-modified by UV irradiation, corona discharge, plasma, or the like.
  • the exposure amount of UV irradiation is preferably 10 to 2000 mJ/cm 2 , more preferably 50 to 1000 mJ/cm 2 .
  • Light sources for UV irradiation include low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, carbon arc lamps, metal halide lamps, xenon lamps, chemical lamps, electrodeless discharge lamps, and light-emitting diodes that emit light in the wavelength range of 150 to 450 nm. can be mentioned. Lamp output and illuminance can be adjusted as appropriate.
  • Examples of the temporary support include a biaxially stretched polyethylene terephthalate film with a thickness of 16 ⁇ m, a biaxially stretched polyethylene terephthalate film with a thickness of 12 ⁇ m, and a biaxially stretched polyethylene terephthalate film with a thickness of 9 ⁇ m.
  • the temporary support may be a recycled product. Examples of recycled products include those obtained by cleaning and chipping used films and the like, and making films from the obtained materials. Examples of commercially available recycled products include 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 handling properties.
  • 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.
  • Commercially available temporary supports include, for example, Lumirror 16FB40, Lumirror 16KS40, Lumirror #38-U48, Lumirror #75-U34, and Lumirror #25T60 (all manufactured by Toray Industries, Inc.); Cosmoshine A4100, Cosmoshine A4160, and Cosmoshine. Examples include Shine A4300, Cosmoshine A4360, and Cosmoshine A8300 (all manufactured by Toyobo Co., Ltd.).
  • the photosensitive layer contains resin X.
  • Resin X is a resin selected from the group consisting of polyimide, polybenzoxazole, and precursors thereof. In the photosensitive layer, resin X may be used alone or in combination of two or more. Further, resin X is a compound different from various components (for example, compound Y, etc.) described below.
  • the polyimide precursor is a resin that is converted into polyimide through heat treatment or chemical treatment.
  • the polybenzoxazole precursor is a resin that is converted into polybenzoxazole by heat treatment or chemical treatment.
  • Resin X may have a polymerizable group.
  • the polymerizable group include known polymerizable groups such as a radically polymerizable group, an epoxy group, an oxetanyl group, a methylol group, and an alkoxymethyl group.
  • the radically polymerizable group is preferably a group having an ethylenically unsaturated bond.
  • the group having an ethylenically unsaturated bond include a (meth)acrylamide group and a (meth)acryloyl group, with a (meth)acryloyl group being preferred.
  • the resin X has a polymerizable group that can be polymerized with a polymerizable group in the polymerizable compound described below.
  • Polyimide and polyimide precursor Polyimide is a resin having an imide structure.
  • the polyimide is preferably a resin having a cyclic imide structure, and may have a substituent.
  • a resin synthesized from a polyimide precursor having a repeating unit represented by formula (1) described below (for example, a resin obtained by a ring-closing reaction) is preferable. It is preferable that the polyimide precursor has a repeating unit represented by formula (1).
  • a 1 and A 2 each independently represent an oxygen atom or -NH-.
  • R 111 represents a divalent organic group.
  • R 113 and R 114 each independently represent a hydrogen atom or a monovalent organic group.
  • R 115 represents a tetravalent organic group.
  • a 1 and A 2 each independently represent an oxygen atom or -NH-. As A 1 and A 2 , oxygen atoms are preferable.
  • R 111 represents a divalent organic group.
  • the divalent organic group include an aliphatic group, an aromatic ring group, and a combination thereof.
  • the divalent organic group is preferably an aliphatic group having 2 to 20 carbon atoms, an aromatic ring group having 6 to 20 carbon atoms, or a combination thereof, and more preferably an aromatic ring group having 6 to 20 carbon atoms.
  • the aliphatic group may be linear, branched, or cyclic.
  • the aromatic ring group may be either monocyclic or polycyclic.
  • the aliphatic group and the aromatic ring group may have a heteroatom.
  • Heteroatoms may be included in the divalent organic group, for example, as groups such as -O-, -CO-, -S-, -SO 2 -, and -NHCO-.
  • R 111 a divalent organic group derived from diamine is also preferable.
  • diamine diamines used in the production of polyimide precursors are preferred, and aliphatic diamines or aromatic diamines are more preferred.
  • the above-mentioned diamines include a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, and a cyclic aliphatic group having 6 to 20 carbon atoms.
  • a diamine having an aromatic ring group or a combination thereof is preferable, and a diamine having an aromatic ring group having 6 to 20 carbon atoms (aromatic diamine) is more preferable.
  • the aromatic ring group include groups having the following structures.
  • A is a divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms which may have a fluorine atom, -O-, -CO-, -S-, -SO 2 -, -NHCO -, a group combining these, or a single bond.
  • A is preferably at least one selected from the group consisting of an alkylene group having 1 to 3 carbon atoms which may have a fluorine atom, -O-, -CO-, -S-, and -SO 2 -.
  • R 111 is also preferably *-Ar 0 -L 0 -Ar 0 -*.
  • Ar 0 represents an aromatic hydrocarbon group.
  • L 0 is an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may have a fluorine atom, -O-, -CO-, -S-, -SO 2 -, -NHCO-, or Represents a combined group or a single bond. * represents the bonding position.
  • Ar 0 may be the same or different.
  • the aromatic hydrocarbon group represented by Ar 0 preferably has 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and even more preferably 6 to 10 carbon atoms.
  • a phenyl group is preferable.
  • L 0 has the same meaning as A in AR-8 described above, and preferred embodiments are also the same.
  • diamine examples include 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, 1,6-diaminohexane; 1,2- or 1,3- Diaminocyclopentane, 1,2-, 1,3- or 1,4-diaminocyclohexane, 1,2-, 1,3- or 1,4-bis(aminomethyl)cyclohexane, bis-(4-aminocyclohexyl) Methane, bis-(3-aminocyclohexyl)methane, 4,4'-diamino-3,3'-dimethylcyclohexylmethane or isophoronediamine; meta- or para-phenylenediamine, diaminotoluene, 4,4'- or 3,3' -diaminobiphenyl, 4,4'-diaminodiphenyl ether, 3,
  • diamines include diamines having two or more alkylene glycol units in the main chain, and examples of diamines having two or more alkylene glycol units in the main chain include one or both of an ethylene glycol chain and a propylene glycol chain. Diamines containing two or more diamines in one molecule are preferred. Also preferred is a diamine that does not contain an aromatic ring. Examples of the above diamine include Jeffamine (registered trademark) series (KH-511, ED-600, ED-900, ED-2003, EDR-148, EDR-176, D-200, D-400, D-2000).
  • R 113 and R 114 each independently represent a hydrogen atom or a monovalent organic group. At least one of R 113 and R 114 preferably represents a group having a polymerizable group, and more preferably both R 113 and R 114 represent a group having a polymerizable group. Examples of the polymerizable group include the groups exemplified as the polymerizable group that resin X may have.
  • the monovalent organic group may be a monovalent organic group X described below.
  • R 113 and R 114 a group having an ethylenically unsaturated group is preferable, and a vinyl group, an allyl group, a (meth)acryloyl group, or a group represented by formula (III) is more preferable.
  • R 200 represents a hydrogen atom or a methyl group.
  • R 201 represents an alkylene group having 2 to 12 carbon atoms, -CH 2 CH(OH)CH 2 -, or a (poly)oxyalkylene group having 4 to 30 carbon atoms. * represents the bonding position.
  • R 200 represents a hydrogen atom or a methyl group. As R 200 , a methyl group is preferred.
  • R 201 represents an alkylene group having 2 to 12 carbon atoms, -CH 2 CH(OH)CH 2 -, or a (poly)oxyalkylene group having 4 to 30 carbon atoms.
  • the alkylene group constituting the above (poly)oxyalkylene group preferably has 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and even more preferably 1 to 3 carbon atoms.
  • the repeating number of oxyalkylene constituting the above (poly)oxyalkylene group is preferably 1 to 12, more preferably 1 to 6, and even more preferably 1 to 3.
  • R 201 examples include ethylene group, propylene group, trimethylene group, tetramethylene group, 1,2-butanediyl group, 1,3-butanediyl group, pentamethylene group, hexamethylene group, octamethylene group, dodecamethylene group, and -CH 2 CH(OH)CH 2 -, with ethylene group, propylene group, trimethylene group, or -CH 2 CH(OH)CH 2 - being preferred, and ethylene group being more preferred.
  • the monovalent organic group represented by R 113 or R 114 includes an aliphatic group, an aromatic ring group, and an arylalkyl group having 1 to 3 acid groups. Examples include an aromatic ring group having 6 to 20 carbon atoms and having an acid group, and an arylalkyl group having 7 to 25 carbon atoms having an acid group. More specifically, a phenyl group having an acid group and a benzyl group having an acid group can be mentioned.
  • the acid group is preferably a hydroxyl group or a carboxy group.
  • R 113 and R 114 a hydrogen atom, 2-hydroxybenzyl, 3-hydroxybenzyl, or 4-hydroxybenzyl is also preferred.
  • R 115 represents a tetravalent organic group.
  • the tetravalent organic group is preferably a tetravalent organic group having an aromatic ring, and more preferably a group represented by formula (5) or a group represented by formula (6).
  • R 112 is a divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms which may have a fluorine atom, -O-, -CO-, -S-, -SO 2 - , -NHCO-, a group combining these, or a single bond. * represents the bonding position. In formula (6), * represents the bonding position.
  • R 112 has the same meaning as A in AR-8 described above, and preferred embodiments are also the same.
  • tetravalent organic group examples include, for example, a tetracarboxylic acid residue remaining after removing an acid dianhydride group from a tetracarboxylic dianhydride.
  • the tetracarboxylic dianhydride is preferably a compound represented by formula (7).
  • R 115 represents a tetravalent organic group.
  • R 115 in formula (7) has the same meaning as R 115 in formula (1), and preferred embodiments are also the same.
  • tetracarboxylic dianhydride examples include pyromellitic acid, pyromellitic dianhydride (PMDA), 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4, 4'-diphenylsulfidetetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 3 , 3',4,4'-diphenylmethanetetracarboxylic dianhydride, 2,2',3,3'-diphenylmethanetetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride Anhydride, 2,3,3',4'-benzophenonetetracarboxylic dianhydride, 4,4'-benz
  • Examples of the tetracarboxylic dianhydride include compounds represented by any of formulas (DAA-1) to (DAA-5).
  • the monovalent organic group X is preferably an alkyl group that may have a substituent or an aromatic ring group that may have a substituent, and an alkyl group that may have an aromatic ring group. is more preferable.
  • the alkyl group may be linear, branched, or cyclic.
  • the cyclic ring may be either monocyclic or polycyclic.
  • the linear or branched alkyl group preferably has 1 to 30 carbon atoms.
  • the number of carbon atoms in the cyclic alkyl group (cycloalkyl group) is preferably 3 to 30.
  • alkyl group examples include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group, tetradecyl group, octadecyl group, isopropyl group, Linear or branched alkyl groups such as isobutyl group, sec-butyl group, t-butyl group, 1-ethylpentyl group, and 2-ethylhexyl group; cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, Monocyclic cycloalkyl groups such as cycloheptyl group and cyclooctyl group; adamantyl group, norbornyl group, bornyl group, camphenyl group, decahydronaph
  • the aromatic ring group may be either an aromatic hydrocarbon ring group or an aromatic heterocyclic group. Further, the aromatic ring group may be either monocyclic or polycyclic. Rings constituting aromatic ring groups include benzene ring, naphthalene ring, biphenyl ring, fluorene ring, pentalene ring, indene ring, azulene ring, heptalene ring, indacene ring, perylene ring, pentacene ring, acenaphthene ring, phenanthrene ring, and anthracene ring.
  • aromatic hydrocarbon rings such as ring, naphthacene ring, chrysene ring, and triphenylene ring; fluorene ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, indolizine ring, indole ring, benzofuran ring, benzothiophene ring, isobenzofuran ring, quinolidine ring, quinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinoxazoline ring, isoquinoline ring, carbazole ring, phenanthridine ring, acridine aromatic heterocyclic groups such as ring, phenanthroline ring, thianthrene ring, chromen
  • the polyimide precursor has a fluorine atom.
  • the content of fluorine atoms in the polyimide precursor is preferably 10% by mass or more, more preferably 20% by mass or more, based on the total mass of the polyimide precursor.
  • the upper limit is preferably 50% by mass or less.
  • the polyimide precursor may be obtained by copolymerizing the repeating unit represented by formula (1) with an aliphatic group having a siloxane structure, since it can improve the adhesion to the base material.
  • the aliphatic group having a siloxane structure include bis(3-aminopropyl)tetramethyldisiloxane and bis(para-aminophenyl)octamethylpentasiloxane.
  • the repeating unit represented by formula (1) is preferably a repeating unit represented by formula (1-A) or a repeating unit represented by formula (1-B).
  • a 11 and A 12 represent an oxygen atom or -NH-.
  • R 111 and R 112 each independently represent a divalent organic group.
  • R 113 and R 114 each independently represent a hydrogen atom or a monovalent organic group.
  • a 11 , A 12 , R 111 , R 113 , and R 114 have the same meaning as A 1 , A 2 , R 111 , R 113 , and R 114 , respectively, in formula (1).
  • the preferred embodiments are also the same.
  • R 112 has the same meaning as R 112 in formula (5), and preferred embodiments are also the same.
  • the bonding positions of the carbonyl group to the benzene ring are preferably 4, 5, 3', and 4' in formula (1-A).
  • the bonding positions of the carbonyl group to the benzene ring are preferably 1, 2, 4, and 5 in formula (1-B).
  • the polyimide precursor may contain other repeating units in addition to the repeating unit represented by formula (1).
  • the content of the repeating unit represented by formula (1) is preferably 50 mol% or more, more preferably 70 mol% or more, and even more preferably 90 mol% or more, based on all the repeating units of the polyimide precursor.
  • the upper limit is preferably 100 mol% or less.
  • the weight average molecular weight (Mw) of the polyimide precursor is preferably 2,000 to 500,000, more preferably 5,000 to 100,000, and even more preferably 10,000 to 50,000.
  • the number average molecular weight (Mn) of the polyimide precursor is preferably 800 to 250,000, more preferably 2,000 to 50,000, and even more preferably 4,000 to 25,000.
  • the degree of dispersion (Mw/Mn) of the polyimide precursor is preferably 1.5 to 3.5, more preferably 2.0 to 3.0.
  • Polybenzoxazole and polybenzoxazole precursor Polybenzoxazole is a resin having a benzoxazole ring.
  • the polybenzoxazole is not particularly limited as long as it is a resin having a benzoxazole ring, and may have a substituent.
  • a resin synthesized from a polybenzoxazole precursor having a repeating unit represented by formula (2) described below (for example, a resin obtained by a ring-closing reaction, etc.) is preferable. It is preferable that the polybenzoxazole precursor has a repeating unit represented by formula (2).
  • R 121 represents a divalent organic group.
  • R 122 represents a tetravalent organic group.
  • R 123 and R 124 each independently represent a hydrogen atom or a monovalent organic group.
  • R 121 represents a divalent organic group.
  • the divalent organic group include a divalent organic group represented by R 111 .
  • R 122 represents a tetravalent organic group.
  • examples of the tetravalent organic group include a tetravalent organic group represented by R 115 .
  • R 123 and R 124 each independently represent a hydrogen atom or a monovalent organic group.
  • R 123 and R 124 have the same meaning as R 113 and R 114 , and preferred embodiments are also the same.
  • the polybenzoxazole precursor may contain other repeating units in addition to the repeating unit represented by formula (2).
  • Examples of other repeating units include repeating units having a siloxane structure. Examples of the above-mentioned other repeating units include repeating units described in paragraphs 0150 to 0154 of JP-A No. 2020-154205.
  • the weight average molecular weight (Mw) of the polybenzoxazole precursor is preferably 2,000 to 500,000, more preferably 5,000 to 100,000, and even more preferably 10,000 to 50,000.
  • the number average molecular weight (Mn) of the polybenzoxazole precursor is preferably 800 to 250,000, more preferably 2,000 to 50,000, and even more preferably 4,000 to 25,000.
  • the degree of dispersion (Mw/Mn) of the polybenzoxazole precursor is preferably 1.5 to 3.5, more preferably 2.0 to 3.0.
  • Resin X may be used alone or in combination of two or more.
  • the content of resin X is preferably 5.0% by mass or more, more preferably 10.0% by mass or more, based on the total mass of the photosensitive layer.
  • the upper limit is preferably 80.0% by mass or less, more preferably 70.0% by mass or less, even more preferably 65.0% by mass or less, based on the total mass of the photosensitive layer.
  • the upper limit of the content of resin X relative to the total mass of the photosensitive layer is preferably 50.0% by mass or less, more preferably 30.0% by mass or less.
  • the photosensitive layer contains a photoinitiator.
  • the photopolymerization initiator include radical photopolymerization initiators, cationic photopolymerization initiators, and anionic photopolymerization initiators, with radical photopolymerization initiators being preferred.
  • photopolymerization initiators examples include oxime ester compounds (photopolymerization initiators having an oxime ester structure), aminoacetophenone compounds (photopolymerization initiators having an aminoacetophenone structure), and hydroxyacetophenone compounds (photopolymerization initiators having a hydroxyacetophenone structure).
  • (initiator) an acylphosphine oxide compound (a photopolymerization initiator having an acylphosphine oxide structure), and a bistriphenylimidazole compound (a photopolymerization initiator 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)] (trade name: IRGACURE OXE-01, manufactured by BASF), ethanone ,1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-,1-(0-acetyloxime) (trade 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), 1-[4-[4-(2-benzofuranylcarbonyl)phenyl]thio]phen
  • aminoacetophenone compounds include 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone (trade name: Omnirad 379EG, IGM Resins B.V.), 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one (product name: Omnirad 907, IGM Resins B.V.), APi -307 (1-(biphenyl-4-yl)-2-methyl-2-morpholinopropan-1-one, manufactured by Shenzhen UV-ChemTech Ltd.).
  • photopolymerization initiator for example, 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-propane-1 -one (product name: Omnirad 1173), 1-hydroxy-cyclohexyl-phenyl-ketone (product name: Omnirad 184), 2,2-dimethoxy-1,2-diphenylethan-1-one (product 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).
  • photopolymerization initiator examples include the photopolymerization initiators described in paragraphs 0031 to 0042 of JP-A No. 2011-095716 and paragraphs 0064 to 0081 of JP-A No. 2015-014783.
  • the photopolymerization initiators 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 photosensitive layer.
  • the lower limit is preferably 0.1% by mass or more.
  • the photosensitive layer contains compound Y.
  • Compound Y is a compound different from the photopolymerization initiator described above, and also different from the thermal base generator described later.
  • Compound Y is a compound having a molecular weight of 200 to 1000 and a boiling point of 230 to 500°C.
  • the above molecular weight of compound Y is intended to be a weight average molecular weight.
  • the boiling point of the compound Y is intended to be a value determined by the following measurement method.
  • the boiling point is the gas temperature at the point when the evaporated gas begins to condense (measured from 23 ° C to 300 ° C, heating rate 1 ° C / min). .
  • 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.
  • a similar distillation is performed in the order of atmospheric pressure 100 mmHg, 50 mmHg, and 5 mmHg (from 23°C to 300°C, if the distillation does not start at 300°C, go to the next atmospheric pressure), and the figure is calculated from the temperature and pressure at which the evaporated gas begins to condense.
  • the boiling point under normal pressure determined using the nomograph shown in 2 is the boiling point (calculated value). 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. Note that the method of using the nomograph is as known. Specifically, connect the boiling point of reduced pressure on line A and the degree of reduced pressure on line C with a straight line (step 1), read the value at the intersection of the straight line drawn in step 1 and line B (step 2), and always check this. It is regarded as the boiling point at pressure.
  • the polymerizable compound has a methacryloyl group. Since the polymerizable compound corresponding to compound Y is a compound having a methacryloyl group, depolymerization of the polymer derived from the above polymerizable compound is likely to occur in the heat treatment after development when forming the resin pattern, and the resin pattern The amount remaining in the system tends to be small. On the other hand, when the polymerizable compound is a compound having an acryloyl group, depolymerization of the polymer derived from the polymerizable compound is unlikely to occur in the heat treatment after development when forming a resin pattern, and this does not meet the purpose of the present invention. It is difficult to obtain the desired effect.
  • the lower limit of the molecular weight of compound Y is preferably 250 or more, more preferably 300 or more. Moreover, as an upper limit, 800 or less is preferable, and 600 or less is more preferable.
  • the lower limit of the boiling point of compound Y is preferably 250°C or higher, more preferably 280°C or higher, even more preferably 300°C or higher, and particularly preferably 350°C or higher. Moreover, as an upper limit, 480 degrees C or less is preferable, and 450 degrees C or less is more preferable.
  • the upper limit of 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. Further, the lower limit is preferably 0.01 mPa ⁇ s or more, more preferably 0.05 mPa ⁇ s or more, and even more preferably 0.1 mPa ⁇ s or more.
  • the viscosity can be measured using a B-type viscometer.
  • the specific type of compound Y is not particularly limited, but it is preferably one or more selected from a polymerizable compound having a methacryloyl group and a solvent, since the effects of the present invention are more excellent. That is, the specific type of compound Y is a polymerizable compound having a molecular weight of 200 to 1000, a boiling point of 230 to 500°C, and a methacryloyl group (hereinafter also referred to as "polymerizable compound YM"). , and a solvent having a molecular weight of 200 to 1000 and a boiling point of 230 to 500°C (hereinafter also referred to as "solvent YN").
  • solvent YN a solvent having a molecular weight of 200 to 1000 and a boiling point of 230 to 500°C
  • the polymerizable compound YM has a molecular weight of 200 to 1000, a boiling point of 230 to 500°C, and has one or more methacryloyl groups in the molecule.
  • the polymerizable compound YM is preferably a photopolymerizable compound.
  • the polymerizable compound YM may have a polymerizable group other than the methacryloyl group.
  • Other polymerizable groups include acryloyl groups, vinyl groups, and styryl groups.
  • the polymerizable compound YM is preferably a polymerizable compound having 1 to 5 polymerizable groups in one molecule, and particularly a polymerizable compound having two polymerizable groups (hereinafter referred to as a "bifunctional compound"). (Also referred to as "polymerizable compound.”) is more preferable, and dimethacrylate compound is even more preferable.
  • Examples of the monofunctional polymerizable compound YM include phenoxy methacrylate, dicyclopentanyl methacrylate, isobornyl methacrylate, phenoxyethyl methacrylate, and 2-hydroxyethyl methacrylate.
  • Commercial products of the monofunctional polymerizable compound YM include, for example, EBECRYLIBOMA (manufactured by Daicel Allnex Corporation) and Viscoat #192 (manufactured by Osaka Organic Chemical Industry Co., Ltd.).
  • bifunctional polymerizable compound YM examples include diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tricyclodecane dimethanol dimethacrylate, tricyclodecane dimethanol dimethacrylate, 1,4-butanediol dimethacrylate, 1, Examples include 9-nonanediol dimethacrylate and 1,6-hexanediol dimethacrylate.
  • bifunctional polymerizable compounds YM 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.), and tricyclodecane dimethacrylate (3G, manufactured by Shin Nakamura Chemical Co., Ltd.).
  • Examples include methanol dimethacrylate (DCP, manufactured by Shin-Nakamura Chemical Industries, Ltd.).
  • trifunctional polymerizable compound YM examples include trimethylpropane trimethacrylate (molecular weight: 338, boiling point: 347°C).
  • examples of commercially available trifunctional polymerizable compounds YM include EBECRYLTMPTMA (manufactured by Daicel Allnex Corporation).
  • the polymerizable compound YM preferably has a structure containing -O-(AL YM1 -O)n-, for example, from the viewpoint of better step followability.
  • AL YM1 represents a linear, branched, or cyclic alkylene group.
  • n represents an integer from 1 to 10.
  • the alkylene group represented by AL YM1 preferably has 1 to 20 carbon atoms, more preferably 1 to 14 carbon atoms, and still more preferably 1 to 12 carbon atoms.
  • n is preferably 1 to 8, more preferably 1 to 6.
  • the polymerizable compound YM in particular, a homopolymer derived from the polymerizable compound YM is used, since depolymerization of the polymer derived from the polymerizable compound YM is likely to occur during heat treatment after development when forming a resin pattern. It is preferable that the decomposition temperature is 300°C or less.
  • the decomposition temperature of the homopolymer derived from the polymerizable compound YM is below X°C
  • Ratio of the weight average molecular weight of the homopolymer derived from the polymerizable compound YM before heat treatment to the weight average molecular weight of the same polymer after heat treatment weight average molecular weight of the homopolymer derived from the polymerizable compound YM after heat treatment/ It means that the weight average molecular weight of the homopolymer derived from the polymerizable compound YM (before heat treatment) is 1/3 or less.
  • the decomposition temperature of the homopolymer derived from the polymerizable compound YM is 300° C. or lower, it means that the ratio before and after the heat treatment at 300° C. for 3 hours is 1/3 or lower.
  • the weight average molecular weight (weight average molecular weight before heat treatment) of the homopolymer derived from the polymerizable compound YM used in the measurement is preferably 10,000 or more, and preferably 10,000 to 100,000.
  • the weight average molecular weight can be measured using GPC (device: manufactured by Tosoh Corporation, Tosoh High Speed GPC device HLC-8420GPC (trade name)).
  • the temperature at which the polymer derived from the polymerizable compound YM decomposes is more preferably 230°C or lower. Further, the lower limit of the decomposition temperature is preferably 50°C or higher, more preferably 100°C or higher.
  • Solvent YM has a molecular weight of 200 to 1000 and a boiling point of 230 to 500°C.
  • the solvent YM include benzyl benzoate, triacetin glycerol triacetate, 1,6-hexanediol diacetate, diethylene glycol monobutyl ether acetate, hexaethylene glycol monomethyl ether, pentaethylene glycol monomethyl ether, tetraethylene glycol monomethyl ether, and heptaethylene glycol.
  • Examples include monomethyl ether, octaethylene glycol monomethyl ether, nonaethylene glycol monomethyl ether, tetraethylene glycol dimethyl ether, pentaethylene glycol dimethyl ether, hexaethylene glycol dimethyl ether, heptaethylene glycol dimethyl ether, octaethylene glycol dimethyl ether, and nonaethylene glycol dimethyl ether.
  • Suitable examples of the structure of the solvent YM include polyethylene glycol monoalkyl ether and polyethylene glycol dialkyl ether, which have a molecular weight of 200 to 1000 and a boiling point of 230 to 500°C.
  • Compound Y may be used alone or in combination of two or more.
  • the compound Y preferably contains one or more selected from the group consisting of a compound Y with a boiling point of 230°C or more and less than 350°C and a compound Y with a boiling point of 350°C or more and 500°C or less. Further, it is also preferable that the compound Y contains both a polymerizable compound YM and a solvent YN, such as a polymerizable compound YM with a boiling point of 230°C or more and less than 350°C, and a solvent YN with a boiling point of 350°C or more and 500°C or less. It is more preferable to include both.
  • 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, and even more preferably 5.0% by mass or more, based on the total mass of the photosensitive layer.
  • the upper limit is preferably 60.0% by mass or less, more preferably 50.0% by mass or less, even more preferably 35.0% by mass or less, and particularly preferably 25.0% by mass or less.
  • the content of the polymerizable compound YM which is one type of compound Y, is preferably 1.0% by mass or more, more preferably 3.0% by mass or more, and 5.0% by mass based on the total mass of the photosensitive layer. % or more is more preferable.
  • the upper limit is preferably 60.0% by mass or less, more preferably 50.0% by mass or less, even more preferably 35.0% by mass or less, and particularly preferably 25.0% by mass or less.
  • the content of the solvent YN which is one type of compound Y, is preferably 1.0% by mass or more, more preferably 3.0% by mass or more, and 5.0% by mass or more based on the total mass of the photosensitive layer. is even more preferable.
  • the upper limit is preferably 60.0% by mass or less, more preferably 50.0% by mass or less, even more preferably 35.0% by mass or less, and particularly preferably 25.0% by mass or less.
  • the mass ratio (specific mass ratio) of the content of compound Y to the content of resin X is 0.40 to 1.50.
  • the lower limit of the specific mass ratio is preferably 0.50 or more, more preferably 0.51 or more, and even more preferably 0.52 or more.
  • the upper limit of the specific mass ratio is preferably 1.20 or less, more preferably 1.00 or less.
  • the photosensitive layer preferably contains a filler, since the effects of the present invention are more excellent.
  • the content of the filler is preferably 20.0% by mass or more, more preferably 30.0% by mass or more, and 40.0% by mass or more based on the total mass of the photosensitive layer. is even more preferable.
  • the upper limit is preferably 90.0% by mass or less, more preferably 80.0% by mass or less.
  • the average particle diameter of the filler is preferably 300 nm or less, more preferably 200 nm or less, and even more preferably 100 nm or less.
  • the lower limit is preferably more than 0 nm, more preferably 5 nm or more, and even more preferably 10 nm or more.
  • the average particle diameter of the filler is preferably 5 to 100 nm.
  • the average particle diameter of the filler is calculated by the following particle diameter measurement method. Particle size measurement method: A rectangular area of 3 ⁇ m x 10 ⁇ m in the cross section along the normal direction of the surface of the photosensitive layer is observed with a scanning electron microscope, and the major axis of all fillers observed in the above area is measured. This operation is performed at five different locations on the photosensitive layer, and the average value of the major diameters of all the fillers measured in each operation is taken as the average particle diameter of the filler.
  • the long axis refers to the length of the longest line segment among the line segments connecting any two points on the outline of the filler in the observed image. Further, when fillers are aggregated to form an aggregate in the observed image, the major axis of each filler forming the aggregate is measured.
  • fillers include organic fillers and inorganic fillers, with inorganic fillers being preferred.
  • examples of fillers include silicon dioxide (silica); silicates such as kaolinite, kaolin clay, calcined clay, talc, and glass fillers such as thian-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 silicate, and more preferably contains silicon dioxide (silica
  • the shape of the filler may be either spherical or non-spherical (for example, crushed or fibrous), and spherical is preferred.
  • the filler may be surface-treated. Examples of the surface treatment include treatment to introduce a functional group and treatment using a known surface modifier. Examples of the functional group include a polymerizable group (for example, a polymerizable group included in a polymerizable compound described below) and a hydrophobic group. Examples of the surface modifier include known surface modifiers such as silane coupling agents, titanate coupling agents, and silazane compounds.
  • fillers examples include Seahoster KE-S30 (manufactured by Nippon Shokubai Co., Ltd., silicon dioxide, solid content concentration 100% by mass), NHM-3N (manufactured by Tokuyama Corporation, silicon dioxide, solid content concentration 100% by mass), YA050C-MJE (manufactured by Tokuyama Corporation, silicon dioxide, solid content concentration 100% by mass), Admatex, silicon dioxide, solid content concentration 50% by mass MEK slurry), SFP-20M (Denka, silicon dioxide), PMA-ST (Nissan Chemical, silicon dioxide), MEK-ST-L (Nissan MEK-AC-5140Z (manufactured by Nissan Chemical Co., Ltd., silicon dioxide), MEK-EC-2430Z (manufactured by Nissan Chemical Co., Ltd., solid content concentration 30% by mass), barium sulfate (manufactured by Nippon Solvay Co., Ltd., Solid content concentration 100% by mass), NHM-5N (manufactured by Tokuyama
  • the refractive index of the filler is preferably 0.5 to 3.0, more preferably 1.2 to 1.8.
  • the refractive index can be measured by the method described above.
  • the fillers may be used alone or in combination of two or more.
  • the photosensitive layer may contain a thermal base generator.
  • resin X contains a polyimide precursor and a polybenzoxazole precursor
  • the photosensitive layer contains a thermal base generator, the ring-closing reaction of the polyimide precursor and polybenzoxazole precursor is promoted, and polyimide and polybenzoxazole are likely to be produced.
  • the thermal base generator is preferably an acidic compound or an onium salt compound (a compound consisting of a cation and an anion) that generates a base when heated.
  • onium salt compounds include ammonium salt compounds (compounds consisting of an ammonium cation and anion), iminium salt compounds (compounds consisting of an iminium cation and anion), and sulfonium salt compounds (compounds consisting of a sulfonium cation and anion).
  • an iodonium salt compound (a compound consisting of an iodonium cation and an anion), or a phosphonium salt compound (a compound consisting of a phosphonium cation and an anion) are preferable, and iminium salt compounds are more preferable.
  • the anion constituting the onium salt compound is preferably a carboxylic acid anion, a phenol anion, a phosphate anion, or a sulfate anion, and more preferably a carboxylic acid anion. It is preferable that the anion constituting the ammonium salt compound further has an aromatic ring. Examples of the aromatic ring include aromatic rings constituting an aromatic ring group represented by A a1 in formula (A1) described below.
  • the temperature at which the acidic compound and the onium salt compound generate a base is preferably the heating temperature in step X4 in the method for producing a laminate described later.
  • the temperature at which the thermal base generator generates a base can be determined, for example, by heating the compound to be measured in a pressure-resistant capsule up to 250°C at 5°C/min using differential scanning calorimetry, and then reading the peak temperature of the lowest exothermic peak. , the peak temperature can be taken as the base generation temperature.
  • the base generated by the thermal base generator is preferably a secondary amine or a tertiary amine, more preferably a tertiary amine.
  • the base may be linear, branched, or cyclic, with cyclic being preferred.
  • a a1 represents a p-valent organic group.
  • R a1 represents a monovalent organic group.
  • L a1 represents a (m+1)-valent linking group.
  • m represents an integer of 1 or more.
  • p represents an integer of 1 or more.
  • a a1 represents a p-valent organic group.
  • the organic group include an aliphatic hydrocarbon group and an aromatic ring group, with the aromatic ring group being preferred.
  • Examples of the monovalent aliphatic hydrocarbon group include an alkyl group and an alkenyl group.
  • the alkyl group may be linear, branched, or cyclic. The number of carbon atoms in the alkyl group is preferably 1 to 30, more preferably 1 to 20, even more preferably 1 to 10.
  • alkyl group examples include methyl group, ethyl group, tert-butyl group, dodecyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, and adamantyl group.
  • the alkenyl group may be linear, branched, or cyclic.
  • the alkenyl group preferably has 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, and still more preferably 2 to 10 carbon atoms.
  • Examples of the alkenyl group include a vinyl group, an allyl group, and a methallyl group.
  • the p-valent aliphatic hydrocarbon group (when p is an integer of 2 or more) is, for example, formed by removing (p-1) hydrogen atoms from the above monovalent aliphatic hydrocarbon group. Examples include groups.
  • the aliphatic hydrocarbon group may further have a substituent.
  • the aromatic ring group may be monocyclic or polycyclic.
  • the aromatic ring group may be either an aromatic hydrocarbon ring group or an aromatic heterocyclic group.
  • aromatic ring groups include benzene ring group, naphthalene ring group, pentalene ring group, indene ring group, azulene ring group, heptalene ring group, indacene ring group, perylene ring group, pentacene ring group, acenaphthene ring group, and phenanthrene ring group.
  • R a1 represents a monovalent organic group.
  • the monovalent organic group include a monovalent aliphatic hydrocarbon group and a monovalent aromatic ring group represented by A a1 .
  • the monovalent organic group may further have a substituent. As the above-mentioned substituent, a carboxy group is preferable.
  • L a1 represents a (m+1)-valent linking group.
  • (m+1)-valent linking groups include ether group (-O-), carbonyl group (-CO-), ester group (-COO-), thioether group (-S-), -SO 2 -, - NR N - (R N represents a hydrogen atom or a substituent), a divalent linking group such as an alkylene group (preferably having 1 to 10 carbon atoms), and an alkenylene group (preferably having 2 to 10 carbon atoms);
  • a trivalent linking group having a group represented by "-N ⁇ " and a trivalent linking group having a group represented by "-CR ⁇ " (R represents a hydrogen atom or a substituent); Examples include a tetravalent linking group having a group represented by ">C ⁇ "; a k-valent linking group having a ring group such as an aromatic ring group and an alicyclic group; and a group combining these.
  • m represents an integer of 1 or more. As m, 1 or 2 is preferable, and 1 is more preferable.
  • p represents an integer of 1 or more. As p, 1 or 2 is preferable, and 1 is more preferable.
  • the ammonium cation constituting the ammonium salt compound is preferably a cation represented by formula (101).
  • a cation represented by formula (102) is preferable.
  • R 1 to R 4 each independently represent a hydrogen atom or an aliphatic group. At least two of R 1 to R 4 may be bonded to each other to form a ring.
  • R 5 and R 6 each independently represent a hydrogen atom or an aliphatic group.
  • R 7 represents an aliphatic group. At least two of R 5 to R 7 may be bonded to each other to form a ring.
  • the aliphatic groups represented by R 1 to R 4 and R 5 to R 7 may be linear, branched, or cyclic.
  • the number of carbon atoms in the aliphatic group is preferably 1 to 10.
  • the aliphatic group is preferably an alkyl group or an alkenyl group, and more preferably an alkyl group.
  • the aliphatic group may have a substituent. Examples of the substituent include an arylcarbonyl group.
  • the methylene group (-CH 2 -) in the group is a hetero atom (for example, an oxygen atom, a sulfur atom, and -NR-, etc., where R represents a hydrogen atom or a substituent).
  • At least one of R 5 to R 7 is preferably an aliphatic group having -NR-, more preferably an alkyl group having -NR-. At least two of R 5 to R 7 may be bonded to each other to form a ring, and preferably R 5 and R 7 and R 6 and R 7 are bonded to each other to form a ring.
  • the ring formed above is preferably a polycyclic heterocycle, more preferably a bicyclic heterocycle.
  • thermal base generator examples include the thermal base generator described in International Publication No. 2018/038002.
  • Thermal base generators may be used alone or in combination of two or more.
  • the content of the thermal base generator 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 photosensitive layer.
  • the lower limit is preferably more than 0% by mass, more preferably 0.1% by mass or more.
  • the mass ratio of the content of the thermal base generator to the content of the resin X is preferably 1.00 or less, more preferably 0.10 or less, and 0. 05 or less is more preferable.
  • the lower limit is preferably greater than 0.
  • the photosensitive layer may contain a surfactant.
  • the surfactant include the surfactants described in paragraph 0017 of Japanese Patent No. 04502784 and paragraphs 0060 to 0071 of JP2009-237362.
  • the surfactant examples include hydrocarbon surfactants, fluorine surfactants, and silicone surfactants. In terms of improving environmental suitability, the surfactant preferably does not contain fluorine atoms.
  • hydrocarbon surfactants or silicone surfactants are preferred.
  • Commercially available fluorosurfactants include Megafac F-171, F-172, F-173, F-176, F-177, F-141, F-142, F-143, F-144.
  • fluorine-based surfactants include acrylic compounds that have a molecular structure that includes a functional group having a fluorine atom, and when heat is applied, the functional group having a fluorine atom is cut off and the fluorine atom is volatilized.
  • fluorine-based surfactants include the Megafac DS series (manufactured by DIC, Chemical Daily (February 22, 2016), Nikkei Sangyo Shimbun (February 23, 2016), and Megafac DS- 21 etc.).
  • the fluorine-based surfactant 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 includes a repeating unit derived from a (meth)acrylate compound having a fluorine atom and a (meth) having two or more (preferably five or more) alkyleneoxy groups (preferably ethyleneoxy or propyleneoxy groups). )
  • examples of the fluorine-containing surfactant include fluorine-containing polymers having a group having an ethylenically unsaturated group in a side chain.
  • Specific examples include Megafac RS-101, RS-102, RS-718K, and RS-72-K (all manufactured by DIC).
  • fluorine-based surfactants compounds having a linear perfluoroalkyl group having 7 or more carbon atoms, such as perfluorooctanoic acid (PFOA) and perfluorooctane sulfonic acid (PFOS), are preferred from the viewpoint of improving environmental suitability.
  • PFOA perfluorooctanoic acid
  • PFOS perfluorooctane sulfonic acid
  • Surfactants derived from alternative materials are preferred.
  • hydrocarbon surfactants include glycerol, trimethylolpropane, trimethylolethane, and their ethoxylates and propoxylates (e.g., glycerol propoxylate and glycerol ethoxylate), polyoxyethylene lauryl ether, polyoxyethylene lauryl ether, Examples include oxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, and sorbitan fatty acid ester.
  • hydrocarbon surfactant examples include Pluronic (registered trademark) L10, L31, L61, L62, 10R5, 17R2, and 25R2, Tetronic 304, 701, 704, 901, 904, and 150R1, and HYDROPALAT WE.
  • silicone surfactants include linear polymers consisting of siloxane bonds, modified siloxane polymers with organic groups introduced into the side chains and/or terminals, repeating units having hydrophilic groups in the side chains, and Examples include polymers having repeating units having groups having siloxane bonds in side chains.
  • the silicone surfactant is preferably a polymer having a repeating unit having a hydrophilic group in its side chain and a repeating unit having a group having a siloxane bond in its side chain.
  • the above polymer may be either a random copolymer or a block copolymer.
  • the repeating unit having a group having a siloxane bond in its 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.
  • R 1 represents a hydrogen atom or a methyl group.
  • L 1 represents a single bond or a divalent organic group. When a plurality of R's exist, 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 from 5 to 50.
  • repeating unit having a hydrophilic group in the side chain a repeating unit represented by formula (SX3) is preferable.
  • R 4 and R 5 each independently represent a hydrogen atom or a methyl group.
  • n represents an integer from 1 to 4.
  • m represents an integer from 1 to 100.
  • silicone surfactants include EXP. S-309-2, EXP. S-315, EXP. S-503-2, and EXP. S-505-2 (manufactured by DIC); DOWSIL 8032 ADDITIVE, Tore Silicone DC3PA, Tore Silicone SH7PA, Tore Silicone DC11PA, Tore Silicone SH21PA, Tore Silicone SH28PA, Tore Silicone SH29PA, Tore Silicone SH30PA , and Toray Silicone SH8400 (manufactured by Toray Dow Corning); X-22-4952, X-22-4272, KF-643, X-22-6191, KP-109, KP-112, KP-120, KP-121, KP-124, KP-125, KP-301, KP-306, KP-310, KP-322, KP-323, KP-327, KP- 341, KP-368, KP-369, KP-611, KP-620, KP-621, KP
  • examples of the surfactant include nonionic surfactants.
  • the surfactants may be used alone or in combination of two or more.
  • the content of the surfactant is preferably 0.01 to 3.0% by mass, more preferably 0.01 to 1.0% by mass, and 0.05 to 0.8% by mass based on the total mass of the photosensitive layer. Mass % is more preferred.
  • the photosensitive layer may contain other additives in addition to the above various components.
  • other additives include heterocyclic compounds (e.g., triazole, tetrazole, benzotriazole, and derivatives thereof), aliphatic thiol compounds, thermally crosslinkable compounds, polymerization inhibitors, hydrogen-donating compounds, solvents, and impurities. , plasticizers, sensitizers, and alkoxysilane compounds.
  • the compound Y may contain a polymerizable compound or a solvent that does not correspond to the compound Y.
  • heterocyclic compound examples include various components described in International Publication No. 2022/039027.
  • plasticizer, sensitizer, and alkoxysilane compound examples include paragraphs 0097 to 0119 of International Publication No. 2018/179640.
  • the photosensitive layer may contain impurities.
  • impurities include sodium, potassium, magnesium, calcium, iron, manganese, copper, aluminum, titanium, chromium, cobalt, nickel, zinc, tin, halogen, and ions thereof. Since halide ions, sodium ions, and potassium ions are likely to be mixed in as impurities, it is preferable to set the content as shown below.
  • the content of impurities is preferably 80 mass ppm or less, more preferably 10 mass ppm or less, and even more preferably 2 mass ppm or less, based on the total mass of the photosensitive layer.
  • the lower limit is often 0 mass ppb or more, 1 mass ppb or more, or 0.1 mass ppm or more based on the total mass of the photosensitive layer.
  • Specific examples of the amount of impurities include a chloride ion concentration of 15 mass ppm, a bromide ion concentration of 1 mass ppm, a sodium ion concentration of 5 mass ppm, and an iron ion concentration of 1 mass ppm, based on the total mass of the photosensitive layer. Can be done.
  • Methods for adjusting the content of impurities include, for example, methods of using raw materials with a low content of impurities as raw materials for various components that may be included in the photosensitive layer, and methods of purifying and using various components that may be included in the photosensitive layer. and a method of preventing contamination of impurities during formation of the photosensitive layer.
  • the content of impurities can be determined 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 may be small. preferable.
  • the content 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, based on the total mass of the photosensitive layer.
  • the lower limit may be 10 mass ppb or more, or 100 mass ppb or more, based on the total mass of the photosensitive layer.
  • the content of these compounds can be adjusted in the same manner as for the above impurities. Moreover, these compounds can be quantified by known measuring methods.
  • the water content of the photosensitive layer is preferably 3.0% by mass or less based on the total mass of the photosensitive layer, from the viewpoint of improving reliability, improving handling of the transfer film, improving lamination properties, etc. It is more preferably 0% by mass or less, and even more preferably 1.0% by mass or less.
  • the lower limit is preferably 0.0001% by mass or more, more preferably 0.01% by mass or more, and even more preferably 0.1% by mass or more.
  • Specific examples of the water content in the photosensitive layer include 2.5% by weight, 1.5% by weight, and 0.3% by weight based on the total weight of the photosensitive layer.
  • the amount of residual solvent in the photosensitive layer is preferably 6.0% by mass or less based on the total mass of the photosensitive layer, from the viewpoint of improving reliability, improving handling of the transfer film, improving lamination properties, etc.
  • the content is more preferably .0% by mass or less, even more preferably 2.0% by mass or less, and particularly preferably 1.0% by mass or less.
  • the lower limit is preferably 0.0001% by mass or more, more preferably 0.01% by mass or more, and even more preferably 0.1% by mass or more.
  • Specific examples of the amount of residual solvent in the photosensitive layer are 3.5% by mass, 2.5% by mass, 1.5% by mass, and 0.3% by mass based on the total mass of the photosensitive layer. can be mentioned.
  • the lower limit of the average thickness of the photosensitive 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.
  • 40 micrometers or less are preferable, 25 micrometers or less are more preferable, 20 micrometers or less are still more preferable, and 19 micrometers or less are especially preferable. It is preferable that the average thickness of the photosensitive layer is 40 ⁇ m or less because the pattern resolution is excellent, and when the average thickness of the photosensitive layer is 0.5 ⁇ m or more, the reliability is excellent.
  • Requirement 1 When the photosensitive layer is heated at 350° C. for 1 hour, the weight loss of the photosensitive layer is 10.0% by mass or more. The amount of weight loss of the photosensitive layer when the photosensitive layer is heated at 350° C. for 1 hour is more preferably 10% by mass or more, and even more preferably 12% by mass or more. Further, the upper limit is preferably 50% by mass or less, more preferably 40% by mass or less, and even more preferably 30% by mass or less. The amount of weight loss when the photosensitive layer is heated at 350° C. for 1 hour can be measured by the following procedure.
  • the two transfer films are pasted together so that the photosensitive layers of each transfer film face each other, then one of the two temporary supports is peeled off, and the temporary support and the two are separated.
  • a laminate 1 having a photosensitive layer is obtained.
  • the transfer film from which the protective film has been peeled off is attached to the laminate 1 so that the photosensitive layer of the transfer film faces the photosensitive layer of the laminate 1, and then one of the two temporary supports is One side is peeled off to obtain a laminate 2 having a temporary support and three photosensitive layers.
  • a laminate 1 is prepared separately, and the photosensitive layer of the laminate 1 and the photosensitive layer of the laminate 2 are pasted together so that the photosensitive layers face each other, and the laminate 3 (temporary support/5 layers photosensitive layer/temporary support). Finally, the two temporary supports are peeled off from the laminate 3 to obtain a sample for evaluation.
  • thermogravimetric loss rate of the evaluation sample was measured using a TG-DTA device (simultaneous thermogravimetric/differential thermal analyzer), and the average value of the three measurements was calculated as the value when the photosensitive layer was heated at 350°C for 1 hour. Let it be the thermogravimetric reduction rate.
  • the measurement is preferably carried out under the conditions shown below.
  • the final thermogravimetric loss rate is measured in the range of room temperature to 350°C (under nitrogen atmosphere, heating rate 10°C/min, held at 350°C for 1 hour).
  • TG-DTA device for example, "TG/DTA6200" manufactured by Seiko Instruments, etc. can be used.
  • the melt viscosity of the photosensitive layer at 100° C. is preferably 5.0 ⁇ 10 6 Pa ⁇ s or less, more preferably 3.0 ⁇ 10 6 Pa ⁇ s or less, and 1.0 ⁇ 10 6 Pa ⁇ s or less. More preferred.
  • the lower limit is preferably 1.0 ⁇ 10 2 Pa ⁇ s or more.
  • the melt viscosity of the photosensitive layer at 100° C. can be measured by the following procedure.
  • the complex viscosity of the evaluation sample is measured using a rheometer, and the average value of three measurements is taken as the melt viscosity of the photosensitive layer at 100°C.
  • the measurement is preferably carried out under the conditions shown below.
  • a 20 mm ⁇ parallel plate and a Peltier plate are set at a gap of 0.5 mm, and measurements are performed at a temperature of 20 to 105°C, a heating rate of 5°C/min, and a strain of 0.5%.
  • the sample is melted (80° C.) on a Peltier plate, and then cooled to 20° C. (temperature reduction rate 5° C./m) before starting measurement.
  • the same evaluation sample as explained in ⁇ Amount of weight loss when photosensitive layer is heated at 350° C. for 1 hour> is used.
  • a rheometer a rheometer "DHR-2" manufactured by TA Instruments, etc. can be used.
  • the linear expansion coefficient of the cured product of the photosensitive layer is preferably 20 ppm/K or less, more preferably 17 ppm/K or less.
  • the lower limit is preferably 0 ppm/K or more.
  • the linear expansion coefficient of the cured product of the photosensitive layer can be measured by the following procedure.
  • the evaluation sample was the same evaluation sample as explained in ⁇ Amount of weight loss when the photosensitive layer was heated at 350°C for 1 hour>, with the two temporary supports remaining without peeling. use something That is, the laminate 3 having the structure of temporary support/5 photosensitive layers/temporary support was used as an evaluation sample.
  • CTE coefficient of linear expansion
  • the measurement conditions are a temperature increase rate of 10°C/min, a distance between chucks of 16mm, and a load of 49mN, and the measurement is carried out in a temperature range of -60°C to 350°C.
  • the linear expansion coefficient is a value (ppm/K) in the range of 50° C. to 150° C. when the temperature is increased, and the average value of three measurements is taken as the linear expansion coefficient of the cured product of the photosensitive 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 paragraphs 0164 to 0204 of International Publication No. 2021/166719, the contents of which are incorporated herein.
  • the transfer film may have a cover film.
  • the number of fish eyes with a diameter of 80 ⁇ m or more contained in the cover film is preferably 5 pieces/m 2 or less.
  • Fish eyes are foreign matter, undissolved matter, and/or oxidized deterioration of materials that occur when producing films by heat-melting materials, kneading, extrusion and/or biaxial stretching, casting methods, etc. was captured in the film.
  • the number of particles with a diameter of 3 ⁇ m or more contained in the cover film is preferably 30 particles/mm 2 or less, more preferably 10 particles/mm 2 or less, and even more preferably 5 particles/mm 2 or less. This can suppress defects caused by the transfer of unevenness caused by particles contained in the cover film 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 such a range, for example, when the transfer film is long, the winding performance when winding up the transfer film is excellent. In addition, in terms 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 polyethylene terephthalate film, polypropylene film, polystyrene film, and polycarbonate film.
  • cover film examples include those described in paragraphs 0083 to 0087 and 0093 of JP-A No. 2006-259138.
  • cover film 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.), and Therapel (registered trademark) 25WZ (Toray Film Co., Ltd.). and Lumirror (registered trademark) 16QS62 (16KS40) (manufactured by Toray Industries, Inc.).
  • the cover film may be a recycled product. Examples of recycled products include those obtained by cleaning and chipping used films and the like, and making films from the obtained materials. Examples of commercially available recycled products include the Ecouse series (manufactured by Toray Industries, Inc.).
  • the transfer film may include other layers in addition to the layers described above.
  • Examples of other layers include a high refractive index layer.
  • Examples of the high refractive index layer include paragraphs 0168 to 0188 of International Publication No. 2021/187549, the contents of which are incorporated herein.
  • a known manufacturing method can be applied to the method of manufacturing the transfer film.
  • a method for manufacturing the transfer film 100 shown in FIG. 1 includes a step of applying a photosensitive composition to the surface of a temporary support to form a coating film, and further drying this coating film to form a photosensitive layer.
  • Examples include methods including:
  • the transfer film 100 shown in FIG. 1 is manufactured by press-bonding a cover film onto the photosensitive layer of the transfer film manufactured by the above manufacturing method.
  • the transfer film 100 shown in FIG. 1 may be wound up after manufacturing and stored as a roll-shaped transfer film 100.
  • the transfer film 100 in the form of a roll can be provided as it is in the step of laminating it with a base material in a roll-to-roll method, which will be described later.
  • the transfer film may have an intermediate layer and/or a thermoplastic resin layer between the temporary support and the photosensitive 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 include paragraphs 0133 to 0136 and paragraph 0143 of International Publication No. 2021/033451. ⁇ 0144, the contents of which are incorporated herein.
  • a known method can be used to form the photosensitive layer, such as a method in which it is formed by applying and drying a photosensitive composition.
  • the photosensitive composition preferably contains a solvent (solvent) that does not correspond to compound Y in order to improve coating properties.
  • the solvent is not particularly limited as long as it does not apply to compound Y and can dissolve or disperse various components that may be included in the photosensitive composition.
  • solvents include water, alkylene glycol ether solvents, alkylene glycol ether acetate solvents, alcohol solvents (such as methanol and ethanol), ketone solvents (such as acetone and methyl ethyl ketone), and aromatic hydrocarbon solvents (such as toluene).
  • aprotic polar solvents e.g., N,N-dimethylformamide, etc.
  • cyclic ether solvents e.g., tetrahydrofuran, etc.
  • ester solvents e.g., n-propyl acetate, etc.
  • amide solvents lactone solvents, and these solvents.
  • solvents containing two or more of them The solvents may be used alone or in combination of two or more.
  • the content of the solvent is preferably 50 to 1900 parts by weight, more preferably 100 to 1200 parts by weight, and even more preferably 100 to 900 parts by weight, based on 100 parts by weight of the total solid content of the composition.
  • Examples of the coating method include slit coating, spin coating, curtain coating, and inkjet coating.
  • a resin pattern obtained from a photosensitive layer formed using a transfer film can be applied to various uses. For example, it can be applied to electrode protection films, insulating films, planarization films, overcoat films, hard coat films, passivation films, partition walls, spacers, microlenses, optical filters, antireflection films, etching resists, and plating members. More specifically, 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, and colors. Examples include filters, overcoat films for color filters, and etching resists for forming wiring.
  • the method for producing the laminate is not particularly limited as long as it uses the transfer film described above.
  • the method for manufacturing the laminate preferably includes steps X1 to X4.
  • process Synthesis step Step X2: Exposure step of exposing the photosensitive layer in a pattern
  • Step X3 Development step of developing the exposed photosensitive layer to form a resin pattern precursor
  • Step X4 Heating the resin pattern precursor to form a resin pattern Heating step to form
  • the method for producing a resin pattern includes a peeling step of peeling off the temporary support from the photosensitive layer-coated substrate between the bonding step and the exposure step, or between the exposure step and the development step. It is preferable to have the following.
  • Step X1 is a step of forming a photosensitive layer on a base material using a transfer film.
  • the bonding method include known transfer methods and lamination methods, and a method of stacking a base material on the surface of the photosensitive layer and applying pressure and heating using a roll or the like is preferable.
  • the above-mentioned laminating method include known laminators such as a vacuum laminator and an auto-cut laminator.
  • the lamination temperature is not particularly limited, but is preferably 70 to 130°C. It is preferable that step X1 is performed by a roll-to-roll method.
  • the base material to which the transfer film is bonded include a resin film and a resin film having a conductive layer.
  • the roll-to-roll method uses a base material that can be rolled up and unrolled as a base material, and includes a step of unrolling the base material before any of the steps included in the method for producing a laminate of the present invention. , a step of winding up the base material after any of the steps, and a method in which at least one of the steps (preferably all steps or all steps other than the heating step) is carried out while conveying the base material.
  • any known method may be used in a manufacturing method applying a roll-to-roll system.
  • the base material examples include a glass substrate, a glass epoxy substrate, a silicon substrate, a resin substrate, and a substrate having a conductive layer.
  • the refractive index of the base material is preferably 1.50 to 1.52.
  • the base material may be composed of a light-transmitting substrate such as a glass substrate, and for example, tempered glass such as Corning's Gorilla Glass can also be used.
  • examples of the material included in the base material include materials used in JP-A No. 2010-086684, JP-A No. 2010-152809, and JP-A No. 2010-257492.
  • a resin film with small optical distortion and/or high transparency is more preferable as the resin substrate. Specific examples include polyethylene terephthalate (PET), polyethylene naphthalate, polycarbonate, triacetylcellulose, cycloolefin polymer, and polyimide.
  • a resin substrate having a conductive layer is preferable, and a resin film having a conductive layer is more preferable since it is manufactured by a roll-to-roll method.
  • the conductive layer examples include any conductive layer used for general circuit wiring or touch panel wiring.
  • the conductive layer is selected from the group consisting of a metal layer (for example, metal foil, etc.), a conductive metal oxide layer, a graphene layer, a carbon nanotube layer, and a conductive polymer layer in terms of conductivity and fine line formation.
  • a metal layer for example, metal foil, etc.
  • a conductive metal oxide layer for example, metal foil, etc.
  • a graphene layer for example, metal foil, etc.
  • a carbon nanotube layer a conductive polymer layer in terms of conductivity and fine line formation.
  • One or more layers are preferred, metal layers are more preferred, and copper or silver layers are even more preferred.
  • the number of conductive layers in the substrate having a conductive layer may be one layer or two or more layers.
  • each conductive layer is preferably made of a different material. Examples of the material for the conductive layer include simple metals and conductive metal oxides.
  • Examples of the metal element include Al, Zn, Cu, Fe, Ni, Cr, Mo, Ag, and Au.
  • Examples of the conductive metal oxide include ITO (Indium Tin Oxide), IZO (Indium Zinc Oxide), and SiO 2 .
  • Electric conductivity means that the volume resistivity is less than 1 ⁇ 10 6 ⁇ cm, and preferably the volume resistivity is less than 1 ⁇ 10 4 ⁇ cm.
  • At least one of the conductive layers contains a conductive metal oxide.
  • Step X2 is a step of exposing the photosensitive layer in a pattern after the above step X1.
  • pattern exposure refers to exposure in a pattern, that is, an exposure in which exposed areas and unexposed areas exist.
  • the positional relationship between the exposed portion and the unexposed portion in pattern exposure is not particularly limited and may be adjusted as appropriate.
  • the photosensitive layer may be exposed from the side opposite to the substrate, or the photosensitive layer may be exposed from the substrate side.
  • the light source used for exposure is light in a wavelength range to which various photosensitive components (e.g., photopolymerization initiators, photoacid generators, etc.) in the photosensitive layer can be sensitized (e.g., 254 nm, 313 nm, 365 nm, and light in a wavelength range of 405 nm, etc.) may be selected as appropriate.
  • various photosensitive components e.g., photopolymerization initiators, photoacid generators, etc.
  • specific examples include ultra-high pressure mercury lamps, high-pressure mercury lamps, metal halide lamps, and LEDs (Light Emitting Diodes).
  • the exposure amount is preferably 5 to 200 mJ/cm 2 , more preferably 10 to 200 mJ/cm 2 .
  • the step It's okay.
  • the pattern exposure may be exposure through a mask or direct exposure using a laser or the like.
  • examples of the mask include a quartz mask, a soda lime glass mask, and a film mask.
  • a quartz mask is preferable because it has excellent dimensional accuracy, and a film mask is preferable because it can be easily made large.
  • polyester film is preferred, and polyethylene terephthalate film is more preferred.
  • examples of the material for the film mask include XPR-7S SG (manufactured by Fujifilm Global Graphic Systems).
  • the temporary support is preferably peeled off from the photosensitive layer before step X3, which will be described later.
  • Step X3 is a step of developing the exposed photosensitive layer to form a resin pattern precursor after step X2.
  • Step X3 can be performed using a developer.
  • the developer include an alkaline developer and an organic solvent developer.
  • the developer preferably contains at least one selected from the group consisting of cyclopentanone, an aqueous tetramethylammonium hydroxide solution, an aqueous sodium hydroxide solution, an aqueous sodium carbonate solution, and an aqueous potassium carbonate solution.
  • alkaline developer As the alkaline developer, an alkaline aqueous solution is preferred.
  • An alkaline aqueous developer containing a compound having a pKa of 7 to 13 at a concentration of 0.05 to 5 mol/L is preferred.
  • the content of water in the alkaline developer is preferably 50% by mass or more, more preferably 60% by mass or more, even more preferably 85% by mass or more, particularly preferably 90% by mass or more, based on the total mass of the alkaline developer. , 95% by mass or more is most preferred.
  • the upper limit is preferably less than 100% by mass based on the total mass of the alkaline developer.
  • Examples of the alkaline developer include a sodium carbonate aqueous solution, a potassium carbonate aqueous solution, a sodium hydroxide aqueous solution, a potassium hydroxide aqueous solution, and a tetramethylammonium hydroxide aqueous solution.
  • Examples of the concentration of the alkaline developer include a 0.1% by mass aqueous solution, a 1.0% by mass aqueous solution, and a 2.38% by mass aqueous solution.
  • the alkaline developer may contain a water-soluble organic solvent, a surfactant, and the like. Examples of the alkaline developer include the developer described in paragraph 0194 of International Publication No. 2015/093271.
  • organic solvent developer examples include those containing organic solvents such as ketone solvents, ester solvents, alcohol solvents, amide solvents, ether solvents, and hydrocarbon solvents.
  • organic solvent developer examples include cyclopentanone and propylene glycol monomethyl ether acetate, with cyclopentanone being preferred.
  • a plurality of organic solvents may be mixed, or may be mixed with an organic solvent other than the above or water.
  • the content of water in the organic solvent developer is preferably less than 10% by mass, and more preferably substantially free of water, based on the total mass of the organic solvent developer.
  • the content of the organic solvent in the organic solvent developer is preferably 50% by mass or more, more preferably 60% by mass or more, even more preferably 85% by mass or more, and 90% by mass or more, based on the total mass of the organic solvent developer. is particularly preferred, and most preferably 95% by mass or more.
  • the upper limit is preferably 100% by mass or less based on the total mass of the organic solvent developer.
  • Examples of development methods include paddle development, shower development, spin development, and dip development.
  • shower development unnecessary portions can be removed by spraying a developer onto the exposed photosensitive layer using a shower.
  • a cleaning agent or the like in a shower and remove development residues while rubbing with a brush or the like.
  • the temperature of the developer is preferably 20 to 40°C.
  • Step X4 is a step of heating the resin pattern precursor obtained in Step X3 to form a resin pattern.
  • compound Y is removed, and the linear thermal expansion coefficient of the resulting resin pattern can be reduced.
  • the photosensitive layer contains a polyimide precursor and a polybenzoxazole precursor
  • the ring-closing reaction of those precursors is promoted in step X4, and polyimide and polybenzoxazole can be produced.
  • step X4 it is presumed that by carrying out step X4, not only the above-mentioned compound Y but also other impurities contained in the resin pattern precursor are removed.
  • the resin pattern precursor obtained in step X3 includes compound Y and a polymer derived from each polymerizable compound that may be produced in step X2 (for example, a polymer derived from polymerizable compound YM) etc. may be included.
  • a polymer derived from each polymerizable compound that may be produced in step X2 for example, a polymer derived from polymerizable compound YM
  • By-products produced by the ring-closing reaction for example, compounds produced by decomposition of some groups of the polyimide precursor and polybenzoxazole precursor
  • the purity of the resin pattern means that various components contained in the pattern are substantially composed only of polyimide and polybenzoxazole.
  • the total content of polyimide and polybenzoxazole is preferably 90% by mass or more, more preferably 95% by mass or more, based on the total mass of the pattern.
  • the upper limit is preferably 100% by mass or less.
  • the temperature and time of the heat treatment in step X4 are not particularly limited as long as the temperature and time are such that the ring-closing reaction of the polyimide precursor and polybenzoxazole precursor is promoted.
  • the temperature of the heat treatment is preferably 120 to 400°C, more preferably 150 to 400°C, even more preferably 190 to 350°C.
  • the heat treatment time is preferably 1 to 24 hours, more preferably 1 to 12 hours, and even more preferably 1 to 9 hours.
  • the heat treatment may be performed in either an air environment or a nitrogen-substituted environment.
  • the atmospheric pressure in the heat treatment environment is preferably 8.1 kPa or higher, more preferably 50.66 kPa or higher.
  • the upper limit is preferably 121.6 kPa or less, more preferably 111.46 kPa or less, and even more preferably 101.3 kPa or less.
  • the method for manufacturing a laminate may include steps other than those described above. Examples of other steps include the following steps.
  • ⁇ Cover film peeling process> In the case where the transfer film has a cover film in the method for manufacturing the laminate, it is preferable to include a step of peeling off the cover film of the transfer film. A known method can be used to peel off the cover film.
  • the method for manufacturing the laminate may further include a step of performing a treatment to reduce the visible light reflectance of the conductive layer.
  • the treatment to reduce the visible light reflectance may be performed on some of the conductive layers, or on all the conductive layers. You may.
  • An example of the treatment for reducing visible light reflectance is oxidation treatment. For example, by oxidizing copper to form copper oxide, the visible light reflectance of the conductive layer can be reduced by turning it black.
  • the method for manufacturing the laminate described above uses the pattern (film) formed in step X3 or step
  • the method may include a step of etching the conductive layer (etching step).
  • the etching treatment method include a wet etching method described in paragraphs 0048 to 0054 of JP-A-2010-152155, and a known dry etching method such as plasma etching.
  • the substrate having a plurality of conductive layers on both surfaces, and pattern the conductive layers formed on both surfaces sequentially or simultaneously.
  • the first conductive pattern can be formed on one surface of the substrate, and the second conductive pattern can be formed on the other surface. It is also preferable to form from both sides of the base material by roll-to-roll.
  • the method for manufacturing the circuit wiring is not particularly limited as long as it uses a transfer film.
  • the surface of the transfer film on the side opposite to the temporary support side is brought into contact with a conductive layer in a substrate having a conductive layer, and the photosensitive layer has a substrate, a conductive layer, a photosensitive layer, and a temporary support in this order.
  • the method preferably includes a heating step of forming a resin pattern, and an etching step of etching the conductive layer in a region where the resin pattern is not arranged. Furthermore, the method for manufacturing circuit wiring includes a peeling process of peeling off the temporary support from the photosensitive layer-coated substrate between the bonding process and the exposure process, or between the exposure process and the development process. is preferable.
  • each step in the method for manufacturing circuit wiring of the present invention examples include each step in the method for manufacturing the laminate described above. It is also preferable that the method for manufacturing circuit wiring of the present invention is such that a plurality of sets of steps from the bonding step to the etching step are repeated.
  • the film used as the etching resist film can also be used as a protective film (insulating film) for the formed circuit wiring.
  • Examples of the semiconductor package manufacturing method include known manufacturing methods such as a build-up board manufacturing method. Specifically, a manufacturing method including steps Z1 to Z5 in this order can be mentioned.
  • Step Z1 The surface of the transfer film on the opposite side of the temporary support is brought into contact with and laminated onto the substrate having the conductive layer to form a substrate with a photosensitive layer having the base material, the photosensitive layer, and the temporary support in this order.
  • Step Z2 An exposure step of exposing the photosensitive layer in a pattern
  • Step Z3 A step of developing the exposed photosensitive layer to form a resin pattern precursor having vias
  • Step Z4 The above resin pattern precursor A heating step of heating to form a resin pattern having vias.
  • Step Z5 A circuit pattern forming step of forming a circuit pattern on the resin pattern. Furthermore, the method for manufacturing a semiconductor package includes a step between the bonding step and the exposure step, or It is preferable to include a peeling process of peeling off the temporary support from the photosensitive layer-coated substrate between the exposure process and the development process.
  • Steps Z1, Z2, and Z4 in the method for manufacturing a semiconductor package can be carried out using the same procedures as steps X1, X2, and X4, respectively.
  • Step Z3 is a step of developing the exposed photosensitive layer to form a resin pattern precursor having vias.
  • the developing step can be performed using a developer. Examples of the method of developing using a developer include the method of developing using a developer in step X3.
  • Examples of the shape of the vias included in the pattern include, for example, a cross-sectional shape of a square, a trapezoid, and an inverted trapezoid; a front shape (the shape when the via is observed from the direction in which the bottom of the via is seen) is a circle and a square.
  • the cross-sectional shape of the vias in the pattern is preferably an inverted trapezoid, since the plated copper is more likely to cover the via wall surface.
  • the via size is often 300 ⁇ m or less, preferably 200 ⁇ m or less, more preferably less than 40 ⁇ m, even more preferably 30 ⁇ m or less, even more preferably 20 ⁇ m or less, particularly preferably 10 ⁇ m or less, and most preferably 5 ⁇ m or less.
  • the lower limit is preferably 1 ⁇ m or more, more preferably 5 ⁇ m or more.
  • the number of vias may be one or more, preferably two or more.
  • Step Z5 is a step of forming a circuit pattern on the resin pattern having vias.
  • a semi-additive process is preferable because it allows formation of fine wiring.
  • a seed layer is formed by electroless copper plating using a palladium catalyst or the like on the entire surface of the via bottom, via wall surface, and pattern after the step Z3.
  • the seed layer is used to form a power supply layer for electrolytic copper plating, and the thickness of the seed layer is preferably 0.1 to 2.0 ⁇ m.
  • Electroless copper plating is performed by depositing metallic copper on the surface of a pattern having vias through a reaction between copper ions and a reducing agent. Examples of the electroless plating method and the electrolytic plating method include known plating methods.
  • a palladium-tin mixed catalyst is preferred.
  • the average primary particle diameter of the mixed catalyst is preferably 10 nm or less.
  • the plating composition in the electroless plating process preferably contains hypophosphorous acid as a reducing agent.
  • commercially available electroless copper plating solutions include, for example, "MSK-DK” manufactured by Atotech Japan Co., Ltd. and “Surcup (registered trademark) PEA ver. 4" series manufactured by Uemura Kogyo Co., Ltd.
  • the thickness of the photosensitive layer is preferably 5 to 30 ⁇ m since it can be made higher than the wiring height after electrolytic copper plating.
  • the photosensitive layer is exposed to light through a mask on which a desired wiring pattern is drawn, for example. Examples of the above-mentioned exposure method include the same method as the exposure method in step X2. After exposure, the temporary support of the transfer film is peeled off, and the exposed photosensitive layer is developed using an alkaline developer to form a pattern.
  • the development residue of the composition may be removed using plasma or the like.
  • electrolytic copper plating is performed to form a copper circuit layer and to perform via filling.
  • the pattern is removed using an alkaline aqueous solution or an amine release agent.
  • the seed layer between the wirings is removed (flash etching). Flash etching is performed using, for example, an oxidizing solution containing sulfuric acid and an acidic solution such as hydrogen peroxide. Examples of the oxidizing solution include "SAC" manufactured by JCU Corporation and "CPE-800” manufactured by Mitsubishi Gas Chemical Company.
  • palladium and the like attached to the areas between the wirings are removed if necessary. Palladium can be removed using acidic solutions such as nitric acid and hydrochloric acid.
  • the post-baking treatment sufficiently heat-cures unreacted thermosetting components, thereby improving electrical insulation reliability, curing properties, and adhesive strength with plated copper.
  • the heat curing conditions it is preferable that the curing temperature is 150 to 240°C and the curing time is 15 to 500 minutes.
  • the method for manufacturing a semiconductor package may include a roughening process of roughening a pattern having vias.
  • the roughening step is preferably performed after the step Z4 and before the step Z5.
  • the surface of the pattern can be roughened to improve adhesion to circuit wiring.
  • smear can be removed at the same time.
  • the roughening step include a known desmear treatment, and a treatment in which a roughening liquid is brought into contact is preferred.
  • the roughening liquid examples include a roughening liquid containing chromium and sulfuric acid, a roughening liquid containing an alkali permanganate (e.g., sodium permanganate roughening liquid, etc.), sodium fluoride, chromium, and sulfuric acid. Roughening liquid can be mentioned.
  • a semiconductor package can be manufactured by repeating each of the above steps depending on the number of layers required. Moreover, it is preferable to form a solder resist on the outermost layer.
  • the method for manufacturing a touch panel is not particularly limited as long as it is a method for manufacturing a touch panel using a transfer film.
  • a conductive layer in a substrate having a conductive layer preferably a patterned conductive layer, specifically a conductive pattern such as a touch panel electrode pattern or wiring) on the surface opposite to the temporary support in the transfer film.
  • a bonding step to obtain a photosensitive layer-attached substrate having a substrate, a conductive layer, a photosensitive layer, and a temporary support in this order; a step of exposing the photosensitive layer in a pattern; developing the conductive layer to form a patterned protective film or insulating film precursor of the conductive layer; heating the patterned protective film or insulating film precursor of the conductive layer;
  • the method includes a heating step of forming a patterned protective film or insulating film of the layer.
  • the method for manufacturing a touch panel includes a peeling process of peeling off the temporary support from the photosensitive layer-coated substrate between the bonding process and the exposure process, or between the exposure process and the development process. is preferred.
  • a known manufacturing method can be applied to the semiconductor device manufacturing method. Specifically, there may be mentioned a method of manufacturing a semiconductor device including the method of manufacturing a laminate described above or the method of manufacturing a semiconductor package described above.
  • Semiconductor devices include, for example, 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.). Examples include various semiconductor devices.
  • the semiconductor package is not particularly limited as long as it includes a resin pattern obtained from a photosensitive layer formed using the above-described transfer film.
  • the resin pattern may be used as an insulating film, or as an organic interposer or an insulating film in a so-called build-up substrate.
  • a mixture was prepared by mixing various components in the amounts (based on mass) shown in "Photosensitive layer” in the table. Next, the above mixture was diluted so that the solid content concentration was 30% by mass, the concentration of MEK (methyl ethyl ketone) was 20% by mass, and the concentration of NMP (N-methylpyrrolidone) was 50% by mass.
  • the silica was not a slurry (when it was a powder)
  • the silica was dispersed in a 50% by mass MEK solution to form a slurry, and then mixed at the end to prepare a composition.
  • Resin A to Resin D are resins corresponding to Resin X.
  • ODPA 4,4'-oxydiphthalic dianhydride
  • BPDA diphenyl-3,3',4,4'-tetracarboxylic dianhydride
  • HEMA 2-hydroxyethyl methacrylate
  • ⁇ -butyrolactone 400 mL
  • Resin B which is a powdered polyimide precursor.
  • Mw weight average molecular weight
  • the content of imide groups in the polyimide obtained from resin B was 27.4% by mass per repeating unit.
  • Resin C which is a polyimide precursor, was obtained using 4,4'-diaminodiphenyl ether as the diamine and 4,4'-oxydiphthalic anhydride as the dianhydride.
  • the weight average molecular weight of Resin C was 15,000.
  • Resin D which is a polybenzoxazole precursor, was prepared using 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane as the diamine and 4,4'-oxybis(benzoyl chloride) as the acid chloride. I got it.
  • the weight average molecular weight of Resin D was 15,000.
  • ⁇ HD-N 1,6-hexanediol dimethacrylate ( "HD-N” manufactured by Shin-Nakamura Kogyo Co., Ltd.)
  • BDDMA 1,4-butanediol dimethacrylate (manufactured by TCI)
  • NOD-N 1,9-nonanediol dimethacrylate (“NOD-N” manufactured by Shin Nakamura Kogyo Co., Ltd.)
  • ⁇ DOD-N 1,10-decanediol dimethacrylate (“DOD-N” manufactured by Shin Nakamura Industries Co., Ltd.)
  • ⁇ Polymerizable compound corresponding to comparative compound RY> ⁇ DPHA: Dipentaerythritol hexaacrylate (“A-DPH” manufactured by Shin Nakamura Chemical Co., Ltd.)
  • ⁇ HC Cyclohexyl methacrylate (Kyoeisha Chemical "Light Ester HC")
  • A-HD-N 1,6-hexanediol diacrylate (“A-HD-N” manufactured by Shin Nakamura Industries Co., Ltd.)
  • ⁇ DPHMA Dipentaerythritol hexamethacrylate (A synthetic product synthesized by transesterification of dipentaerythritol and methacrylic acid was used.)
  • Non-polymerizable compound ⁇ Non-polymerizable compound corresponding to compound Y> ⁇ mPEG6-OH: Hexaethylene glycol monomethyl ether (manufactured by TCI) ⁇ mPEG5-OH: Pentaethylene glycol monomethyl ether (manufactured by TCI) ⁇ BB: Benzyl benzoate (manufactured by Kishida Chemical Co., Ltd.) ⁇ DRA-150: Triacetin glycerin triacetate (manufactured by Daicel Corporation) ⁇ 1,6-HDDA: 1,6-hexanediol diacetate (manufactured by Daicel Corporation)
  • ⁇ YA050C-MJE Spherical silica slurry, methacrylic surface treatment product, MEK slurry with solid content concentration 50% by mass, manufactured by Admatex ⁇ YA50SP-AM1: Silicon dioxide, manufactured by Admatex ⁇ YA50SZ-AM1: Silicon dioxide, Admatex MEK-ST-ZL: Silicon dioxide, hydrophobic surface treated product, manufactured by Nissan Chemical Co., Ltd. PMA-ST: Silicon dioxide, hydrophobic surface treated product, manufactured by Nissan Chemical Co., Ltd. MEK-ST-ZL: Silicon dioxide, Hydrophobic surface treatment product, manufactured by Nissan Chemical Co., Ltd./NHM-3N: Silicon dioxide, manufactured by Tokuyama Corporation
  • ⁇ U-CAT SA506 p-toluenesulfonate of 1,8-diazabicyclo[5.4.0]undecene-7, manufactured by San-Apro Co., Ltd.
  • F551A Megafac (registered trademark) F551A, fluorine surfactant, manufactured by DIC Corporation
  • S-324 Silicone surfactant, manufactured by DIC Corporation
  • the photosensitive layer of the transfer film of each Example and Comparative Example was transferred onto a glass substrate to produce a glass substrate with a photosensitive layer.
  • a cross section along the normal direction of the surface of the photosensitive layer was cut out, and the cross section was observed with a scanning electron microscope.
  • the major axis of all fillers observed within a region having a length of 10 ⁇ m in the orthogonal lateral direction was measured.
  • the above operation was performed at five different locations on the photosensitive layer, and the average value (arithmetic average value) of the long diameters of all the fillers measured in each operation was taken as the average particle size of the filler.
  • the photosensitive layer on the glass substrate with a photosensitive layer was heated at 230°C for 8 hours, and then the same operation as above was performed.
  • the average particle diameter was measured according to the method, it was found to be the same value as the average particle diameter before heat treatment.
  • the transfer film from which the protective film has been peeled off is attached to the laminate 1 so that the photosensitive layer of the transfer film faces the photosensitive layer of the laminate 1, and then one of the two temporary supports is One side was peeled off to obtain a laminate 2 having a temporary support and three photosensitive layers.
  • a laminate 1 is separately produced, and the photosensitive layer of the laminate 1 and the photosensitive layer of the laminate 2 produced above are bonded together so that the photosensitive layers face each other, and the laminate 3 (temporarily supported A body/5 photosensitive layers/temporary support) was obtained.
  • the two temporary supports were peeled off from the laminate 3 to obtain a sample for evaluation.
  • thermogravimetric reduction rate when heating the photosensitive layer at 350°C for 1 hour>
  • the obtained evaluation sample was measured using a TG-DTA device ("TG/DTA6200" manufactured by Seiko Instruments), and the average value of the thermogravimetric reduction rate measured three times was evaluated according to the following evaluation criteria. The measurements were carried out under the conditions shown below. The final thermogravimetric loss rate was measured in the range of room temperature to 350°C (under nitrogen atmosphere, heating rate 10°C/min, held at 350°C for 1 hour). (Evaluation criteria (thermal weight loss rate)) "A”: 10% by mass or more "B”: Less than 10% by mass
  • the cover film was peeled off from the transfer film, and laminated onto a 10 x 10 cm 2 piece of glass (Eagle , conveyance speed 1 m/min)).
  • glass/photosensitive layer/temporary support/mask were laminated in this order, and exposed using an ultra-high pressure mercury lamp from the mask side.
  • the mask used had a circular light-shielding portion with a diameter of 100 ⁇ m ⁇ and a distance between adjacent light-shielding portions of 300 ⁇ m or more. Further, during exposure, the exposure amount measured with a 365 nm illuminance meter was 10 mJ/cm 2 .
  • the sample was allowed to stand for 30 minutes and the temporary support was peeled off, followed by development for 90 seconds at room temperature using the developer listed in the table. After development, a rinsing process was performed for 20 seconds at room temperature using a rinsing liquid, and the remaining rinsing liquid was further removed by blowing air.
  • a rinsing solution water is used when the developer is an aqueous solution (Na 2 CO 3 aq or TMAHaq.), and propylene glycol monoethyl is used when the developer is an organic solvent (cyclopentanone). Ether acetate was used. The samples obtained by the above procedure were observed and evaluated according to the following criteria.
  • the cover film was peeled off from the transfer film, and laminated onto a 10 x 10 cm 2 piece of glass (Eagle , conveyance speed 1 m/min)).
  • the temporary support was peeled off, and the photosensitive layer was pattern-exposed using a projection exposure apparatus (UX-4 manufactured by Ushio Inc.).
  • the exposure pattern used had circular non-exposed portions with a diameter of 100 ⁇ m ⁇ , and the distance between adjacent non-exposed portions was 300 ⁇ m or more. Further, the exposure amount measured with a 365 nm illuminance meter was 400 mJ/cm 2 .
  • the sample After exposure, the sample was allowed to stand for 30 minutes, and then developed for 90 seconds at room temperature using the developer listed in the table. After development, a rinsing process was performed for 20 seconds at room temperature using a rinsing liquid, and the remaining rinsing liquid was further removed by blowing air.
  • a rinsing solution water is used when the developer is an aqueous solution (Na 2 CO 3 aq or TMAHaq.), and propylene glycol monoethyl is used when the developer is an organic solvent (cyclopentanone). Ether acetate was used.
  • the measurement conditions were a temperature increase rate of 10° C./min, a distance between chucks of 16 mm, and a load of 49 mN.
  • the measurements were 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 temperature rise, and was determined as the average value of three measurements.
  • Vacuum lamination was carried out at a temperature of 100° C. and a conveyance speed of 1 m/min so that the photosensitive layer of the transfer film from which the protective film was peeled faced the surface of the test board on which the wiring was formed.
  • the space between the two types of copper patterns after lamination was observed using an optical microscope, and evaluated based on the following criteria.
  • B Some air entered between the wires (air bubble area was 10% or more and less than 40% of the area between the wires).
  • the cover film was peeled off from the transfer film, and laminated onto a 10 x 10 cm 2 piece of glass (Eagle , conveyance speed 1 m/min).
  • glass/photosensitive layer/temporary support/mask were laminated in this order, and exposed using an ultra-high pressure mercury lamp from the mask side.
  • the mask used had a circular light-shielding portion with a diameter of 100 ⁇ m ⁇ and a distance between adjacent light-shielding portions of 300 ⁇ m or more. Further, during exposure, the exposure amount measured with a 365 nm illuminance meter was 10 mJ/cm 2 .
  • the sample was allowed to stand for 30 minutes and the temporary support was peeled off, followed by development for 90 seconds at room temperature using the developer listed in the table.
  • a rinsing process was performed for 20 seconds at room temperature using a rinsing liquid, and the remaining rinsing liquid was further removed by blowing air.
  • the rinsing solution water is used when the developer is an aqueous solution (Na2CO3aq or TMAHaq.), and propylene glycol monoethyl ether acetate is used when the developer is an organic solvent (cyclopentanone). there was.
  • heat treatment was performed at 230° C. for 3 hours to produce a resin pattern in which holes of 100 ⁇ m ⁇ were formed on the base material.
  • Table 1 is shown below.
  • Table 1 data related to Examples and Comparative Examples are shown separately in the left column (Table 1-X1 to Table 1-X6) and the right column (Table 1-Y1 to Table 1-Y6).
  • Table 1-X1 to Table 1-X6 data related to Examples and Comparative Examples are shown separately in the left column (Table 1-X1 to Table 1-X6) and the right column (Table 1-Y1 to Table 1-Y6).
  • Table 1-XN data related to Examples and Comparative Examples
  • Table 1-Y1 to Table 1-Y6 Table 1 to 6
  • 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, 1-X5 and Table 1-Y5, Table 1-X6 and Table 1-Y6 are combined, and the temporary support, photosensitive layer (resin, initiator, compound Y and comparative Compound RY, Wb/Wa, filler, thermal base generator, surfactant), physical properties of the photosensitive layer, and evaluation).
  • the components of the photosensitive layer are Resin A (resin), Oxe01 (initiator), NK3G (polymerizable compound), YA050C-MJE (filler), and Compound A (thermal base generator).
  • F551A surfactant).
  • the transfer films of Examples have excellent step followability when laminated to objects to be laminated after storage, excellent removability of the temporary support, and linear expansion of the cured photosensitive layer. It is clear that the coefficient is small (in other words, the resin pattern formed from the photosensitive layer of the transfer film has a small coefficient of linear expansion).
  • the photosensitive layer of the transfer film contains a filler and the content of the filler is 30% by mass based on the total mass of the photosensitive layer, it is possible to paste it onto the object after storage. It was confirmed that the adhesive had better step followability when mating, and also had better releasability of the temporary support.
  • Example 1A The transfer film of Example 1 was laminated on both sides of a glass epoxy base material (CCL-EL190T, thickness 1.0 mm, manufactured by Mitsubishi Gas Chemical Co., Ltd.) on which a circuit pattern was formed, and the photosensitive layer was attached to the glass epoxy base material. Formed on both sides. At this time, a vacuum laminator was used. Lamination was performed using a vacuum laminator manufactured by MCK under the conditions of substrate temperature: 40° C., rubber roller temperature of 100° C., linear pressure of 3 N/cm, and conveyance speed of 2 m/min.
  • a vacuum laminator manufactured by MCK under the conditions of substrate temperature: 40° C., rubber roller temperature of 100° C., linear pressure of 3 N/cm, and conveyance speed of 2 m/min.
  • a semiconductor package was produced by performing the steps from lamination to heat treatment described above three times in total, and finally forming a solder resist as the outermost layer, and further sealing and mounting a semiconductor element.
  • a semiconductor package substrate was obtained by mounting the obtained semiconductor package at a predetermined position on a printed wiring board. It was confirmed that the obtained semiconductor package substrate operated normally.
  • Examples 2A to 123A A semiconductor package was created in the same manner as in Example 1A, except that the transfer film of Example 1 was changed to each of Examples 2 to 123, and a semiconductor package substrate was obtained (Examples 2A to 123A). ). It was confirmed that all of the obtained semiconductor package substrates operated normally.
  • Example 1B A transfer film of Example 1B was produced in the same manner as in Example 1 except that the thickness of the photosensitive layer in the transfer film of Example 1 was changed to 25 ⁇ m. Next, a semiconductor package substrate was produced in the same manner as in Example 1A except that the transfer film used was changed to the transfer film of Example 1B. It was confirmed that the obtained semiconductor package substrate operated normally.

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Abstract

Un premier problème abordé par la présente invention consiste à fournir un film de transfert qui présente une excellente couverture de pas lorsqu'il est collé à une partie adhérée après avoir été entreposé, d'excellentes propriétés de pelage de support temporaire, et un faible coefficient de dilatation linéaire d'un produit durci d'une couche photosensible. Un second problème abordé par la présente invention consiste à fournir un stratifié, un procédé de fabrication de stratifié, et un procédé de fabrication de boîtier de semi-conducteur.　Un film de transfert selon la présente invention comporte un support temporaire et une couche photosensible disposée sur le support temporaire. La couche photosensible comprend une résine X choisie parmi les polyimides, les polybenzoxazoles, et les précurseurs de ceux-ci, un initiateur de photopolymérisation, et un composé Y qui est différent de l'initiateur de photopolymérisation ; le composé Y a un poids moléculaire de 200 à 1000 et un point d'ébullition de 230 à 500 °C ; le rapport en masse de la teneur du composé Y à la teneur de la résine X est de 0,40 à 1,50 ; et si le composé Y est un composé polymérisable, le composé polymérisable a un groupe méthacryloyle.
PCT/JP2023/027215 2022-07-29 2023-07-25 Film de transfert, procédé de fabrication de stratifié, stratifié et procédé de fabrication de boîtier de semi-conducteur WO2024024783A1 (fr)

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Citations (4)

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JP2008070477A (ja) * 2006-09-12 2008-03-27 Nippon Steel Chem Co Ltd 感光性樹脂フィルムとこれを用いた回路基板の製造方法
JP2020154205A (ja) * 2019-03-22 2020-09-24 富士フイルム株式会社 パターン形成方法、硬化性樹脂組成物、膜、硬化膜、積層体、及び、半導体デバイス
JP2020533419A (ja) * 2017-09-11 2020-11-19 フジフイルム エレクトロニック マテリアルズ ユー．エス．エー．， インコーポレイテッド 誘電フィルム形成用組成物
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