Transfer film, method for manufacturing laminate, laminate, and method for manufacturing semiconductor package

Abstract

A first problem addressed by the present invention is to provide a transfer film in which step coverage is excellent when adhered to an adherend after storage, the peeling properties of a temporary carrier are excellent, and the linear expansion coefficient of a cured product of a photosensitive layer is low. A second problem addressed by the present invention is to provide a laminate, a method for manufacturing a laminate, and a method for manufacturing a semiconductor package.　A transfer film according to the present invention has a temporary carrier and a photosensitive layer disposed on the temporary carrier, wherein: the photosensitive layer includes a resin X selected from the group consisting of polyimides, polybenzoxazoles, and precursors thereof, a photopolymerization initiator, and a compound Y which is different from the photopolymerization initiator; the compound Y has a molecular weight of 200-1000 and a boiling point of 230-500°C; the mass ratio of the content of the compound Y to the content of the resin X is 0.40-1.50; and if the compound Y is a polymerizable compound, the polymerizable compound has a methacryloyl group.

Description

Transfer film, laminate manufacturing method, laminate, and semiconductor package manufacturing method

[0001] 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.

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

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

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

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

[0006] The present inventors prepared and studied a transfer film using a photosensitive resin composition as described in Patent Document 1, and found that there is room for improvement in the linear expansion coefficient of the cured product formed by the photosensitive layer of the transfer film (specifically, reducing the linear expansion coefficient). Furthermore, the transfer film is also required to have basic performance characteristics, such as excellent peelability of the temporary support and excellent conformability to unevenness when attached to an object to be attached. Here, "excellent conformability to unevenness when attached to an object to be attached" specifically means that when the photosensitive layer of the transfer film is attached (laminated) to the object to be attached, air bubbles are unlikely to form between the object to be attached and the photosensitive layer. In other words, for example, when the object to be attached is a substrate with unevenness such as wiring, the ability to attach the object to the photosensitive layer of the transfer film while suppressing the inclusion of air bubbles due to the influence of the unevenness of the object to be attached. In particular, nowadays, transfer films are sometimes stored for a certain period of time before being used for pattern formation, and therefore, there is a demand for the film to have excellent conformability to unevenness when it is attached to an object to be attached after storage.

[0007] Therefore, an object of the present invention is to provide a transfer film that has excellent step-following properties when attached to an object to be attached after storage, excellent releasability of the temporary support, and a low linear expansion coefficient of the cured product of the photosensitive layer. Another object of the present invention is to provide a laminate manufacturing method, a laminate manufacturing method, and a semiconductor package manufacturing method using the above transfer film.

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

[0009] [1] A transfer film having a temporary support and a photosensitive layer, wherein the photosensitive layer comprises: a resin X selected from the group consisting of polyimide, polybenzoxazole, and precursors thereof; a photopolymerization initiator; and a compound Y different from the photopolymerization initiator, wherein the compound Y has a molecular weight of 200 to 1000 and a boiling point of 230 to 500°C, and the mass ratio of the content of the compound Y to the content of the resin X is 0.40 to 1.50, and when the compound Y is a polymerizable compound, the polymerizable compound has a methacryloyl group. [2] The transfer film according to [1], wherein the photosensitive layer satisfies the following Requirement 1. Requirement 1: When the photosensitive layer is heated at 350°C for 1 hour, the weight loss of the photosensitive layer is 10.0 mass% or more. [3] The transfer film according to [1] or [2], wherein the mass ratio of the content of the compound Y to the content of the resin X is 0.50 to 1.00. [4] The transfer film according to any one of [1] to [3], wherein the compound Y is one or more selected from a polymerizable compound having a methacryloyl group and a solvent. [5] The transfer film according to any one of [1] to [4], wherein the compound Y includes a polymerizable compound having a methacryloyl group, and wherein the decomposition temperature of a homopolymer derived from the polymerizable compound is 300°C or less. [6] The melt viscosity of the photosensitive layer at 100°C is 5.0 x 10 ６[7] The transfer film according to any one of [1] to [5], wherein the viscosity of compound Y at 25°C is 500 mPa·s or less. [8] The transfer film according to any one of [1] to [7], wherein the content of resin X is 65.0 mass% or less, relative to the total mass of the photosensitive layer. [9] The transfer film according to any one of [1] to [8], wherein the content of compound Y is 5.0 to 50.0 mass%, relative to the total mass of the photosensitive layer.

[10] The transfer film according to any one of [1] to [9], wherein the content of compound Y is 5.0 to 25.0 mass%, relative to the total mass of the photosensitive layer.

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

[10] , wherein the content of the photopolymerization initiator is 5.0 mass% or less, relative to the total mass of the photosensitive layer.

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

[11] , further comprising a filler, the content of which is 30.0 mass % or more relative to the total mass of the photosensitive layer.

[13] The transfer film according to

[12] , wherein the average particle diameter of the filler calculated by the particle diameter measurement method described below is 10 to 300 nm.

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

[13] , wherein the thickness of the photosensitive layer is 5.0 to 19 μm.

[15] A method for producing a laminate, comprising: a laminating step of contacting and laminating a surface of the transfer film according to any one of [1] to

[14] opposite to the temporary support to a substrate, to obtain a substrate with a photosensitive layer having the substrate, the photosensitive layer, and the temporary support in this order; an exposure step of patternwise exposing the photosensitive layer; a development step of developing the exposed photosensitive layer to form a resin pattern precursor; a heating step of heating the resin pattern precursor to form a resin pattern; and a peeling step of peeling the temporary support from the substrate with a photosensitive layer between the laminating step and the exposure step or between the exposure step and the development step.

[16] A laminate obtained by the method for producing a laminate according to

[15] .

[17] A method for producing a semiconductor package, comprising the method for producing a laminate according to

[15] .

[0010] According to the present invention, there is provided a transfer film that has excellent step-following properties when attached to an object to be attached after storage, has excellent releasability of the temporary support, and has a small linear expansion coefficient of the cured product of the photosensitive layer. Furthermore, according to the present invention, there are provided a method for manufacturing a laminate, a laminate, and a semiconductor package using the above transfer film.

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

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

[0013] Furthermore, the term "process" in this specification does not only refer to an independent process, but also includes a process that cannot be clearly distinguished from other processes as long as the intended purpose of the process is achieved.

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

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

[0016] In this specification, "actinic rays" or "radiation" means, for example, the bright line spectrum of a mercury lamp, such as g-line, h-line, and i-line, far ultraviolet light typified by excimer lasers, extreme ultraviolet light (EUV light), X-rays, and electron beams (EB). In addition, in the present invention, light means actinic rays or radiation.

[0017] In this specification, unless otherwise specified, "exposure" includes not only exposure using far ultraviolet light, extreme ultraviolet light, X-rays, EUV light, etc., as typified by mercury lamps and excimer lasers, but also exposure using particle beams such as electron beams and ion beams.

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

[0019] In this specification, unless otherwise specified, when a molecular weight distribution exists, the molecular weight is the weight average molecular weight (Mw). In this specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are values ​​determined by gel permeation chromatography (GPC) in terms of polystyrene.

[0020] In this specification, "(meth)acrylic acid" is a concept that encompasses both acrylic acid and methacrylic acid, "(meth)acryloyl group" is a concept that encompasses both acryloyl group and methacryloyl group, "(meth)acrylate" is a concept that encompasses both acrylate and methacrylate, and "(poly)oxyalkylene group" is a concept that encompasses both oxyalkylene group and polyoxyalkylene group.

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

[0022] In this specification, the "solid content" of a composition refers to the components that form a composition layer formed using the composition. Usually, when a composition contains a solvent (e.g., an organic solvent and water), it refers to all components excluding the solvent. Furthermore, liquid components that form a composition layer are also considered to be solid content. However, when the photosensitive layer of the transfer film contains a solvent (solvent) with a boiling point of 230°C or higher that may be a type of compound Y, the solvent (solvent) with a boiling point of 230°C or higher that may be a type of compound Y in the photosensitive composition (composition for forming the photosensitive layer) is considered to be "solid content."

[0023] In this specification, unless otherwise specified, the thickness (film thickness) of a layer is the average thickness measured using a scanning electron microscope (SEM) for thicknesses of 0.5 μm or more, and the average thickness measured using a transmission electron microscope (TEM) for thicknesses of less than 0.5 μm. The average thickness is obtained by cutting a sample to be measured using an ultramicrotome, measuring the thickness at any five points, and calculating the arithmetic average of the thicknesses.

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

[0025] [Transfer Film] The transfer film of the present invention is a transfer film having a temporary support and a photosensitive layer, wherein the photosensitive layer comprises: a resin X (hereinafter abbreviated as "resin X") selected from the group consisting of polyimide, polybenzoxazole, and precursors thereof; a photopolymerization initiator; and a compound Y (hereinafter abbreviated as "compound Y") different from the photopolymerization initiator, wherein the compound Y has a molecular weight of 200 to 1000 and a boiling point of 230 to 500°C, and the mass ratio (hereinafter also referred to as "specific mass ratio") of the content of the compound Y to the content of the resin X is 0.40 to 1.50, and when the compound Y is a polymerizable compound, the polymerizable compound has a methacryloyl group.

[0026] The transfer film having the above configuration has excellent step-conforming properties when attached to a substrate after storage, excellent releasability of the temporary support, and a small linear expansion coefficient of the cured product of the photosensitive layer. Although the detailed mechanism of action of the transfer film is unclear, the inventor speculates as follows: When the photosensitive layer of the transfer film is attached (laminated) to a substrate and a resin pattern (corresponding to the cured product of the photosensitive layer) is formed by exposure treatment, development treatment, and post-development heat treatment, compound Y functions as a component to ensure the plasticity of the resin in the photosensitive layer, and is removed by volatilization when the post-development heat treatment is performed, making it difficult to remain in the resin pattern system. In other words, due to the above-mentioned action of compound Y, when the photosensitive layer of the transfer film is attached to a substrate, the transfer film has excellent step-conforming properties due to the plasticizing effect of compound Y, and it is speculated that the resin pattern formed by the transfer film has a smaller thermal expansion coefficient due to the reduced content of compound Y.

[0027] Furthermore, since the photosensitive layer of the transfer film contains the compound Y and the resin X and compound Y are in a specific mass ratio, it is presumed that the three effects of step conformability when attached to a substrate after storage, releasability of the temporary support, and linear expansion coefficient of the cured product of the photosensitive layer are balanced 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 environmental influences during storage of the transfer film, and therefore are unlikely to contribute to improving step conformability when attached to a substrate after storage. On the other hand, compounds with a molecular weight of more than 1000 and / or a boiling point of more than 500°C are likely to remain in the system of the resin pattern (cured product of the photosensitive layer) formed by the transfer film and are unlikely to contribute to reducing the thermal expansion coefficient (which may be one of the factors that increase the thermal expansion coefficient). Furthermore, it has been confirmed that if the specific mass ratio is less than 0.40, the transfer film has poor conformability to unevenness when it is attached to an object after storage, and if the specific mass ratio is more than 1.50, the temporary support has poor releasability.

[0028] Hereinafter, "the effect of the present invention is better" may mean that the transfer film has better conformability to unevenness when it is attached to an object to be attached after storage, that the temporary support has better peelability, and / or that the linear expansion coefficient of the cured product of the photosensitive layer is smaller.

[0029] The transfer film will be described below. 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 other layers other than the photosensitive layer on the temporary support. In the following, the photosensitive layer disposed on the temporary support and other layers optionally included may be collectively referred to as the "composition layer." The transfer film may also have a configuration having a protective film (hereinafter also referred to as a "cover film") on the composition layer.

[0030] FIG. 1 is a cross-sectional schematic diagram showing an example of an embodiment of a transfer film. The transfer film 100 shown in FIG. 1 has a configuration in which a temporary support 12, a photosensitive layer 14, and a cover film 16 are laminated in this order. Although the transfer film 100 shown in FIG. 1 has the cover film 16, the transfer film may have no cover film 16. Furthermore, as described below, the transfer film may further have an intermediate layer and / or a thermoplastic resin layer. Each component of the transfer film will be described in detail below.

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

[0032] The temporary support may have either a single-layer structure or a multi-layer structure. The temporary support is preferably a film, more preferably a resin film. The temporary support is also preferably a film that is flexible and does not significantly deform, shrink, or stretch under pressure, or under pressure and heat. Examples of the film include polyethylene terephthalate films (e.g., biaxially oriented polyethylene terephthalate films), polymethyl methacrylate films, cellulose triacetate films, polystyrene films, polyimide films, and polycarbonate films, with polyethylene terephthalate films being preferred. Furthermore, the temporary support is preferably free of deformations such as wrinkles and scratches.

[0033] The temporary support preferably has high transparency in order to allow pattern exposure through the temporary support. Specifically, the transmittance at each of the wavelengths of 313 nm, 365 nm, 405 nm, and 436 nm is preferably 60% or more, more preferably 70% or more, even more preferably 80% or more, and most preferably 90% or more. The upper limit is preferably less than 100%. Preferred values ​​of the transmittance at each of the above wavelengths include, for example, 87%, 92%, and 98%. In terms of the pattern formability during pattern exposure through the temporary support and the transparency of the temporary support, the haze of the temporary support is preferably small. Specifically, the haze value of the temporary support is preferably 2% or less, more preferably 0.5% or less, and even more preferably 0.1% or less. The lower limit is preferably 0% or more. In terms of the pattern formability during pattern exposure through the temporary support and the transparency of the temporary support, the number of fine particles, foreign matter, and defects contained in the temporary support is preferably small. The number of particles, foreign matter, and defects with a diameter of 1 μm or more on the temporary support is 50 / 10 mm ２ Preferably, 10 pieces / 10 mm or less ２ More preferably, 3 pieces / 10 mm or less ２ More preferably, 0 pieces / 10 mm or less ２ is particularly preferred.

[0034] The thickness of the temporary support is preferably 5 to 200 μm, and from the viewpoint of ease of handling and versatility, more preferably 5 to 150 μm, still more preferably 5 to 50 μm, and particularly preferably 5 to 35 μm. The thickness of the temporary support can be calculated as the average value of any five points measured by cross-sectional observation using an SEM (scanning electron microscope).

[0035] In order to improve the adhesion between the temporary support and the composition layer, the surface of the temporary support that comes into contact with the composition layer may be surface-modified by UV irradiation, corona discharge, plasma, etc. When the surface is modified by UV irradiation, the exposure dose of UV irradiation is 10 to 2000 mJ / cm. ２ is preferred, and 50 to 1000 mJ / cm ２ Examples of light sources for UV irradiation include low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, carbon arc lamps, metal halide lamps, xenon lamps, chemical lamps, electrodeless discharge lamps, and light-emitting diodes that emit light in the wavelength range of 150 to 450 nm. The lamp output and illuminance can be adjusted as appropriate.

[0036] Examples of the temporary support include a biaxially oriented polyethylene terephthalate film having a thickness of 16 μm, a biaxially oriented polyethylene terephthalate film having a thickness of 12 μm, and a biaxially oriented polyethylene terephthalate film having a thickness of 9 μm. The temporary support may be a recycled product. Examples of the recycled product include a film obtained by cleaning and chipping used films. Examples of commercially available recycled products include the Ecouse series (manufactured by Toray Industries, Inc.).

[0037] Examples of temporary supports include those described in paragraphs 0017 to 0018 of JP-A-2014-085643, paragraphs 0019 to 0026 of JP-A-2016-027363, paragraphs 0041 to 0057 of WO 2012 / 081680, and paragraphs 0029 to 0040 of WO 2018 / 179370, the contents of which are incorporated herein by reference.

[0038] The temporary support may have a layer containing fine particles (lubricant layer) on one or both sides of the temporary support in order to provide handleability. The diameter of the fine particles contained in the lubricant layer is preferably 0.05 to 0.8 μm. The film thickness of the lubricant layer is preferably 0.05 to 1.0 μm. Commercially available temporary supports include, for example, Lumirror 16FB40, Lumirror 16KS40, Lumirror #38-U48, Lumirror #75-U34, and Lumirror #25T60 (all manufactured by Toray Industries, Inc.); and Cosmoshine A4100, Cosmoshine A4160, Cosmoshine A4300, Cosmoshine A4360, and Cosmoshine A8300 (all manufactured by Toyobo Co., Ltd.).

[0039] [Photosensitive Layer] First, various components contained in the photosensitive layer will be described below.

[0040] <Resin X> 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 singly or in combination of two or more types. Resin X is a compound different from the various components described below (e.g., compound Y, etc.). The polyimide precursor is a resin that can be converted into polyimide by heat treatment or chemical treatment. The polybenzoxazole precursor is a resin that can be converted into polybenzoxazole by heat treatment or chemical treatment.

[0041] Resin X may have a polymerizable group. Examples of the polymerizable group include known polymerizable groups such as a radical polymerizable group, an epoxy group, an oxetanyl group, a methylol group, and an alkoxymethyl group. The radical polymerizable group is preferably a group having an ethylenically unsaturated bond. Examples of the group having an ethylenically unsaturated bond include a (meth)acrylamide group and a (meth)acryloyl group, with a (meth)acryloyl group being preferred. Resin X preferably has a polymerizable group that can polymerize with a polymerizable group in a polymerizable compound described below.

[0042] (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. The polyimide is preferably a resin synthesized from a polyimide precursor having a repeating unit represented by formula (1) described later (for example, a resin obtained by a ring-closing reaction). The polyimide precursor preferably has a repeating unit represented by formula (1).

[0043]

[0044] In formula (1), A １ and A ２ R each independently represents an oxygen atom or —NH—. １１１ represents a divalent organic group. １１３ and R １１４ R each independently represents a hydrogen atom or a monovalent organic group. １１５ represents a tetravalent organic group.

[0045] In formula (1), A １ and A ２ each independently represents an oxygen atom or —NH—. １ and A ２ is preferably an oxygen atom.

[0046] In formula (1), R １１１ represents a divalent organic group. Examples of the divalent organic group include an aliphatic group, an aromatic ring group, and a group formed by combining these. 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 group formed by combining these, 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 monocyclic or polycyclic. The aliphatic group and the aromatic ring group may have a heteroatom. Examples of the heteroatom include -O-, -CO-, -S-, and -SO. ２ It may be contained in the divalent organic group as a group such as - and -NHCO-. １１１As the diamine, a divalent organic group derived from a diamine is also preferred. The diamine is preferably a diamine used in the production of a polyimide precursor, with aliphatic diamines or aromatic diamines being more preferred. The diamine is preferably a diamine having a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic ring group having 6 to 20 carbon atoms, or a group combining these, with diamines having an aromatic ring group having 6 to 20 carbon atoms (aromatic diamines) being more preferred. Examples of the aromatic ring group include groups having the following structure:

[0047]

[0048] In the above formula, A represents a divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms which may have a fluorine atom, -O-, -CO-, -S-, -SO ２ A represents an alkylene group having 1 to 3 carbon atoms which may have a fluorine atom, -O-, -CO-, -S-, or -SO ２ - is preferably at least one selected from the group consisting of -CH ２ -, -O-, -S-, -SO ２ -, -C(CF ３ ) ２ -, and -C(CH ３ ) ２ At least one selected from the group consisting of - is more preferred, and -O- is even more preferred.

[0049] R １１１ is *-Ar ０ -L ０ -Ar ０ -* is also preferred. ０ represents an aromatic hydrocarbon group. ０ represents an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may have a fluorine atom, —O—, —CO—, —S—, —SO ２ -, -NHCO-, or a group formed by combining these, or a single bond. * indicates the bonding position. Ar ０ They may be the same or different.

[0050] Ar０ The number of carbon atoms in the aromatic hydrocarbon group represented by the formula (I) is preferably 6 to 22, more preferably 6 to 18, and even more preferably 6 to 10. The aromatic hydrocarbon group is preferably a phenyl group. ０ has the same meaning as A in the above-mentioned AR-8, and the preferred embodiments are also the same.

[0051] Examples of diamines include 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, 1,6-diaminohexane; 1,2- or 1,3-diaminocyclopentane, 1,2-, 1,3-, or 1,4-diaminocyclohexane, 1,2-, 1,3-, or 1,4-bis(aminomethyl)cyclohexane, bis-(4-aminocyclohexyl)methane, bis-(3-aminocyclohexyl)methane, 4,4'-diamino-3,3'-dimethylcyclohexylmethane, or isophoronediamine; meta- or para- Phenylenediamine, diaminotoluene, 4,4'- or 3,3'-diaminobiphenyl, 4,4'-diaminodiphenyl ether, 3,3-diaminodiphenyl ether, 4,4'- or 3,3'-diaminodiphenylmethane, 4,4'- or 3,3'-diaminodiphenyl sulfone, 4,4'- or 3,3'-diaminodiphenyl sulfide, 4,4'- or 3,3'-diaminobenzophenone, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl (4,4'-diamino-2,2'-dimethyl biphenyl), 3,3'-dimethoxy-4,4'-diaminobiphenyl, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis(3-hydroxy-4-aminophenyl)propane, 2,2-bis(3-hydroxy-4-aminophenyl)hexafluoropropane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, bis(3-amino-4-hydroxyphenyl)sulfone, bis(4 -amino-3-hydroxyphenyl)sulfone, 4,4'-diaminoparaterphenyl, 4,4'-bis(4-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, bis[4-(2-aminophenoxy)phenyl]sulfone, 1,4-bis(4-aminophenoxy)benzene, 9,10-bis(4-aminophenyl)anthracene, 3,3'-dimethyl-4,4'-diaminodiphenylsulfone, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 9,10-bis(4-aminophenyl)anthracene, 3,3'-dimethyl-4,4'-diaminodiphenylsulfone, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenyl)anthracene ...3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenyl)benzene, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 4,4'-diaminooctafluorobiphenyl, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 9,9-bis(4-aminophenyl)-10-hydroanthracene, 3,3',4,4'-tetraafluorobenzoate aminobiphenyl, 3,3',4,4'-tetraaminodiphenyl ether, 1,4-diaminoanthraquinone, 1,5-diaminoanthraquinone, 3,3-dihydroxy-4,4'-diaminobiphenyl, 9,9'-bis(4-aminophenyl)fluorene, 4,4'-dimethyl-3,3'-diaminodiphenyl sulfone, 3,3',5,5'-tetramethyl-4,4'-diaminodiphenylmethane, 2-(3',5'-diaminobenzoyloxy)ethyl methacrylate, 2,4- or 2,5-diaminocumene, 2,5- Dimethyl-paraphenylenediamine, acetoguanamine, 2,3,5,6-tetramethyl-paraphenylenediamine, 2,4,6-trimethyl-metaphenylenediamine, bis(3-aminopropyl)tetramethyldisiloxane, 2,7-diaminofluorene, 2,5-diaminopyridine, 1,2-bis(4-aminophenyl)ethane, diaminobenzanilide, esters of diaminobenzoic acid, 1,5-diaminonaphthalene, diaminobenzotrifluoride, 1,3-bis(4-aminophenyl)hexafluoropropane , 1,4-bis(4-aminophenyl)octafluorobutane, 1,5-bis(4-aminophenyl)decafluoropentane, 1,7-bis(4-aminophenyl)tetradecafluoroheptane, 2,2-bis[4-(3-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(2-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)-3,5-dimethylphenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)-3,4,4'-bis(4-amino-2-trifluoromethylphenoxy)diphenyl sulfone, 4,4'-bis(3-amino-5-trifluoromethylphenoxy)diphenyl sulfone, 2,2-bis[4-(4-amino-3-trifluoromethylphenoxy)phenyl]hexafluoropropane, 3,3',5,5'-tetramethyl-4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, 2,2',5,5',6,6'-hexafluorotolidine, and 4,4'-diaminoquaterphenyl. Further, examples of diamines include compounds represented by any one of formulas (DA-1) to (DA-18).

[0052]

[0053]

[0054] Further, the diamine also includes a diamine having two or more alkylene glycol units in the main chain, and as the diamine having two or more alkylene glycol units in the main chain, a diamine containing two or more ethylene glycol chains and / or two or more propylene glycol chains in total per molecule is preferred. Diamines not containing aromatic rings are also preferred. Examples of the diamine include the Jeffamine (registered trademark) series (KH-511, ED-600, ED-900, ED-2003, EDR-148, EDR-176, D-200, D-400, D-2000, and D-4000, manufactured by HUNTSMAN), 1-(2-(2-(2-aminopropoxy)ethoxy)propoxy)propan-2-amine, and 1-(1-(1-(2-aminopropoxy)propan-2-yl)oxy)propan-2-amine.

[0055] R １１３ and R １１４R each independently represents a hydrogen atom or a monovalent organic group. １１３ and R １１４ Preferably, at least one of R represents a group having a polymerizable group, １１３ and R １１４ It is more preferable that both R and R represent a group having a polymerizable group. Examples of the polymerizable group include the groups exemplified as the polymerizable group that the resin X may have. The monovalent organic group may be the monovalent organic group X described below. １１３ and R １１４ As the alkyl group, a group having an ethylenically unsaturated group is preferred, and a vinyl group, an allyl group, a (meth)acryloyl group, or a group represented by formula (III) is more preferred.

[0056]

[0057] In formula (III), R ２００ represents a hydrogen atom or a methyl group. ２０１ represents an alkylene group having 2 to 12 carbon atoms, —CH ２ CH(OH)CH ２ - or a (poly)oxyalkylene group having 4 to 30 carbon atoms. * indicates the bonding position.

[0058] In formula (III), R ２００ represents a hydrogen atom or a methyl group. ２００ As the alkyl group, a methyl group is preferred.

[0059] In formula (III), R ２０１ represents an alkylene group having 2 to 12 carbon atoms, —CH ２ CH(OH)CH ２ -, or a (poly)oxyalkylene group having 4 to 30 carbon atoms. The number of carbon atoms in the alkylene group constituting the (poly)oxyalkylene group is preferably 1 to 12, more preferably 1 to 6, and even more preferably 1 to 3. The number of repetitions of oxyalkylene constituting the (poly)oxyalkylene group is preferably 1 to 12, more preferably 1 to 6, and even more preferably 1 to 3. R ２０１Examples of the alkyl group include an ethylene group, a propylene group, a trimethylene group, a tetramethylene group, a 1,2-butanediyl group, a 1,3-butanediyl group, a pentamethylene group, a hexamethylene group, an octamethylene group, a dodecamethylene group, and —CH ２ CH(OH)CH ２ -, and an ethylene group, a propylene group, a trimethylene group, or -CH ２ CH(OH)CH ２ - is preferred, and an ethylene group is more preferred.

[0060] R １１３ or R １１４ Examples of the monovalent organic group represented by the formula (I) include an aliphatic group, an aromatic ring group, and an arylalkyl group having 1 to 3 acid groups. Examples include an aromatic ring group having 6 to 20 carbon atoms and having an acid group, and an arylalkyl group having 7 to 25 carbon atoms and having an acid group. More specifically, examples include a phenyl group having an acid group and a benzyl group having an acid group. The acid group is preferably a hydroxyl group or a carboxyl group. R １１３ and R １１４ Also preferred as is a hydrogen atom, 2-hydroxybenzyl, 3-hydroxybenzyl, or 4-hydroxybenzyl.

[0061] In formula (1), R １１５ represents a tetravalent organic group. As the tetravalent organic group, a tetravalent organic group having an aromatic ring is preferred, and a group represented by formula (5) or a group represented by formula (6) is more preferred.

[0062]

[0063] In formula (5), R １１２ represents a divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms which may have a fluorine atom, -O-, -CO-, -S-, -SO ２ * represents a bonding position. In formula (6), * represents a bonding position.

[0064] In formula (5), R １１２ has the same meaning as A in the above-mentioned AR-8, and the preferred embodiments are also the same.

[0065] The tetravalent organic group may be, for example, a tetracarboxylic acid residue remaining after removing the acid dianhydride group from a tetracarboxylic acid dianhydride. The tetracarboxylic acid dianhydride is preferably a compound represented by formula (7).

[0066]

[0067] In formula (7), R １１５ represents a tetravalent organic group. １１５ is R in formula (1). １１５ The same definition and preferred embodiments are also the same.

[0068] Examples of tetracarboxylic dianhydrides include pyromellitic acid, pyromellitic dianhydride (PMDA), 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfidetetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, and 3,3',4,4'-diphenylmethanetetracarboxylic dianhydride. hydrate, 2,2',3,3'-diphenylmethanetetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-benzophenonetetracarboxylic dianhydride, 4,4'-oxydiphthalic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,7-naphthalenetetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl)propane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 1,3-diphenylhexafluoropropane-3,3,4,4-tetracarboxylic dianhydride, 1,4,5,6-naphthalenetetracarboxylic dianhydride, 2,2',3,3'-diphenyltetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 1,2,4,5-naphthalene Examples thereof include tetracarboxylic acid dianhydride, 1,4,5,8-naphthalenetetracarboxylic acid dianhydride, 1,8,9,10-phenanthrenetetracarboxylic acid dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, 1,2,3,4-benzenetetracarboxylic acid dianhydride, and alkyl derivatives having 1 to 6 carbon atoms and alkoxy derivatives having 1 to 6 carbon atoms.

[0069] Examples of the tetracarboxylic dianhydride include compounds represented by any one of formulas (DAA-1) to (DAA-5).

[0070]

[0071] (Monovalent Organic Group X) The monovalent organic group X is preferably an alkyl group which may have a substituent or an aromatic ring group which may have a substituent, and more preferably an alkyl group which may have an aromatic ring group. The alkyl group may be linear, branched, or cyclic. The cyclic group may be monocyclic or polycyclic. The number of carbon atoms in the linear or branched alkyl group is preferably 1 to 30. The number of carbon atoms in the cyclic alkyl group (cycloalkyl group) is preferably 3 to 30. Examples of the alkyl group include linear or branched alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, octadecyl, isopropyl, isobutyl, sec-butyl, t-butyl, 1-ethylpentyl, and 2-ethylhexyl; monocyclic cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl; and polycyclic cycloalkyl groups such as adamantyl, norbornyl, bornyl, camphenyl, decahydronaphthyl, tricyclodecanyl, tetracyclodecanyl, campholoyl, dicyclohexyl, and pinenyl. The substituent that the alkyl group may have is preferably an aromatic ring group, as described below.

[0072] The aromatic ring group may be either an aromatic hydrocarbon ring group or an aromatic heterocyclic group. The aromatic ring group may be either a monocyclic or polycyclic ring. Examples of rings constituting the aromatic ring group include aromatic hydrocarbon rings such as a benzene ring, a naphthalene ring, a biphenyl ring, a fluorene ring, a pentalene ring, an indene ring, an azulene ring, a heptalene ring, an indacene ring, a perylene ring, a pentacene ring, an acenaphthene ring, a phenanthrene ring, an anthracene ring, a naphthacene ring, a chrysene ring, and a triphenylene ring; a fluorene ring, a pyrrole ring, a furan ring, a thiophene ring, an imidazole ring, an oxazole ring, a thiazole ring, a pyridine ring, a pyrazine ring, a pyridine ... Examples of the aromatic heterocyclic group include an imidine ring, a pyridazine ring, an indolizine ring, an indole ring, a benzofuran ring, a benzothiophene ring, an isobenzofuran ring, a quinolizine ring, a quinoline ring, a phthalazine ring, a naphthyridine ring, a quinoxaline ring, a quinoxazoline ring, an isoquinoline ring, a carbazole ring, a phenanthridine ring, an acridine ring, a phenanthroline ring, a thianthrene ring, a chromene ring, a xanthene ring, a phenoxathiin ring, a phenothiazine ring, and a phenazine ring. The substituent that the aromatic ring group may have is preferably the alkyl group described above.

[0073] The polyimide precursor preferably contains fluorine atoms. The content of fluorine atoms in the polyimide precursor is preferably 10% by mass or more, more preferably 20% by mass or more, based on the total mass of the polyimide precursor. The upper limit is preferably 50% by mass or less.

[0074] The polyimide precursor may be obtained by copolymerizing the repeating unit represented by formula (1) with an aliphatic group having a siloxane structure, which can improve adhesion to a substrate. Examples of the aliphatic group having a siloxane structure include bis(3-aminopropyl)tetramethyldisiloxane and bis(paraaminophenyl)octamethylpentasiloxane.

[0075] 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).

[0076]

[0077] A １１ and A １２ represents an oxygen atom or —NH—. １１１ and R １１２ R each independently represents a divalent organic group. １１３ and R １１４ each independently represents a hydrogen atom or a monovalent organic group.

[0078] In formula (1-A), A １１ , A １２ , R １１１ , R １１３ , and R １１４ are respectively represented by A in formula (1). １ , A ２ , R １１１ , R １１３ , and R １１４ The same definition and preferred embodiments are also the same.

[0079] In formula (1-A), R １１２ In formula (5), R １１２ The same definition and preferred embodiments are also the same.

[0080] In formula (1-A), the bonding positions of the carbonyl group to the benzene ring are preferably 4, 5, 3', and 4' in formula (1-A).In (1-B), the bonding positions of the carbonyl group to the benzene ring are preferably 1, 2, 4, and 5 in formula (1-B).

[0081] The polyimide precursor may contain other repeating units in addition to the repeating unit represented by formula (1).

[0082] The content of the repeating unit represented by formula (1) is preferably 50 mol% or more, more preferably 70 mol% or more, and even more preferably 90 mol% or more, based on the total repeating units of the polyimide precursor. The upper limit is preferably 100 mol% or less.

[0083] The weight-average molecular weight (Mw) of the polyimide precursor is preferably 2,000 to 500,000, more preferably 5,000 to 100,000, and even more preferably 10,000 to 50,000. The number-average molecular weight (Mn) of the polyimide precursor is preferably 800 to 250,000, more preferably 2,000 to 50,000, and even more preferably 4,000 to 25,000. The polyimide precursor has a dispersity (Mw / Mn) of preferably 1.5 to 3.5, and more preferably 2.0 to 3.0.

[0084] (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. As the polybenzoxazole, a resin synthesized from a polybenzoxazole precursor having a repeating unit represented by formula (2) described later (for example, a resin obtained by a ring-closing reaction) is preferred. The polybenzoxazole precursor preferably has a repeating unit represented by formula (2).

[0085]

[0086] In formula (2), R １２１ represents a divalent organic group. １２２ represents a tetravalent organic group. １２３ and R １２４ each independently represents a hydrogen atom or a monovalent organic group.

[0087] In formula (2), R １２１ represents a divalent organic group. Examples of the divalent organic group include R １１１ Examples of the divalent organic group include a divalent organic group represented by the following formula:

[0088] In formula (2), R １２２ represents a tetravalent organic group. As the tetravalent organic group, R １１５ Examples of the tetravalent organic group include a tetravalent organic group represented by the following formula:

[0089] In formula (2), R １２３ and R １２４ R each independently represents a hydrogen atom or a monovalent organic group. １２３and R １２４ is R １１３ and R １１４ The same definition and preferred embodiments are also the same.

[0090] The polybenzoxazole precursor may contain other repeating units in addition to the repeating unit represented by formula (2). Examples of the other repeating units include repeating units having a siloxane structure. Examples of the other repeating units include the repeating units described in paragraphs 0150 to 0154 of JP 2020-154205 A.

[0091] The weight-average molecular weight (Mw) of the polybenzoxazole precursor is preferably 2,000 to 500,000, more preferably 5,000 to 100,000, and even more preferably 10,000 to 50,000. The number-average molecular weight (Mn) of the polybenzoxazole precursor is preferably 800 to 250,000, more preferably 2,000 to 50,000, and even more preferably 4,000 to 25,000. The polybenzoxazole precursor has a dispersity (Mw / Mn) of preferably 1.5 to 3.5, and more preferably 2.0 to 3.0.

[0092] Resin X may be used alone or in combination of two or more. The content of resin X is preferably 5.0% by mass or more, more preferably 10.0% by mass or more, relative to the total mass of the photosensitive layer. The upper limit is preferably 80.0% by mass or less, more preferably 70.0% by mass or less, and even more preferably 65.0% by mass or less, relative to the total mass of the photosensitive layer. When the photosensitive layer contains a filler described below, 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.

[0093] <Photopolymerization Initiator> The photosensitive layer contains a photopolymerization initiator. Examples of the photopolymerization initiator include a photoradical polymerization initiator, a photocationic polymerization initiator, and a photoanionic polymerization initiator, and a photoradical polymerization initiator is preferred.

[0094] Examples of the photopolymerization initiator include an oxime ester compound (a photopolymerization initiator having an oxime ester structure), an aminoacetophenone compound (a photopolymerization initiator having an aminoacetophenone structure), a hydroxyacetophenone compound (a photopolymerization initiator having a hydroxyacetophenone structure), an acylphosphine oxide compound (a photopolymerization initiator having an acylphosphine oxide structure), and a bistriphenylimidazole compound (a photopolymerization initiator having a bistriphenylimidazole structure). As the photopolymerization initiator, an oxime ester compound or an aminoacetophenone compound is preferred, and an oxime ester compound is more preferred.

[0095] Examples of the oxime ester compound include 1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2-(O-benzoyloxime)] (trade name: IRGACURE OXE-01, manufactured by BASF), ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime) (trade name: IRGACURE OXE-02, manufactured by BASF), [8-[5-(2,4,6-trimethylphenyl)-11-(2-ethylhexyl)-11H-benzo[a]carbazol-3-yl]-[2-(2,2,3,3-tetrafluoropropoxy)phenyl]methanone-(O-acetyloxime) (trade name: IRGACURE OXE-03, manufactured by BASF), and OXE-03, manufactured by BASF), 1-[4-[4-(2-benzofuranylcarbonyl)phenyl]thio]phenyl]-4-methylpentanone-1-(O-acetyloxime) (trade name: IRGACURE OXE-04, manufactured by BASF and trade name: Lunar 6, manufactured by DKSH Japan Co., Ltd.), 1-[4-(phenylthio)phenyl]-3-cyclopentylpropane-1,2-dione-2-(O-benzoyloxime) (trade name: TR-PBG-305, manufactured by Changzhou New Power Electronic Materials Co., Ltd.), 1,2-propanedione,3-cyclohexyl-1-[9-ethyl-6-(2-furanylcarbonyl)-9H-carbazol-3-yl]-,2-(O-acetyloxime) (trade name: TR-PBG-326, manufactured by Changzhou New Power Electronic Materials Co., Ltd.), and 3-cyclohexyl-1-(6-(2-(benzoyloxyimino)hexanoyl)-9-ethyl-9H-carbazol-3-yl)-propane-1,2-dione-2-(O-benzoyloxime) (trade name: TR-PBG-391, manufactured by Changzhou New Power Electronic Materials Co., Ltd.).

[0096] Examples of aminoacetophenone compounds include 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone (trade name: Omnirad 379EG, manufactured by IGM Resins B.V.), 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one (trade name: Omnirad 907, manufactured by IGM Resins B.V.), and API-307 (1-(biphenyl-4-yl)-2-methyl-2-morpholinopropan-1-one, manufactured by Shenzhen UV-ChemTech Ltd.).

[0097] Examples of the photopolymerization initiator include 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]phenyl}-2-methyl-propan-1-one (trade name: Omnirad 127), 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1 (trade name: Omnirad 369), 2-hydroxy-2-methyl-1-phenyl-propan-1-one (trade name: Omnirad 1173), 1-hydroxy-cyclohexyl-phenyl-ketone (trade name: Omnirad 184), 2,2-dimethoxy-1,2-diphenylethan-1-one (trade name: Omnirad 651), 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (trade name: Omnirad TPO), and H), and bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (trade name: Omnirad 819).

[0098] Examples of the photopolymerization initiator include the photopolymerization initiators described in paragraphs 0031 to 0042 of JP-A No. 2011-095716 and paragraphs 0064 to 0081 of JP-A No. 2015-014783.

[0099] The photopolymerization initiator may be used alone or in combination of two or more. The content of the photopolymerization initiator is preferably 10.0% by mass or less, more preferably 5.0% by mass or less, and even more preferably 1.0% by mass or less, based on the total mass of the photosensitive layer. The lower limit is preferably 0.1% by mass or more.

[0100] <Compound Y> The photosensitive layer contains compound Y. Compound Y is a compound different from the photopolymerization initiator described above and different from the thermal base generator described below. Compound Y is a compound having a molecular weight of 200 to 1000 and a boiling point of 230 to 500°C. In addition, when compound Y has a molecular weight distribution, the molecular weight of compound Y refers to the weight average molecular weight. In this specification, the boiling point of compound Y refers to the value determined by the following measurement method. When compound Y is distilled under atmospheric pressure (760 mmHg), the boiling point is the gas temperature at which condensation of the evaporated gas begins (measured from 23°C to 300°C, with a temperature increase rate of 1°C / min). Distillation is carried out using a Liebig condenser, and if distillation does not begin at 300°C under atmospheric pressure, distillation is carried out under reduced pressure. Similar distillation was performed at pressures of 100 mmHg, 50 mmHg, and 5 mmHg in that order (23°C to 300°C, and if distillation does not begin at 300°C, the next pressure was used). The boiling point at atmospheric pressure was calculated using the nomograph shown in Figure 2 (Source: Science of Petroleum, Vol. II, p. 1281 (1938)) based on the temperature and pressure at which condensation of the evaporated gas began. If distillation does not begin at 300°C under 5 mmHg, the boiling point at atmospheric pressure is deemed to be greater than 500°C. The method of using a nomograph is well known. Specifically, a straight line is drawn between the boiling point at reduced pressure (line A) and the degree of reduced pressure (line C) (Procedure 1), and the value at the intersection of the line drawn in Procedure 1 and Line B is read (Procedure 2). This value is deemed to be the boiling point at atmospheric pressure.

[0101] Furthermore, when compound Y is a polymerizable compound, the polymerizable compound has a methacryloyl group. When the polymerizable compound corresponding to compound Y is a compound having a methacryloyl group, depolymerization of the polymer derived from the polymerizable compound is likely to occur in a heat treatment after development when forming a resin pattern, and the amount of the polymer derived from the polymerizable compound remaining in the system is likely 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 a heat treatment after development when forming a resin pattern, and the expected effects of the present invention are difficult to achieve.

[0102] The lower limit of the molecular weight of compound Y is preferably 250 or more, more preferably 300 or more, and the upper limit is preferably 800 or less, more preferably 600 or less.

[0103] The lower limit of the boiling point of compound Y is preferably 250° C. or higher, more preferably 280° C. or higher, even more preferably 300° C. or higher, and particularly preferably 350° C. or higher. The upper limit is preferably 480° C. or lower, more preferably 450° C. or lower.

[0104] 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. 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.

[0105] The specific type of compound Y is not particularly limited, but in terms of achieving better effects of the present invention, it is preferably one or more selected from a polymerizable compound having a methacryloyl group and a solvent. That is, specific types of compound Y are preferably 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"). The polymerizable compound YM and solvent YN will be described below.

[0106] (Polymerizable Compound YM) The polymerizable compound YM is a compound having a molecular weight of 200 to 1000, a boiling point of 230 to 500°C, and 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. Examples of the other polymerizable group include an acryloyl group, a vinyl group, and a styryl group.

[0107] The polymerizable compound YM is preferably a polymerizable compound having 1 to 5 polymerizable groups in one molecule, more preferably a polymerizable compound having two polymerizable groups (hereinafter also referred to as a "bifunctional polymerizable compound"), and even more preferably a dimethacrylate compound.

[0108] Examples of the monofunctional polymerizable compound YM include phenoxy methacrylate, dicyclopentanyl methacrylate, isobornyl methacrylate, phenoxyethyl methacrylate, and 2-hydroxyethyl methacrylate. Examples of commercially available monofunctional polymerizable compound YM include EBECRYLIBOMA (manufactured by Daicel Allnex Corporation) and Viscoat #192 (manufactured by Osaka Organic Chemical Industry Ltd.).

[0109] Examples of the bifunctional polymerizable compound YM include diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tricyclodecane dimethanol dimethacrylate, tricyclodecane dimenanol dimethacrylate, 1,4-butanediol dimethacrylate, 1,9-nonanediol dimethacrylate, and 1,6-hexanediol dimethacrylate. Examples of commercially available bifunctional polymerizable compounds YM include diethylene glycol dimethacrylate (2G, manufactured by Shin-Nakamura Chemical Co., Ltd.), triethylene glycol dimethacrylate (3G, manufactured by Shin-Nakamura Chemical Co., Ltd.), and tricyclodecane dimethanol dimethacrylate (DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.).

[0110] An example of the trifunctional polymerizable compound YM is trimethylpropane trimethacrylate (molecular weight: 338, boiling point: 347° C.). An example of a commercially available trifunctional polymerizable compound YM is EBECRYLTMPPTMA (manufactured by Daicel Allnex Corporation).

[0111] As the polymerizable compound YM, in terms of superior conformability to unevenness, for example, —O—(AL ＹＭ１ A structure containing —O)n- is preferred. ＹＭ１represents a linear, branched, or cyclic alkylene group, and n represents an integer of 1 to 10. ＹＭ１ The number of carbon atoms in the alkylene group represented by the formula (I) is preferably 1 to 20, more preferably 1 to 14, and still more preferably 1 to 12. n is preferably 1 to 8, and more preferably 1 to 6.

[0112] Among the polymerizable compounds YM, those having a decomposition temperature of 300°C or lower are preferred because the polymer derived from the polymerizable compound YM is likely to depolymerize during heat treatment after development when forming a resin pattern. Here, "the decomposition temperature of the homopolymer derived from the polymerizable compound YM is X°C or lower" means that when the homopolymer derived from the polymerizable compound YM is heat-treated at X°C for 3 hours under a nitrogen atmosphere, the ratio of the weight-average molecular weight of the homopolymer derived from the polymerizable compound YM after heat treatment to the weight-average molecular weight of the homopolymer derived from the polymerizable compound YM before heat treatment (weight-average molecular weight of the homopolymer derived from the polymerizable compound YM after heat treatment / weight-average molecular weight of the homopolymer derived from the polymerizable compound YM before heat treatment) is 1 / 3 or lower. In other words, when the decomposition temperature of the homopolymer derived from the polymerizable compound YM is 300°C or lower, this means that the ratio before and after 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 more preferably 10,000 to 100,000. The weight-average molecular weight can be measured using GPC (apparatus: Tosoh high-speed GPC apparatus HLC-8420GPC (trade name), manufactured by Tosoh Corporation).

[0113] The temperature at which the polymer derived from the polymerizable compound YM decomposes is more preferably 230° C. or lower. The lower limit of the decomposition temperature is preferably 50° C. or higher, more preferably 100° C. or higher.

[0114] (Solvent YM) Solvent YM is a solvent having a molecular weight of 200 to 1000 and a boiling point of 230 to 500° C. Examples of solvent YM include benzyl benzoate, triacetin glycerin triacetate, 1,6-hexanediol diacetate, diethylene glycol monobutyl ether acetate, hexaethylene glycol monomethyl ether, pentaethylene glycol monomethyl ether, tetraethylene glycol monomethyl ether, heptaethylene glycol 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.

[0115] A preferred example of the structure of the solvent YM is polyethylene glycol monoalkyl ether or polyethylene glycol dialkyl ether, which has a molecular weight of 200 to 1000 and a boiling point of 230 to 500°C.

[0116] The compound Y may be used alone or in combination of two or more.

[0117] The compound Y preferably includes at least one selected from the group consisting of a compound Y having a boiling point of 230° C. or higher and lower than 350° C. and a compound Y having a boiling point of 350° C. or higher and 500° C. or lower. The compound Y also preferably includes both a polymerizable compound YM and a solvent YN, and more preferably includes both a polymerizable compound YM having a boiling point of 230° C. or higher and lower than 350° C. and a solvent YN having a boiling point of 350° C. or higher and 500° C. or lower.

[0118] 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, relative to the total mass of the photosensitive layer, and 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.

[0119] The content of the polymerizable compound YM, which is one of the compounds 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, relative to 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 solvent YN, which is one of the compounds 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, relative to 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.

[0120] In the photosensitive layer, 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, and more preferably 1.00 or less.

[0121] <Filler> The photosensitive layer preferably contains a filler, as this provides better effects of the present invention. When the photosensitive layer contains a filler, the filler content is preferably 20.0% by mass or more, more preferably 30.0% by mass or more, and even more preferably 40.0% by mass or more, relative to the total mass of the photosensitive layer. The upper limit is preferably 90.0% by mass or less, and more preferably 80.0% by mass or less. The average particle size of the filler is preferably 300 nm or less, more preferably 200 nm or less, and even more preferably 100 nm or less. The lower limit is preferably more than 0 nm, more preferably 5 nm or more, and even more preferably 10 nm or more. The average particle size of the filler is also preferably 5 to 100 nm. The average particle size of the filler is calculated using the following particle size measurement method. Particle size measurement method: A rectangular region of 3 μm × 10 μm in a cross section of the photosensitive layer along the normal direction to the surface is observed with a scanning electron microscope, and the long diameters of all fillers observed in the region are measured at five different locations on the photosensitive layer. The average value of the long diameters of all fillers measured in each measurement is taken as the average particle size of the filler.

[0122] The procedure for the particle size measurement method is described in detail below. A cross section along the normal direction of the surface of the photosensitive layer (the surface opposite the temporary support side) is cut out, and a rectangular region of 3 μm × 10 μm on the cross section is observed with a scanning electron microscope, and the major axis of all fillers observed within the region is measured. A Hitachi High-Tech S-4800 scanning electron microscope is used as the scanning electron microscope. The magnification for observation is 50,000 times. The above procedure is performed at five different locations on the photosensitive layer, and the average (arithmetic mean) of the major axes of all fillers measured in each procedure is taken as the average particle size of the filler. The major axis refers to the length of the longest line segment connecting any two points on the outline of the filler in the observed image. Furthermore, if the filler aggregates to form aggregates in the observed image, the major axis of each filler constituting the aggregate is measured.

[0123] Examples of fillers include organic fillers and inorganic fillers, with inorganic fillers being preferred. Examples of fillers include silicon dioxide (silica); silicates such as kaolinite, kaolin clay, calcined clay, talc, and glass fillers such as chion-doped glass; alumina, barium sulfate, mica powder, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum borate, barium titanate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, barium zirconate, calcium zirconate, zirconium phosphate, cordierite, zirconium tungstate, and manganese nitride. The filler preferably contains at least one selected from the group consisting of silicon dioxide (silica), boron nitride, barium sulfate, and silicates, and more preferably contains silicon dioxide (silica).

[0124] The shape of the filler may be either spherical or non-spherical (e.g., crushed or fibrous), with spherical being preferred. The filler may be surface-treated. Examples of surface treatments include treatments to introduce functional groups and treatments using known surface modifiers. Examples of the functional groups include polymerizable groups (e.g., polymerizable groups contained in polymerizable compounds described below) and hydrophobic groups. Examples of surface modifiers include known surface modifiers such as silane coupling agents, titanate coupling agents, and silazane compounds.

[0125] Examples of fillers include Seahoster KE-S30 (manufactured by Nippon Shokubai Co., Ltd., silicon dioxide, solid content concentration 100% by mass), NHM-3N (manufactured by Tokuyama Corporation, silicon dioxide, solid content concentration 100% by mass), YA050C-MJE (manufactured by Admatechs Co., Ltd., silicon dioxide, MEK slurry with a solid content concentration of 50% by mass), SFP-20M (manufactured by Denka Co., Ltd., silicon dioxide), PMA-ST (manufactured by Nissan Chemical Industries, Ltd., silicon dioxide), MEK-ST-L (manufactured by Nissan Chemical Industries, Ltd., silicon dioxide), and MEK-AC-5140. Z (manufactured by Nissan Chemical Industries, Ltd., silicon dioxide), MEK-EC-2430Z (manufactured by Nissan Chemical Industries, Ltd., solids concentration 30% by mass), barium sulfate (manufactured by Nippon Solvay K.K., solids concentration 100% by mass), NHM-5N (manufactured by Tokuyama Corporation, silicon dioxide, solids concentration 100% by mass), Y50SP-AM1 (manufactured by Admatechs Co., Ltd., silicon dioxide, MEK slurry with a solids concentration of 50% by mass), and Y50SZ-AM1 (manufactured by Admatechs Co., Ltd., silicon dioxide, MEK slurry with a solids concentration of 50% by mass).

[0126] 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.

[0127] The fillers may be used alone or in combination of two or more.

[0128] <Thermal Base Generator> The photosensitive layer may contain a thermal base generator. In particular, when Resin X contains a polyimide precursor and a polybenzoxazole precursor, it is preferable that the photosensitive layer contains a thermal base generator. When the photosensitive layer contains a thermal base generator, the ring-closing reaction of the polyimide precursor and the polybenzoxazole precursor is promoted, making it easier to produce polyimide and polybenzoxazole.

[0129] The thermal base generator is preferably an acidic compound or an onium salt compound (a compound consisting of a cation and an anion) that generates a base upon heating. The onium salt compound is preferably an ammonium salt compound (a compound consisting of an ammonium cation and an anion), an iminium salt compound (a compound consisting of an iminium cation and an anion), a sulfonium salt compound (a compound consisting of a sulfonium cation and an anion), an iodonium salt compound (a compound consisting of an iodonium cation and an anion), or a phosphonium salt compound (a compound consisting of a phosphonium cation and an anion), with an iminium salt compound being more preferred. The anion constituting the onium salt compound is preferably a carboxylate anion, a phenol anion, a phosphate anion, or a sulfate anion, with a carboxylate anion being more preferred. The anion constituting the ammonium salt compound preferably further has an aromatic ring. The aromatic ring may, for example, be A in the formula (A1) described below. ａ１ Examples of the temperature at which the acidic compound and the onium salt compound generate a base include aromatic rings that constitute aromatic ring groups represented by the formula: 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 laminate manufacturing method described below. The temperature at which the thermal base generator generates a base can be determined, for example, by using differential scanning calorimetry to heat the compound to be measured in a pressure-resistant capsule to 250°C at 5°C / min, and reading the peak temperature of the lowest exothermic peak, and using this peak temperature as the base generation temperature.

[0130] The base generated by the thermal base generator is preferably a secondary amine or a tertiary amine, more preferably a tertiary amine. The base may be linear, branched, or cyclic, and is preferably cyclic.

[0131] The acidic compound is preferably a compound represented by formula (A1).

[0132]

[0133] In formula (A1), A ａ１ represents a p-valent organic group. ａ１ represents a monovalent organic group. ａ１represents an (m+1)-valent linking group, m represents an integer of 1 or more, and p represents an integer of 1 or more.

[0134] In formula (A1), A ａ１ represents a p-valent organic group. Examples of the organic group include an aliphatic hydrocarbon group and an aromatic ring group, with an aromatic ring group being preferred. Examples of the monovalent aliphatic hydrocarbon group include an alkyl group and an alkenyl group. The alkyl group may be linear, branched, or cyclic. The alkyl group preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and even more preferably 1 to 10 carbon atoms. Examples of the alkyl group include a methyl group, an ethyl group, a tert-butyl group, a dodecyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and an adamantyl group. The alkenyl group may have a linear, branched, or cyclic structure. The alkenyl group preferably has 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, and even more preferably 2 to 10 carbon atoms. Examples of the alkenyl group include a vinyl group, an allyl group, and a methallyl group. Examples of p-valent aliphatic hydrocarbon groups (where p is an integer of 2 or greater) include groups formed by removing (p-1) hydrogen atoms from the above-mentioned monovalent aliphatic hydrocarbon groups. The aliphatic hydrocarbon group may further have a substituent.

[0135] The aromatic ring group may be either a monocyclic or polycyclic ring. The aromatic ring group may be either an aromatic hydrocarbon ring group or an aromatic heterocyclic group. Examples of the aromatic ring group include a benzene ring group, a naphthalene ring group, a pentalene ring group, an indene ring group, an azulene ring group, a heptalene ring group, an indacene ring group, a perylene ring group, a pentacene ring group, an acenaphthene ring group, a phenanthrene ring group, an anthracene ring group, a naphthacene ring group, a chrysene ring group, a triphenylene ring group, a fluorene ring group, a biphenyl ring group, a pyrrole ring group, a furan ring group, a thiophene ring group, an imidazole ring group, an oxazole ring group, a thiazole ring group, a pyridine ring group, a pyrazine ring group, a pyrimidine ring group, a pyridazine ... phenanthrene ring group, an anthracene ring group, a naphthacene ring group, a chrysene ring group, a triphenylene ring group, a fluorene ring group, a biphenyl ring group, a pyrrole ring group, a furan ring group, a thiophene ring group, an imidazole ring group, an oxazole ring group, a thiazole ring group, a pyr Examples of the aromatic ring group include a benzene ring group, an indolizine ring group, an indole ring group, a benzofuran ring group, a benzothiophene ring group, an isobenzofuran ring group, a quinolizine ring group, a quinoline ring group, a phthalazine ring group, a naphthyridine ring group, a quinoxaline ring group, a quinoxazoline ring group, an isoquinoline ring group, a carbazole ring group, a phenanthridine ring group, an acridine ring group, a phenanthroline ring group, a thianthrene ring group, a chromene ring group, a xanthene ring group, a phenoxathiin ring group, a phenothiazine ring group, and a phenazine ring group, and a benzene ring group is preferred. The aromatic ring group may further have a substituent.

[0136] In formula (A1), R ａ１ represents a monovalent organic group. Examples of the monovalent organic group include A ａ１ Examples of the monovalent organic group include a monovalent aliphatic hydrocarbon group and a monovalent aromatic ring group represented by the following formula: The monovalent organic group may further have a substituent. The substituent is preferably a carboxy group.

[0137] In formula (A1), L ａ１ represents an (m+1)-valent linking group. Examples of the (m+1)-valent linking group include an ether group (—O—), a carbonyl group (—CO—), an ester group (—COO—), a thioether group (—S—), and —SO ２ -, -NR Ｎ - (R Ｎrepresents a hydrogen atom or a substituent.), divalent linking groups such as alkylene groups (preferably having 1 to 10 carbon atoms) and alkenylene groups (preferably having 2 to 10 carbon atoms); trivalent linking groups having a group represented by "-N<" and trivalent linking groups having a group represented by "-CR<" (R represents a hydrogen atom or a substituent); tetravalent linking groups having a group represented by ">C<"; k-valent linking groups having a cyclic group such as an aromatic ring group or an alicyclic group; and groups combining these.

[0138] In formula (A1), m represents an integer of 1 or greater. m is preferably 1 or 2, and more preferably 1.

[0139] In formula (A1), p represents an integer of 1 or greater. p is preferably 1 or 2, and more preferably 1.

[0140] The ammonium cation constituting the ammonium salt compound is preferably a cation represented by formula (101). The iminium cation constituting the iminium salt compound is preferably a cation represented by formula (102).

[0141]

[0142] In formula (101), R １ ~R ４ R each independently represents a hydrogen atom or an aliphatic group. １ ~R ４ At least two of R may be bonded to each other to form a ring. ５ and R ６ R each independently represents a hydrogen atom or an aliphatic group. ７ represents an aliphatic group. ５ ~R ７ At least two of these may be bonded to each other to form a ring.

[0143] R １ ~R ４ and R ５ ~R ７The aliphatic group represented by the formula (I) 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, more preferably an alkyl group. The aliphatic group may have a substituent. Examples of the substituent include an arylcarbonyl group. The aliphatic group may have a substituent such that the methylene group (-CH ２ -) may be replaced with a heteroatom (for example, an oxygen atom, a sulfur atom, or -NR-, where R represents a hydrogen atom or a substituent). ５ ~R ７ At least one of the R is preferably an aliphatic group having —NR—, and more preferably an alkyl group having —NR—. ５ ~R ７ At least two of R may be bonded to each other to form a ring; ５ and R ７ and R ６ and R ７ are preferably bonded to each other to form a ring. In other words, the ring formed is preferably a polycyclic heterocycle, more preferably a bicyclic heterocycle.

[0144] Examples of the thermal base generator include the thermal base generators described in WO 2018 / 038002.

[0145] The thermal base generator 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, relative to the total mass of the photosensitive layer. The lower limit is preferably more than 0% by mass, and more preferably 0.1% by mass or more. The mass ratio of the content of the thermal base generator to the content of resin X (content of thermal base generator / content of resin X) is preferably 1.00 or less, more preferably 0.10 or less, and even more preferably 0.05 or less. The lower limit is preferably more than 0.

[0146] <Surfactant> The photosensitive layer may contain a surfactant. Examples of the surfactant include those described in paragraph 0017 of Japanese Patent No. 04502784 and paragraphs 0060 to 0071 of JP-A No. 2009-237362.

[0147] Examples of surfactants include hydrocarbon surfactants, fluorine surfactants, and silicone surfactants. From the viewpoint of improving environmental friendliness, it is preferable that the surfactant does not contain a fluorine atom. The surfactant is preferably a hydrocarbon surfactant or a silicone surfactant. Commercially available fluorine-based surfactants include, for example, Megafac F-171, F-172, F-173, F-176, F-177, F-141, F-142, F-143, F-144, F-437, F-475, F-477, F-479, F-482, F-551-A, F-552, F-554, F-555-A, F-556, F-557, F-558, F-559, F-560, F-561, F-565, F-563, F-568, F-575, and F-780 (all manufactured by DIC Corporation); EXP. MFS-324, EXP. MFS-330, EXP. MFS-578, EXP. MFS-578-2, EXP. MFS-579, EXP. MFS-586, EXP. MFS-587, EXP. MFS-628, EXP. MFS-631, EXP. MFS-603, R-41, R-41-LM, R-01, R-40, R-40-LM, RS-43, TF-1956, RS-90, R-94, RS-72-K, and DS-21 (all manufactured by DIC Corporation); Fluorad FC430, FC431, and FC171 (all manufactured by Sumitomo 3M Limited); Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, and KH-40 (all manufactured by AGC); PolyFox Examples include PF636, PF656, PF6320, PF6520, and PF7002 (manufactured by OMNOVA); Ftergent 710FL, 710FM, 610FM, 601AD, 601ADH2, 602A, 215M, 245F, 251, 212M, 250, 209F, 222F, 208G, 710LA, 710FS, 730LM, 650AC, 681, and 683 (manufactured by NEOS Corporation); and U-120E (manufactured by Unichem).

[0148] Examples of fluorosurfactants include acrylic compounds that have a molecular structure containing a functional group having a fluorine atom, and when heated, the functional group having the fluorine atom is cleaved, causing the fluorine atom to volatilize. Examples of such fluorosurfactants include the Megafac DS series (manufactured by DIC Corporation, Chemical Daily (February 22, 2016), Nikkei Business Daily (February 23, 2016), and Megafac DS-21). Furthermore, the fluorosurfactant may be a polymer of a fluorine-containing vinyl ether compound having a fluorinated alkyl group or a fluorinated alkylene ether group, and a hydrophilic vinyl ether compound. The fluorosurfactant may be a block polymer. The fluorosurfactant may also be a fluorine-containing polymer compound containing a repeating unit derived from a (meth)acrylate compound having a fluorine atom and a repeating unit derived from a (meth)acrylate compound having two or more (preferably five or more) alkyleneoxy groups (preferably ethyleneoxy groups or propyleneoxy groups). Further, examples of fluorine-based surfactants include fluorine-containing polymers having a group having an ethylenically unsaturated group in the side chain, such as Megafac RS-101, RS-102, RS-718K, and RS-72-K (all manufactured by DIC Corporation).

[0149] As the fluorine-based surfactant, from the viewpoint of improving environmental compatibility, surfactants derived from alternative materials to compounds having a linear perfluoroalkyl group having 7 or more carbon atoms, such as perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic acid (PFOS), are preferred.

[0150] Examples of hydrocarbon surfactants include glycerol, trimethylolpropane, trimethylolethane, and their ethoxylates and propoxylates (e.g., glycerol propoxylate and glycerol ethoxylate), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, and sorbitan fatty acid esters. Examples of hydrocarbon surfactants include Pluronic (registered trademark) L10, L31, L61, L62, 10R5, 17R2, and 25R2, Tetronic 304, 701, 704, 901, 904, and 150R1, and HYDROPALAT WE 3323 (all manufactured by BASF); Solsperse 20000 (manufactured by Lubrizol Japan); NCW-101, NCW-1001, and NCW-1002 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.); Paionin D-1105, D-6112, D-6112-W, and D-6315 (manufactured by Takemoto Oil & Fat Co., Ltd.); and Olfine E1010, Surfynol 104, 400, and 440 (manufactured by Nissin Chemical Industry Co., Ltd.).

[0151] Examples of silicone surfactants include linear polymers consisting of siloxane bonds, modified siloxane polymers with organic groups introduced into the side chains and / or terminals, and polymers having a repeating unit with a hydrophilic group in the side chain and a repeating unit with a group having a siloxane bond in the side chain.Preferred silicone surfactants are polymers having a repeating unit with a hydrophilic group in the side chain and a repeating unit with a group having a siloxane bond in the side chain.The polymers may be either random copolymers or block copolymers.

[0152] The repeating unit having a group having a siloxane bond in the side chain is preferably a repeating unit represented by formula (SX1) or a repeating unit represented by formula (SX2).

[0153]

[0154] In formula (SX1), each R independently represents an alkyl group having 1 to 3 carbon atoms. １ represents a hydrogen atom or a methyl group. １ represents a single bond or a divalent organic group. When a plurality of R's are present, the R's may be the same or different.

[0155]

[0156] In formula (SX2), R １ represents a hydrogen atom or a methyl group. ２ represents an alkylene group having 1 to 10 carbon atoms. ３ represents an alkyl group having 1 to 4 carbon atoms, and n represents an integer of 5 to 50.

[0157] The repeating unit having a hydrophilic group in the side chain is preferably a repeating unit represented by formula (SX3).

[0158]

[0159] In formula (SX3), R ４ and R ５ each independently represents a hydrogen atom or a methyl group, n represents an integer of 1 to 4, and m represents an integer of 1 to 100.

[0160] Examples of silicone surfactants include EXP.S-309-2, EXP.S-315, EXP.S-503-2, and EXP.S-505-2 (all manufactured by DIC Corporation); DOWSIL 8032 ADDITIVE, Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, and Toray Silicone SH8400 (all manufactured by Dow Corning Toray Co., Ltd.); X-22-4952, X-22-4272, and X-22-6266 , KF-351A, K354L, KF-355A, KF-945, KF-640, KF-642, KF-643, X-22-6191, X-22-4515, KF-6004, KF-6001, K F-6002, KP-101KP-103, KP-104, KP-105, KP-106, KP-109, KP-109, KP-112, KP-120, KP-121, KP-124, KP-12 No. 5, KP-301, KP-306, KP-310, KP-322, KP-323, KP-327, KP-341, KP-368, KP-369, KP-611, KP-620, KP-621, KP-626, and KP-652 (all manufactured by Shin-Etsu Silicone Co., Ltd.); F-4440, TSF-4300, TSF-4445, TSF-4460, and TSF-4452 (all manufactured by Momentive Perform BYK300, BYK306, BYK307, BYK310, BYK320, BYK323, BYK325, BYK330, BYK313, BYK315N, BYK331, BYK333, BYK345, BYK347, BYK348, BYK349, BYK370, BYK377, BYK378, and BYK323 (all manufactured by BYK-Chemie).

[0161] The surfactant also includes a nonionic surfactant.

[0162] The surfactant content is preferably from 0.01 to 3.0% by mass, more preferably from 0.01 to 1.0% by mass, and even more preferably from 0.05 to 0.8% by mass, based on the total mass of the photosensitive layer.

[0163] <Other Additives> The photosensitive layer may contain other additives in addition to the various components described above. Examples of other additives include heterocyclic compounds (e.g., triazole, tetrazole, benzotriazole, and derivatives thereof), aliphatic thiol compounds, thermally crosslinkable compounds, polymerization inhibitors, hydrogen donor compounds, solvents, impurities, plasticizers, sensitizers, and alkoxysilane compounds. The photosensitive layer may also contain polymerizable compounds or solvents that do not fall under the category of Compound Y. Examples of heterocyclic compounds, aliphatic thiol compounds, thermally crosslinkable compounds, polymerization inhibitors, and hydrogen donor compounds include, for example, the various components described in WO 2022 / 039027. Examples of plasticizers, sensitizers, and alkoxysilane compounds include, for example, paragraphs 0097 to 0119 of WO 2018 / 179640.

[0164] The photosensitive layer may contain impurities. Examples of impurities include sodium, potassium, magnesium, calcium, iron, manganese, copper, aluminum, titanium, chromium, cobalt, nickel, zinc, tin, halogens, and ions thereof. Halide ions, sodium ions, and potassium ions are likely to be mixed in as impurities, so the following contents are preferred.

[0165] The content of impurities is preferably 80 mass ppm or less, more preferably 10 mass ppm or less, and even more preferably 2 mass ppm or less, relative to the total mass of the photosensitive layer. The lower limit is often 0 mass ppb or more, but may be 1 mass ppb or more, or even 0.1 mass ppm or more, relative to 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, relative to the total mass of the photosensitive layer.

[0166] Methods for adjusting the content of impurities include, for example, using raw materials with low impurity contents as raw materials for the various components that may be contained in the photosensitive layer, purifying the various components that may be contained in the photosensitive layer before use, and preventing the incorporation of impurities when forming the photosensitive layer.

[0167] The content of impurities can be determined by known methods such as ICP (Inductively Coupled Plasma) emission spectroscopy, atomic absorption spectroscopy, and ion chromatography.

[0168] The content of compounds such as benzene, formaldehyde, trichloroethylene, 1,3-butadiene, carbon tetrachloride, chloroform, N,N-dimethylformamide, N,N-dimethylacetamide, and hexane in the photosensitive layer is preferably low. Specifically, the content of each of these compounds is preferably 100 ppm by mass or less, more preferably 20 ppm by mass or less, and even more preferably 4 ppm by mass or less, relative to the total mass of the photosensitive layer. The lower limit may be 10 ppb by mass or more, or 100 ppb by mass or more, relative to the total mass of the photosensitive layer. The content of these compounds can be adjusted using the same method as for the impurities described above. Furthermore, these compounds can be quantified using known measurement methods.

[0169] From the viewpoints of improving reliability, improving the handling properties of the transfer film, and improving lamination properties, the moisture content of the photosensitive layer is preferably 3.0% by mass or less, more preferably 2.0% by mass or less, and even more preferably 1.0% by mass or less, relative to the total mass of the photosensitive layer. The lower limit is preferably 0.0001% by mass or more, more preferably 0.01% by mass or more, and even more preferably 0.1% by mass or more. Specific examples of the moisture content in the photosensitive layer include 2.5% by mass, 1.5% by mass, and 0.3% by mass, relative to the total mass of the photosensitive layer.

[0170] From the viewpoints of improving reliability, improving the handling properties of the transfer film, and improving lamination properties, the amount of residual solvent in the photosensitive layer is preferably 6.0% by mass or less, more preferably 4.0% by mass or less, even more preferably 2.0% by mass or less, and particularly preferably 1.0% by mass or less, relative to the total mass of the photosensitive layer. The lower limit is preferably 0.0001% by mass or more, more preferably 0.01% by mass or more, and even more preferably 0.1% by mass or more. Specific examples of the amount of residual solvent in the photosensitive layer include 3.5% by mass, 2.5% by mass, 1.5% by mass, and 0.3% by mass, relative to the total mass of the photosensitive layer.

[0171] <Thickness of Photosensitive Layer> The lower limit of the average thickness of the photosensitive layer is preferably 0.5 μm or more, more preferably 1.0 μm or more, even more preferably 3.0 μm or more, and particularly preferably 5.0 μm or more. The upper limit is preferably 40 μm or less, more preferably 25 μm or less, even more preferably 20 μm or less, and particularly preferably 19 μm or less. When the average thickness of the photosensitive layer is 40 μm or less, it is preferable in terms of excellent pattern resolution, and when the average thickness of the photosensitive layer is 0.5 μm or more, it is preferable in terms of excellent reliability.

[0172] <Weight Loss Amount When Photosensitive Layer is Heated at 350°C for 1 Hour> The photosensitive layer preferably satisfies the following Requirement 1. 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 weight loss of the photosensitive layer when heated at 350°C for 1 hour is more preferably 10% by mass or more, and even more preferably 12% by mass or more. 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 weight loss of the photosensitive layer when heated at 350°C for 1 hour can be measured by the following procedure.

[0173] (Preparation of Evaluation Sample) Two transfer films from which the protective films have been peeled are bonded together so that the photosensitive layers of each transfer film face each other, and then one of the two temporary supports is peeled off to obtain a laminate 1 having a temporary support and two photosensitive layers. Next, the transfer film from which the protective film has been peeled off is bonded to the laminate 1 so that the photosensitive layer of this transfer film faces the photosensitive layer of the laminate 1, and then one of the two temporary supports is peeled off to obtain a laminate 2 having a temporary support and three photosensitive layers. Then, the laminate 1 is separately prepared, and the photosensitive layer of the laminate 1 and the photosensitive layer of the laminate 2 are bonded together so that the photosensitive layers face each other to obtain a laminate 3 (temporary support / five photosensitive layers / temporary support). Finally, the two temporary supports are peeled off from the laminate 3 to obtain an evaluation sample.

[0174] (Measurement of the rate of thermal weight loss when the photosensitive layer is heated at 350°C for 1 hour) The rate of thermal weight loss of the evaluation sample is measured using a TG-DTA device (simultaneous thermogravimetry / differential thermal analysis device), and the average value of three measurements is taken as the rate of thermal weight loss when the photosensitive layer is heated at 350°C for 1 hour. The measurement is preferably carried out under the following conditions. The final rate of thermal weight loss is measured in the range of room temperature to 350°C (under a nitrogen atmosphere, at a heating rate of 10°C / min, and held at 350°C for 1 hour). As the TG-DTA device, for example, the "TG / DTA6200" manufactured by Seiko Instruments Inc. can be used.

[0175] <Melt Viscosity of Photosensitive Layer at 100°C> The melt viscosity of the photosensitive layer at 100°C is 5.0 × 10 ６ Pa s or less is preferable, and 3.0 × 10 ６ Pa s or less is more preferable, and 1.0 × 10 ６ The lower limit is preferably 1.0×10 Pa·s or less. ２ The melt viscosity of the photosensitive layer at 100° C. is preferably Pa·s or more. The melt viscosity of the photosensitive layer at 100° C. can be measured by the following procedure.

[0176] (Measurement of Melt Viscosity of Photosensitive Layer at 100°C) 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 following conditions. 20 mm diameter parallel plates and a Peltier plate are set at a gap of 0.5 mm, and the measurement is carried out under the following conditions: temperature 20 to 105°C, heating rate 5°C / min, and strain 0.5%. Prior to measurement, the sample is melted (80°C) on the Peltier plate and then cooled to 20°C (cooling rate 5°C / min) before starting the measurement. The evaluation sample used is the same as the evaluation sample described in <Weight Loss of Photosensitive Layer When Heated at 350°C for 1 Hour>. The rheometer used may be a rheometer such as the "DHR-2" manufactured by TA Instruments.

[0177] [Coefficient of linear expansion (CTE) of cured product of photosensitive layer] The coefficient of linear expansion 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 coefficient of linear expansion of the cured product of the photosensitive layer can be measured by the following procedure.

[0178] (Preparation of Evaluation Sample) The evaluation sample used was the same evaluation sample as that described in <Weight loss amount of photosensitive layer when heated at 350° C. for 1 hour>, except that the two temporary supports were left unpeeled. In other words, the evaluation sample was a laminate 3 having a structure of temporary support / five photosensitive layers / temporary support.

[0179] (Measurement of coefficient of linear expansion (CTE) of cured product of photosensitive layer) A high-pressure mercury lamp (25 mJ / cm) was irradiated from one temporary support side of the evaluation sample. ２After performing an exposure treatment by irradiating the laminate with UV light, the two temporary supports were peeled off from the exposed laminate and subjected to a heat treatment at 230°C (oven setting temperature) for 8 hours to obtain a free-standing film. The produced free-standing film was cut into strips (19mm x 5mm) and the linear expansion coefficient was measured using a TMA (thermomechanical analyzer, "TMA450EM" manufactured by TA Instruments). The measurement conditions were a heating rate of 10°C / min, a chuck distance of 16mm, and a load of 49mN, and the measurement was carried out in a temperature range of -60°C to 350°C. The linear expansion coefficient was measured as a value (ppm / K) in the temperature range of 50°C to 150°C during heating, and the average value of three measurements was taken as the linear expansion coefficient of the cured product of the photosensitive layer.

[0180] [Intermediate layer and thermoplastic resin layer] The transfer film may have an intermediate layer and / or a thermoplastic resin layer. Examples of the intermediate layer and the thermoplastic resin layer include those described in paragraphs 0164 to 0204 of WO 2021 / 166719, the contents of which are incorporated herein by reference.

[0181] [Cover Film] The transfer film may have a cover film.

[0182] The number of fish eyes with a diameter of 80 μm or more contained in the cover film is 5 / m ２ The following are preferred: Fisheyes are foreign matter, undissolved matter, and / or oxidized and deteriorated matter of the material that is introduced into the film when the material is thermally melted and then kneaded, extruded and / or biaxially stretched, cast, or other methods are used to produce the film.

[0183] The number of particles with a diameter of 3 μm or more contained in the cover film is 30 / mm ２ Preferably, 10 pieces / mm or less ２ More preferably, 5 or less pieces / mm ２ The following is more preferable: This can suppress defects caused by the transfer of irregularities due to particles contained in the cover film to the composition layer.

[0184] The arithmetic mean roughness Ra of the surface of the cover film is preferably 0.01 μm or more, more preferably 0.02 μm or more, and even more preferably 0.03 μm or more.If Ra is within this range, for example, when the transfer film is long, the winding property of the transfer film is excellent.In addition, from the viewpoint of suppressing defects during transfer, Ra is preferably less than 0.50 μm, more preferably 0.40 μm or less, and even more preferably 0.30 μm or less.

[0185] Examples of the cover film include polyethylene terephthalate film, polypropylene film, polystyrene film, and polycarbonate film, and examples of the cover film include those described in paragraphs 0083 to 0087 and 0093 of JP-A No. 2006-259138.

[0186] Examples of cover films include Alphan (registered trademark) FG-201 (manufactured by Oji F-Tex Co., Ltd.), Alphan (registered trademark) E-201F (manufactured by Oji F-Tex Co., Ltd.), Therapeel (registered trademark) 25WZ (manufactured by Toray Advanced Film Co., Ltd.), and Lumirror (registered trademark) 16QS62 (16KS40) (manufactured by Toray Industries, Inc.). The cover film may be a recycled product. Examples of recycled products include those obtained by cleaning and chipping used films and then forming the resulting material into films. Examples of commercially available recycled products include the Ecouse series (manufactured by Toray Industries, Inc.).

[0187] [Other Layers] The transfer film may include other layers in addition to the above-described layers. Examples of other layers include a high refractive index layer. Examples of high refractive index layers include those described in paragraphs 0168 to 0188 of International Publication No. 2021 / 187549, the contents of which are incorporated herein by reference.

[0188] [Method for Producing Transfer Film] The method for producing the transfer film can be a known method, and is preferably a method for producing the transfer film in which a photosensitive composition is applied to a temporary support to form a photosensitive layer.

[0189] For example, 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 then drying this coating film to form a photosensitive layer. Furthermore, the transfer film 100 shown in Fig. 1 is manufactured by pressing 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 also be wound up after manufacturing and stored as a roll-form transfer film 100. The roll-form transfer film 100 can be provided in its original form for the lamination step with a substrate in a roll-to-roll system described below.

[0190] As described above, the transfer film may have an intermediate layer and / or a thermoplastic resin layer between the temporary support and the photosensitive layer. Examples of the intermediate layer-forming composition, the method for forming the intermediate layer, the thermoplastic resin layer-forming composition, and the method for forming the thermoplastic resin layer are described in paragraphs 0133 to 0136 and 0143 to 0144 of International Publication No. 2021 / 033451, the contents of which are incorporated herein by reference.

[0191] <Method of Forming Photosensitive Layer> A known method can be used to form the photosensitive layer, and examples thereof include a method of forming the layer by applying and drying a photosensitive composition.

[0192] The various components that can be contained in the photosensitive composition are synonymous with, for example, the various components that can be contained in the photosensitive layer described above, and the preferred embodiments are also the same. However, the preferred ranges of the contents of the various components in the photosensitive composition are the same as the preferred ranges obtained by replacing the above-mentioned "contents (% by mass) of the various components relative to the total mass of the photosensitive layer" with "contents (% by mass) of the various components relative to the total solid content of the photosensitive composition." Specifically, the statement "The content of resin X is preferably 5.0% by mass or more relative to the total mass of the photosensitive layer" should be replaced with "The content of resin X is preferably 5.0% by mass or more relative to the total solid content of the photosensitive composition." In addition, the photosensitive composition preferably contains a solvent (solvent) that does not fall under the category of compound Y in order to improve coatability.

[0193] The solvent is not particularly limited as long as it does not fall under the category of compound Y and can dissolve or disperse various components that may be contained in the photosensitive composition. Examples of solvents include water, alkylene glycol ether solvents, alkylene glycol ether acetate solvents, alcohol solvents (e.g., methanol and ethanol), ketone solvents (e.g., acetone and methyl ethyl ketone), aromatic hydrocarbon solvents (e.g., toluene), aprotic polar solvents (e.g., N,N-dimethylformamide), cyclic ether solvents (e.g., tetrahydrofuran), ester solvents (e.g., n-propyl acetate), amide solvents, lactone solvents, and solvents containing two or more of these. Solvents may be used alone or in combination. The content of the solvent is preferably 50 to 1900 parts by mass, more preferably 100 to 1200 parts by mass, and even more preferably 100 to 900 parts by mass, per 100 parts by mass of the total solids content of the composition.

[0194] Examples of coating methods include slit coating, spin coating, curtain coating, and inkjet coating.

[0195] [Uses] The resin pattern obtained from the photosensitive layer formed using the transfer film can be used in a variety of applications. For example, it can be used for electrode protective films, insulating films, planarizing films, overcoat films, hard coat films, passivation films, partition walls, spacers, microlenses, optical filters, anti-reflection films, etching resists, and plating members. More specifically, it can be used for protective films or insulating films for touch panel electrodes, protective films or insulating films for printed wiring boards, protective films or insulating films for TFT substrates, interlayer insulating films in build-up substrates for semiconductor packages, organic interposers, color filters, overcoat films for color filters, and etching resists for wiring formation.

[0196] [Method for producing laminate] The method for producing the laminate is not particularly limited as long as it is a method using the transfer film. The method for producing the laminate preferably includes steps X1 to X4. Step X1: a lamination step in which the surface of the transfer film opposite to the temporary support is brought into contact with a substrate and laminated to obtain a substrate with a photosensitive layer having the substrate, photosensitive layer, and temporary support in this order; Step X2: an exposure step in which the photosensitive layer is patternwise exposed to light; Step X3: a development step in which the exposed photosensitive layer is developed to form a resin pattern precursor; Step X4: a heating step in which the resin pattern precursor is heated to form a resin pattern. Furthermore, the method for producing a resin pattern preferably includes a peeling step in which the temporary support is peeled from the substrate with a photosensitive layer between the lamination step and the exposure step, or between the exposure step and the development step.

[0197] Each step of the method for producing the laminate will be described in detail below.

[0198] <Step X1> Step X1 is a step of forming a photosensitive layer on a substrate using a transfer film. Examples of lamination methods include known transfer methods and lamination methods. A preferred method involves placing a substrate on the surface of the photosensitive layer and applying pressure and heat using a roll or the like. Examples of lamination methods 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. Step X1 is preferably performed using a roll-to-roll method. Examples of substrates to which the transfer film can be laminated include resin films and resin films having a conductive layer. In particular, the effects of the transfer film of the present invention can be more effectively achieved when the substrate has steps, such as a wiring board. The roll-to-roll method refers to a method in which a substrate that can be wound up and unwound is used as the substrate, and includes a step of unwinding the substrate before any of the steps included in the method for producing a laminate of the present invention, and a step of winding the substrate after any of the steps, and at least any of the steps (preferably all of the steps or all of the steps other than the heating step) is performed while the substrate is being transported. As the unwinding method in the unwinding step and the winding method in the winding step, any method known in the art for production methods that apply the roll-to-roll method may be used.

[0199] (Substrate) Examples of the substrate include a glass substrate, a glass epoxy substrate, a silicon substrate, a resin substrate, and a substrate having a conductive layer. The refractive index of the substrate is preferably 1.50 to 1.52. The substrate may be composed of a light-transmitting substrate such as a glass substrate, and tempered glass, such as Corning Gorilla Glass, can also be used. Materials contained in the substrate include, for example, materials used in JP 2010-086684 A, JP 2010-152809 A, and JP 2010-257492 A. When the substrate includes a resin substrate, a resin film with low optical distortion and / or high transparency is more preferred. Specific examples include polyethylene terephthalate (PET), polyethylene naphthalate, polycarbonate, triacetyl cellulose, cycloolefin polymer, and polyimide.

[0200] As the substrate having a conductive layer, a resin substrate having a conductive layer is preferred, and a resin film having a conductive layer is more preferred, in view of being produced by a roll-to-roll method.

[0201] Examples of the conductive layer include any conductive layer used in general circuit wiring or touch panel wiring. From the viewpoints of conductivity and fine line formability, the conductive layer is preferably one or more layers selected from the group consisting of a metal layer (e.g., metal foil, etc.), a conductive metal oxide layer, a graphene layer, a carbon nanotube layer, and a conductive polymer layer, more preferably a metal layer, and even more preferably a copper layer or a silver layer. Furthermore, the conductive layer in the substrate having a conductive layer may be either one layer or two or more layers. When the substrate having a conductive layer includes two or more conductive layers, it is preferable that each conductive layer be made of a different material. Examples of materials for the conductive layer include simple metals and conductive metal oxides. Examples of simple metals include Al, Zn, Cu, Fe, Ni, Cr, Mo, Ag, and Au. Examples of conductive metal oxides include ITO (indium tin oxide), IZO (indium zinc oxide), and SiO ２ The conductivity is such that the volume resistivity is 1×10 ６It means that the volume resistivity is less than 1×10 ４ It is preferably less than Ωcm.

[0202] When the substrate has two or more conductive layers, it is preferable that at least one of the conductive layers contains a conductive metal oxide.

[0203] <Step X2> Step X2 is a step of patternwise exposing the photosensitive layer after step X1. Note that "patternwise exposure" refers to a form of patternwise exposure, that is, exposure in a form in which exposed and unexposed areas exist. The positional relationship between the exposed and unexposed areas in the patternwise exposure is not particularly limited and may be adjusted as appropriate. Exposure may be performed from the side opposite the substrate of the photosensitive layer, or from the substrate side of the photosensitive layer.

[0204] The light source used for exposure can be appropriately selected as long as it irradiates light in a wavelength range (e.g., light in wavelength ranges of 254 nm, 313 nm, 365 nm, and 405 nm) to which various photosensitive components (e.g., photopolymerization initiators, photoacid generators, etc.) in the photosensitive layer are photosensitive. Specific examples include ultra-high pressure mercury lamps, high pressure mercury lamps, metal halide lamps, and LEDs (light-emitting diodes).

[0205] The exposure dose is 5 to 200 mJ / cm ２ is preferred, and 10 to 200 mJ / cm ２ is more preferred.

[0206] In step X2, pattern exposure may be performed after peeling the temporary support from the photosensitive layer, or pattern exposure may be performed through the temporary support before peeling the temporary support, and then the temporary support may be peeled off. To prevent mask contamination due to contact between the photosensitive layer and the mask and to avoid the influence of foreign matter attached to the mask on the exposure, it is preferable to perform pattern exposure without peeling off the temporary support. The pattern exposure may be performed through a mask or by direct exposure using a laser or the like. When exposure is performed through a mask, examples of the mask include a quartz mask, a soda-lime glass mask, and a film mask. Quartz masks are preferred because of their excellent dimensional accuracy, and film masks are preferred because they can be easily made into large sizes. As a material for the film mask, polyester film is preferred, and polyethylene terephthalate film is more preferred. As a material for the film mask, for example, XPR-7S SG (manufactured by Fujifilm Global Graphic Systems Co., Ltd.) is exemplified. It is preferable to peel the temporary support from the photosensitive layer before step X3, which will be described later.

[0207] <Step X3> Step X3 is a step of developing the exposed photosensitive layer after Step X2 to form a resin pattern precursor. Step X3 can be performed using a developer. Examples of 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.

[0208] (Alkaline Developer) The alkaline developer is preferably an alkaline aqueous solution. 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 water content in the alkaline developer is preferably 50% by mass or more, more preferably 60% by mass or more, even more preferably 85% by mass or more, particularly preferably 90% by mass or more, and most preferably 95% by mass or more, based on the total mass of the alkaline developer. The upper limit is preferably less than 100% by mass, based on the total mass of the alkaline developer. Examples of alkaline developers include aqueous sodium carbonate solutions, aqueous potassium carbonate solutions, aqueous sodium hydroxide solutions, aqueous potassium hydroxide solutions, and aqueous tetramethylammonium hydroxide solutions. Examples of the concentration of the alkaline developer (the alkaline component constituting the alkaline developer) include 0.1% by mass aqueous solutions, 1.0% by mass aqueous solutions, and 2.38% by mass aqueous solutions. The alkaline developer may also contain a water-soluble organic solvent, a surfactant, and the like. Examples of the alkaline developer include the developer described in paragraph 0194 of WO 2015 / 093271.

[0209] (Organic Solvent Developer) Examples of the organic solvent developer include developers containing organic solvents such as ketone solvents, ester solvents, alcohol solvents, amide solvents, ether solvents, and hydrocarbon solvents. Examples of the organic solvent developer include cyclopentanone and propylene glycol monomethyl ether acetate, with cyclopentanone being preferred. In the organic solvent developer, a plurality of organic solvents may be mixed, or may be mixed with an organic solvent other than the above or water. The water content of the organic solvent developer is preferably less than 10% by mass, more preferably substantially free of water, based on the total mass of the organic solvent developer. The organic solvent content of the organic solvent developer is preferably 50% by mass or more, more preferably 60% by mass or more, even more preferably 85% by mass or more, particularly preferably 90% by mass or more, and most preferably 95% by mass or more, based on the total mass of the organic solvent developer. The upper limit is preferably 100% by mass or less, based on the total mass of the organic solvent developer.

[0210] Examples of development methods include puddle development, shower development, spin development, and dip development. In shower development, unnecessary portions can be removed by spraying a developer onto the photosensitive layer after exposure. It is also preferable to spray a detergent or the like onto the layer after development and remove development residues by rubbing with a brush or the like. The temperature of the developer is preferably 20 to 40°C.

[0211] <Step X4> Step X4 is a step of heating the resin pattern precursor obtained in Step X3 to form a resin pattern. By performing Step X4, compound Y is removed, thereby reducing the coefficient of linear thermal expansion of the resulting resin pattern. Furthermore, when the photosensitive layer contains a polyimide precursor and a polybenzoxazole precursor, Step X4 promotes the ring-closing reaction of these precursors, producing polyimide and polybenzoxazole. Furthermore, it is believed that performing Step X4 removes not only the above-mentioned compound Y but also other impurities contained in the resin pattern precursor.

[0212] For example, the resin pattern precursor obtained in step X3 may contain compound Y and polymers derived from each polymerizable compound produced in step X2 (e.g., polymers derived from polymerizable compound YM). By subjecting this resin pattern precursor to step X4, compound Y is removed, depolymerization of the polymers occurs, and the depolymerized polymers are removed. Furthermore, by-products produced by the ring-closing reaction of the polyimide precursor and the polybenzoxazole precursor (e.g., compounds produced by decomposition of some groups of the polyimide precursor and the polybenzoxazole precursor) are removed, resulting in improved purity of the resin pattern. The purity of the resin pattern means that the various components contained in the pattern are essentially composed only of polyimide and polybenzoxazole. Specifically, 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.

[0213] The temperature and time of the heat treatment in step X4 are not particularly limited, as long as they are a temperature and time that promote the ring-closure reaction of the polyimide precursor and the polybenzoxazole precursor. The heat treatment temperature is preferably 120 to 400°C, more preferably 150 to 400°C, and 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 more, more preferably 50.66 kPa or more. The upper limit is preferably 121.6 kPa or less, more preferably 111.46 kPa or less, and even more preferably 101.3 kPa or less.

[0214] [Other Steps] The method for producing a laminate may include other steps in addition to those described above. Examples of other steps include the following steps.

[0215] <Cover Film Peeling Step> When the transfer film has a cover film in the laminate manufacturing method, it is preferable to include a step of peeling off the cover film of the transfer film. As the method for peeling off the cover film, a known method can be applied.

[0216] <Step of Reducing Visible Light Reflectance> When the substrate is a substrate having a conductive layer, the method for producing the laminate may further include a step of performing a treatment to reduce the visible light reflectance of the conductive layer. When the substrate is a substrate having a plurality of conductive layers, the treatment to reduce the visible light reflectance may be performed on some or all of the conductive layers. Examples of treatments to reduce the visible light reflectance include oxidation treatments. For example, copper can be oxidized to copper oxide, thereby blackening the conductive layer, thereby reducing the visible light reflectance of the conductive layer. Suitable embodiments of treatments to reduce the visible light reflectance are described in paragraphs 0017 to 0025 of JP 2014-150118 A and paragraphs 0041, 0042, 0048, and 0058 of JP 2013-206315 A, the contents of which are incorporated herein by reference.

[0217] <Etching Step> When the base material is a substrate having a conductive layer, the method for producing a laminate may include a step (etching step) of etching the conductive layer in an area where the etching resist film is not disposed, using the pattern (film) formed in step X3 or step X4 as an etching resist film. Examples of the etching method include the wet etching method described in paragraphs 0048 to 0054 of JP 2010-152155 A and known dry etching methods such as plasma etching.

[0218] The method for producing the laminate also preferably uses a substrate having a plurality of conductive layers on both surfaces thereof, and sequentially or simultaneously forms patterns on the conductive layers formed on both surfaces. With this configuration, a first conductive pattern can be formed on one surface of the substrate, and a second conductive pattern can be formed on the other surface. Formation from both surfaces of the substrate by roll-to-roll is also preferred.

[0219] [Circuit Wiring Manufacturing Method] The circuit wiring manufacturing method is not particularly limited as long as it is a circuit wiring manufacturing method using a transfer film. It preferably includes a lamination step in which the surface of the transfer film opposite to the temporary support side is brought into contact with a conductive layer in a substrate having a conductive layer and laminated to obtain a substrate with a photosensitive layer having a substrate, a conductive layer, a photosensitive layer, and a temporary support in this order; an exposure step in which the photosensitive layer is pattern-exposed; a development step in which the exposed photosensitive layer is developed to form a resin pattern precursor; a heating step in which the resin pattern precursor is heat-treated to form a resin pattern; and an etching step in which the conductive layer in the area where the resin pattern is not arranged is etched. Furthermore, the circuit wiring manufacturing method preferably includes a peeling step in which the temporary support is peeled from the substrate with a photosensitive layer between the lamination step and the exposure step, or between the exposure step and the development step.

[0220] Examples of the steps in the method for producing circuit wiring of the present invention include the steps in the method for producing the laminate. The method for producing circuit wiring of the present invention also preferably includes repeating a plurality of sets of steps, each set consisting of the steps from the laminating step to the etching step. The film used as the etching resist film can also be used as a protective film (insulating film) for the formed circuit wiring.

[0221] [Method for Manufacturing a Semiconductor Package] Examples of methods for manufacturing a semiconductor package include known manufacturing methods such as methods for manufacturing build-up substrates. Specifically, examples include manufacturing methods that include steps Z1 to Z5 in this order. Step Z1: a laminating step in which the surface of the transfer film opposite the temporary support is brought into contact with a substrate having a conductive layer and laminated to obtain a substrate with a photosensitive layer having a base material, a photosensitive layer, and a temporary support in this order; Step Z2: an exposure step in which the photosensitive layer is pattern-exposed; Step Z3: a step in which the exposed photosensitive layer is developed to form a resin pattern precursor having vias; Step Z4: a heating step in which the resin pattern precursor is heated to form a resin pattern having vias; and Step Z5: a circuit pattern forming step in which a circuit pattern is formed on the resin pattern. Furthermore, the method for manufacturing a semiconductor package preferably includes a peeling step in which the temporary support is peeled off from the substrate with a photosensitive layer between the laminating step and the exposure step, or between the exposure step and the development step.

[0222] As steps Z1, Z2, and Z4 in the method for manufacturing a semiconductor package, the same procedures as steps X1, X2, and X4 can be performed, respectively.

[0223] [Step Z3] Step Z3 is a step of developing the exposed photosensitive layer to form a resin pattern precursor having vias. The developing step can be carried out using a developer. Examples of the method of developing using a developer include the method of developing using the developer in Step X3.

[0224] The shape of the vias in the pattern may be, for example, a square, trapezoid, or inverted trapezoid in cross section; or a circle or square in front view (the shape of the via when observed from the direction in which the via bottom is visible). The shape of the vias in the pattern is preferably an inverted trapezoid in cross section, as this improves the adhesion of plated copper to the via wall surface. The via size (diameter) is often 300 μm or less, preferably 200 μm or less, more preferably less than 40 μm, even more preferably 30 μm or less, even more preferably 20 μm or less, particularly preferably 10 μm or less, and most preferably 5 μm or less. The lower limit is preferably 1 μm or more, more preferably 5 μm or more. The number of vias may be 1 or 2 or more, preferably 2 or more.

[0225] [Step Z5] Step Z5 is a step of forming a circuit pattern on a resin pattern having vias. A semi-additive process is preferred as a method for forming a circuit pattern because it allows for the formation of fine wiring. In the semi-additive process, a seed layer is first formed by electroless copper plating using a palladium catalyst or the like on the via bottoms, via walls, and the entire surface of the pattern after step Z3. The seed layer serves to form a power supply layer for electrolytic copper plating, and the seed layer thickness is preferably 0.1 to 2.0 μm. A seed layer thickness of 0.1 μm or more tends to suppress a decrease in connection reliability during electrolytic copper plating. A seed layer thickness of 2.0 μm or less tends to eliminate the need for a large etching amount when flash etching the seed layer between wirings, thereby suppressing damage to the wiring during etching. The electroless copper plating process is performed by depositing metallic copper on the surface of a pattern having vias through a reaction between copper ions and a reducing agent. Examples of electroless plating methods and electrolytic plating methods include known plating methods. The catalyst used in the electroless plating process is preferably a palladium-tin mixed catalyst. The average primary particle size of the mixed catalyst is preferably 10 nm or less. The plating composition used in the electroless plating process preferably contains hypophosphorous acid as a reducing agent. Commercially available electroless copper plating solutions include, for example, "MSK-DK" manufactured by Atotech Japan and the "Sulcup (registered trademark) PEA ver. 4" series manufactured by Uemura Kogyo Co., Ltd.

[0226] After electroless copper plating, it is preferable to thermocompress the surface of the photosensitive layer of any transfer film opposite the temporary support onto the electroless copper plating using a roll laminator. The thickness of the photosensitive layer is preferably 5 to 30 μm, since it can be made thicker than the wiring height after electrolytic copper plating. After thermocompression bonding of the transfer film, the photosensitive layer is exposed, for example, through a mask on which the desired wiring pattern is drawn. Examples of the exposure method include the same exposure method as 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. Furthermore, after forming the pattern, development residues of the composition may be removed using plasma or the like. After development, electrolytic copper plating is performed to form a copper circuit layer and via filling. After electrolytic copper plating, the pattern is peeled off using an alkaline aqueous solution or an amine-based stripper. After peeling the pattern, the seed layer between the wiring is removed (flash etching). Flash etching is performed, for example, using an oxidizing solution containing sulfuric acid and an acidic solution such as hydrogen peroxide. Examples of oxidizing solutions include "SAC" manufactured by JCU Corporation and "CPE-800" manufactured by Mitsubishi Gas Chemical Company, Inc. After flash etching, palladium and other materials adhering to the portions between the wirings are removed as necessary. Palladium can be removed using an acidic solution such as nitric acid and hydrochloric acid.

[0227] After the pattern is peeled off or after the flash etching step, a post-baking treatment is preferably performed. The post-baking treatment sufficiently heat-cures any unreacted thermosetting components, thereby improving the electrical insulation reliability, curing characteristics, and adhesive strength with plated copper. The preferred heat-curing conditions are a curing temperature of 150 to 240°C and a curing time of 15 to 500 minutes.

[0228] The method for manufacturing a semiconductor package may include a roughening step of roughening a pattern having vias. The roughening step is preferably performed after step Z4 and before step Z5. By performing the roughening step, the pattern surface can be roughened to improve adhesion with the circuit wiring. Smears can also be removed at the same time. Examples of the roughening step include known desmearing treatments, and treatments involving contact with a roughening liquid are preferred. Examples of roughening liquids include roughening liquids containing chromium and sulfuric acid, roughening liquids containing alkaline permanganate (e.g., sodium permanganate roughening liquid, etc.), and roughening liquids containing sodium fluoride, chromium, and sulfuric acid.

[0229] The above-described steps are repeated depending on the number of layers required to manufacture a semiconductor package. It is preferable to form a solder resist on the outermost layer.

[0230] [Touch Panel Manufacturing Method] 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. The surface of the transfer film opposite the temporary support is brought into contact with 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) and bonded to obtain a substrate with a photosensitive layer having a substrate, a conductive layer, a photosensitive layer, and a temporary support in this order. It is preferable to include: a step of pattern-exposing the photosensitive layer; a step of developing the exposed photosensitive layer to form a precursor of a patterned protective film or insulating film for the conductive layer; and a heating step of heating the precursor of the patterned protective film or insulating film for the conductive layer to form a patterned protective film or insulating film for the conductive layer. Furthermore, the method for manufacturing a touch panel preferably includes a peeling step of peeling the temporary support from the substrate with a photosensitive layer between the bonding step and the exposure step, or between the exposure step and the development step.

[0231] [Method for Manufacturing Semiconductor Device] A known manufacturing method can be applied to the method for manufacturing a semiconductor device. Specific examples include a method for manufacturing a semiconductor device that includes the above-described method for manufacturing a laminate or the above-described method for manufacturing a semiconductor package. Examples of semiconductor devices include various semiconductor devices such as semiconductor packages used in electrical appliances (e.g., computers, mobile phones, digital cameras, televisions, etc.) and vehicles (e.g., motorcycles, automobiles, trains, ships, aircraft, etc.).

[0232] [Semiconductor Package] The semiconductor package is not particularly limited as long as it includes a resin pattern obtained from the photosensitive layer formed using the transfer film described above. The resin pattern may be used as an insulating film, or may be used as an organic interposer or insulating film in a so-called build-up substrate.

[0233] The present invention will be described in more detail below based on examples. The materials, amounts used, ratios, processing details, processing procedures, etc. shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be interpreted as being limited by the examples shown below. In the following, "%" is based on mass unless otherwise specified.

[0234] [Preparation of Composition] A mixture was prepared by mixing various components in the amounts (by mass) shown under "Photosensitive Layer" in the table. Next, the mixture was diluted to a solids concentration of 30 mass%, a MEK (methyl ethyl ketone) concentration of 20 mass%, and a NMP (N-methylpyrrolidone) concentration of 50 mass%. Note that when the silica was not in a slurry form (when it was in a powder form), the silica was dispersed in a 50 mass% MEK solution to form a slurry, and then finally mixed to prepare the composition.

[0235] [Preparation of Transfer Film] The obtained composition was applied to a temporary support shown in the table and dried at 100°C to form a photosensitive layer. The film thickness of the photosensitive layer after drying was set to the thickness shown in the table. Next, a protective film (Oji F-Tex Co., Ltd., polypropylene film, FG-201, thickness 30 μm) was laminated to the side of the photosensitive layer opposite the temporary support to obtain a transfer film.

[0236] [Various Components Constituting Temporary Support and Photosensitive Layer] The various components contained in the temporary support and the photosensitive layer are shown below. [Temporary Support] PET1: 16 μm thick PET film ("Lumirror 16FB40", manufactured by Toray Industries, Inc.) PET2: 50 μm thick PET film ("Lumirror #50-T60", manufactured by Toray Industries, Inc.)

[0237] [Resin] Resins A to D are resins that correspond to Resin X.

[0238] <Synthesis of Resin A> 4,4'-oxydiphthalic anhydride (dried at 140°C for 12 hours, 20.0 g, 64.5 mmol), 2-hydroxyethyl methacrylate (16.8 g, 129 mmol), hydroquinone (0.05 g), pyridine (20.4 g, 258 mmol), and diglyme (100 g) were mixed and stirred at 60°C for 18 hours to produce a diester of 4,4'-oxydiphthalic acid and 2-hydroxyethyl methacrylate. The resulting diester was then dissolved in SOCl ２ The reaction mixture was chlorinated with HCl to obtain a reaction mixture. Next, a solution of 4,4'-diaminodiphenyl ether (11.08 g, 58.7 mmol) dissolved in N-methylpyrrolidone (100 mL) was added dropwise to the reaction mixture over 20 minutes at -5 to 0°C. The reaction mixture was then reacted at 0°C for 1 hour, after which ethanol (70 g) was added and the mixture was stirred at room temperature for 1 day. The polyimide precursor was then precipitated in 5 L of water, and the water-polyimide precursor mixture was stirred at 5,000 rpm for 15 minutes. The polyimide precursor was removed from the mixture by filtration, stirred in 4 L of water for 30 minutes, and filtered again. The resulting polyimide precursor was then dried under reduced pressure at 45°C for 3 days to obtain Resin A, a polyimide precursor. Resin A had a weight-average molecular weight of 18,000.

[0239] <Resin B> 4,4'-oxydiphthalic dianhydride (ODPA, Mw = 310.22, 77.6 g) and diphenyl-3,3',4,4'-tetracarboxylic dianhydride (BPDA, Mw = 294.2, 73.6 g) were placed in a 2 L separable flask, 2-hydroxyethyl methacrylate (HEMA, 134.0 g) and γ-butyrolactone (400 mL) were added, and pyridine (79.1 g) was added while stirring at room temperature to obtain a reaction mixture. After the heat generated by the reaction had ceased, the mixture was allowed to cool to room temperature and allowed to stand for an additional 16 hours. Next, a solution of dicyclohexylcarbodiimide (DCC, 206.3 g) dissolved in γ-butyrolactone (180 mL) was added to the reaction mixture over 40 minutes while stirring under ice cooling. Next, a suspension of 4,4'-oxydianiline (ODA, Mw = 200.24, 93.0 g) in γ-butyrolactone (350 mL) was added over 60 minutes with stirring. After further stirring at room temperature for 2 hours, ethyl alcohol (30 mL) was added and stirred for 1 hour, after which γ-butyrolactone (400 mL) was added. The precipitate formed in the reaction mixture was removed by filtration to obtain a reaction solution. The resulting reaction solution was added to ethyl alcohol (3 L) to obtain a crude polymer precipitate. The resulting crude polymer was collected by filtration and dissolved in tetrahydrofuran (1.5 L) to obtain a crude polymer solution. The resulting crude polymer solution was purified using an anion exchange resin (Amberlyst TM15, manufactured by Organo Corporation) to obtain a polymer solution. The resulting polymer solution was added dropwise to water (28 L) to precipitate the polymer, and the resulting precipitate was collected by filtration and dried under vacuum to obtain Resin B, a powdered polyimide precursor. The weight average molecular weight (Mw) of Resin B was 22,000. The imide group content of the polyimide obtained from Resin B was 27.4 mass % per repeating unit.

[0240] <Resin C> Using 4,4'-diaminodiphenyl ether as the diamine and 4,4'-oxydiphthalic anhydride as the dianhydride, a polyimide precursor, Resin C, was obtained. The weight average molecular weight of Resin C was 15,000.

[0241] <Resin D> Using 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane as the diamine and 4,4'-oxybis(benzoyl chloride) as the acid chloride, a polybenzoxazole precursor, Resin D, was obtained. The weight average molecular weight of Resin D was 15,000.

[0242]

[0243] [Photopolymerization initiator] Oxe01: IRGACURE OXE-01, manufactured by BASF Oxe02: IRGACURE OXE-02, manufactured by BASF Omnirad 379EG: manufactured by IGM Resins B.V. API 307: manufactured by Shenzhen UV-ChemTech Ltd. Omnirad 907: manufactured by IGM Resins B.V.

[0244] [Polymerizable Compounds] <Polymerizable compounds corresponding to compound Y> NK3G: NK ester 3G (triethylene glycol methacrylate), manufactured by Shin-Nakamura Chemical Co., Ltd. NK2G: NK ester 2G (diethylene glycol methacrylate), manufactured by Shin-Nakamura Chemical Co., Ltd. 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 Kogyo Co., Ltd.)

[0245] <Polymerizable compounds corresponding to comparative compound RY> DPHA: dipentaerythritol hexaacrylate ("A-DPH" manufactured by Shin-Nakamura Chemical Co., Ltd.) HC: cyclohexyl methacrylate ("Light Ester HC" manufactured by Kyoeisha Chemical Co., Ltd.) A-HD-N: 1,6-hexanediol diacrylate ("A-HD-N" manufactured by Shin-Nakamura Chemical Co., Ltd.) DPHMA: dipentaerythritol hexamethacrylate (a synthetic product synthesized by transesterification of dipentaerythritol and methacrylic acid was used.)

[0246] [Non-polymerizable compounds] <Non-polymerizable compounds 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)

[0247] <Non-polymerizable compounds corresponding to comparative compound RY> PC: propylene carbonate (manufactured by Kishida Chemical Co., Ltd.)

[0248] [Fillers] YA050C-MJE: Spherical silica slurry, methacrylic surface treated, MEK slurry with a solid content of 50% by mass, manufactured by Admatechs Co., Ltd. YA50SP-AM1: Silicon dioxide, manufactured by Admatechs Co., Ltd. YA50SZ-AM1: Silicon dioxide, manufactured by Admatechs Co., Ltd. MEK-ST-L: Silicon dioxide, hydrophobic surface treated, manufactured by Nissan Chemical Industries, Ltd. PMA-ST: Silicon dioxide, hydrophobic surface treated, manufactured by Nissan Chemical Industries, Ltd. MEK-ST-ZL: Silicon dioxide, hydrophobic surface treated, manufactured by Nissan Chemical Industries, Ltd. NHM-3N: Silicon dioxide, manufactured by Tokuyama Corporation

[0249] [Thermal Base Generator] Compound A (see structural formula below)

[0250]

[0251] U-CAT SA506: p-toluenesulfonate of 1,8-diazabicyclo[5.4.0]undecene-7, manufactured by San-Apro Co., Ltd.

[0252] [Surfactants] F551A: Megafac (registered trademark) F551A, a fluorine-based surfactant, manufactured by DIC Corporation S-324: a silicone-based surfactant, manufactured by DIC Corporation

[0253] [Developers] Developer A: Cyclopentanone Developer B: 1% by mass aqueous sodium carbonate solution (Na ２ CO ３ aq.) Developer C: 2.38% by mass tetramethylammonium hydroxide aqueous solution (TMAHaq.)

[0254] [Measurement of various physical properties of compound Y and comparative compound RY] The viscosity of the compounds shown in the "compound Y and comparative compound RY" column in the table was measured by the following procedure. In addition, when compound Y and comparative compound RY were polymerizable compounds, the decomposition temperature of the homopolymer derived from the compound was measured by the following procedure. The results are shown in Table 1.

[0255] <Measurement of Viscosity> The viscosity was measured at 25°C using a Brookfield viscometer (LVDVE manufactured by Eiko Seiki Co., Ltd.) and the average value of three measurements was calculated. Note that a low viscosity adapter (LVDV2T) was used for the measurement.

[0256] <Measurement of Decomposition Temperature of Homopolymer> When compound Y and comparative compound RY were polymerizable compounds, the polymerizable compounds were polymerized to synthesize homopolymers having a weight-average molecular weight of 10,000 or more (specifically, 10,000 to 100,000). The weight-average molecular weights of the obtained homopolymers before and after heat treatment (heat treatment at 300°C for 3 hours) were measured using GPC (apparatus: Tosoh high-speed GPC apparatus HLC-8420GPC (trade name), manufactured by Tosoh Corporation), and evaluation was performed based on the following evaluation criteria. (Evaluation Criteria) "A": The weight-average molecular weight after heating was less than ⅓ of the weight-average molecular weight before heating "B": The weight-average molecular weight after heating was ⅓ or more of the weight-average molecular weight before heating

[0257] [Measurement of Average Particle Diameter] The photosensitive layer of each transfer film of each Example and Comparative Example was transferred onto a glass substrate to prepare a glass substrate with a photosensitive layer. Next, a cross section of the photosensitive layer was cut out along the normal direction to the surface, and the cross section was observed under a scanning electron microscope. The major axes of all fillers observed within a region measuring 3 μm in the longitudinal direction parallel to the thickness direction of the photosensitive layer and 10 μm in the transverse direction perpendicular to the longitudinal direction were measured. The above procedure was performed at five different locations on the photosensitive layer, and the average (arithmetic mean) of the major axes of all fillers measured in each procedure was taken as the average particle diameter of the filler. After measuring the average particle diameter of each transfer film of each Example and Comparative Example as described above, the photosensitive layer on the glass substrate with a photosensitive layer was heated at 230° C. for 8 hours, and then the average particle diameter was measured according to the same procedure as described above. The average particle diameter was the same as the average particle diameter before the heat treatment.

[0258] [Evaluation of Transfer Films] The transfer films of the Examples and Comparative Examples were evaluated as follows. The results are shown in Table 1.

[0259] [Measurement of Melt Viscosity of Photosensitive Layer at 100°C] <Preparation of Evaluation Samples> Five transfer films of each of the Examples and Comparative Examples were prepared, and evaluation samples were prepared according to the following procedure. Two transfer films from which the protective films had been peeled were bonded together so that the photosensitive layers of each transfer film faced each other, and then one of the two temporary supports was peeled off to obtain Laminate 1 having a temporary support and two photosensitive layers. Next, the transfer film from which the protective film had been peeled off was bonded to Laminate 1 so that the photosensitive layer of this transfer film faced the photosensitive layer of Laminate 1, and then one of the two temporary supports was peeled off to obtain Laminate 2 having a temporary support and three photosensitive layers. Laminate 1 was then separately prepared, and the photosensitive layer of Laminate 1 and the photosensitive layer of Laminate 2 prepared above were bonded together so that the photosensitive layers faced each other to obtain Laminate 3 (temporary support / five-layer photosensitive layer / temporary support). Finally, the two temporary supports were peeled off from the laminate 3 to obtain a sample for evaluation.

[0260] <Measurement of Melt Viscosity of Photosensitive Layer at 100°C> The complex viscosity of the obtained evaluation sample was measured using a rheometer "DHR-2" manufactured by TA Instruments, and the average value of three measurements was evaluated according to the following criteria. The measurement was carried out under the conditions shown below. 20 mmφ parallel plates and a Peltier plate were set with a gap of 0.5 mm, and the measurement was carried out under the conditions of a temperature of 20 to 105°C, a heating rate of 5°C / min, and a strain of 0.5%. Prior to the measurement, the sample was melted (80°C) on the Peltier plate and then cooled to 20°C (cooling rate of 5°C / min) before the measurement was started.

[0261] (Evaluation Criteria) "A": The complex viscosity (melt viscosity) of the photosensitive layer at 100°C is 5.0 x 10 ６ Pa s or less "B": The complex viscosity (melt viscosity) of the photosensitive layer at 100°C is 5.0 x 10 ６ Greater than Pa·s

[0262] [Evaluation of thermal weight loss rate when photosensitive layer is heated at 350°C for 1 hour] <Preparation of evaluation sample> Evaluation samples shown in <Preparation of evaluation sample> in [Measurement of melt viscosity of photosensitive layer at 100°C] were prepared and subjected to the measurement described below.

[0263] <Measurement of Thermal Weight Loss Rate When Photosensitive Layer is Heated at 350°C for 1 Hour> The obtained evaluation sample was measured using a TG-DTA device ("TG / DTA6200" manufactured by Seiko Instruments Inc.), and the average value of the thermal weight loss rate measured three times was evaluated according to the following evaluation criteria. The measurement was carried out under the conditions shown below. The final thermal weight loss rate was measured in the range from room temperature to 350°C (under a nitrogen atmosphere, at a temperature increase rate of 10°C / min, and 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

[0264] [Evaluation of photolithography properties] The cover film was peeled off from the transfer film, and a 10 × 10 cm glass plate (Corning Eagle XG) with a thickness of 0.1 mm was placed on the transfer film. ２ (Lamination conditions: rubber roller temperature (lamination temperature) 140°C, linear pressure 3 N / cm, conveying speed 1 m / min) Next, the glass / photosensitive layer / temporary support / mask were laminated in this order, and exposed from the mask side using an ultra-high pressure mercury lamp. The mask used had circular light-shielding portions with a diameter of 100 μm, and the distance between adjacent light-shielding portions was 300 μm or more. During exposure, the exposure dose measured with a 365 nm illuminometer was 10 mJ / cm. ２ After the exposure, the film was left to stand for 30 minutes, the temporary support was peeled off, and then development processing was carried out for 90 seconds at room temperature using the developer shown in the table. After development, a rinse processing was carried out for 20 seconds at room temperature using a rinse liquid, and further, air was blown to remove the remaining rinse liquid. Note that the rinse liquid was an aqueous developer (Na ２ CO ３ aq, or TMAHaq.), water was used, and when the developer was an organic solvent (cyclopentanone), propylene glycol monoethyl ether acetate was used. The samples obtained by the above procedure were observed and evaluated according to the following criteria.

[0265] (Evaluation criteria (100 μmΦ)) "A": A via with a diameter of 100 μmΦ could be formed. "B": A residual film (residue) with a thickness of 1 / 10 or more of the film thickness was found in the via formation area, and a via with a diameter of 100 μmΦ could not be formed. "C": It was not possible to laminate onto glass (in other words, the photosensitive layer remained on the temporary support side), and the developability could not be evaluated.

[0266] In addition, in the evaluation of photolithography properties, the same results were obtained when the exposure method was changed as follows: The cover film was peeled off from the transfer film, and a 10 × 10 cm glass (Corning Eagle XG) with a thickness of 0.1 mm was placed on the transfer film. ２ (Lamination conditions: rubber roller temperature (lamination temperature) 140°C, linear pressure 3 N / cm, transport speed 1 m / min) The temporary support was peeled off, and the photosensitive layer was subjected to pattern exposure using a projection exposure device (UX-4 manufactured by Ushio Inc.). The exposure pattern had circular non-exposed areas with a diameter of 100 μmΦ, and the distance between adjacent non-exposed areas was 300 μm or more. The exposure dose measured with a 365 nm illuminometer was 400 mJ / cm. ２ After exposure, the film was left to stand for 30 minutes, and then developed for 90 seconds at room temperature using the developer shown in the table. After development, the film was rinsed for 20 seconds at room temperature using a rinse solution, and the remaining rinse solution was removed by blowing air. The rinse solution was an aqueous solution of developer (Na ２ CO ３ aq, or TMAHaq.), water was used, and when the developer was an organic solvent (cyclopentanone), propylene glycol monoethyl ether acetate was used.

[0267] [Evaluation of coefficient of linear expansion (CTE) of cured product of photosensitive layer] <Preparation of evaluation sample> The evaluation sample shown in <Preparation of evaluation sample> in [Measurement of melt viscosity of photosensitive layer at 100°C] was prepared. At that time, the two temporary supports were left in place without being peeled off. In other words, a laminate 3 having a configuration of temporary support / five-layer photosensitive layer / temporary support was used as the evaluation sample.

[0268] <Evaluation of the coefficient of linear expansion (CTE) of the cured product of the photosensitive layer> A high-pressure mercury lamp (exposure amount: 25 mJ / cm) was irradiated from one of the temporary support sides of the prepared evaluation sample. ２ After performing an exposure treatment by irradiating the laminate with UV light, two temporary supports were peeled off from the exposed laminate and subjected to a heat treatment at 230 ° C (oven setting temperature) for 8 hours to obtain a free-standing film. The produced free-standing film was cut into strips (19 mm x 5 mm) and the linear expansion coefficient was measured using a TMA (thermomechanical analyzer, "TMA450EM" manufactured by TA Instruments). The measurement conditions were a heating rate of 10 ° C / min, a chuck distance of 16 mm, and a load of 49 mN. The measurement was performed in a temperature range of -60 ° C to 350 ° C. The linear expansion coefficient was measured as a value (ppm / K) in the range of 50 ° C to 150 ° C during heating, and was calculated as the average value of three measurements.

[0269] (Evaluation criteria (CTE)) "A": 20 ppm / K or less "B": more than 20 ppm / K and less than 60 ppm / K "C": more than 60 ppm / K

[0270] [Evaluation of temporary support releasability] The cover film was peeled off from the transfer film (9 cm x 9 cm), and a 10 x 10 cm piece of glass (Corning Eagle XG) with a thickness of 0.1 mm was applied. ２ (Lamination conditions: rubber roller temperature (lamination temperature) 140°C, linear pressure 3 N / cm, transport speed 1 m / min.) After leaving it for 30 minutes, the temporary support was peeled off at a peel angle of 120°, and the proportion of the photosensitive layer remaining on the temporary support was evaluated according to the following criteria.

[0271] (Evaluation criteria (removability of temporary support) "A": The photosensitive layer remaining on the temporary support accounted for less than 10% of the surface area of ​​the temporary support. "B": The photosensitive layer remaining on the temporary support accounted for 10% or more and less than 50% of the surface area of ​​the temporary support. "C": The photosensitive layer remaining on the temporary support accounted for 50% or more of the surface area of ​​the temporary support. "D": It was not possible to laminate onto glass, and it was not possible to evaluate the removability of the temporary support.

[0272] [Evaluation of Step Conformity (Fresh)] <Evaluation of Step Conformity (Fresh)> A test substrate was prepared by forming a 2 μm-thick copper pattern (line / space = 2 μm / 2 μm, 5 μm / 5 μm) in a comb-like wiring pattern on a silicon wafer. The transfer film, from which the protective film had been peeled off, was vacuum-laminated at a temperature of 100° C. and a conveying speed of 1 m / min so that the photosensitive layer faced the wiring-formed surface of the test substrate. The gap between the two copper patterns after lamination was observed with an optical microscope and evaluated according to the following criteria.

[0273] (Evaluation criteria (2 μm and 5 μm step conformability)) "A": No air had entered between the wirings, or only a small amount of air had entered between the wirings (air bubble area less than 10% of the area between the wirings). "B": Some air had entered between the wirings (air bubble area 10% or more but less than 40% of the area between the wirings). "C": Air had entered between the wirings (air bubble area 40% or more of the area between the wirings).

[0274] <Evaluation of step-conforming ability (after storage)> The transfer film was stored for 180 days under conditions of 30°C and 50% RH. The step-conforming ability after storage was evaluated in the same manner as in <Evaluation of step-conforming ability (fresh)>, except that the transfer film after storage was used.

[0275] <Resin Pattern Producibility> It was confirmed that a resin pattern could be formed using the transfer film of the example. The specific procedure was as follows.

[0276] Peel off the cover film from the transfer film and place it on a 10 x 10 cm glass sheet (Corning Eagle XG) with a thickness of 0.1 mm. ２ (Lamination conditions: rubber roller temperature (lamination temperature) 140°C, linear pressure 3 N / cm, transport speed 1 m / min). Next, the glass / photosensitive layer / temporary support / mask were laminated in this order, and exposed from the mask side using an ultra-high pressure mercury lamp. The mask used had circular light-shielding areas with a diameter of 100 μmΦ, and the distance between adjacent light-shielding areas was 300 μm or more. During exposure, the exposure dose measured with a 365 nm illuminometer was 10 mJ / cm. ２The results were as follows: After exposure, the sample was left to stand for 30 minutes, the temporary support was peeled off, and then development was carried out for 90 seconds at room temperature using the developer listed in the table. After development, a rinse was carried out for 20 seconds at room temperature using a rinse solution, and then air was blown to remove any remaining rinse solution. When the developer was an aqueous solution (Na2CO3 aq or TMA Haq), water was used as the rinse solution; when the developer was an organic solvent (cyclopentanone), propylene glycol monoethyl ether acetate was used. After the above procedure, a heat treatment was carried out at 230°C for 3 hours, and a resin pattern with 100 μm diameter holes was formed on the substrate.

[0277] Table 1 is shown below. In Table 1 below, data related to Examples and Comparative Examples are divided into left columns (Table 1-X1 to Table 1-X6) and right columns (Table 1-Y1 to Table 1-Y6). That is, the configurations of the transfer films and the evaluation results in Table 1 are shown by combining Examples or Comparative Examples with the same numbers in Table 1-XN (N: 1 to 6) and Table 1-YN (N: 1 to 6) (specifically, Table 1-X1 and Table 1-Y1, Table 1-X2 and Table 1-Y2, Table 1-X3 and Table 1-Y3, Table 1-X4 and Table 1-Y4, Table 1-X5 and Table 1-Y5, and Table 1-X6 and Table 1-Y6 are each combined, and for each Example and Comparative Example, 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 are shown in this order). For example, in Example 1, the components of the photosensitive layer are Resin A (resin), Oxe01 (initiator), NK3G (polymerizable compound), YA050C-MJE (filler), Compound A (thermal base generator), and F551A (surfactant).

[0278]

[0279]

[0280]

[0281]

[0282]

[0283]

[0284]

[0285]

[0286]

[0287]

[0288]

[0289]

[0290] From the results shown in Table 1, the transfer films of the examples have excellent step-following properties when attached to an object to be attached after storage, excellent releasability of the temporary support, and a small linear expansion coefficient of the cured product of the photosensitive layer (in other words, the resin pattern formed from the photosensitive layer of the transfer film has a small linear expansion coefficient). Furthermore, from a comparison of the examples, it was confirmed that when the photosensitive layer of the transfer film contains a filler, and the filler content is 30% by mass relative to the total mass of the photosensitive layer, the film has excellent step-following properties when attached to an object to be attached after storage, and also has excellent releasability of the temporary support. Furthermore, from a comparison of the examples, it was confirmed that when the mass ratio of the content of compound Y to the content of resin X is 0.50 to 1.00 (preferably, 0.52 to 1.00), the linear expansion coefficient of the cured product of the photosensitive layer is smaller (in other words, the resin pattern formed from the photosensitive layer of the transfer film has a smaller linear expansion coefficient).

[0291] On the other hand, the transfer film of the comparative example did not provide the desired effect.

[0292] Example 1A: The transfer film of Example 1 was laminated on both sides of a glass epoxy substrate (CCL-EL190T, 1.0 mm thick, manufactured by Mitsubishi Gas Chemical Co., Ltd.) on which a circuit pattern had been formed, and photosensitive layers were formed on both sides of the glass epoxy substrate. A vacuum laminator was used for this. Lamination was performed using a vacuum laminator manufactured by MCK Corporation under conditions of a substrate temperature of 40°C, a rubber roller temperature of 100°C, a linear pressure of 3 N / cm, and a conveying speed of 2 m / min. A pattern with vias at predetermined positions was formed on the prepared photosensitive layer using the same method as in the above [Photolithography], except that the via diameter was φ60 μm. The residue was then removed using a sodium permanganate aqueous solution as a roughening solution, and electroless plating was performed. Next, a resist pattern was formed at predetermined positions using a known dry film resist, and electrolytic plating was performed. The resist pattern was then peeled off using a stripping solution. Finally, a seed layer etching process was performed, followed by a heat treatment (160°C, 1 hour) to form copper wiring on the cured film. The above process from lamination to heat treatment was repeated three times, and finally, a solder resist was formed as the outermost layer. A semiconductor element was then sealed and mounted to produce a semiconductor package. The resulting semiconductor package was mounted in a predetermined position on a printed wiring board to obtain a semiconductor package substrate. The resulting semiconductor package substrate was confirmed to operate normally.

[0293] [Examples 2A to 123A] Semiconductor packages were produced and semiconductor package substrates were obtained in the same manner as in Example 1A, except that the transfer film of Example 1 was replaced with each of the transfer films of Examples 2 to 123 (Examples 2A to 123A). It was confirmed that all of the obtained semiconductor package substrates operated normally.

[0294] [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 μm. 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.

[0295] 12: Temporary support 14: Composition layer 16: Cover film 100: Transfer film

Claims

1. A transfer film having a temporary support and a photosensitive layer, The photosensitive layer comprises Resin X selected from the group consisting of polyimide, polybenzoxazole, and precursors thereof; A photopolymerization initiator; and 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.; a 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.

2. The transfer film according to claim 1 , wherein the photosensitive layer satisfies the following requirement 1: 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.

3. 3. The transfer film according to claim 1, wherein a mass ratio of the content of the compound Y to the content of the resin X is 0.50 to 1.

00.

4. The transfer film according to claim 1 or 2, wherein the compound Y is at least one selected from the group consisting of a polymerizable compound having a methacryloyl group and a solvent.

5. The compound Y includes a polymerizable compound having a methacryloyl group, and The transfer film according to claim 1 or 2, wherein the decomposition temperature of the homopolymer derived from the polymerizable compound is 300° C. or lower.

6. The melt viscosity of the photosensitive layer at 100° C. is 5.0×10 ６ The transfer film according to claim 1 or 2, having a viscosity of Pa·s or less.

7. The transfer film according to claim 1 or 2, wherein the compound Y has a viscosity at 25° C. of 500 mPa·s or less.

8. The transfer film according to claim 1 or 2, wherein the content of the resin X is 65.0 mass % or less with respect to the total mass of the photosensitive layer.

9. 3. The transfer film according to claim 1, wherein the content of the compound Y is 5.0 to 50.0% by mass based on the total mass of the photosensitive layer.

10. 3. The transfer film according to claim 1, wherein the content of the compound Y is 5.0 to 25.0% by mass based on the total mass of the photosensitive layer.

11. The transfer film according to claim 1 or 2, wherein the content of the photopolymerization initiator is 5.0 mass % or less based on the total mass of the photosensitive layer.

12. Further, the composition contains a filler. The transfer film according to claim 1 or 2, wherein the content of the filler is 30.0% by mass or more based on the total mass of the photosensitive layer.

13. The transfer film according to claim 12, wherein the average particle diameter of the filler calculated by the following particle diameter measurement method is 10 to 300 nm. Particle size measurement method: A rectangular region of 3 μm × 10 μm in a cross section along the normal direction of the surface of the photosensitive layer is observed with a scanning electron microscope, and the operation of measuring the long diameters of all the fillers observed within the region is performed at five different points on the photosensitive layer, and the average value of the long diameters of all the fillers measured in each operation is regarded as the average particle size of the filler.

14. 3. The transfer film according to claim 1, wherein the photosensitive layer has a thickness of 5.0 to 19 μm.

15. a lamination step of contacting a surface of the transfer film according to claim 1 or 2 opposite to the temporary support with a substrate to obtain a substrate with a photosensitive layer having the substrate, the photosensitive layer, and the temporary support in this order; an exposure step of pattern-exposing the photosensitive layer; a developing step of developing the exposed photosensitive layer to form a resin pattern precursor; a heating step of heating the resin pattern precursor to form a resin pattern; The method for producing a laminate further comprises a peeling step of peeling the temporary support from the substrate with the photosensitive layer between the laminating step and the exposing step, or between the exposing step and the developing step.

16. A laminate obtained by the method for producing a laminate according to claim 15.

17. A method for manufacturing a semiconductor package, comprising the method for manufacturing the laminate according to claim 15.

18. The photosensitive layer further comprises a filler, the content of the filler is 30.0% by mass or more based on the total mass of the photosensitive layer, The transfer film according to claim 1 or 2, wherein the resin X comprises at least a resin selected from the group consisting of a polyimide precursor, a polybenzoxazole precursor, and a polybenzoxazole.

19. The transfer film according to claim 1, wherein the resin X comprises at least a resin selected from the group consisting of a polybenzoxazole precursor and a polybenzoxazole.

20. The photosensitive layer further comprises a filler, The transfer film according to claim 1 or 2, wherein the content of the filler is 66.4 mass % or more based on the total mass of the photosensitive layer.