Photosensitive resin composition and transfer film

Abstract

To provide a photosensitive resin composition enabling formation of a photosensitive resin layer with reduced time-dependent change in pattern formation performance after transfer to a transfer target, and to provide a transfer film and a method for producing a laminate with a conductor pattern.SOLUTION: A photosensitive resin composition comprises an alkali-soluble resin, a polymerizable compound, a photopolymerization initiator, and a surfactant, wherein the value of ΔHSP1 calculated by the following formula (F1) is 6.0 MPa0.5 or less. The formula (F1): ΔHSP1=(4(δDM-δDS)2+(δHM-δHS)2+(δPM-δPS)2)0.5.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a photosensitive resin composition and a transfer film. [Background technology]

[0002] Because the number of steps required to obtain a desired pattern is small, a pattern formation method in which a photosensitive resin layer is placed on a substrate of choice using a transfer film, and the photosensitive resin is then exposed to light through a mask and developed is widely used. The photosensitive resin layer of the transfer film is typically formed by coating a photosensitive resin composition, and often contains a surfactant to improve the surface condition during coating (for example, to reduce film irregularities and suppress composition fluctuations). For example, Patent Document 1 discloses a photosensitive film including a support film, a positive photosensitive resin layer containing a fluorine-based surfactant, and a protective layer. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Laid-Open No. 2012-226148 Summary of the Invention [Problem to be solved by the invention]

[0004] The present inventors have conducted various studies on transfer films having a negative photosensitive resin layer containing a fluororesin surfactant, with reference to the transfer film having a positive photosensitive resin layer containing a fluororesin surfactant described in Patent Document 1, and have found that when a transfer film that has been stored for a long period of time is used to form a pattern on a substrate, a decrease in pattern formation performance may occur due to a decrease in adhesion to the substrate, etc.

[0005] Therefore, an object of the present invention is to provide a photosensitive resin composition capable of forming a photosensitive resin layer that is less susceptible to changes over time in pattern forming performance after being transferred to a transfer target. Another object of the present invention is to provide a transfer film. [Means for solving the problem]

[0006] 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.

[0007] [1] A photosensitive resin composition comprising an alkali-soluble resin, a polymerizable compound, a photopolymerization initiator, and a surfactant, The value of ΔHSP1 calculated by the formula (F1) described later is 6.0 MPa. 0.5 A photosensitive resin composition, which is: [2] A photosensitive resin composition comprising an alkali-soluble resin, a polymerizable compound, a photopolymerization initiator, and a surfactant, the surfactant is a resin having a first repeating unit containing an atom selected from the group consisting of a silicon atom and a fluorine atom, and a second repeating unit containing neither a silicon atom nor a fluorine atom, The value of ΔHSP2 calculated by the formula (F2) described later is 4.0 MPa. 0.5 A photosensitive resin composition as follows: However, when at least one selected from the group consisting of the alkali-soluble resin and the polymerizable compound has one of an electron-accepting group and an electron-donating group, the surfactant does not have the other of the electron-accepting group and the electron-donating group. [3] A photosensitive resin composition comprising an alkali-soluble resin, a polymerizable compound, a photopolymerization initiator, and a surfactant, A photosensitive resin composition, wherein the surfactant and at least one member selected from the group consisting of the alkali-soluble resin and the polymerizable compound each have an aromatic ring structure in the molecule. [4] A photosensitive resin composition comprising an alkali-soluble resin, a polymerizable compound, a photopolymerization initiator, and a surfactant, a photosensitive resin composition, wherein at least one compound selected from the group consisting of the alkali-soluble resin and the polymerizable compound has one of an electron-accepting group and an electron-donating group, and the surfactant has the other of the electron-accepting group and the electron-donating group. [5] The photosensitive resin composition according to any one of [1] to [4], wherein the surfactant does not contain a fluorine atom. [6] The photosensitive resin composition according to any one of [1] to [5], wherein the surfactant is a resin having at least one repeating unit selected from the group consisting of a repeating unit represented by formula (A-1) described later and a repeating unit represented by formula (A-2) described later. [7] The photosensitive resin composition according to any one of [1] to [6], wherein the polymerizable compound includes a compound represented by formula (P1) described below. [8] The photosensitive resin composition according to any one of [1] to [7], wherein the alkali-soluble resin comprises a resin having one or more repeating units selected from the group consisting of a repeating unit represented by formula (R1) described later and a repeating unit represented by formula (R2) described later. [9] The photosensitive resin composition according to any one of [1] to [8], wherein the photopolymerization initiator comprises at least one selected from the group consisting of an acridine-based photopolymerization initiator, an oxime ester-based photopolymerization initiator, a biimidazole-based photopolymerization initiator, an alkylphenone-based photopolymerization initiator, an acetophenone-based photopolymerization initiator, and an acylphosphine oxide-based photopolymerization initiator.

[10] A transfer film having, in this order, a temporary support, a photosensitive resin layer formed from the photosensitive resin composition according to any one of [1] to [9], and a protective layer.

[11] The transfer film according to

[10] , which is used in a process of forming a circuit on a semiconductor substrate by plating.

[12] The transfer film according to

[10] , which is used in a process of forming a circuit by etching on a metal substrate or a resin substrate with a metal layer. [Effects of the Invention]

[0008] According to the present invention, it is possible to provide a photosensitive resin composition capable of forming a photosensitive resin layer that is less susceptible to changes over time in pattern forming performance after being transferred to a transfer target. The present invention also provides a transfer film. [Brief explanation of the drawings]

[0009] [Figure 1] FIG. 2 is a schematic diagram for explaining the shape of a transfer film. DETAILED DESCRIPTION OF THE INVENTION

[0010] 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 the present specification, in the numerical ranges described in stages, the upper or lower limit value described in a certain numerical range may be replaced with the upper or lower limit value of another numerical range described in stages. Furthermore, in the numerical ranges described in the present specification, the upper or lower limit value described in a certain numerical range may be replaced with a value shown in the examples.

[0011] In this specification, the term "process" includes not only an independent process but also a process that cannot be clearly distinguished from other processes, as long as the intended purpose of the process is achieved.

[0012] In this specification, unless otherwise specified, the term "transparent" means that the average transmittance of visible light with a wavelength of 400 to 700 nm is 80% or more, preferably 90% or more. In this specification, 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.

[0013] In this specification, unless otherwise specified, the weight-average molecular weight (Mw) and number-average molecular weight (Mn) are values ​​converted using a polystyrene standard substance measured with a gel permeation chromatography (GPC) analyzer using a TSKgel GMHxL, TSKgel G4000HxL, or TSKgel G2000HxL (all trade names manufactured by Tosoh Corporation) column, THF (tetrahydrofuran) as an eluent, a differential refractometer as a detector, and polystyrene as a standard substance. In this specification, unless otherwise specified, the molecular weight of a compound having a molecular weight distribution is the weight average molecular weight (Mw). In this specification, unless otherwise specified, the content of metal elements is a value measured using an inductively coupled plasma (ICP) spectroscopic analyzer.

[0014] In this specification, "(meth)acrylic" is a concept that includes both acrylic and methacrylic, "(meth)acryloyloxy" is a concept that includes both acryloyloxy and methacryloyloxy, "(meth)acrylamide" is a concept that includes both acrylamide and methacrylamide, "(meth)acrylate" is a concept that includes both acrylate and methacrylate, and (meth)acrylonitrile is a concept that includes both acrylonitrile and methacrylonitrile.

[0015] In this specification, "alkali-soluble" means that the solubility in 100 g of a 1% by mass aqueous sodium carbonate solution at a liquid temperature of 22° C. is 0.1 g or more. Therefore, for example, an alkali-soluble resin refers to a resin that satisfies the above-mentioned solubility conditions.

[0016] As used herein, "water-soluble" means that the solubility in 100 g of water having a pH of 7.0 and a liquid temperature of 22° C. is 0.1 g or more. Therefore, for example, a water-soluble resin refers to a resin that satisfies the above-mentioned solubility conditions.

[0017] In this specification, the "solid content" of a composition refers to components that form a composition layer (e.g., a photosensitive resin layer) formed using the composition, and when the composition contains a solvent (e.g., an organic solvent, water, etc.), refers to all components excluding the solvent. Furthermore, liquid components that form a composition layer are also considered to be solid content.

[0018] In this specification, the thickness of each layer is calculated as the average value of any five points measured by cross-sectional observation using an SEM (Scanning Electron Microscope).

[0019] [Photosensitive resin composition of the first embodiment] The photosensitive resin composition of the first embodiment (hereinafter also referred to as the "first composition") comprises: A photosensitive resin composition comprising an alkali-soluble resin, a polymerizable compound, a photopolymerization initiator, and a surfactant, wherein the value of ΔHSP1 calculated by the formula (F1) described below is 6.0 MPa. 0.5 The following is the result.

[0020] When a transfer film having a photosensitive resin layer formed from the first composition having the above-described configuration is transferred to a transfer substrate after long-term storage and then used to form a pattern, the pattern forming performance is unlikely to change over time. In other words, even when a transfer film having a photosensitive resin layer formed from the first composition is transferred to a transfer substrate and used to form a pattern after long-term storage, it exhibits pattern forming performance equivalent to that when it is transferred to a transfer substrate immediately after production and used to form a pattern.

[0021] The mechanism by which the first composition provides the above-mentioned effects is not clear, but the present inventors speculate as follows. In the prior art, when a transfer film that had been stored for a long period of time was used to form a pattern on a substrate, the change in pattern formation performance over time was thought to be due to poor compatibility between the surfactant and the alkali-soluble resin and polymerizable compound that correspond to the matrix components of the photosensitive resin layer, which caused the surfactant to weep due to environmental changes such as temperature changes during storage of the transfer film and become unevenly distributed on the surface of the photosensitive resin layer, resulting in a decrease in adhesion between the photosensitive resin layer and the substrate after transfer. Furthermore, it is thought that as a result, parts with weak adhesion are easily peeled off during development, which can cause fluctuations in the pattern formation performance formed on the substrate. In contrast, the first composition has an HSP distance (ΔHSP1 value) between the surfactant and the alkali-soluble resin and polymerizable compound corresponding to the matrix component of the photosensitive resin layer of 6.0 MPa. 0.5 Therefore, it is presumed that even when the composition is transferred to a transfer target and a pattern is formed after long-term storage, the pattern forming performance is unlikely to change. In the following, when a transfer film having a photosensitive resin layer formed from the first composition is used after long-term storage to transfer onto a substrate to form a pattern, the fact that changes in pattern formation performance are more suppressed is also referred to as "the effect of the present invention being better."

[0022] The first composition will be described in detail below. The first composition has a ΔHSP1 value calculated by the following formula (F1) of 6.0 MPa 0.5 The effect of the present invention is more excellent, and the pressure is 5.7 MPa or less. 0.5 Preferably less than 5.5MPa 0.5 Less than 5.0MPa is more preferable. 0.5 The lower limit is preferably 0.0 MPa. 0.5 It is sufficient if it is above 3.0MPa. 0.5 In many cases, this is the case.

[0023] Formula (F1): ΔHSP1 = (4(δDM - δDS) 2 +(δHM-δHS) 2 +(δPM-δPS)2 ) 0.5 In formula (F1), δDM represents the weighted average value of the dispersion term of the Hansen solubility parameter of the alkali-soluble resin and the dispersion term of the Hansen solubility parameter of the polymerizable compound, calculated by the following formula (F1A). δHM represents the weighted average value of the hydrogen bond term of the Hansen solubility parameter of the alkali-soluble resin and the hydrogen bond term of the Hansen solubility parameter of the polymerizable compound, calculated by the following formula (F1B). δPM represents the weighted average value of the polar term of the Hansen solubility parameter of the alkali-soluble resin and the polar term of the Hansen solubility parameter of the polymerizable compound, calculated by the following formula (F1C). δDS represents the dispersion term of the Hansen solubility parameter of the surfactant. δHS represents the hydrogen bond term of the Hansen solubility parameter of the surfactant. δPS represents the polar term of the Hansen solubility parameter of the surfactant. Formula (F1A): δDM=δDb×Wb / (Wb+Wm)+δDm×Wm / (Wb+Wm) Formula (F1B): δHM=δHb×Wb / (Wb+Wm)+δHm×Wm / (Wb+Wm) Formula (F1C): δPM=δPb×Wb / (Wb+Wm)+δPm×Wm / (Wb+Wm) In formula (F1A), ΔDb represents the variance term of the Hansen solubility parameter of the alkali-soluble resin, and ΔDm represents the variance term of the Hansen solubility parameter of the polymerizable compound. In formula (F1B), ΔHb represents the hydrogen bond term of the Hansen solubility parameter of the alkali-soluble resin, and ΔHm represents the hydrogen bond term of the Hansen solubility parameter of the polymerizable compound. In formula (F1C), ΔPb represents the polar term of the Hansen solubility parameter of the alkali-soluble resin, and ΔPm represents the polar term of the Hansen solubility parameter of the polymerizable compound. In formulas (F1A) to (F1C), Wb represents the mass fraction of the alkali-soluble resin relative to the total solid content in the first composition, and Wm represents the mass fraction of the polymerizable compound relative to the total solid content in the first composition.

[0024] The dispersion term δDb, hydrogen bond term δHb, and polar term δPb of the Hansen solubility parameters of alkali-soluble resins, the dispersion term δDm, hydrogen bond term δHm, and polar term δPm of the Hansen solubility parameters of polymerizable compounds, and the dispersion term δDS, hydrogen bond term δHS, and polar term δPS of the Hansen solubility parameters of surfactants can be calculated using the commercially available Windows software "HSPiP (developed by www.hansen-solubility.com)".

[0025] The first composition may contain only one surfactant, or two or more surfactants may be used in combination. When the first composition contains only one surfactant, the dispersion term δDS, hydrogen bond term δHS, and polar term δPS of the Hansen solubility parameter of the surfactant in formula (F1) respectively represent the dispersion term δDS, hydrogen bond term δHS, and polar term δPS of the Hansen solubility parameter of a single surfactant contained in the first composition. When the first composition contains two or more surfactants, the dispersion term δDS, hydrogen bond term δHS, and polar term δPS of the Hansen solubility parameter of the surfactant in formula (F1) respectively represent the weighted average of the dispersion term of each Hansen solubility parameter of two or more surfactants, the weighted average of the hydrogen bond term of each Hansen solubility parameter of two or more surfactants, and the weighted average of the polar term of each Hansen solubility parameter of two or more surfactants. When the first composition contains two or more surfactants, the weighted average value of the variance terms of the Hansen solubility parameters of the two or more surfactants is calculated by the following formula (S1). Formula (S1): δDS=δDS1×WS1+δDS2×WS2+‥‥δDS n ×WS n Here, δDS1 to δDS n represents the dispersion term value of each Hansen solubility parameter of n surfactants contained in the first composition, and WS n represents the content of each surfactant (the content (mass fraction) of each surfactant relative to the total content of n types of surfactants). That is, for example, when the first composition contains equal amounts of two types of surfactants, ΔDS is expressed as ΔDS=ΔDS1×0.5+ΔDS2×0.5. The weighted average value of the hydrogen bond term and the weighted average value of the polarity term of the Hansen solubility parameters of two or more surfactants can also be determined in the same manner as above.

[0026] In the first composition, the alkali-soluble resin may be used alone or in combination of two or more kinds. When the first composition contains only one alkali-soluble resin, the dispersion term δDb, hydrogen bond term δHb, and polar term δPb of the Hansen solubility parameter of the alkali-soluble resin in formula (F1A) respectively represent the dispersion term δDb, hydrogen bond term δHb, and polar term δPb of the Hansen solubility parameter of a single alkali-soluble resin contained in the first composition. When the first composition contains two or more alkali-soluble resins, the "δDb" part in formula (F1A) is expressed as "δDb1 × Wb1 + δDb2 × Wb2 + ‥‥δDb n ×Wb n " where δDb1 to δDb n represents the value of the dispersion term of each Hansen solubility parameter of n kinds of alkali-soluble resins contained in the first composition, and Wb1 to Wb n represents the content (mass fraction) of each alkali-soluble resin relative to the total content of n types of alkali-soluble resins in the first composition. In other words, when the first composition contains two types of alkali-soluble resins, the "δDb" portion in formula (F1A) can be calculated by replacing it with "δDb1 × Wb1 + δDb2 × Wb2." When two or more types of alkali-soluble resins are contained in the first composition, the "δHb" portion in formula (F1B) is expressed as "δHb1 × Wb1 + δHb2 × Wb2 + ‥ δHb n ×Wb n " is calculated in the same manner as in formula (F1A) (where ΔHb1 to ΔHb n represents the value of the hydrogen bond term of each Hansen solubility parameter of n alkali-soluble resins contained in the first composition, and Wb1 to Wb nrepresents the content (mass fraction) of each alkali-soluble resin relative to the total content of n types of alkali-soluble resins in the first composition.) The "ΔPb" part in formula (F1C) is expressed as "ΔPb1 × Wb1 + ΔPb2 × Wb2 + ... ΔPb n ×Wb n " is calculated in the same manner as in formula (F1A) (where ΔPb1 to ΔPb n represents the polar term value of each Hansen solubility parameter of n alkali-soluble resins contained in the first composition, and Wb1 to Wb n represents the content (mass fraction) of each alkali-soluble resin relative to the total content of n types of alkali-soluble resins in the first composition.

[0027] In the first composition, the polymerizable compound may be used alone or in combination of two or more kinds. When the first composition contains only one polymerizable compound, the dispersion term δDm, hydrogen bond term δHm, and polar term δPm of the Hansen solubility parameter of the polymerizable compound in formula (F1A) respectively represent the dispersion term δDm, hydrogen bond term δHm, and polar term δPm of the Hansen solubility parameter of a single polymerizable compound contained in the first composition. When the first composition contains two or more polymerizable compounds, the "δDm" part in formula (F1A) is expressed as "δDm1 × Wm1 + δDm2 × Wm2 + ... δDm n ×Wm n " where δDm1 to δDm n represents the value of the dispersion term of each Hansen solubility parameter of n types of polymerizable compounds contained in the first composition, and Wm1 to Wm n represents the content (mass fraction) of each polymerizable compound relative to the total content of n types of polymerizable compounds in the first composition. In other words, when the first composition contains two types of polymerizable compounds, the "δDm" portion in formula (F1A) can be calculated by replacing it with "δDm1 × Wm1 + δDm2 × Wm2." When two or more polymerizable compounds are contained in the first composition, the "δHm" part in formula (F1B) is expressed as "δHm1 × Wm1 + δHm2 × Wm2 + ‥‥δHm n×Wmn" and calculated in the same manner as in formula (F1A) (where ΔHm1 to ΔHm n represents the value of the hydrogen bond term of each Hansen solubility parameter of n polymerizable compounds contained in the first composition, and Wm1 to Wm n represents the content (mass fraction) of each polymerizable compound relative to the total content of n types of polymerizable compounds in the first composition. Also, the "δPm" part in formula (F1C) is expressed as "δPm1 × Wm1 + δPm2 × Wm2 + ‥‥ δPm n ×Wm n " is calculated in the same manner as in formula (F1A) (where ΔPm1 to ΔPm n represents the polar term value of each Hansen solubility parameter of n types of polymerizable compounds contained in the first composition, and Wm1 to Wm n represents the content (mass fraction) of each polymerizable compound relative to the total content of n types of polymerizable compounds in the first composition).

[0028] [Various ingredients] The various components that the first composition may contain are described in detail below. The first composition contains an alkali-soluble resin, a polymerizable compound, a photopolymerization initiator, and a surfactant.

[0029] <Alkali-soluble resin> A preferred embodiment of the alkali-soluble resin is a (meth)acrylic resin, which has excellent alkali developability and film formability. In this specification, the (meth)acrylic resin refers to a resin having repeating units derived from a (meth)acrylic compound. The content of the repeating units derived from a (meth)acrylic compound is, for example, preferably 30% by mass or more, more preferably 40% by mass or more, based on the total repeating units of the (meth)acrylic resin. The (meth)acrylic resin may be composed solely of repeating units derived from (meth)acrylic compounds, or may contain repeating units derived from polymerizable monomers other than (meth)acrylic compounds. That is, the upper limit of the content of repeating units derived from (meth)acrylic compounds is 100% by mass or less based on the total repeating units of the (meth)acrylic resin.

[0030] Examples of the (meth)acrylic compound include (meth)acrylic acid, (meth)acrylic acid esters, (meth)acrylamides, and (meth)acrylonitrile. Examples of (meth)acrylic acid esters include (meth)acrylic acid alkyl esters, (meth)acrylic acid tetrahydrofurfuryl esters, (meth)acrylic acid dimethylaminoethyl esters, (meth)acrylic acid diethylaminoethyl esters, (meth)acrylic acid glycidyl esters, 2,2,2-trifluoroethyl (meth)acrylate, 2,2,3,3-tetrafluoropropyl (meth)acrylate, and (meth)acrylic acid esters having an aromatic ring structure represented by formula (A) (for example, (meth)acrylic acid benzyl ester, etc.), and among these, (meth)acrylic acid alkyl esters or (meth)acrylic acid esters having an aromatic ring structure represented by formula (A) are preferred.

[0031] Formula (A): CH=C(R 1 )-COO-L-Ar In formula (A), R 1 represents a hydrogen atom or a methyl group. L represents a single bond or a divalent linking group. Ar represents an aromatic ring group which may have a substituent. Examples of the divalent linking group represented by L include -O-, -S-, -CO-, and -NR T Examples of the linking group include a divalent linking group selected from the group consisting of -, an alkylene group, and a combination thereof. The alkylene group is preferably linear or branched. The alkylene group preferably has 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, and even more preferably 1 to 6 carbon atoms. The divalent linking group represented by L preferably has 1 to 20 atoms, more preferably 1 to 12 atoms, and even more preferably 1 to 6 atoms, excluding hydrogen atoms. R T represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and preferably a hydrogen atom. The aromatic ring constituting the aromatic ring group represented by Ar is preferably an aromatic hydrocarbon ring, more preferably a benzene ring or a naphthalene ring. The substituent that Ar may have is not particularly limited, and examples thereof include an alkyl group.

[0032] Examples of the (meth)acrylic acid alkyl ester include (meth)acrylic acid alkyl esters having an alkyl group having 1 to 12 carbon atoms, such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, and dodecyl (meth)acrylate. As the (meth)acrylic acid ester, a (meth)acrylic acid alkyl ester having an alkyl group having 1 to 4 carbon atoms is preferred, and methyl (meth)acrylate or ethyl (meth)acrylate is more preferred.

[0033] Examples of (meth)acrylamides include acrylamides such as diacetone acrylamide.

[0034] The (meth)acrylic resin preferably contains a repeating unit derived from a (meth)acrylic acid alkyl ester. The content of the (meth)acrylic acid alkyl ester in the (meth)acrylic resin is, for example, preferably 10 to 90 mass%, more preferably 15 to 70 mass%, and even more preferably 15 to 40 mass%, based on the total repeating units of the (meth)acrylic resin.

[0035] The (meth)acrylic resin may have a repeating unit other than the repeating unit derived from the (meth)acrylic compound. The polymerizable monomer that forms the repeating unit is not particularly limited as long as it is a compound other than a (meth)acrylic compound that is copolymerizable with a (meth)acrylic compound, and examples thereof include styrene compounds that may have a substituent at the α-position or on the aromatic ring, such as styrene, vinyltoluene, and α-methylstyrene; vinyl alcohol esters such as acrylonitrile and vinyl-n-butyl ether; maleic acid monoesters such as maleic acid, maleic anhydride, monomethyl maleate, monoethyl maleate, and monoisopropyl maleate; fumaric acid, cinnamic acid, α-cyanocinnamic acid, itaconic acid, and crotonic acid. These polymerizable monomers may be used alone or in combination of two or more.

[0036] In order to improve alkaline developability, the (meth)acrylic resin preferably contains a repeating unit having an acid group, such as a carboxy group, a sulfo group, a phosphate group, or a phosphonate group. As the repeating unit having an acid group, a repeating unit having a carboxy group is preferred, and a repeating unit derived from (meth)acrylic acid is more preferred.

[0037] When the (meth)acrylic resin contains a repeating unit having an acid group, the content of the repeating unit having an acid group is preferably 10% by mass or more relative to all repeating units of the resin in order to obtain superior developability. Although there is no particular upper limit, the content is preferably 50% by mass or less, and more preferably 40% by mass or less, in order to obtain superior alkali resistance.

[0038] As the (meth)acrylic resin, a resin having both a repeating unit derived from (meth)acrylic acid and a repeating unit derived from a (meth)acrylic acid alkyl ester is also preferred.

[0039] Another preferred embodiment of the alkali-soluble resin is a styrene-acrylic copolymer. In this specification, the term "styrene-acrylic copolymer" refers to a resin having repeating units derived from a styrene compound and repeating units derived from a (meth)acrylic compound. The total content of the repeating units derived from a styrene compound and the repeating units derived from a (meth)acrylic compound is preferably 30% by mass or more, more preferably 50% by mass or more, based on the total repeating units of the copolymer. The content of repeating units derived from a styrene compound is preferably 1% by mass or more, more preferably 5% by mass or more, and even more preferably 5 to 80% by mass, based on the total repeating units of the copolymer. The content of repeating units derived from a (meth)acrylic compound is preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 20 to 95% by mass, based on all repeating units of the copolymer.

[0040] The alkali-soluble resin preferably has a repeating unit having a reactive group. The reactive group is preferably a radically polymerizable group, more preferably an ethylenically unsaturated group, and even more preferably an allyl group or a (meth)acryloxy group.

[0041] In order to further improve compatibility with surfactants and achieve the effects of the present invention, it is also preferable that at least one of the alkali-soluble resins contained in the first composition is a resin containing a repeating unit containing an aromatic ring structure. The aromatic ring structure is more preferably an aromatic hydrocarbon ring structure, and even more preferably a benzene ring structure or a naphthalene ring structure. The alkali-soluble resin preferably includes a resin containing one or more repeating units (hereinafter also referred to as "repeating unit A") selected from the group consisting of repeating units represented by the following formula (R1) and repeating units represented by the following formula (R2):

[0042] [ka]

[0043] In formula (R1) and formula (R2), R1 represents a hydrogen atom or a methyl group. L represents a single bond or a divalent linking group. Examples of the divalent linking group represented by L include the same groups as L in the (meth)acrylic acid ester having an aromatic ring structure represented by formula (A) above.

[0044] The content of the repeating unit containing an aromatic ring structure (preferably repeating unit A) in the resin is preferably 5 to 90 mass %, more preferably 10 to 80 mass %, and even more preferably 20 to 70 mass %, of all repeating units in the resin. The repeating unit containing an aromatic ring structure (repeating unit A) may be contained in the resin alone or in combination of two or more types. When the resin contains two or more types of repeating units containing an aromatic ring structure (preferably repeating unit A), the above content is preferably the total content.

[0045] The weight average molecular weight (Mw) of the alkali-soluble resin is preferably 5,000 or more, more preferably 10,000 or more, further preferably 10,000 to 100,000, and particularly preferably 15,000 to 80,000, in terms of achieving better effects of the present invention.

[0046] The acid value of the alkali-soluble resin is preferably 10 to 200 mgKOH / g, more preferably 60 to 200 mgKOH / g, still more preferably 60 to 150 mgKOH / g, and particularly preferably 60 to 130 mgKOH / g, as measured according to the method described in JIS K0070:1992.

[0047] The first composition may contain one type of alkali-soluble resin alone, or may contain two or more types of alkali-soluble resins. The content of the alkali-soluble resin is preferably 10 to 90 mass %, more preferably 20 to 80 mass %, and even more preferably 30 to 70 mass %, based on the total solid content of the first composition, in terms of achieving better effects of the present invention.

[0048] <Polymerizable compound> The first composition includes a polymerizable compound. The polymerizable compound is a compound having a polymerizable group. Examples of the polymerizable group include a radically polymerizable group and a cationic polymerizable group, and the radically polymerizable group is preferred.

[0049] The polymerizable compound preferably contains a radical polymerizable compound having an ethylenically unsaturated group (hereinafter also simply referred to as "ethylenically unsaturated compound"). The ethylenically unsaturated group is preferably a (meth)acryloxy group. The number of ethylenically unsaturated groups in the ethylenically unsaturated compound is not particularly limited as long as it is one or more, but is preferably 1 to 6, more preferably 1 to 3, and even more preferably 2 or 3. The ethylenically unsaturated compound in this specification is a compound other than the above-mentioned alkali-soluble resin, and preferably has a molecular weight of less than 5,000.

[0050] The ethylenically unsaturated compound may have an alkyleneoxy group. The alkylene group is preferably an ethyleneoxy group or a propyleneoxy group, more preferably an ethyleneoxy group. The number of alkyleneoxy groups added to a polymerizable compound per molecule is preferably 2 to 60, more preferably 2 to 30, and even more preferably 2 to 20.

[0051] ·Polymerizable compound B1 The first composition preferably contains a polymerizable compound having an aromatic ring structure in the molecule, in order to obtain a more excellent effect of the present invention. The polymerizable compound having an aromatic ring structure in the molecule preferably contains a polymerizable compound B1 having an aromatic ring and two ethylenically unsaturated groups.

[0052] Examples of the aromatic ring contained in the polymerizable compound B1 include aromatic hydrocarbon rings such as a benzene ring, a naphthalene ring, and an anthracene ring; aromatic heterocycles such as a thiophene ring, a furan ring, a pyrrole ring, an imidazole ring, a triazole ring, and a pyridine ring; and condensed rings thereof, with an aromatic hydrocarbon ring being preferred, and a benzene ring being more preferred. The aromatic ring may have a substituent. The polymerizable compound B1 may have one or more aromatic rings.

[0053] The polymerizable compound B1 preferably has a bisphenol structure, since this inhibits swelling of the first composition due to a developer, thereby improving resolution. Examples of the bisphenol structure include a bisphenol A structure derived from bisphenol A (2,2-bis(4-hydroxyphenyl)propane), a bisphenol F structure derived from bisphenol F (2,2-bis(4-hydroxyphenyl)methane), and a bisphenol B structure derived from bisphenol B (2,2-bis(4-hydroxyphenyl)butane), with the bisphenol A structure being preferred.

[0054] Examples of the polymerizable compound B1 having a bisphenol structure include a compound having a bisphenol structure and two polymerizable groups (preferably (meth)acryloyl groups) bonded to both ends of the bisphenol structure. The two polymerizable groups may be bonded to both ends of the bisphenol structure directly or via one or more alkyleneoxy groups. The alkyleneoxy groups added to both ends of the bisphenol structure are preferably ethyleneoxy groups or propyleneoxy groups, and more preferably ethyleneoxy groups. The number of alkyleneoxy groups (preferably ethyleneoxy groups) added to the bisphenol structure is preferably 2 to 60 per molecule, more preferably 2 to 30, and even more preferably 2 to 20. Examples of the polymerizable compound B1 having a bisphenol structure include those described in paragraphs

[0072] to

[0080] of JP-A-2016-224162, the contents of which are incorporated herein by reference.

[0055] As the polymerizable compound B1, a bifunctional ethylenically unsaturated compound having a bisphenol A structure is preferred, and 2,2-bis(4-((meth)acryloxypolyalkoxy)phenyl)propane is more preferred. Examples of 2,2-bis(4-((meth)acryloxypolyalkoxy)phenyl)propane include ethoxylated bisphenol A dimethacrylates (BPE series, manufactured by Shin-Nakamura Chemical Co., Ltd.) such as 2,2-bis(4-(methacryloxydiethoxy)phenyl)propane (FA-324M, manufactured by Hitachi Chemical Co., Ltd.), 2,2-bis(4-(methacryloxyethoxypropoxy)phenyl)propane, and 2,2-bis(4-(methacryloxypentaethoxy)phenyl)propane, 2,2-bis(4-(methacryloxydodecaethoxytetrapropoxy)phenyl)propane (FA-3200MY, manufactured by Hitachi Chemical Co., Ltd.), and ethoxylated (10) bisphenol A diacrylate (NK Ester A-BPE-10, manufactured by Shin-Nakamura Chemical Co., Ltd.).

[0056] The polymerizable compound B1 is preferably a compound represented by the following formula (P1).

[0057] [ka]

[0058] In the formula, R1 and R2 each independently represent a hydrogen atom or a methyl group. A represents -C2H4-. B represents -C3H6-. n1 and n3 each independently represent an integer of 1 to 39, and n1 + n3 represents an integer of 2 to 40. n2 and n4 each independently represent an integer of 0 to 29, and n2 + n4 represents an integer of 0 to 30. The arrangement of the -(AO)- and -(BO)- repeating units may be random or block. When the arrangement is block, either -(AO)- or -(BO)- may be on the bisphenyl group side. n1+n2+n3+n4 is preferably 2 to 20, more preferably 2 to 16, and still more preferably 2 to 12. Furthermore, n2+n4 is preferably 0 to 10, and more preferably 0 to 4.

[0059] The content of the polymerizable compound B1 is preferably 10% by mass or more, more preferably 20% by mass or more, and even more preferably 25% by mass or more, based on the total solid content of the first composition, from the viewpoint of better resolution. The upper limit is preferably 90% by mass or less, more preferably 70% by mass or less, from the viewpoint of transferability and edge fusion (a phenomenon in which the first composition seeps out from the edge of a transfer film).

[0060] The content of the polymerizable compound B1 is preferably 40% by mass or more, more preferably 50% by mass or more, even more preferably 55% by mass or more, and particularly preferably 60% by mass or more, based on the total mass of the polymerizable compounds, from the viewpoint of superior resolution. The upper limit, based on the total mass of the polymerizable compounds, is preferably 100% by mass or less, more preferably 99% by mass or less, and even more preferably 95% by mass or less, based on the total mass of the polymerizable compounds, from the viewpoint of releasability.

[0061] Other ethylenically unsaturated compounds other than polymerizable compound B1 The ethylenically unsaturated compound other than the polymerizable compound B1 is not particularly limited, and examples thereof include a compound having one ethylenically unsaturated group in the molecule (monofunctional ethylenically unsaturated compound), a bifunctional ethylenically unsaturated compound having no aromatic ring, and a trifunctional or higher ethylenically unsaturated compound.

[0062] Examples of monofunctional ethylenically unsaturated compounds include ethyl (meth)acrylate, ethylhexyl (meth)acrylate, 2-(meth)acryloyloxyethyl succinate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, and phenoxyethyl (meth)acrylate.

[0063] Examples of bifunctional ethylenically unsaturated compounds having no aromatic ring include alkylene glycol di(meth)acrylate, polyalkylene glycol di(meth)acrylate, urethane di(meth)acrylate, and trimethylolpropane diacrylate. Examples of alkylene glycol di(meth)acrylates include tricyclodecane dimethanol diacrylate (A-DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.), tricyclodecane dimethanol dimethacrylate (DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.), 1,9-nonanediol diacrylate (A-NOD-N, manufactured by Shin-Nakamura Chemical Co., Ltd.), 1,6-hexanediol diacrylate (A-HD-N, manufactured by Shin-Nakamura Chemical Co., Ltd.), ethylene glycol dimethacrylate, 1,10-decanediol diacrylate, and neopentyl glycol di(meth)acrylate. Examples of polyalkylene glycol di(meth)acrylates include polyethylene glycol di(meth)acrylate (NK Ester 4G, etc., manufactured by Shin-Nakamura Chemical Co., Ltd.), dipropylene glycol diacrylate, tripropylene glycol diacrylate, and polypropylene glycol di(meth)acrylate (Aronix M-270, etc., manufactured by Toagosei Co., Ltd.). Examples of urethane di(meth)acrylates include propylene oxide-modified urethane di(meth)acrylates, and ethylene oxide- and propylene oxide-modified urethane di(meth)acrylates. Commercially available urethane di(meth)acrylates include 8UX-015A (manufactured by Taisei Fine Chemical Co., Ltd.), UA-32P (manufactured by Shin-Nakamura Chemical Co., Ltd.), and UA-1100H (manufactured by Shin-Nakamura Chemical Co., Ltd.).

[0064] Examples of tri- or higher functional ethylenically unsaturated compounds include dipentaerythritol (tri / tetra / penta / hexa)(meth)acrylate, pentaerythritol (tri / tetra)(meth)acrylate, trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, trimethylolethane tri(meth)acrylate, isocyanuric acid tri(meth)acrylate, glycerin tri(meth)acrylate, and alkylene oxide-modified products thereof. The term "(tri / tetra / penta / hexa)(meth)acrylate" encompasses tri(meth)acrylate, tetra(meth)acrylate, penta(meth)acrylate, and hexa(meth)acrylate. The term "(tri / tetra)(meth)acrylate" encompasses tri(meth)acrylate and tetra(meth)acrylate.

[0065] Examples of alkylene oxide-modified trifunctional or higher ethylenically unsaturated compounds include caprolactone-modified (meth)acrylate compounds (KAYARAD (registered trademark) DPCA-20 manufactured by Nippon Kayaku Co., Ltd., and A-9300-1CL manufactured by Shin-Nakamura Chemical Co., Ltd.), alkylene oxide-modified (meth)acrylate compounds (KAYARAD RP-1040 manufactured by Nippon Kayaku Co., Ltd., ATM-35E and A-9300 manufactured by Shin-Nakamura Chemical Co., Ltd., and EBECRYL (registered trademark) manufactured by Daicel-Allnex Co., Ltd.), and the like. 135, etc.), ethoxylated glycerin triacrylate (A-GLY-9E, etc., manufactured by Shin-Nakamura Chemical Co., Ltd.), Aronix (registered trademark) TO-2349 (manufactured by Toagosei Co., Ltd.), Aronix M-520 (manufactured by Toagosei Co., Ltd.), Aronix M-510 (manufactured by Toagosei Co., Ltd.), and SR454 (manufactured by Tomoe Chemical Cooperative).

[0066] The polymerizable compound may be an ethylenically unsaturated compound having an acid group (for example, a carboxy group), and the acid group may form an acid anhydride group. Examples of ethylenically unsaturated compounds having an acid group include Aronix (registered trademark) TO-2349 (manufactured by Toagosei Co., Ltd.), Aronix (registered trademark) M-520 (manufactured by Toagosei Co., Ltd.), and Aronix (registered trademark) M-510 (manufactured by Toagosei Co., Ltd.). Examples of the ethylenically unsaturated compound having an acid group include the polymerizable compounds described in paragraphs

[0025] to

[0030] of JP-A No. 2004-239942.

[0067] The polymerizable compounds may be used alone or in combination of two or more. The content of the polymerizable compound is preferably from 10 to 70 mass %, more preferably from 15 to 70 mass %, and even more preferably from 20 to 70 mass %, based on the total solid content of the first composition. The content of the ethylenically unsaturated compound is preferably from 10 to 70 mass %, more preferably from 15 to 70 mass %, and even more preferably from 20 to 70 mass %, based on the total solid content of the first composition.

[0068] <Photopolymerization initiator> The first composition includes a photopolymerization initiator. A photopolymerization initiator is a compound that initiates polymerization of a polymerizable compound upon exposure to actinic rays such as ultraviolet light, visible light, and X-rays. Examples of the photopolymerization initiator include known photopolymerization initiators. Examples of the photopolymerization initiator include photoradical polymerization initiators and photocationic polymerization initiators. Photoradical polymerization initiators are preferred, and one or more selected from the group consisting of acridine-based photopolymerization initiators, oxime ester-based photopolymerization initiators, biimidazole-based photopolymerization initiators, alkylphenone-based photopolymerization initiators, acetophenone-based photopolymerization initiators, and acylphosphine oxide-based photopolymerization initiators are more preferred.

[0069] The photopolymerization initiator may be used alone or in combination of two or more. The content of the photopolymerization initiator is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, based on the total solid content of the first composition, and the upper limit is preferably 20% by mass or less, more preferably 15% by mass or less, and even more preferably 10% by mass or less, based on the total solid content of the first composition.

[0070] <Surfactant> The first composition comprises a surfactant. Examples of surfactants include nonionic surfactants, fluorine-containing surfactants, and silicone surfactants, among which silicone surfactants are preferred. Examples of silicone surfactants include linear polymers consisting of siloxane bonds and modified siloxane polymers having organic groups introduced into the side chains and / or terminals. Furthermore, the surfactant is preferably a crosslinked resin, such as a resin having repeating units represented by formula (B-3) and formula (B-4) described below. As the surfactant, known surfactants can be used.

[0071] It is also preferable that the surfactant does not contain a fluorine atom, since this makes it easier to adjust ΔHSP1 within a predetermined range and the effects of the present invention are more excellent.

[0072] As the surfactant, a resin containing at least one repeating unit (hereinafter also referred to as "repeating unit α") selected from the group consisting of repeating units represented by the following formula (A-1) and repeating units represented by the following formula (A-2) is preferred, as ΔHSP1 can be easily adjusted to a predetermined range and the effects of the present invention are more excellent.

[0073] [ka]

[0074] In formula (A-1), R1 represents a hydrogen atom or a methyl group, R2 represents an alkylene group having 1 to 10 carbon atoms, R3 represents an alkyl group having 1 to 4 carbon atoms, and 1 represents an integer of 5 to 100.

[0075] In formula (A-2), R4 represents a hydrogen atom or a methyl group, R5 represents an alkylene group having 1 to 10 carbon atoms, and L represents a trimethylsilyl group or a tris(trimethylsiloxy)silyl group.

[0076] The content of the repeating unit α in the resin is preferably 20 to 90 mass%, more preferably 30 to 90 mass%, and even more preferably 40 to 80 mass%, based on the total repeating units in the resin. The resin may contain one type of repeating unit α, or two or more types. When two or more types of repeating units α are contained, the content is preferably the total content of the repeating units α.

[0077] As the surfactant, a resin having a first repeating unit (polar portion) containing an atom selected from the group consisting of silicon atoms and fluorine atoms and a second repeating unit (non-polar portion) containing neither silicon atoms nor fluorine atoms is preferred, as ΔHSP1 can be easily adjusted within a predetermined range and the effects of the present invention are more excellent. Among these, the resin is more preferably a resin having a first repeating unit containing silicon atoms and the second repeating unit.

[0078] Specific examples of the first repeating unit include the repeating units represented by the above formula (A-1) or formula (A-2).

[0079] Specific examples of the second repeating unit are not particularly limited as long as it does not contain either a silicon atom or a fluorine atom, but a repeating unit having an aromatic ring structure is preferred in terms of achieving better effects of the present invention. Examples of the second repeating unit include repeating units represented by the following formulas (B-1) to (B-4).

[0080] [ka]

[0081] In formula (B-1), R B11 represents a hydrogen atom or a methyl group. B11 represents a single bond or -COO-. B12 represents a single bond or a divalent linking group. B12 represents a monovalent aromatic ring group which may have a substituent.

[0082] L B12 Examples of the divalent linking group represented by the formula: T Examples of the linking group include a divalent linking group selected from the group consisting of -, an alkylene group, and a combination thereof. The alkylene group is preferably a chain (straight chain or branched chain). The alkylene group preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, still more preferably 1 to 10 carbon atoms, and particularly preferably 1 to 6 carbon atoms. LB12 The number of atoms excluding hydrogen atoms of the divalent linking group represented by the following formula is preferably 1 to 30, more preferably 1 to 20, and even more preferably 1 to 10. R T represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and preferably a hydrogen atom. L B12 Examples of the divalent linking group represented by the formula (I) include -AL1-, -(AL2-O)p-, and -(AL2-O)n-CO-. AL1 and AL2 represent an alkylene group. p represents an integer of 1 to 10 (preferably 1 to 6). The alkylene group represented by AL2 preferably has 2 to 6 carbon atoms, more preferably 2 to 4 carbon atoms. AL1 and AL2 may have a substituent such as a hydroxyl group. When there are multiple p's and multiple n's, the multiple AL2's may be the same or different. R B12 The monovalent aromatic ring group represented by the formula (I) is preferably a monovalent aromatic hydrocarbon ring group, more preferably a phenyl group or a naphthyl group. The monovalent aromatic ring group may further have a substituent. The substituent is not particularly limited, but examples thereof include a hydroxyl group, an alkyl group, an alkoxy group, an alkoxycarbonyl group, and a monovalent aromatic ring group (for example, a monovalent aromatic hydrocarbon ring group such as a phenyl group). Furthermore, examples of the substituent that the monovalent aromatic ring group may have include monovalent groups represented by the following formula (M1).

[0083] Formula (M1): *-L M1 -(A M1 -L M2 ) q -R M1 In the formula, L M1 and L M2 represents a single bond, -O-, -S-, -CO-, -NR T and a divalent linking group selected from the group consisting of -, -, and combinations thereof, such as -O-, -CO-, and -COO-. T represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and preferably a hydrogen atom. A M1represents a divalent aromatic ring group which may have a substituent or a divalent alicyclic group which may have a substituent. As the divalent aromatic ring group, a divalent aromatic hydrocarbon ring group is preferred, and a phenylene group or a naphthylene group is more preferred. As the divalent alicyclic group, a divalent aliphatic hydrocarbon ring group is preferred, and a divalent cyclohexane ring group is more preferred. Furthermore, the substituents that the divalent aromatic ring group and the divalent alicyclic group may have are not particularly limited, and examples thereof include a hydroxyl group, an alkyl group (linear, branched, and cyclic), an alkoxy group, an alkoxycarbonyl group, and a monovalent aromatic ring group (for example, a monovalent aromatic hydrocarbon ring group such as a phenyl group). q represents an integer of 1 to 6, preferably 1 to 3. R M1 represents a hydrogen atom or a substituent. M1 The substituent represented by is not particularly limited, but examples thereof include a hydroxyl group, an alkyl group (straight-chain, branched-chain, and cyclic), an alkoxy group, an alkoxycarbonyl group, a cyano group, a primary to tertiary amino group, and an acylamino group. R M1 The number of carbon atoms in the alkyl group, alkoxy group, and alkoxycarbonyl group represented by the formula (I) is, for example, preferably 1 to 10, and more preferably 1 to 6. Primary to tertiary amino groups include -NH2 and -NHR Y , and -NR Y 2 etc. R Y represents an alkyl group. The acylamino group is -NHCOR Y and -NR Y COR Y etc. R Y represents an alkyl group. R Y The alkyl group mentioned above is preferably a straight-chain or branched-chain group, and preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms.

[0084] R in formula (B-1) B12 and R in formula (M1). M1The substituent represented by the formula (I) is preferably an electron-accepting group or an electron-donating group, and is preferably an electron-donating group. Examples of the electron-donating group include an unsubstituted or substituted amino group, a substituted or unsubstituted acylamino group, a nitro group, a cyano group, a halogen-substituted saturated or unsaturated hydrocarbon group (e.g., a halogen-substituted alkyl group, a halogen-substituted alkenyl group, a halogen-substituted aromatic hydrocarbon ring group), a nitrogen-containing heterocyclic group, an oxygen-containing heterocyclic group, and a sulfur-containing heterocyclic group. The unsubstituted or substituted amino group includes -NH2, -NHR Y , and -NR Y 2 etc. R Y represents an alkyl group. The substituted or unsubstituted acylamino group includes -NHCOR Y and -NR Y COR Y etc. R Y represents an alkyl group. R Y The alkyl group mentioned above is preferably a straight-chain or branched-chain group, and preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms. Examples of the electron-accepting group include acid groups, and specific examples thereof include a carboxy group, a phenolic hydroxyl group (corresponding to a hydroxyl group substituted on an aromatic ring), a sulfonic acid group, and a phosphoric acid group.

[0085] [ka]

[0086] In formula (B-2), R B21 represents a hydrogen atom or a methyl group. B21 represents a single bond or -COO-. B22 represents a single bond or a divalent linking group. B22 represents a hydrogen atom or a substituent other than an aromatic group.

[0087] L B22 Examples of the divalent linking group represented by the formula: TExamples of the linking group include a divalent linking group selected from the group consisting of -, an alkylene group, and a combination thereof. The alkylene group is preferably a chain (straight chain or branched chain). The alkylene group preferably has 1 to 100 carbon atoms, more preferably 1 to 50 carbon atoms, and even more preferably 1 to 30 carbon atoms. L B22 The number of atoms excluding hydrogen atoms of the divalent linking group represented by the following formula is preferably 1 to 100, more preferably 1 to 50, and even more preferably 1 to 30. R T represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and preferably a hydrogen atom. L B22 Examples of the divalent linking group represented by the formula (I) include -AL1- and -(AL2-O)q-. AL1 and AL2 represent an alkylene group. q represents an integer of 1 to 60 (preferably 1 to 20). The alkylene group represented by AL2 preferably has 2 to 6 carbon atoms, more preferably 2 to 4 carbon atoms. AL1 and AL2 may have a substituent such as a hydroxyl group. When there are multiple q's, the multiple AL2's may be the same or different. R B22 The substituents other than the aromatic group represented by the formula (I) are not particularly limited, and examples thereof include a hydroxyl group, an alkyl group, an alkoxy group, an alkoxycarbonyl group, and an unsubstituted or substituted amino group (-NH, -NHR Y , and -NR Y 2) etc. R Y represents an alkyl group. The alkyl group and the R Y The number of carbon atoms in the alkyl group represented by the formula (I) and the number of carbon atoms in the alkyl group moiety (preferably linear or branched) in the alkoxy group and the alkoxycarbonyl group is, for example, preferably 1 to 10, more preferably 1 to 6. Y The alkyl group represented by the formula (I), the alkoxy group, and the alkoxycarbonyl group may have a substituent such as a hydroxyl group. R in formula (B-2) B22The substituent other than the aromatic group represented by the formula (I) is preferably an electron-accepting group or an electron-donating group, and among these, an electron-donating group is preferred. Specific examples of the electron-accepting group and the electron-donating group are as described above.

[0088] [ka]

[0089] In formula (B-3), R B31 and R B34 Each of L independently represents a hydrogen atom or a methyl group. B31 and L B33 Each of L independently represents a single bond or a divalent linking group. B32 is a single bond or -C(R w )2-. R w Each independently represents a hydrogen atom or a monovalent organic group. B31 and Ar B32 each independently represents a divalent aromatic ring group which may have a substituent.

[0090] L B31 and L B33 The divalent linking group represented by the formula (I) is not particularly limited, but examples thereof include -O-, -S-, -CO-, -NR T -, an alkylene group, and a divalent linking group selected from the group consisting of a combination thereof. The alkylene group is preferably a chain (straight chain or branched chain). The alkylene group preferably has 1 to 100 carbon atoms, more preferably 1 to 50 carbon atoms, and even more preferably 1 to 30 carbon atoms. L B31 and L B33 The number of atoms excluding hydrogen atoms of the divalent linking group represented by the following formula is preferably 1 to 100, more preferably 1 to 50, and even more preferably 1 to 30. R T represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and preferably a hydrogen atom. L B31 and L B33Examples of the divalent linking group represented by the formula include -CO-O- and -CO-O-(AL-O)r-. AL represents an alkylene group. r represents an integer of 1 to 60 (preferably 3 to 20). The alkylene group represented by AL preferably has 2 to 6 carbon atoms, more preferably 2 to 4 carbon atoms. AL may have a substituent such as a hydroxyl group. When there are multiple r's, the multiple AL's may be the same or different.

[0091] R w Examples of the monovalent organic group represented by the formula include an alkyl group and a monovalent aromatic ring group. The alkyl group is preferably a chain (straight chain or branched chain) and preferably has 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms. The monovalent aromatic ring group is preferably a monovalent aromatic hydrocarbon ring group, and a phenyl group is preferred. The monovalent aromatic ring group may further have a substituent. The substituent is not particularly limited, but examples thereof include a hydroxyl group, an alkyl group, an alkoxy group, an alkoxycarbonyl group, and a monovalent aromatic ring group (for example, a monovalent aromatic hydrocarbon ring group such as a phenyl group).

[0092] Ar B11 and Ar B12 The divalent aromatic ring group represented by the formula (I) is preferably a divalent aromatic hydrocarbon ring group (preferably having 6 to 10 carbon atoms), more preferably a phenylene group. The divalent aromatic ring group may further have a substituent, which is not particularly limited, but examples thereof include a hydroxyl group, an alkyl group, an alkoxy group, an alkoxycarbonyl group, and a monovalent aromatic ring group (for example, a monovalent aromatic hydrocarbon ring group such as a phenyl group).

[0093] [ka]

[0094] In formula (B-4), R B41 and R B42Each of L independently represents a hydrogen atom or a methyl group. B41 ~L B43 each independently represents a single bond or a divalent linking group. B41 represents a divalent aromatic ring group which may have a substituent. p represents an integer of 1 or more. When p represents an integer of 2 or more, a plurality of Ar B41 L B42 They may be the same or different from each other.

[0095] L B41 ~L B43 The divalent linking group represented by the formula (I) is not particularly limited, and examples thereof include, for example, B31 and L B33 Examples of the divalent linking group include those similar to those represented by the following formula: B42 Among them, the divalent linking group represented by the formula: T -, -OCH2-, and the like are preferred.

[0096] Ar B41 The divalent aromatic ring group represented by the formula (I) is preferably a divalent aromatic hydrocarbon ring group (preferably having 6 to 10 carbon atoms), more preferably a phenylene group. The divalent aromatic ring group may further have a substituent, which is not particularly limited, but examples thereof include a hydroxyl group, an alkyl group, an alkoxy group, an alkoxycarbonyl group, and a monovalent aromatic ring group (for example, a monovalent aromatic hydrocarbon ring group such as a phenyl group).

[0097] The content of the first repeating unit in the resin is preferably 20 to 90% by mass, more preferably 30 to 90% by mass, and even more preferably 40 to 80% by mass, based on the total repeating units in the resin. The resin may contain one type of first repeating unit, or two or more types. When two or more types of first repeating units are contained, the content is preferably the total content of the first repeating units. The content of the second repeating unit in the resin is preferably 10 to 80% by mass, more preferably 20 to 70% by mass, and even more preferably 20 to 60% by mass, based on the total repeating units in the resin. The resin may contain only one type of second repeating unit, or two or more types. When two or more types of second repeating units are contained, the content is preferably the total content of the second repeating units.

[0098] The weight-average molecular weight (Mw) of the surfactant is preferably at least 500, more preferably at least 1,000, even more preferably at least 10,000, particularly preferably at least 15,000, and most preferably at least 18,000. The upper limit is preferably at most 100,000, more preferably at most 80,000.

[0099] The content of the surfactant is preferably from 0.01 to 5 mass %, more preferably from 0.01 to 3 mass %, and even more preferably from 0.05 to 1 mass %, based on the total solid content of the first composition.

[0100] Specific examples of surfactants are listed below, but the present invention is not limited to these.

[0101] [ka] TIFF2025080214000010.tif3383TIFF2025080214000011.tif36112TIFF2025080214000012.tif32118

[0102] [ka] JPEG2025080214000014.jpg29148

[0103] [ka]

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[0106] [ka]

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[0108] <Other additives> The first composition may contain other additives in addition to the various components described above. Other additives include, for example, triazole, benzotriazole, tetrazole and derivatives thereof, aliphatic thiol compounds, thermal crosslinking compounds, polymerization inhibitors, hydrogen donor compounds, solvents, impurities, plasticizers, sensitizers, and alkoxysilane compounds. Examples of compounds that can be used include triazole, benzotriazole, tetrazole, and derivatives thereof, aliphatic thiol compounds, thermally crosslinkable compounds, polymerization inhibitors, and hydrogen donor compounds, such as those described in International Publication No. 2022 / 039027. Examples of the plasticizer, sensitizer, and alkoxysilane compound include those described in paragraphs 0097 to 0119 of WO 2018 / 179640.

[0109] The solvent is not particularly limited as long as it can dissolve or disperse various components other than the solvent that may be contained in the photosensitive resin composition. Examples of the solvent include water, alkylene glycol ether solvents, alkylene glycol ether acetate solvents, alcohol solvents (e.g., methanol and ethanol), ketone solvents (e.g., acetone and methyl ethyl ketone), aromatic hydrocarbon solvents (e.g., toluene), aprotic polar solvents (e.g., dimethyl sulfoxide and sulfolane), amide solvents, cyclic ether solvents (e.g., tetrahydrofuran), ester solvents (e.g., n-propyl acetate), amide solvents (e.g., N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, N-ethylpyrrolidone), lactone solvents, and mixed solvents containing two or more of these. The solvent may be used alone or in combination of two or more. The content of the solvent is preferably 50 to 1900 parts by mass, more preferably 100 to 1200 parts by mass, and even more preferably 100 to 900 parts by mass, relative to 100 parts by mass of the total solid content of the photosensitive resin composition.

[0110] The first composition 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 easily mixed in as impurities, so it is preferable to set the contents to the following values.

[0111] The content of impurities is preferably 80 ppm by mass or less, more preferably 10 ppm by mass or less, and even more preferably 2 ppm by mass or less, relative to the total solid content of the first composition. The lower limit is often 0 ppb by mass or more, but may be 1 ppb by mass or more, or 0.1 ppm by mass or more, relative to the total solid content of the first composition.

[0112] 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 first composition, methods for purifying the various components that may be contained in the first composition, and methods for preventing the inclusion of impurities when preparing the first composition.

[0113] The content of impurities can be measured by known methods such as ICP (Inductively Coupled Plasma) emission spectroscopy, atomic absorption spectroscopy, and ion chromatography.

[0114] The first composition preferably contains a small amount of compounds such as benzene, formaldehyde, trichloroethylene, 1,3-butadiene, carbon tetrachloride, chloroform, and hexane. Specifically, the content of each of these compounds is preferably 100 ppm by mass or less, more preferably 20 ppm by mass or less, and even more preferably 4 ppm by mass or less, based on the total solid content of the first composition. The lower limit of each of these compounds may be 10 ppb by mass or more, or 100 ppb by mass or more, based on the total solid content of the first composition. The content of these compounds can be adjusted in the same manner as for the above-mentioned impurities, and can be measured by known measuring methods.

[0115] [Preferred embodiment of the first composition] The first composition preferably has each of the following aspects (1A) to (1C) in terms of achieving better effects of the present invention. (1A) The surfactant is a resin (hereinafter also referred to as "specific surfactant") having a first repeating unit (polar moiety) containing an atom selected from the group consisting of silicon atoms and fluorine atoms, and a second repeating unit (non-polar moiety) containing neither silicon atoms nor fluorine atoms, and the value of ΔHSP2 calculated by formula (F2) described later as the configuration of the second composition is 4.0 MPa 0.5 However, when at least one selected from the group consisting of alkali-soluble resins and polymerizable compounds has either an electron-accepting group or an electron-donating group, the surfactant does not have the other of the electron-accepting group or the electron-donating group. (1B) At least one selected from the group consisting of alkali-soluble resins and polymerizable compounds, and the surfactant each have an aromatic ring structure in the molecule. (1C) At least one selected from the group consisting of alkali-soluble resins and polymerizable compounds has one of an electron-accepting group and an electron-donating group, and the surfactant has the other of the electron-accepting group and the electron-donating group.

[0116] In the above (1A), specific examples of the resin having a first repeating unit (polar portion) containing an atom selected from the group consisting of silicon atoms and fluorine atoms and a second repeating unit (non-polar portion) containing neither silicon atoms nor fluorine atoms include the same specific surfactants as those described in the second composition below.

[0117] In the above (1A) and (1C), examples of the electron-donating group include an unsubstituted or substituted amino group, a substituted or unsubstituted acylamino group, a nitro group, a cyano group, a halogen-substituted saturated or unsaturated hydrocarbon group (for example, a halogen-substituted alkyl group, a halogen-substituted alkenyl group, or a halogen-substituted aromatic hydrocarbon ring group), a nitrogen-containing heterocyclic group, an oxygen-containing heterocyclic group, and a sulfur-containing heterocyclic group. The unsubstituted or substituted amino group includes -NH2, -NHR Y , and -NR Y 2 etc. R Y represents an alkyl group. The substituted or unsubstituted acylamino group includes -NHCOR Y and -NR Y COR Y etc. R Y represents an alkyl group. R Y The alkyl group mentioned above is preferably a straight-chain or branched-chain group, and preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms. Examples of the electron-accepting group include acid groups, and specific examples thereof include a carboxy group, a phenolic hydroxyl group (corresponding to a hydroxyl group substituted on an aromatic ring), a sulfonic acid group, and a phosphoric acid group.

[0118] In the above (1B), the aromatic ring constituting the aromatic ring structure may be either a monocyclic or polycyclic ring. The aromatic ring constituting the aromatic ring structure may be either an aromatic hydrocarbon ring or an aromatic heterocyclic ring, but is preferably an aromatic hydrocarbon ring, and more preferably a benzene ring or a naphthalene ring.

[0119] [Photosensitive resin composition of second embodiment] The photosensitive resin composition of the second embodiment (hereinafter also referred to as the "second composition") comprises: A photosensitive resin composition comprising an alkali-soluble resin, a polymerizable compound, a photopolymerization initiator, and a surfactant, the surfactant is a resin (hereinafter also referred to as "specific surfactant") having a first repeating unit (polar moiety) containing an atom selected from the group consisting of silicon atoms and fluorine atoms, and a second repeating unit (non-polar moiety) containing neither silicon atoms nor fluorine atoms, The value of ΔHSP2 calculated by the formula (F2) described later is 4.0 MPa. 0.5 However, when at least one selected from the group consisting of the alkali-soluble resin and the polymerizable compound has either an electron-accepting group or an electron-donating group, the surfactant does not have the other of the electron-accepting group or the electron-donating group.

[0120] When a transfer film having a photosensitive resin layer formed from the second composition having the above-described configuration is transferred to a transfer substrate after long-term storage and then used to form a pattern, the pattern forming performance is unlikely to change over time. In other words, even when the transfer film having a photosensitive resin layer formed from the second composition is transferred to a transfer substrate and used to form a pattern after long-term storage, it exhibits pattern forming performance equivalent to that when it is transferred to a transfer substrate immediately after production and used to form a pattern.

[0121] The mechanism by which the second composition provides the above-mentioned effects is not clear, but the present inventors speculate as follows. In the prior art, when a transfer film that had been stored for a long period of time was used to form a pattern on a substrate, the change in pattern formation performance over time was thought to be due to poor compatibility between the surfactant and the alkali-soluble resin and polymerizable compound that correspond to the matrix components of the photosensitive resin layer, which caused the surfactant to weep due to environmental changes such as temperature changes during storage of the transfer film and become unevenly distributed on the surface of the photosensitive resin layer, resulting in a decrease in adhesion between the photosensitive resin layer and the substrate after transfer.Furthermore, it is thought that as a result, parts with weak adhesion are easily peeled off during development, which can cause fluctuations in the pattern formation performance formed on the substrate. In contrast, the second composition contains a specific surfactant, and the HSP distance (ΔHSP2 value) between the non-polar portion of the specific surfactant (described later) and the alkali-soluble resin and polymerizable compound corresponding to the matrix component of the photosensitive resin layer is 4.0 MPa. 0.5 Since the distance is close to the above range, surfactant bleeding is unlikely to occur. It is presumed that at the interface of the photosensitive resin layer, the polar portion of the specific surfactant, which will be described later, faces the outside of the layer, and the non-polar portion of the specific surfactant, which will be described later, faces the inside of the layer. By shortening the HSP distance between the non-polar portion of the specific surfactant, which will be described later, and the alkali-soluble resin and polymerizable compound, which correspond to the matrix components of the photosensitive resin layer, surfactant bleeding can be suppressed. Therefore, it is presumed that the pattern formation performance is unlikely to change even when the pattern is formed by transferring the specific surfactant to a transfer substrate after long-term storage. In the following, when a transfer film having a photosensitive resin layer formed from the second composition is used after long-term storage to transfer onto a substrate to form a pattern, the fact that changes in pattern formation performance are more suppressed is also referred to as "the effect of the present invention being better."

[0122] The second composition will be described in detail below. First, the specific surfactant contained in the second composition will be described below. Note that the various components (alkali-soluble resin, polymerizable compound, photopolymerization initiator, and other additives) other than the specific surfactant that the second composition may contain and their contents are the same as the various components and their contents of the first composition described above, and the preferred embodiments are also the same. However, when at least one selected from the group consisting of the alkali-soluble resin and the polymerizable compound has either an electron-accepting group or an electron-donating group, the specific surfactant does not have the other. Here, specific examples of the electron-donating group include unsubstituted or substituted amino groups, substituted or unsubstituted acylamino groups, nitro groups, cyano groups, halogen-substituted saturated or unsaturated hydrocarbon groups (e.g., halogen-substituted alkyl groups, halogen-substituted alkenyl groups, halogen-substituted aromatic hydrocarbon ring groups), nitrogen-containing heterocyclic groups, oxygen-containing heterocyclic groups, and sulfur-containing heterocyclic groups. Examples of the electron-accepting group include acid groups, specifically carboxy groups, phenolic hydroxyl groups (e.g., hydroxyl groups substituted on aromatic rings), sulfonic acid groups, and phosphate groups.

[0123] [Specific surfactant] The second composition contains a resin (specific surfactant) having a first repeating unit (polar portion) containing an atom selected from the group consisting of silicon atoms and fluorine atoms, and a second repeating unit (non-polar portion) containing neither silicon atoms nor fluorine atoms. Among these, the specific surfactant is more preferably a resin having a first repeating unit containing a silicon atom and the above-mentioned second repeating unit.

[0124] Specific examples of the first repeating unit include the repeating unit represented by formula (A-1) or formula (A-2) described in the first composition.

[0125] Specific examples of the second repeating unit are not limited as long as it does not contain either a silicon atom or a fluorine atom, but a repeating unit having an aromatic ring structure is preferred in terms of achieving better effects of the present invention. Examples of the second repeating unit include the repeating units represented by formulas (B-1) to (B-4) described in the first composition.

[0126] In the specific surfactant, the content of the first repeating unit is preferably 20 to 90 mass %, more preferably 30 to 90 mass %, and even more preferably 40 to 80 mass %, based on the total repeating units of the resin (specific surfactant). The specific surfactant may contain only one type of first repeating unit, or two or more types. When two or more types of first repeating units are contained, the above content is preferably the total content of the first repeating units. In the specific surfactant, the content of the second repeating unit is preferably 10 to 80 mass %, more preferably 20 to 70 mass %, and even more preferably 20 to 60 mass %, based on the total repeating units of the resin (specific surfactant). Only one type of second repeating unit may be contained, or two or more types may be contained. When two or more types of second repeating units are contained, the above content is preferably the total content of the second repeating units.

[0127] Specific examples of the specific surfactant are the same as the compounds given as exemplary surfactant compounds in the first composition.

[0128] The weight-average molecular weight (Mw) of the specific surfactant is preferably at least 500, more preferably at least 1,000, even more preferably at least 10,000, particularly preferably at least 15,000, and most preferably at least 18,000. The upper limit is preferably at most 100,000, more preferably at most 80,000.

[0129] The content of the specific surfactant is preferably from 0.01 to 5 mass %, more preferably from 0.01 to 3 mass %, and even more preferably from 0.05 to 1 mass %, relative to the total solid content of the second composition.

[0130] [ΔHSP2] The second composition has a ΔHSP2 value calculated by the following formula (F2) of 4.0 MPa 0.5 The effect of the present invention is more excellent, and the pressure is 3.5 MPa or less. 0.5 Preferably less than 3.0 MPa 0.5 Less than 2.8MPa is more preferable. 0.5 The lower limit is preferably 0.0 MPa. 0.5 It is sufficient if it is above 0.5MPa. 0.5 In many cases, this is the case.

[0131] Formula (F2): ΔHSP2 = (4(δDM-δDSs) 2 +(δHM-δHSs) 2 +(δPM-δPSs) 2 ) 0.5 In formula (F2), δDM represents the weighted average of the dispersion term of the Hansen solubility parameter of the alkali-soluble resin and the dispersion term of the Hansen solubility parameter of the polymerizable compound, calculated by the following formula (F2A). δHM represents the weighted average of the hydrogen bond term of the Hansen solubility parameter of the alkali-soluble resin and the hydrogen bond term of the Hansen solubility parameter of the polymerizable compound, calculated by the following formula (F2B). δPM represents the weighted average of the polar term of the Hansen solubility parameter of the alkali-soluble resin and the polar term of the Hansen solubility parameter of the polymerizable compound, calculated by the following formula (F2C). δDSs is the dispersion term of the Hansen solubility parameter at the non-polar portion of the specific surfactant. When the specific surfactant has only one type of second repeat unit, it represents the dispersion term of the Hansen solubility parameter of the second repeat unit. When the specific surfactant has two or more types of second repeat units, it represents the weighted average of the dispersion terms of the Hansen solubility parameters of each of the two or more second repeat units. δHSs is the hydrogen bond term of the Hansen solubility parameter in the non-polar region of a specific surfactant. If the specific surfactant has only one type of second repeat unit, it represents the hydrogen bond term of the Hansen solubility parameter of the second repeat unit. If the specific surfactant has two or more types of second repeat units, it represents the weighted average of the hydrogen bond terms of the Hansen solubility parameters of each of the two or more second repeat units. δPSs is the polar term of the Hansen solubility parameter in the non-polar region of a specific surfactant. If the specific surfactant has only one type of second repeat unit, it represents the polar term of the Hansen solubility parameter of the second repeat unit. If the specific surfactant has two or more types of second repeat units, it represents the weighted average of the polar terms of the Hansen solubility parameters of each of the two or more second repeat units. Formula (F2A): δDM=δDb×Wb / (Wb+Wm)+δDm×Wm / (Wb+Wm) Formula (F2B): δHM=δHb×Wb / (Wb+Wm)+δHm×Wm / (Wb+Wm) Formula (F2C): δPM=δPb×Wb / (Wb+Wm)+δPm×Wm / (Wb+Wm) In formula (F2A), ΔDb represents the dispersion term of the Hansen solubility parameter of the alkali-soluble resin, and ΔDm represents the dispersion term of the Hansen solubility parameter of the polymerizable compound. In formula (F2B), ΔHb represents the hydrogen bond term of the Hansen solubility parameter of the alkali-soluble resin, and ΔHm represents the hydrogen bond term of the Hansen solubility parameter of the polymerizable compound. In formula (F2C), ΔPb represents the polar term of the Hansen solubility parameter of the alkali-soluble resin, and ΔPm represents the polar term of the Hansen solubility parameter of the polymerizable compound. In formulas (F2A) to (F2C), Wb represents the mass fraction of the alkali-soluble resin relative to the total solid content in the second composition, and Wm represents the mass fraction of the polymerizable compound relative to the total solid content in the second composition.

[0132] The dispersion term δDb, hydrogen bond term δHb, and polar term δP of the Hansen solubility parameters of alkali-soluble resins, the dispersion term δDm, hydrogen bond term δHm, and polar term δm of the Hansen solubility parameters of polymerizable compounds, and the dispersion term δDSs, hydrogen bond term δHSs, and polar term δSs of the Hansen solubility parameters in the non-polar part of a specific surfactant can be calculated using the commercially available Windows software "HSPiP (developed by www.hansen-solubility.com)".

[0133] In the above formula (F2), ΔDSs represents the weighted average of the variance terms of the Hansen solubility parameters of each of the two or more second repeating units when the specific surfactant has two or more types of second repeating units. Here, the weighted average is calculated by the following formula (S2): Formula (S2): δDSs=δDSs1×WSs1+δDSs2×WSs2+‥‥δDSs n ×WSs n Here, δDSs1 to δDSs n represents the dispersion term value of each Hansen solubility parameter of n types of second repeating units contained in a specific surfactant, and WSs1 to WSs nrepresents the content of each second repeating unit (the content (mass fraction) of each second repeating unit relative to the total content of second repeating units in the specific surfactant). That is, for example, when the specific surfactant contains two types of repeating units, ΔDSs is expressed as ΔDSs1 × WSs1 + ΔDSs2 × WSs2. The weighted average value of the hydrogen bond term and the weighted average value of the polarity term of each Hansen solubility parameter of a specific surfactant having two or more types of second repeating units can also be determined in the same manner as above.

[0134] In addition, the specific surfactant may be used alone or in combination with two or more types in the second composition. When only one specific surfactant is contained in the second composition, the dispersion term δDSs, hydrogen bond term δHSs, and polar term δPSs of the Hansen solubility parameter at the non-polar portion of the specific surfactant in formula (F2) respectively represent the dispersion term δDSs, hydrogen bond term δHSs, and polar term δPSs of the Hansen solubility parameter of the single specific surfactant contained in the second composition. When two or more specific surfactants are contained in the second composition, the dispersion term δDSs, hydrogen bond term δHSs, and polar term δPSs of the Hansen solubility parameter at the non-polar portion of the specific surfactant in formula (F2) represent the weighted average value of the dispersion term of the Hansen solubility parameter at each non-polar portion of the two or more specific surfactants, the weighted average value of the hydrogen bond term of the Hansen solubility parameter at each non-polar portion of the two or more specific surfactants, and the weighted average value of the polar term of the Hansen solubility parameter at each non-polar portion of the two or more specific surfactants, respectively.

[0135] In addition, when the second composition contains two or more specific surfactants, the weighted average of the variance terms of the Hansen solubility parameters of the non-polar moieties of the two or more specific surfactants can be calculated using the following formula (S3). Formula (S3): δDSs=δDSs1×WSs1+δDSs2×WSs2+‥‥δDSs n ×WSs n Here, δDSs1 to δDSs nrepresents the value of the dispersion term of the Hansen solubility parameter of the non-polar portion of n specific surfactants contained in the second composition, and WS s1 ~WS sn represents the content of each specific surfactant (the content (mass content) of each specific surfactant relative to the total content of n specific surfactants). That is, for example, when the second composition contains equal amounts of two specific surfactants, ΔDSs is expressed as ΔDSs1 × 0.5 + ΔDSs2 × 0.5. In addition, the weighted average of the hydrogen bond terms of the Hansen solubility parameters of each non-polar portion of two or more specific surfactants and the weighted average of the polarity terms of the Hansen solubility parameters of each non-polar portion of two or more specific surfactants can also be determined by the same method as above.

[0136] In the second composition, the alkali-soluble resin may be used alone or in combination of two or more kinds. When the second composition contains only one alkali-soluble resin, the dispersion term δDb, hydrogen bond term δHb, and polar term δPb of the Hansen solubility parameter of the alkali-soluble resin in formula (F2A) respectively represent the dispersion term δDb, hydrogen bond term δHb, and polar term δPb of the Hansen solubility parameter of a single alkali-soluble resin contained in the second composition. When the second composition contains two or more alkali-soluble resins, the "δDb" part in formula (F2A) is expressed as "δDb1 × Wb1 + δDb2 × Wb2 + ‥‥δDb n ×Wb n " where δDb1 to δDb n represents the value of the dispersion term of each Hansen solubility parameter of n types of alkali-soluble resins contained in the second composition, and Wb1 to Wb n represents the content (mass fraction) of each alkali-soluble resin relative to the total content of n types of alkali-soluble resins in the second composition. In other words, when the second composition contains two types of alkali-soluble resins, the "δDb" portion in formula (F2A) can be calculated by replacing it with "δDb1 × Wb1 + δDb2 × Wb2." When two or more types of alkali-soluble resins are contained in the second composition, the "δHb" portion in formula (F2B) is expressed as "δHb1 × Wb1 + δHb2 × Wb2 + ‥‥δHb n ×Wb n " is calculated in the same manner as in formula (F2A) (where ΔHb1 to ΔHb n represents the value of the hydrogen bond term of each Hansen solubility parameter of n alkali-soluble resins contained in the second composition, and Wb1 to Wb n represents the content (mass fraction) of each alkali-soluble resin relative to the total content of n types of alkali-soluble resins in the second composition.) The "δPb" part in formula (F2C) is expressed as "δPb1 × Wb1 + δPb2 × Wb2 + ... δPb n ×Wb n ", and it can be calculated in the same way as formula (F2A) (where ΔPb1 to ΔPb n represents the polar term value of each Hansen solubility parameter of n alkali-soluble resins contained in the second composition, and Wb1 to Wb n represents the content (mass fraction) of each alkali-soluble resin relative to the total content of n types of alkali-soluble resins in the second composition.

[0137] In the second composition, the polymerizable compound may be used alone or in combination of two or more kinds. When the second composition contains only one polymerizable compound, the dispersion term δDm, hydrogen bond term δHm, and polar term δPm of the Hansen solubility parameter of the polymerizable compound in formula (F2A) respectively represent the dispersion term δDm, hydrogen bond term δHm, and polar term δPm of the Hansen solubility parameter of a single polymerizable compound contained in the second composition. When the second composition contains two or more polymerizable compounds, the "δDm" part in formula (F2A) is expressed as "δDm1 × Wm1 + δDm2 × Wm2 + ‥‥δDm n ×Wm n " where δDm1 to δDm n represents the value of the dispersion term of each Hansen solubility parameter of the n polymerizable compounds contained in the second composition, and Wm1 to Wm nrepresents the content (mass fraction) of each polymerizable compound relative to the total content of n types of polymerizable compounds in the second composition. In other words, when the second composition contains two types of polymerizable compounds, the "δDm" portion in formula (F2A) can be calculated by replacing it with "δDm1 × Wm1 + δDm2 × Wm2." When two or more polymerizable compounds are contained in the second composition, the "δHm" part in formula (F2B) is expressed as "δHm1 × Wm1 + δHm2 × Wm2 + ‥‥δHm n ×Wmn" is replaced with "ΔHm1 to ΔHm n represents the value of the hydrogen bond term of each Hansen solubility parameter of n polymerizable compounds contained in the second composition, and Wm1 to Wm n represents the content (mass fraction) of each polymerizable compound relative to the total content of n types of polymerizable compounds in the second composition. In addition, the "δPm" part in formula (F2C) is expressed as "δPm1 × Wm1 + δPm2 × Wm2 + ‥‥ δPm n ×Wm n " is calculated in the same manner as in formula (F2A) (where ΔPm1 to ΔPm n represents the polar term value of each Hansen solubility parameter of n polymerizable compounds contained in the second composition, and Wm1 to Wm n represents the content (mass fraction) of each polymerizable compound relative to the total content of n types of polymerizable compounds in the second composition).

[0138] [Preferred embodiment of the second composition] The second composition preferably has each of the following aspects (2A) to (2B) in that the effects of the present invention are more excellent. (2A) The value of ΔHSP1 calculated by the formula (F1) explained as the constitution of the first composition in the upper part is 6.0 MPa 0.5 The following is the result. (2B) At least one compound selected from the group consisting of an alkali-soluble resin and a polymerizable compound, and the surfactant each have an aromatic ring structure in the molecule, the definition of which is as explained in embodiment (1B) of the first composition.

[0139] [Photosensitive resin composition of the third embodiment] The photosensitive resin composition of the third embodiment (hereinafter also referred to as the "third composition") is A photosensitive resin composition comprising an alkali-soluble resin, a polymerizable compound, a photopolymerization initiator, and a surfactant, wherein at least one selected from the group consisting of the alkali-soluble resin and the polymerizable compound, and the surfactant each have an aromatic ring structure in the molecule.

[0140] When a transfer film having a photosensitive resin layer formed from the third composition having the above-described configuration is transferred to a transfer substrate after long-term storage and then used to form a pattern, the pattern forming performance is unlikely to change over time. In other words, even when the transfer film having a photosensitive resin layer formed from the third composition is transferred to a transfer substrate and used to form a pattern after long-term storage, it exhibits pattern forming performance equivalent to that when it is transferred to a transfer substrate immediately after production and used to form a pattern.

[0141] The mechanism by which the third composition provides the above-mentioned effects is not clear, but the present inventors speculate as follows. In the prior art, when a transfer film that had been stored for a long period of time was used to form a pattern on a substrate, the change in pattern formation performance over time was thought to be due to poor compatibility between the surfactant and the alkali-soluble resin and polymerizable compound that correspond to the matrix components of the photosensitive resin layer, which caused the surfactant to weep due to environmental changes such as temperature changes during storage of the transfer film and become unevenly distributed on the surface of the photosensitive resin layer, resulting in a decrease in adhesion between the photosensitive resin layer and the substrate after transfer. Furthermore, it is thought that as a result, parts with weak adhesion are easily peeled off during development, which can cause fluctuations in the pattern formation performance formed on the substrate. In contrast, the third composition has at least one selected from the group consisting of alkali-soluble resins and polymerizable compounds, and a surfactant each having an aromatic ring structure in its molecule, thereby improving the compatibility of the components and making it less likely for the surfactant to start bleeding. Therefore, it is presumed that the pattern forming performance is less likely to change even when the composition is transferred to a transfer substrate and a pattern is formed after long-term storage. In the following, when a transfer film having a photosensitive resin layer formed from the third composition is used after long-term storage to transfer onto a substrate to form a pattern, the fact that changes in pattern formation performance are more suppressed is also referred to as "the effect of the present invention being better."

[0142] The third composition will be described in detail below. In the third composition, the surfactant and at least one compound selected from the group consisting of alkali-soluble resins and polymerizable compounds each have an aromatic ring structure in the molecule. The aromatic ring contained in the aromatic ring structure may be either a monocyclic ring or a polycyclic ring. The aromatic ring constituting the aromatic ring structure may be either an aromatic hydrocarbon ring or an aromatic heterocyclic ring, but is preferably an aromatic hydrocarbon ring, and more preferably a benzene ring or a naphthalene ring. In particular, in terms of achieving superior effects of the present invention, it is preferable that both the alkali-soluble resin and the polymerizable compound have an aromatic ring structure in the molecule. In other words, it is preferable that the third composition contains an alkali-soluble resin having an aromatic ring structure and a polymerizable compound having an aromatic ring structure.

[0143] The alkali-soluble resin, polymerizable compound, and surfactant contained in the third composition are described below. Note that the various components (photopolymerization initiator and other additives) other than those described above that the third composition may contain and their contents are the same as the various components and their contents of the first composition described above, and the preferred embodiments are also the same.

[0144] [Alkali-soluble resin] The third composition contains an alkali-soluble resin, such as the same alkali-soluble resin that may be contained in the first composition. In order to obtain a more excellent effect of the present invention, it is preferable that at least one of the alkali-soluble resins contained in the third composition is a resin containing a repeating unit containing an aromatic ring structure in the molecule. As the resin containing a repeating unit containing an aromatic ring structure in the molecule, a resin containing one or more repeating units (hereinafter also referred to as "repeating unit A") selected from the group consisting of the repeating unit represented by formula (R1) and the repeating unit represented by formula (R2), as explained in the first composition, is more preferable. The content of the repeating unit containing an aromatic ring structure (repeating unit A) in the resin is preferably 20 to 90 mass %, more preferably 30 to 90 mass %, and even more preferably 40 to 80 mass %, based on the total repeating units in the resin. The repeating unit containing an aromatic ring structure (repeating unit A) may be contained in the resin alone or in combination of two or more types. When the resin contains two or more types of repeating units containing an aromatic ring structure (repeating unit A), the above content is preferably the total content.

[0145] The weight average molecular weight (Mw) of the alkali-soluble resin is preferably 5,000 or more, more preferably 10,000 or more, further preferably 10,000 to 100,000, and particularly preferably 15,000 to 80,000, in terms of achieving better effects of the present invention.

[0146] The acid value of the alkali-soluble resin is preferably 10 to 200 mgKOH / g, more preferably 60 to 200 mgKOH / g, still more preferably 60 to 150 mgKOH / g, and particularly preferably 60 to 130 mgKOH / g, as measured according to the method described in JIS K0070:1992.

[0147] The third composition may contain one type of alkali-soluble resin alone, or may contain two or more types of alkali-soluble resins. The content of the alkali-soluble resin is preferably 10 to 90 mass %, more preferably 20 to 80 mass %, and even more preferably 30 to 70 mass %, based on the total solid content of the third composition, in terms of achieving better effects of the present invention. The content of the alkali-soluble resin having an aromatic structure in the molecule is preferably 10 to 90 mass %, more preferably 20 to 80 mass %, and even more preferably 30 to 70 mass %, based on the total solid content of the third composition, in order to achieve better effects of the present invention.

[0148] [Polymerizable compound] The third composition contains a polymerizable compound, such as the same polymerizable compounds that may be contained in the first composition. In order to obtain a more excellent effect of the present invention, it is preferable that at least one of the polymerizable compounds contained in the third composition is a polymerizable compound containing an aromatic ring structure in the molecule. As the polymerizable compound containing an aromatic ring structure in the molecule, the polymerizable compound B1 having an aromatic ring and two ethylenically unsaturated groups, as described in the first composition, is more preferable.

[0149] The polymerizable compounds may be used alone or in combination of two or more. The content of the polymerizable compound is preferably from 10 to 70 mass %, more preferably from 15 to 70 mass %, and even more preferably from 20 to 70 mass %, based on the total solid content of the third composition. The content of the polymerizable compound containing an aromatic ring structure in the molecule is preferably 10 to 70 mass %, more preferably 15 to 70 mass %, and even more preferably 20 to 70 mass %, based on the total solid content of the third composition.

[0150] [Surfactant] The third composition contains a surfactant, and examples of the surfactant include the same surfactants that may be contained in the first composition. In terms of achieving better effects of the present invention, it is preferable that at least one of the surfactants contained in the third composition is a surfactant containing an aromatic ring structure in the molecule. The surfactant containing an aromatic ring structure in the molecule is preferably a surfactant having a first repeating unit containing an atom selected from the group consisting of silicon atoms and fluorine atoms, and a second repeating unit containing neither a silicon atom nor a fluorine atom, and wherein at least one of the first repeating unit and the second repeating unit contains an aromatic ring structure; more preferably a resin having a first repeating unit and a second repeating unit containing a silicon atom, and wherein at least one of the first repeating unit and the second repeating unit contains an aromatic ring structure.

[0151] Specific examples of the first repeating unit include the repeating unit represented by formula (A-1) or formula (A-2) described in the first composition.

[0152] Specific examples of the second repeating unit are preferably repeating units having an aromatic ring structure, in that the effects of the present invention are more excellent, and include repeating units represented by formula (B-1), formula (B-3), and formula (B-4) described in the first composition.

[0153] In the surfactant containing an aromatic ring structure in the molecule, the content of the first repeating unit is preferably 20 to 90 mass %, more preferably 30 to 90 mass %, and even more preferably 40 to 80 mass %, based on the total repeating units of the resin. In the surfactant containing an aromatic ring structure in the molecule, only one type of first repeating unit may be contained, or two or more types may be contained. When two or more types of first repeating units are contained, the content is preferably the total content of the first repeating units. In the surfactant containing an aromatic ring structure in the molecule, the content of the second repeating unit is preferably 10 to 80 mass %, more preferably 20 to 70 mass %, and even more preferably 20 to 60 mass %, based on the total repeating units of the resin. In the surfactant containing an aromatic ring structure in the molecule, only one type of second repeating unit may be contained, or two or more types may be contained. When two or more types of second repeating units are contained, the content is preferably the total content of the second repeating units.

[0154] The weight-average molecular weight (Mw) of the surfactant is preferably at least 500, more preferably at least 1,000, even more preferably at least 10,000, particularly preferably at least 15,000, and most preferably at least 18,000. The upper limit is preferably at most 100,000, more preferably at most 80,000.

[0155] The content of the surfactant is preferably from 0.01 to 5 mass %, more preferably from 0.01 to 3 mass %, and even more preferably from 0.05 to 1 mass %, based on the total solid content of the third composition. The content of the surfactant containing an aromatic ring structure in the molecule is preferably 0.01 to 5 mass %, more preferably 0.01 to 3 mass %, and even more preferably 0.05 to 1 mass %, based on the total solid content of the third composition.

[0156] [Preferred embodiment of the third composition] The third composition preferably has each of the following aspects (3A) to (3C) in that the effects of the present invention are more excellent.

[0157] (3A) The value of ΔHSP3 calculated by the following formula (F3) is 10.0 MPa 0.5 The following is the result. Formula (F3): ΔHSP3 = (4(δDM - δDS) 2 +(δHM-δHS) 2 +(δPM-δPS) 2 ) 0.5 In formula (F1), δDM represents the weighted average value of the dispersion term of the Hansen solubility parameter of the alkali-soluble resin and the dispersion term of the Hansen solubility parameter of the polymerizable compound, calculated by the following formula (F3A). δHM represents the weighted average value of the hydrogen bond term of the Hansen solubility parameter of the alkali-soluble resin and the hydrogen bond term of the Hansen solubility parameter of the polymerizable compound, calculated by the following formula (F3B). δPM represents the weighted average value of the polar term of the Hansen solubility parameter of the alkali-soluble resin and the polar term of the Hansen solubility parameter of the polymerizable compound, calculated by the following formula (F3C). δDS represents the dispersion term of the Hansen solubility parameter of the surfactant. δHS represents the hydrogen bond term of the Hansen solubility parameter of the surfactant. δPS represents the polar term of the Hansen solubility parameter of the surfactant. Formula (F3A): δDM=δDb×Wb / (Wb+Wm)+δDm×Wm / (Wb+Wm) Formula (F3B): δHM=δHb×Wb / (Wb+Wm)+δHm×Wm / (Wb+Wm) Formula (F3C): δPM=δPb×Wb / (Wb+Wm)+δPm×Wm / (Wb+Wm) In formula (F3A), ΔDb represents the dispersion term of the Hansen solubility parameter of the alkali-soluble resin, and ΔDm represents the dispersion term of the Hansen solubility parameter of the polymerizable compound. In formula (F3B), ΔHb represents the hydrogen bond term of the Hansen solubility parameter of the alkali-soluble resin, and ΔHm represents the hydrogen bond term of the Hansen solubility parameter of the polymerizable compound. In formula (F3C), ΔPb represents the polar term of the Hansen solubility parameter of the alkali-soluble resin, and ΔPm represents the polar term of the Hansen solubility parameter of the polymerizable compound. In formulas (F3A) to (F3C), Wb represents the mass fraction of the alkali-soluble resin relative to the total solid content in the third composition, and Wm represents the mass fraction of the polymerizable compound relative to the total solid content in the third composition.

[0158] (3B) The surfactant is a resin (hereinafter also referred to as "specific surfactant") having a first repeating unit (polar moiety) containing an atom selected from the group consisting of silicon atoms and fluorine atoms, and a second repeating unit (non-polar moiety) containing neither silicon atoms nor fluorine atoms, and the value of ΔHSP4 calculated by the following formula (F4) is 15.0 MPa 0.5 The following is the result. Formula (F4): ΔHSP4 = (4(δDM-δDSs) 2 +(δHM-δHSs) 2 +(δPM-δPSs) 2 ) 0.5 In formula (F4), δDM represents a weighted average value of the dispersion term of the Hansen solubility parameter of the alkali-soluble resin and the dispersion term of the Hansen solubility parameter of the polymerizable compound, calculated by the following formula (F4A). δHM represents a weighted average value of the hydrogen bond term of the Hansen solubility parameter of the alkali-soluble resin and the hydrogen bond term of the Hansen solubility parameter of the polymerizable compound, calculated by the following formula (F4B). δPM represents a weighted average value of the polar term of the Hansen solubility parameter of the alkali-soluble resin and the polar term of the Hansen solubility parameter of the polymerizable compound, calculated by the following formula (F4C). δDSs is the dispersion term of the Hansen solubility parameter in the non-polar portion of the surfactant, and when the surfactant has only one type of second repeat unit, it represents the dispersion term of the Hansen solubility parameter of the second repeat unit. When the surfactant has two or more types of second repeat unit, it represents the weighted average of the dispersion terms of the Hansen solubility parameters of each of the two or more second repeat units. δHSs is the hydrogen bond term of the Hansen solubility parameter in the non-polar portion of the surfactant, and when the surfactant has only one type of second repeat unit, it represents the hydrogen bond term of the Hansen solubility parameter of the second repeat unit. When the surfactant has two or more types of second repeat unit, it represents the weighted average of the hydrogen bond term of the Hansen solubility parameter of each of the two or more second repeat units. ΔPSs is the polar term of the Hansen solubility parameter at the non-polar portion of the surfactant. When the surfactant has only one type of the second repeat unit, it represents the polar term of the Hansen solubility parameter of the second repeat unit. When the surfactant has two or more types of the second repeat unit, it represents the weighted average value of the polar terms of the Hansen solubility parameters of each of the two or more types of the second repeat unit. Formula (F4A): δDM=δDb×Wb / (Wb+Wm)+δDm×Wm / (Wb+Wm) Formula (F4B): δHM=δHb×Wb / (Wb+Wm)+δHm×Wm / (Wb+Wm) Formula (F4C): δPM=δPb×Wb / (Wb+Wm)+δPm×Wm / (Wb+Wm) In formula (F4A), ΔDb represents the variance term of the Hansen solubility parameter of the alkali-soluble resin, and ΔDm represents the variance term of the Hansen solubility parameter of the polymerizable compound. In formula (F4B), ΔHb represents the hydrogen bond term of the Hansen solubility parameter of the alkali-soluble resin, and ΔHm represents the hydrogen bond term of the Hansen solubility parameter of the polymerizable compound. In formula (F4C), ΔPb represents the polar term of the Hansen solubility parameter of the alkali-soluble resin, and ΔPm represents the polar term of the Hansen solubility parameter of the polymerizable compound. In formulas (F4A) to (F4C), Wb represents the mass fraction of the alkali-soluble resin relative to the total solid content in the third composition, and Wm represents the mass fraction of the polymerizable compound relative to the total solid content in the third composition.

[0159] (3C) At least one selected from the group consisting of alkali-soluble resins and polymerizable compounds has either an electron-accepting group or an electron-donating group, and the surfactant has the other of the electron-accepting group and the electron-donating group, as described in embodiment (1C) of the first composition.

[0160] (Regarding (3A) above) In the above (3A), the value of ΔHSP3 calculated by formula (F3) is 10.0 MPa. 0.5 Preferably less than 9.0 MPa 0.5 Less than 8.0MPa is more preferable. 0.5 The lower limit is preferably 0.0 MPa. 0.5 Above 5.0MPa is sufficient. 0.5 In many cases, this is the case.

[0161] The dispersion term δDb, hydrogen bond term δHb, and polar term δPb of the Hansen solubility parameters of alkali-soluble resins, the dispersion term δDm, hydrogen bond term δHm, and polar term δPm of the Hansen solubility parameters of polymerizable compounds, and the dispersion term δDS, hydrogen bond term δHS, and polar term δPS of the Hansen solubility parameters of surfactants can be calculated using the commercially available Windows software "HSPiP (developed by www.hansen-solubility.com)".

[0162] The third composition may contain only one surfactant, or two or more surfactants may be used in combination. When the third composition contains only one surfactant, the dispersion term δDS, hydrogen bond term δHS, and polar term δPS of the Hansen solubility parameter of the surfactant in formula (F3) respectively represent the dispersion term δDS, hydrogen bond term δHS, and polar term δPS of the Hansen solubility parameter of a single surfactant contained in the third composition. When the third composition contains two or more surfactants, the dispersion term δDS, hydrogen bond term δHS, and polar term δPS of the Hansen solubility parameter of the surfactant in formula (F3) respectively represent the weighted average of the dispersion term of each Hansen solubility parameter of two or more surfactants, the weighted average of the hydrogen bond term of each Hansen solubility parameter of two or more surfactants, and the weighted average of the polar term of each Hansen solubility parameter of two or more surfactants. When the third composition contains two or more surfactants, the weighted average value of the variance terms of the Hansen solubility parameters of the two or more surfactants is calculated by the following formula (S1). Formula (S1): δDS=δDS1×WS1+δDS2×WS2+‥‥δDS n ×WS n Here, δDS1 to δDS n represents the dispersion term value of each Hansen solubility parameter of n surfactants contained in the third composition, and WS n represents the content of each surfactant (the content (mass fraction) of each surfactant relative to the total content of n types of surfactants). That is, for example, if the third composition contains equal amounts of two types of surfactants, ΔDS is expressed as ΔDS=ΔDS1×0.5+ΔDS2×0.5. The weighted average value of the hydrogen bond term and the weighted average value of the polarity term of the Hansen solubility parameters of two or more surfactants can also be determined in the same manner as above.

[0163] In the third composition, the alkali-soluble resin may be used alone or in combination of two or more kinds. When only one alkali-soluble resin is contained in the third composition, the dispersion term δDb, hydrogen bond term δHb, and polar term δPb of the Hansen solubility parameter of the alkali-soluble resin in formula (F3A) respectively represent the dispersion term δDb, hydrogen bond term δHb, and polar term δPb of the Hansen solubility parameter of a single alkali-soluble resin contained in the third composition. When two or more alkali-soluble resins are contained in the third composition, the "δDb" part in formula (F3A) is expressed as "δDb1 × Wb1 + δDb2 × Wb2 + ‥‥δDb n ×Wb n " where δDb1 to δDb n represents the value of the dispersion term of each Hansen solubility parameter of n kinds of alkali-soluble resins contained in the third composition, and Wb1 to Wb n represents the content (mass fraction) of each alkali-soluble resin relative to the total content of n types of alkali-soluble resins in the third composition. In other words, when the third composition contains two types of alkali-soluble resins, the "δDb" portion in formula (F3A) can be calculated by replacing it with "δDb1 × Wb1 + δDb2 × Wb2." When two or more types of alkali-soluble resins are contained in the third composition, the "δHb" part in formula (F3B) is expressed as "δHb1 × Wb1 + δHb2 × Wb2 + ‥‥δHb n ×Wb n " is calculated in the same manner as in formula (F3A) (where ΔHb1 to ΔHb n represents the value of the hydrogen bond term of each Hansen solubility parameter of n alkali-soluble resins contained in the third composition, and Wb1 to Wb nrepresents the content (mass fraction) of each alkali-soluble resin relative to the total content of n types of alkali-soluble resins in the third composition.) The "δPb" part in formula (F3C) is expressed as "δPb1 × Wb1 + δPb2 × Wb2 + ‥‥ δPb n ×Wb n ", and it can be calculated in the same way as in formula (F3A) (where ΔPb1 to ΔPb n represents the polar term value of each Hansen solubility parameter of n alkali-soluble resins contained in the third composition, and Wb1 to Wb n represents the content (mass fraction) of each alkali-soluble resin relative to the total content of n types of alkali-soluble resins in the third composition.

[0164] In the third composition, the polymerizable compound may be used alone or in combination of two or more kinds. When the third composition contains only one polymerizable compound, the dispersion term δDm, hydrogen bond term δHm, and polar term δPm of the Hansen solubility parameter of the polymerizable compound in formula (F3A) respectively represent the dispersion term δDm, hydrogen bond term δHm, and polar term δPm of the Hansen solubility parameter of a single polymerizable compound contained in the third composition. When the third composition contains two or more polymerizable compounds, the "δDm" part in formula (F3A) is expressed as "δDm1 × Wm1 + δDm2 × Wm2 + ‥‥δDm n ×Wm n " where δDm1 to δDm n represents the value of the dispersion term of each Hansen solubility parameter of n types of polymerizable compounds contained in the third composition, and Wm1 to Wm n represents the content (mass fraction) of each polymerizable compound relative to the total content of n types of polymerizable compounds in the third composition. In other words, when the third composition contains two types of polymerizable compounds, the "δDm" portion in formula (F3A) can be calculated by replacing it with "δDm1 × Wm1 + δDm2 × Wm2." When two or more polymerizable compounds are contained in the third composition, the "δHm" part in formula (F3B) is expressed as "δHm1 × Wm1 + δHm2 × Wm2 + ‥‥δHm n×Wmn" is replaced with "ΔHm1 to ΔHm n represents the value of the hydrogen bond term of the Hansen solubility parameter of each of the n polymerizable compounds contained in the third composition, and Wm1 to Wm n represents the content (mass fraction) of each polymerizable compound relative to the total content of n types of polymerizable compounds in the third composition. In addition, the "δPm" part in formula (F3C) is expressed as "δPm1 × Wm1 + δPm2 × Wm2 + ‥‥ δPm n ×Wm n ", and it can be calculated in the same way as in formula (F3A) (where ΔPm1 to ΔPm n represents the polarity term value of each Hansen solubility parameter of n polymerizable compounds contained in the third composition, and Wm1 to Wm n represents the content (mass fraction) of each polymerizable compound relative to the total content of n types of polymerizable compounds in the third composition).

[0165] (Regarding (3B) above) In the above (3B), specific examples of the resin (specific surfactant) having a first repeating unit (polar moiety) containing an atom selected from the group consisting of silicon atoms and fluorine atoms and a second repeating unit (non-polar moiety) containing neither silicon atoms nor fluorine atoms include the same specific surfactants as those already described in the second composition. In addition, in the above (3B), the value of ΔHSP4 calculated by formula (F4) is 15.0 MPa. 0.5 Preferably less than 14.5 MPa 0.5 Less than 14.0 MPa is more preferable. 0.5 The lower limit is preferably 0.0 MPa. 0.5 Above 7.0MPa is sufficient. 0.5 In many cases, this is the case.

[0166] The dispersion term δDb, hydrogen bond term δHb, and polar term δPb of the Hansen solubility parameters of alkali-soluble resins, the dispersion term δDm, hydrogen bond term δHm, and polar term δPm of the Hansen solubility parameters of polymerizable compounds, and the dispersion term δDSs, hydrogen bond term δHSs, and polar term δPSs of the Hansen solubility parameters in the non-polar part of a specific surfactant can be calculated using the commercially available Windows software "HSPiP (developed by www.hansen-solubility.com)".

[0167] In the above formula (F4), ΔDSs represents the weighted average of the variance terms of the Hansen solubility parameters of each of the two or more second repeating units when the specific surfactant has two or more types of second repeating units. Here, the weighted average is calculated by the following formula (S2): Formula (S2): δDSs=δDSs1×WSs1+δDSs2×WSs2+‥‥δDSs n ×WSs n Here, δDSs1 to δDSs n represents the dispersion term value of each Hansen solubility parameter of n types of second repeating units contained in a specific surfactant, and WSs1 to WSs n represents the content of each second repeating unit (the content (mass fraction) of each second repeating unit relative to the total content of second repeating units in the specific surfactant). That is, for example, when the specific surfactant contains two types of repeating units, ΔDSs is expressed as ΔDSs1 × WSs1 + ΔDSs2 × WSs2. The weighted average value of the hydrogen bond term and the weighted average value of the polarity term of each Hansen solubility parameter of a specific surfactant having two or more types of second repeating units can also be determined in the same manner as above.

[0168] In addition, the specific surfactant may be used alone or in combination with two or more types in the third composition. When only one specific surfactant is contained in the third composition, the dispersion term δDSs, hydrogen bond term δHSs, and polar term δPSs of the Hansen solubility parameter at the non-polar portion of the specific surfactant in formula (F4) respectively represent the dispersion term δDSs, hydrogen bond term δHSs, and polar term δPSs of the Hansen solubility parameter of the single specific surfactant contained in the third composition. When two or more specific surfactants are contained in the third composition, the dispersion term δDSs, hydrogen bond term δHSs, and polar term δPSs of the Hansen solubility parameter at the non-polar portion of the specific surfactant in formula (F4) represent the weighted average value of the dispersion term of the Hansen solubility parameter at each non-polar portion of two or more specific surfactants, the weighted average value of the hydrogen bond term of the Hansen solubility parameter at each non-polar portion of two or more specific surfactants, and the weighted average value of the polar term of the Hansen solubility parameter at each non-polar portion of two or more specific surfactants, respectively.

[0169] In addition, when the third composition contains two or more specific surfactants, the weighted average of the variance terms of the Hansen solubility parameters of the non-polar moieties of the two or more specific surfactants can be calculated using the following formula (S3). Formula (S3): δDSs=δDSs1×WSs1+δDSs2×WSs2+‥‥δDSs n ×WSs n Here, δDSs1 to δDSs n represents the value of the dispersion term of the Hansen solubility parameter of the non-polar portion of n specific surfactants contained in the third composition, and WS s1 ~WS sn represents the content of each specific surfactant (the content (mass content) of each specific surfactant relative to the total content of n types of specific surfactants). That is, for example, when the third composition contains equal amounts of two specific surfactants, ΔDSs is expressed as ΔDSs1 × 0.5 + ΔDSs2 × 0.5. In addition, the weighted average of the hydrogen bond terms of the Hansen solubility parameters of each non-polar portion of two or more specific surfactants and the weighted average of the polarity terms of the Hansen solubility parameters of each non-polar portion of two or more specific surfactants can also be determined by the same method as above.

[0170] In the third composition, the alkali-soluble resin may be used alone or in combination of two or more kinds. When only one alkali-soluble resin is contained in the third composition, the dispersion term δDb, hydrogen bond term δHb, and polar term δPb of the Hansen solubility parameter of the alkali-soluble resin in formula (F4A) respectively represent the dispersion term δDb, hydrogen bond term δHb, and polar term δPb of the Hansen solubility parameter of a single alkali-soluble resin contained in the third composition. When two or more alkali-soluble resins are contained in the third composition, the "δDb" part in formula (F4A) is expressed as "δDb1 × Wb1 + δDb2 × Wb2 + ‥‥δDb n ×Wb n " where δDb1 to δDb n represents the value of the dispersion term of each Hansen solubility parameter of n kinds of alkali-soluble resins contained in the third composition, and Wb1 to Wb n represents the content (mass fraction) of each alkali-soluble resin relative to the total content of n types of alkali-soluble resins in the third composition. In other words, when the third composition contains two types of alkali-soluble resins, the "δDb" portion in formula (F4A) can be calculated by replacing it with "δDb1 × Wb1 + δDb2 × Wb2." When two or more types of alkali-soluble resins are contained in the third composition, the "δHb" part in formula (F4B) is expressed as "δHb1 × Wb1 + δHb2 × Wb2 + ‥‥δHb n ×Wb n " is calculated in the same manner as in formula (F4A) (where ΔHb1 to ΔHb n represents the value of the hydrogen bond term of each Hansen solubility parameter of n alkali-soluble resins contained in the third composition, and Wb1 to Wb nrepresents the content (mass fraction) of each alkali-soluble resin relative to the total content of n types of alkali-soluble resins in the third composition.) The "δPb" part in formula (F4C) is expressed as "δPb1 × Wb1 + δPb2 × Wb2 + ‥‥ δPb n ×Wb n ", and it can be calculated in the same way as in formula (F4A) (where ΔPb1 to ΔPb n represents the polar term value of each Hansen solubility parameter of n alkali-soluble resins contained in the third composition, and Wb1 to Wb n represents the content (mass fraction) of each alkali-soluble resin relative to the total content of n types of alkali-soluble resins in the third composition.

[0171] In the third composition, the polymerizable compound may be used alone or in combination of two or more kinds. When the third composition contains only one polymerizable compound, the dispersion term δDm, hydrogen bond term δHm, and polar term δPm of the Hansen solubility parameter of the polymerizable compound in formula (F4A) respectively represent the dispersion term δDm, hydrogen bond term δHm, and polar term δPm of the Hansen solubility parameter of a single polymerizable compound contained in the third composition. When the third composition contains two or more polymerizable compounds, the "δDm" part in formula (F4A) is expressed as "δDm1 × Wm1 + δDm2 × Wm2 + ‥‥δDm n ×Wm n " where δDm1 to δDm n represents the value of the dispersion term of each Hansen solubility parameter of n types of polymerizable compounds contained in the third composition, and Wm1 to Wm n represents the content (mass fraction) of each polymerizable compound relative to the total content of n types of polymerizable compounds in the third composition. In other words, when the third composition contains two types of polymerizable compounds, the "δDm" portion in formula (F4A) can be calculated by replacing it with "δDm1 × Wm1 + δDm2 × Wm2." When two or more polymerizable compounds are contained in the third composition, the "δHm" part in formula (F4B) is expressed as "δHm1 × Wm1 + δHm2 × Wm2 + ‥‥δHm n×Wmn" is replaced with "ΔHm1 to ΔHm n represents the value of the hydrogen bond term of the Hansen solubility parameter of each of the n polymerizable compounds contained in the third composition, and Wm1 to Wm n represents the content (mass fraction) of each polymerizable compound relative to the total content of n types of polymerizable compounds in the third composition. In addition, the "δPm" part in formula (F4C) is expressed as "δPm1 × Wm1 + δPm2 × Wm2 + ‥‥ δPm n ×Wm n ", and is calculated in the same manner as in formula (F4A) (where ΔPm1 to ΔPm n represents the polarity term value of each Hansen solubility parameter of n polymerizable compounds contained in the third composition, and Wm1 to Wm n represents the content (mass fraction) of each polymerizable compound relative to the total content of n types of polymerizable compounds in the third composition).

[0172] [Photosensitive resin composition of the fourth embodiment] The photosensitive resin composition of the fourth embodiment (hereinafter also referred to as the "fourth composition") comprises: A photosensitive resin composition comprising an alkali-soluble resin, a polymerizable compound, a photopolymerization initiator, and a surfactant, wherein at least one selected from the group consisting of the alkali-soluble resin and the polymerizable compound has one of an electron-accepting group and an electron-donating group, and the surfactant has the other of the electron-accepting group and the electron-donating group.

[0173] When a transfer film having a photosensitive resin layer formed from the fourth composition having the above-described configuration is transferred to a transfer substrate after long-term storage and then used to form a pattern, the pattern forming performance is unlikely to change over time. In other words, even when a transfer film having a photosensitive resin layer formed from the fourth composition is transferred to a transfer substrate and used to form a pattern after long-term storage, it exhibits pattern forming performance equivalent to that when it is transferred to a transfer substrate and used to form a pattern immediately after production.

[0174] The mechanism by which the fourth composition provides the above-mentioned effects is not clear, but the present inventors speculate as follows. In the prior art, when a transfer film that had been stored for a long period of time was used to form a pattern on a substrate, the change in pattern formation performance over time was thought to be due to poor compatibility between the surfactant and the alkali-soluble resin and polymerizable compound that correspond to the matrix components of the photosensitive resin layer, which caused the surfactant to weep due to environmental changes such as temperature changes during storage of the transfer film and become unevenly distributed on the surface of the photosensitive resin layer, resulting in a decrease in adhesion between the photosensitive resin layer and the substrate after transfer. Furthermore, it is thought that as a result, parts with weak adhesion are easily peeled off during development, which can cause fluctuations in the pattern formation performance formed on the substrate. In contrast, the fourth composition contains at least one compound selected from the group consisting of an alkali-soluble resin and a polymerizable compound that has either an electron-accepting group or an electron-donating group, and the surfactant has the other of an electron-accepting group and an electron-donating group, thereby improving the compatibility of the components through electronic interaction and making the surfactant less likely to weep. Therefore, it is presumed that the pattern-forming performance is less likely to change even when the composition is transferred to a transfer substrate and a pattern is formed after long-term storage. In the following, when a transfer film having a photosensitive resin layer formed from the fourth composition is used after long-term storage to transfer onto a substrate to form a pattern, the fact that changes in pattern formation performance are more suppressed is also referred to as "the effect of the present invention being better."

[0175] The fourth composition will be described in detail below. In the fourth composition, at least one compound selected from the group consisting of an alkali-soluble resin and a polymerizable compound has one of an electron-accepting group and an electron-donating group, and the surfactant has the other of an electron-accepting group and an electron-donating group. Specific examples of the electron-donating group include an unsubstituted or substituted amino group, a substituted or unsubstituted acylamino group, a nitro group, a cyano group, a halogen-substituted saturated or unsaturated hydrocarbon group (for example, a halogen-substituted alkyl group, a halogen-substituted alkenyl group, or a halogen-substituted aromatic hydrocarbon ring group), a nitrogen-containing heterocyclic group, an oxygen-containing heterocyclic group, and a sulfur-containing heterocyclic group. The unsubstituted or substituted amino group includes -NH2, -NHR Y , and -NR Y 2 etc. R Y represents an alkyl group. The substituted or unsubstituted acylamino group includes -NHCOR Y and -NR Y COR Y etc. R Y represents an alkyl group. R Y The alkyl group mentioned above is preferably a straight-chain or branched-chain group, and preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms. Examples of the electron-accepting group include acid groups, specifically carboxy groups, phenolic hydroxyl groups (which correspond to hydroxyl groups substituted on aromatic rings), sulfonic acid groups, and phosphate groups, and among these, carboxy groups are preferred. Among these, in terms of achieving better effects of the present invention, it is preferable that at least one of the alkali-soluble resin and the polymerizable compound has an electron-accepting group, and the surfactant has an electron-donating group. In addition, in terms of achieving better effects of the present invention, it is also preferable that the alkali-soluble resin has a repeating unit having an electron-accepting group and the surfactant has a repeating unit having an electron-donating group. In other words, it is preferable that the fourth composition contains an alkali-soluble resin having a repeating unit having an electron-accepting group and a surfactant having a repeating unit having an electron-donating group.

[0176] The alkali-soluble resin, polymerizable compound, and surfactant contained in the fourth composition are described below. Note that the various components (photopolymerization initiator and other additives) other than those described above that the fourth composition may contain and their contents are the same as the various components and their contents of the first composition described above, and preferred embodiments are also the same.

[0177] [Alkali-soluble resin] The fourth composition contains an alkali-soluble resin, such as the alkali-soluble resin that may be contained in the first composition. In order to achieve better effects of the present invention, it is preferable that at least one of the alkali-soluble resins contained in the fourth composition is a resin having an electron-accepting group (preferably, a carboxy group), and it is more preferable that it is a resin having a repeating unit having an electron-accepting group (preferably, a carboxy group). The content of repeating units having an electron-accepting group in the resin is preferably from 1 to 50 mass %, more preferably from 2 to 40 mass %, and even more preferably from 3 to 30 mass %, based on all repeating units in the resin. The resin may contain only one type of repeating unit having an electron-accepting group, or two or more types. When the resin contains two or more types of repeating units having an electron-accepting group, the above content is preferably the total content.

[0178] The weight average molecular weight (Mw) of the alkali-soluble resin is preferably 5,000 or more, more preferably 10,000 or more, further preferably 10,000 to 100,000, and particularly preferably 15,000 to 80,000, in terms of achieving better effects of the present invention.

[0179] The acid value of the alkali-soluble resin is preferably 10 to 200 mgKOH / g, more preferably 60 to 200 mgKOH / g, still more preferably 60 to 150 mgKOH / g, and particularly preferably 60 to 130 mgKOH / g, as measured according to the method described in JIS K0070:1992.

[0180] The fourth composition may contain one type of alkali-soluble resin alone, or may contain two or more types of alkali-soluble resins. The content of the alkali-soluble resin is preferably 10 to 90 mass %, more preferably 20 to 80 mass %, and even more preferably 30 to 70 mass %, based on the total solid content of the fourth composition, in terms of achieving better effects of the present invention. The content of the alkali-soluble resin having an electron-accepting group is preferably 10 to 90 mass %, more preferably 20 to 80 mass %, and even more preferably 30 to 70 mass %, relative to the total solid content of the fourth composition, in order to achieve better effects of the present invention.

[0181] [Polymerizable compound] The fourth composition contains a polymerizable compound, which may be the same as the polymerizable compound that may be contained in the first composition. In terms of achieving better effects of the present invention, at least one of the polymerizable compounds contained in the fourth composition is preferably a polymerizable compound containing at least one of an electron-accepting group and an electron-donating group, and more preferably a polymerizable compound containing an electron-accepting group. The number of groups selected from electron-accepting groups and electron-donating groups in the polymerizable compound may be 1 or more, and more preferably 2 or more, with the upper limit being, for example, 6 or less.

[0182] The polymerizable compounds may be used alone or in combination of two or more. The content of the polymerizable compound is preferably from 10 to 70 mass %, more preferably from 15 to 70 mass %, and even more preferably from 20 to 70 mass %, based on the total solid content of the fourth composition. The content of the polymerizable compound containing a group selected from an electron-accepting group and an electron-donating group is preferably 10 to 70 mass %, more preferably 15 to 70 mass %, and even more preferably 20 to 70 mass %, relative to the total solid content of the fourth composition.

[0183] [Surfactant] The fourth composition contains a surfactant, and examples of the surfactant include the same surfactants that may be contained in the first composition. In terms of achieving better effects of the present invention, it is preferable that at least one of the surfactants contained in the fourth composition is a surfactant containing at least one of an electron-accepting group and an electron-donating group, and it is more preferable that it is a surfactant containing an electron-donating group. The surfactant containing an electron-donating group in the molecule is preferably a resin having a first repeating unit (polar portion) containing an atom selected from the group consisting of silicon atoms and fluorine atoms, and a second repeating unit (non-polar portion) containing neither silicon atoms nor fluorine atoms, wherein at least one of the first repeating unit and the second repeating unit contains a group selected from an electron-accepting group and an electron-donating group; more preferably a resin having a first repeating unit and the second repeating unit containing a silicon atom, wherein at least one of the first repeating unit and the second repeating unit contains a group selected from an electron-accepting group and an electron-donating group; and even more preferably a resin having a first repeating unit and the second repeating unit containing a silicon atom, wherein the second repeating unit contains an electron-donating group.

[0184] Specific examples of the first repeating unit include the repeating unit represented by formula (A-1) or formula (A-2) described in the first composition.

[0185] Specific examples of the second repeating unit include the repeating unit represented by formula (B-1) described in the first composition, which has a more excellent effect in the present invention, and in which R B12 an embodiment in which the substituent that the monovalent aromatic ring group represented by formula (B-1) may have represents an electron-donating group; B12 The monovalent aromatic ring group represented by the formula (M1) further has a substituent represented by the formula (M1), and R M1 represents an electron-donating group, and a repeating unit represented by formula (B-2), B22 and the substituent other than the aromatic group represented by the following formula (I) represents an electron-donating group.

[0186] In surfactants containing at least one of an electron-accepting group and an electron-donating group, the content of the first repeating unit is preferably 20 to 90 mass%, more preferably 30 to 90 mass%, and even more preferably 40 to 80 mass%, based on the total repeating units of the resin. In surfactants containing at least one of an electron-accepting group and an electron-donating group, the first repeating unit may be of one type, or may be of two or more types. When two or more types of first repeating units are contained, the above content is preferably the total content of the first repeating units. In surfactants containing at least one of an electron-accepting group and an electron-donating group, the content of the second repeating unit is preferably 10 to 80 mass%, more preferably 20 to 70 mass%, and even more preferably 20 to 60 mass%, based on the total repeating units of the surfactant containing at least one of an electron-accepting group and an electron-donating group. In surfactants containing at least one of an electron-accepting group and an electron-donating group, only one type of second repeating unit may be contained, or two or more types may be contained. Note that when two or more types of second repeating units are contained, the above content is preferably the total content of the second repeating units.

[0187] The weight-average molecular weight (Mw) of the surfactant is preferably at least 500, more preferably at least 1,000, even more preferably at least 10,000, particularly preferably at least 15,000, and most preferably at least 18,000. The upper limit is preferably at most 100,000, more preferably at most 80,000.

[0188] The content of the surfactant is preferably from 0.01 to 5 mass %, more preferably from 0.01 to 3 mass %, and even more preferably from 0.05 to 1 mass %, based on the total solid content of the fourth composition. The content of the surfactant containing at least one of an electron-accepting group and an electron-donating group is preferably 0.01 to 5 mass %, more preferably 0.01 to 3 mass %, and even more preferably 0.05 to 1 mass %, relative to the total solid content of the fourth composition.

[0189] [Preferred embodiment of the fourth composition] The fourth composition preferably has each of the following aspects (4A) to (4C) in that the effects of the present invention are more excellent. (4A) The value of ΔHSP1 calculated by the formula (F1) explained as the constitution of the first composition in the upper part is 6.0 MPa 0.5 The following is the result. (4B) The surfactant is a resin (hereinafter also referred to as "specific surfactant") having a first repeating unit (polar moiety) containing an atom selected from the group consisting of silicon atoms and fluorine atoms, and a second repeating unit (non-polar moiety) containing neither silicon atoms nor fluorine atoms, and the value of ΔHSP4 calculated by formula (F4) described as the configuration of the third composition is 15.0 MPa 0.5 The value of ΔHSP4 is 14.5 MPa. 0.5 Preferably less than 14.0 MPa 0.5 Less than 12.0MPa is more preferable. 0.5 The lower limit is preferably 0.0 MPa. 0.5 Above 5.0MPa is sufficient. 0.5 It may be more than that. (4C) At least one compound selected from the group consisting of an alkali-soluble resin and a polymerizable compound, and the surfactant each have an aromatic ring structure in the molecule, the definition of which is as explained in embodiment (1B) of the first composition.

[0190] In the above (4B), specific examples of the resin (specific surfactant) having a first repeating unit (polar portion) containing an atom selected from the group consisting of silicon atoms and fluorine atoms and a second repeating unit (non-polar portion) containing neither silicon atoms nor fluorine atoms include the same specific surfactants as those described in the second composition in the upper section.

[0191] [Transfer film] The transfer film of the present invention has a temporary support, a photosensitive resin layer formed from a photosensitive resin composition (a composition selected from the first to fourth compositions), and a protective layer (cover film). The transfer film may have a composition layer other than the photosensitive resin layer. Examples of the other composition layer include a thermoplastic resin layer and an intermediate layer. When the transfer film has a thermoplastic resin layer and an intermediate layer, it is preferable that the intermediate layer and the thermoplastic resin layer are located between the temporary support and the photosensitive resin layer in this order from the photosensitive resin layer side.

[0192] FIG. 1 is a cross-sectional view showing an example of an embodiment of a transfer film. The transfer film 10 shown in FIG. 1 has a temporary support 1, a thermoplastic resin layer 3, an intermediate layer 5, a photosensitive resin layer 7, and a protective film 9 in this order. Although the transfer film 10 shown in FIG. 1 has the thermoplastic resin layer 3 and the intermediate layer 5 arranged therein, the thermoplastic resin layer 3 and the intermediate layer 5 do not necessarily have to be arranged. The transfer film may not have the protective film 9. Each component of the transfer film will be described in detail below.

[0193] [Temporary support] The transfer film has a temporary support. The temporary support is a member that supports a composition layer such as a photosensitive resin layer, and is ultimately removed by a peeling treatment.

[0194] 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 preferably a flexible film that does not significantly deform, shrink, or stretch under pressure or under pressure and heat. Examples of such films 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. It is also preferable that the temporary support be free of deformations such as wrinkles and scratches.

[0195] The temporary support is preferably highly transparent in that it can be subjected to 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 particularly 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 pattern formability during pattern exposure through the temporary support and 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 pattern formability during pattern exposure through the temporary support and transparency of the temporary support, it is preferable that the number of fine particles, foreign matter, and defects contained in the temporary support is small. Specifically, the number of fine particles, foreign matter, and defects having a diameter of 1 μm or more in the temporary support is 50 / mm 2 Preferably less than 10 pieces / mm 2 Less than 3 pieces / mm is more preferable. 2 More preferably, 0 pieces / mm 2 is particularly preferred. As a specific example of the number of particles, foreign matter, and defects with a diameter of 1 μm or more on the temporary support, 2 particles / mm 2 , and 0 pieces / mm 2 Examples include:

[0196] The thickness of the temporary support is preferably from 5 to 200 μm, and from the viewpoint of ease of handling and versatility, more preferably from 5 to 150 μm, further preferably from 5 to 50 μm, particularly preferably from 5 to 35 μm. The thickness of the temporary support is the average value of measurements taken at any five points by cross-sectional observation using an SEM.

[0197] In order to improve the adhesion between the temporary support and the photosensitive resin 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, or the like. 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 is more preferred. 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.

[0198] 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 recycled products include those obtained by cleaning and chipping used films and then forming the resulting materials into films. Examples of commercially available recycled products include the Ecouse series (manufactured by Toray Industries, Inc.).

[0199] Examples of temporary supports include those described in paragraphs 0017 to 0018 of JP 2014-085643 A, paragraphs 0019 to 0026 of JP 2016-027363 A, paragraphs 0041 to 0057 of WO 2012 / 081680 A, and paragraphs 0029 to 0040 of WO 2018 / 179370 A, the contents of which are incorporated herein by reference.

[0200] The temporary support may have a layer containing fine particles (lubricant layer) on one or both sides of the temporary support to improve handling properties. The diameter of the fine particles contained in the lubricant layer is preferably 0.05 to 0.8 μm. The 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.).

[0201] [Photosensitive resin layer] The photosensitive resin layer is a layer formed using the above-mentioned photosensitive resin composition. The various components that can be contained in the photosensitive resin layer have the same meanings as, for example, the various components that can be contained in the photosensitive resin composition, and the preferred embodiments are also the same. However, the preferred ranges of the contents of the various components in the photosensitive resin layer are the same as the preferred ranges obtained by replacing the above-mentioned "contents (% by mass) of the various components relative to the total solid content of the photosensitive resin composition" with "contents (% by mass) of the various components relative to the total mass of the photosensitive resin layer." For example, the statement "The content of the alkali-soluble resin is preferably 5.0% by mass or more relative to the total solid content of the photosensitive resin composition" should be replaced with "The content of the alkali-soluble resin is preferably 5.0% by mass or more relative to the total mass of the photosensitive resin layer."

[0202] <Thickness of photosensitive resin layer> The average thickness of the photosensitive resin layer is preferably 0.5 to 40 μm, more preferably 0.5 to 25 μm, and even more preferably 3 to 20 μm. When the average thickness of the photosensitive resin layer is 40 μm or less, it is preferable in terms of excellent pattern resolution, and when the average thickness of the photosensitive resin layer is 0.5 μm or more, it is preferable in terms of excellent reliability.

[0203] [Other layers] The transfer film may include layers other than the above-described layers (hereinafter also referred to as "other layers"). Examples of the other layers include the above-described intermediate layer and thermoplastic resin layer, and known layers can be appropriately used. The intermediate layer is preferably a water-soluble resin layer containing a water-soluble resin. Examples of the intermediate layer (water-soluble resin 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. At least one of the intermediate layer (water-soluble resin layer) and the thermoplastic resin layer (preferably both) may contain at least one of the surfactants contained in the photosensitive resin layer.

[0204] [Protective layer] The transfer film has a protective layer (protective film). Examples of the protective film include resin films having heat resistance and solvent resistance. Specific examples include polyolefin films such as polypropylene film and polyethylene film, polyester films such as polyethylene terephthalate film, polycarbonate film, and polystyrene film. Furthermore, a resin film made of the same material as the temporary support may also be used as the protective film. Examples of the protective film include the descriptions in paragraphs 0083 to 0087 and 0093 of JP-A-2006-259138, the contents of which are incorporated herein by reference. Of these, the protective film is preferably a polyolefin film or a polyester film, and more preferably a polypropylene film or a polyethylene terephthalate film.

[0205] The thickness of the protective film is preferably from 1 to 100 μm, more preferably from 5 to 50 μm, even more preferably from 5 to 40 μm, and particularly preferably from 15 to 30 μm. The thickness of the protective film is preferably 1 μm or more in view of excellent mechanical strength, and is preferably 100 μm or less in view of relatively low cost.

[0206] The number of fisheyes in the protective film with a diameter of 80 μm or more is 5 / m 2 The lower limit is 0 particles / m 2 The above is preferable. "Fisheyes" refer to foreign matter, undissolved matter, oxidized degradation products, etc. that are trapped in the film when the material is thermally melted and then kneaded, extruded, biaxially stretched, cast, or other methods are used to produce the film.

[0207] The number of particles with a diameter of 3 μm or more contained in the protective film is 30 / mm 2 Preferably less than 10 pieces / mm 2 Less than 5 pieces / mm is more preferable. 2 The lower limit is 0 pieces / mm 2 When the content is in the above range, defects caused by unevenness due to particles contained in the protective film being transferred to the photosensitive resin layer or the conductive layer can be suppressed.

[0208] In order to provide good winding properties, the arithmetic mean roughness Ra of the surface of the protective film opposite to or in contact with the photosensitive resin layer is preferably 0.01 μm or more, more preferably 0.02 μm or more, and even more preferably 0.03 μm or more. The upper limit is preferably less than 0.50 μm, more preferably 0.40 μm or less, and even more preferably 0.30 μm or less.

[0209] Specific examples of protective 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 protective film may be a recycled product. Examples of recycled products include those obtained by cleaning used films and cutting them into chips, and then forming the resulting material into a film. Examples of commercially available recycled products include the Ecouse series (manufactured by Toray Industries, Inc.).

[0210] [Transfer film manufacturing method] The method for producing the transfer film is not particularly limited as long as it is a production method using the above-mentioned photosensitive resin composition. In the method for producing the transfer film, the above-mentioned photosensitive resin composition is preferably applied onto a temporary support to form a photosensitive resin layer.

[0211] For example, a method for producing the transfer film 10 shown in Fig. 1 includes a production method including the steps of sequentially forming a thermoplastic resin layer 3 and an intermediate layer 5 on the surface of a temporary support 1, applying a photosensitive resin composition to the surface of the intermediate layer 5 to form a coating film, and then drying the coating film to form a photosensitive resin layer 7. The transfer film 10 shown in Fig. 1 is produced by pressing a protective film onto the photosensitive resin layer 7 of the transfer film 10 produced by the above production method. 1 may be wound up after production and stored as a roll of transfer film 1. The roll of transfer film 1 can be used as is in the lamination step with a substrate in a roll-to-roll system. When the transfer film does not have the thermoplastic resin layer 3 and the intermediate layer 5, the photosensitive resin layer 7 may be formed on the surface of the temporary support. Examples of compositions for forming an intermediate layer and methods for forming an intermediate layer, and compositions for forming a thermoplastic resin layer and methods for forming a thermoplastic resin layer are described in paragraphs 0133 to 0136 and 0143 to 0144 of International Publication No. 2021 / 033451, the contents of which are incorporated herein by reference.

[0212] [Method for forming photosensitive resin layer] The photosensitive resin layer can be formed by, for example, a known method. Specifically, the method includes applying and drying the above-mentioned photosensitive resin composition. Examples of coating methods include slit coating, spin coating, curtain coating, and inkjet coating. The photosensitive resin composition used in the method for forming the photosensitive resin layer preferably contains a solvent. The solvent has the same meaning as the solvent that can be contained in the photosensitive resin composition described above, and preferred embodiments are also the same.

[0213] [Application] The pattern (cured film) obtained from the photosensitive resin layer formed using the transfer film can be used in various applications. For example, it can be used as a resist film in the process of forming a circuit on a semiconductor substrate by plating and the process of forming a circuit on a metal substrate or a resin substrate with a metal layer by etching. It can also be used as a resist film in the production of metal masks. Examples of metal masks include deposition masks used in the production of OLEDs, etc. Examples of deposition masks include the deposition masks described in paragraphs 0245 to 0257 of JP 2022-168819 A.

[0214] The method for producing a laminate having a metal pattern layer using the transfer film preferably includes, for example, the following steps. Step X1: A lamination step in which the transfer film is laminated to a substrate so that the surface exposed by peeling off the protective layer of the transfer film is in contact with the metal layer of the substrate having a metal layer on its surface. Step X2: Exposure step of pattern-exposing the photosensitive resin layer Step X3: A developing step in which the exposed photosensitive resin layer is subjected to a developing treatment using a developer to form a resist pattern. Step X4: An etching step (step X4-1) for etching the metal layer in the area where the resist pattern is not disposed, or a plating step (step X4-2) for plating the metal layer. Step X5: Resist stripping step of stripping the resist pattern Step X6: When the step X4 includes a plating step (step X4-2), this is a removal step of removing the metal layer exposed by the resist stripping step and forming a metal pattern layer on the substrate. Step X7: A temporary support peeling step of peeling off the temporary support between the laminating step and the exposure step, or between the exposure step and the development step.

[0215] Each step will be described in detail below.

[0216] [Process X1 (lamination process)] In lamination, it is preferable that the surface of the transfer film opposite to the temporary support be brought into contact with the metal layer on the substrate and pressure-bonded to it, with the protective layer being peeled off before lamination. Examples of the pressure bonding method include known transfer and lamination methods, and a preferred method is to place the surface of the transfer film opposite to the temporary support on the substrate and apply pressure and heat with a roll or the like. Examples of lamination methods include methods using known laminators such as vacuum laminators and auto-cut laminators. The lamination temperature is preferably 70 to 130°C.

[0217] A substrate having a metal layer on its surface (substrate with a metal layer) has a substrate and a metal layer disposed on the surface of the substrate. The substrate with a metal layer may have any layer other than the metal layer formed on the substrate as needed. That is, the substrate with a metal layer preferably has at least a substrate and a metal layer disposed on the surface of the substrate. Examples of the substrate include a resin substrate, a glass substrate, a ceramic substrate, and a semiconductor substrate, and the substrate described in paragraph

[0140] of WO 2018 / 155193 is preferred. The resin substrate is preferably made of polyethylene terephthalate, cycloolefin polymer, or polyimide. The thickness of the resin substrate is preferably 5 to 200 μm, more preferably 10 to 100 μm.

[0218] The metal layer is a layer containing a metal, and the metal is not particularly limited, and any known metal can be used. The metal layer is preferably a conductive layer. Examples of the main component of the metal layer (so-called main metal) include copper, chromium, lead, nickel, gold, silver, tin, zinc, etc. The main component refers to the metal with the largest content among the metals contained in the metal layer.

[0219] The thickness of the metal layer is not particularly limited, but is preferably 50 nm or more, more preferably 100 nm or more. There is no particular upper limit, but it is preferably 2 μm or less.

[0220] The method for forming the metal layer is not particularly limited, and examples thereof include known methods such as a method of applying a dispersion liquid in which metal fine particles are dispersed and sintering the coating film, a sputtering method, and a vapor deposition method.

[0221] One or more metal layers may be disposed on the substrate. When two or more metal layers are disposed, the two or more disposed metal layers may be the same or different, and are preferably made of different materials. Examples of metals contained in the metal layer include gold, silver, copper, molybdenum, aluminum, titanium, chromium, zinc, and manganese, as well as alloys of these metals. Copper, molybdenum, aluminum, or titanium is preferred, and copper is more preferred.

[0222] [Process X2 (exposure process)] The exposure step is a step of pattern-exposing the photosensitive resin layer. "Pattern exposure" refers to a form of patterned exposure in which exposed areas and non-exposed areas exist. The positional relationship between the exposed portion (exposed region) and the non-exposed portion (non-exposed region) in the pattern exposure can be adjusted as appropriate. The exposure direction may be from the photosensitive resin layer side or the side opposite to the photosensitive resin layer side (substrate side). The exposure step is typically a step of performing pattern exposure through a photomask. In the exposure step, the photomask and the laminate, which is the photosensitive material, may or may not be in contact with each other.

[0223] In the case of the above-mentioned pattern exposure process, a curing reaction of components contained in the photosensitive resin layer may occur in the exposed regions of the photosensitive resin layer (regions corresponding to the openings of the photomask). By carrying out a development process after exposure, the unexposed regions of the photosensitive resin layer are removed, thereby forming a pattern.

[0224] The method of the present invention preferably includes a photomask stripping step between the exposure step and the development treatment, in which the photomask used in the exposure step is stripped off. The photomask peeling step may be, for example, a known peeling step.

[0225] The light source for pattern exposure may be one that can irradiate light in a wavelength range that can cure the photosensitive resin layer (for example, 365 nm and 405 nm), with 365 nm being preferred. "Dominant wavelength" refers to the wavelength with the highest intensity.

[0226] Examples of light sources include various lasers, light-emitting diodes (LEDs), ultra-high pressure mercury lamps, high pressure mercury lamps, and metal halide lamps. The exposure dose is 5 to 200 mJ / cm 2 is preferred, and 10 to 200 mJ / cm 2 is more preferred. Examples of light sources, exposure doses, and exposure methods include those described in paragraphs

[0146] to

[0147] of International Publication No. 2018 / 155193, the contents of which are incorporated herein by reference.

[0227] The exposure method can be selected from a contact exposure method for contact exposure, a proximity exposure method for non-contact exposure, a lens or mirror projection exposure method, and a direct exposure (direct writing exposure) method using an exposure laser or the like. In the case of lens or mirror projection exposure, an exposure machine with an appropriate lens numerical aperture (NA) can be used depending on the required resolution and depth of focus. In the case of direct exposure, writing can be performed directly on the photosensitive resin layer, or reduced projection exposure can be performed on the photosensitive resin layer through a lens. Furthermore, exposure can be performed not only under atmospheric pressure but also under reduced pressure or vacuum, and exposure can also be performed with a liquid such as water interposed between the light source and the transfer layer. From the viewpoint of resolution, the exposure in step X2 is preferably carried out by contact exposure in which the transfer layer is brought into contact with a mask. Furthermore, the exposure in step X2 is preferably carried out by direct writing exposure or projection exposure, from the viewpoint of minimizing the influence on the mask and the photosensitive resin layer.

[0228] [Step X7 (temporary support peeling step)] A temporary support peeling step is carried out between the laminating step and the exposure step, or between the exposure step and the development step. Among these, it is more preferable to have a peeling step between the laminating step and the exposure step. The peeling step is a step of peeling the temporary support from the laminate of the transfer film and the substrate with the metal layer. The temporary support can be peeled off by any known peeling method, for example, including the cover film peeling mechanism described in paragraphs

[0161] to

[0162] of JP-A No. 2010-072589.

[0229] [Process X3 (developing process)] The developing step is a step of developing the exposed photosensitive resin layer using a developer to form a pattern. By developing using the developer, the unexposed areas of the photosensitive resin layer are removed, and a resist pattern is formed in which the openings of the photomask are convex.

[0230] The developer is preferably an alkaline aqueous solution containing an alkali metal salt. The alkali metal salt contained in the developer is preferably a compound that dissolves in water and exhibits alkalinity. Examples of alkali metal salts include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, and potassium bicarbonate. The developer may contain a compound other than an alkali metal salt that exhibits alkalinity when dissolved in water, and examples of such compounds include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, and choline (2-hydroxyethyltrimethylammonium hydroxide). The content of water in the developer is preferably 50% by mass or more and less than 100% by mass, and more preferably 90% by mass or more and less than 100% by mass, based on the total mass of the developer. The content of the alkali metal salt in the developer is preferably from 0.01 to 20% by mass, more preferably from 0.1 to 10% by mass, based on the total mass of the developer.

[0231] The developing method may be, for example, a known developing method. Specific examples include puddle development, shower development, spin development, and dip development. The developing method is preferably the developing method described in paragraph

[0195] of WO 2015 / 093271.

[0232] After development, it is also preferable to carry out a rinsing treatment to remove any remaining developer from the metal layer-formed substrate before proceeding to the next step. Water or the like can be used for the rinsing treatment. After the development and / or rinsing treatment, a drying treatment may be carried out to remove excess liquid from the substrate with the metal layer.

[0233] [Step XA (post-exposure step) and Step XB (post-bake step)] The above-mentioned manufacturing method may further include a step of exposing the resist pattern obtained on the metal layer-formed substrate (hereinafter also referred to as "Step XA" or "Post-exposure step") and / or a step of heating (hereinafter also referred to as "Step XB" or "Post-bake step") between the developing step and the etching step described below. When the above manufacturing method includes both a post-exposure step and a post-bake step, it is preferable to carry out the post-bake step after carrying out the post-exposure step. The exposure dose in the post-exposure process is 100 to 5000 mJ / cm 2 is preferred, and 200 to 3000 mJ / cm 2 is more preferred. The post-baking temperature in the post-baking step is preferably 80 to 250°C, more preferably 90 to 160°C. The post-baking time in the post-baking step is preferably 1 to 180 minutes, more preferably 10 to 60 minutes.

[0234] [Process X4-1 (etching process)] The etching step is a step of etching the metal layer in the area where the resist pattern is not disposed. Specifically, in the etching step, the resist pattern obtained in the above steps is used as an etching resist to etch the metal layer. When the etching step is carried out, the metal layer is removed at the openings of the resist pattern, and the metal layer has the same pattern shape as the resist pattern.

[0235] The etching treatment may be a known method. Examples of the etching treatment include wet etching and dry etching (e.g., plasma etching). Examples of the etching treatment include the method described in paragraphs 0209 to 0210 of JP 2017-120435 A and the method described in paragraphs 0048 to 0054 of JP 2010-152155 A.

[0236] The etching process is preferably wet etching. In wet etching, an etching solution is typically used. The type of etching solution may be selected from acidic and alkaline etching solutions depending on the target to be etched. Examples of acidic etching solutions include aqueous solutions containing at least one acidic component selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid, acetic acid, hydrofluoric acid, oxalic acid, and phosphoric acid. Examples of acidic etching solutions include aqueous solutions containing the above-mentioned acidic component and at least one salt selected from the group consisting of ferric chloride, ammonium fluoride, and potassium permanganate. The acidic component may be a combination of multiple acidic components. Examples of alkaline etching solutions include aqueous solutions containing at least one alkaline component selected from the group consisting of sodium hydroxide, potassium hydroxide, ammonia, organic amines, and salts of organic amines (e.g., tetramethylammonium hydroxide). Examples of alkaline etching solutions include aqueous solutions containing the above-mentioned alkaline component and a salt (e.g., potassium permanganate). The alkaline component may be a combination of multiple alkaline components.

[0237] Furthermore, when the substrate used in step X1 is a metal substrate having a first surface and a second surface opposite to the first surface, the etching process forms through-holes that penetrate the metal substrate.

[0238] (Through hole) A plurality of through holes may be formed. The depth of the through holes corresponds to the thickness of the metal substrate. The through holes are usually defined by the inner surface of the metal substrate. The through holes may be defined by one or more surfaces. The surfaces defining the through holes observed in a cross-sectional view may be straight or curved. The number, shape, and arrangement of the through holes are determined, for example, according to the desired pattern. The through holes extending from the first surface to the second surface form an opening in the first surface and an opening in the second surface. The diameter of the opening formed in the first surface corresponds to the diameter of the through hole in the first surface described below, and the diameter of the opening formed in the second surface corresponds to the diameter of the through hole in the second surface described below. Examples of the shape of the through holes (specifically, the openings) observed in a plan view include a circle, an ellipse, and a rectangle. The shape of the through holes observed in a plan view is preferably a rectangle, and more preferably a square or rectangle. When the shape of the through-hole observed in a plan view is polygonal (for example, quadrangular), some or all of the multiple corners of the polygon may be rounded.

[0239] The average diameter of the through holes formed on the first surface of the metal substrate (hereinafter sometimes referred to as "average diameter D1 of through holes") is preferably 15 μm to 100 μm, more preferably 20 μm to 50 μm, and even more preferably 20 μm to 30 μm. The average diameter of the through holes formed on the second surface of the metal substrate (hereinafter sometimes referred to as "average diameter D2 of through holes") is preferably 25 μm or less, more preferably 20 μm or less, and even more preferably 10 μm or less. There is no lower limit for the average diameter D2 of through holes.

[0240] The average diameter of the through-holes is calculated as the arithmetic mean of the diameters of 10 through-holes measured based on an image obtained using a scanning electron microscope (SEM).

[0241] [Process X4-2 (plating process)] The plating step is a step of forming a plating layer by plating treatment on the metal layer in the area where the resist pattern is not arranged (the metal layer exposed on the surface by the development step). Examples of plating methods include electrolytic plating and electroless plating, with electrolytic plating being preferred from the standpoint of productivity. When the plating step is carried out, a plated layer having a pattern similar to that of the area where the resist pattern is not arranged (openings of the resist pattern) is obtained on the substrate with the metal layer.

[0242] Examples of components of plating solutions used in electroplating include water-soluble copper salts. Examples of water-soluble copper salts that can be used include those commonly used as components of plating solutions. The water-soluble copper salt is preferably at least one selected from the group consisting of inorganic copper salts, copper alkane sulfonates, copper alkanol sulfonates, and copper organic acid salts. Examples of inorganic copper salts include copper sulfate, copper oxide, copper chloride, and copper carbonate. Examples of copper alkane sulfonates include copper methane sulfonate and copper propane sulfonate. Examples of copper alkanol sulfonates include copper isethionate and copper propanol sulfonate. Examples of organic acid copper salts include copper acetate, copper citrate, and copper tartrate. Furthermore, instead of copper, salts of other corresponding metals may be used as components of the plating solution used in electrolytic plating.

[0243] The plating solution may contain sulfuric acid, which allows the pH and sulfate ion concentration of the plating solution to be adjusted.

[0244] The electroplating method and conditions are not limited. For example, by supplying the laminate after the development process to a plating tank containing a plating solution, a metal pattern can be formed on the metal layer in the area where the resin pattern is not disposed. In electroplating, the metal pattern can be formed by controlling, for example, the current density and the substrate transport speed.

[0245] The temperature of the plating solution used in electroplating is preferably 70° C. or less, more preferably 10 to 40° C. The current density in electroplating is 0.1 to 100 A / dm 2 It is preferable that the current is 0.5 to 20 A / dm 2 It is more preferable that the current density is set to 1 / 2 or 1 / 4. By increasing the current density, the productivity of the conductor pattern can be improved. By decreasing the current density, the uniformity of the thickness of the metal pattern can be improved.

[0246] Examples of the metal contained in the plating layer include known metals. Specific examples include metals such as copper, chromium, lead, nickel, gold, silver, tin, and zinc, as well as alloys of these metals. In particular, the plating layer preferably contains copper or an alloy thereof, since this provides a conductive pattern with better electrical conductivity.Furthermore, the plating layer preferably contains copper as a main component, since this provides a conductive pattern with better electrical conductivity.

[0247] The thickness of the plating layer is preferably 0.1 μm or more, more preferably 1 μm, and the upper limit is preferably 20 μm or less.

[0248] [Process X1-C (protective layer formation process)> The above manufacturing method preferably includes a protective layer forming step between the plating step and the resist stripping step described below. The protective layer laminating step is a step of forming a protective layer on the plating layer. The protective layer is preferably made of a material that is resistant to the stripping solution and / or etching solution used in the resist stripping and / or removal process. Examples of the material include metals such as nickel, chromium, tin, zinc, magnesium, gold, and silver, alloys thereof, and resins. Of these, nickel or chromium is preferred as the protective layer material.

[0249] Examples of methods for forming the protective layer include electroless plating and electroplating, with electroplating being preferred.

[0250] The thickness of the protective layer is not particularly limited to a lower limit, but is preferably 0.3 μm or more, more preferably 0.5 μm or more, and is not particularly limited to an upper limit, but is preferably 3.0 μm or less, more preferably 2.0 μm or less.

[0251] <Process X5 (resist removal process)> The resist stripping step is a step of removing the resist pattern remaining after the etching step of step X4-1, or a step of removing the resist pattern remaining after the plating step or protective layer forming step of step X4-2. The remaining resist pattern can be removed by, for example, chemical treatment, and is preferably removed using a stripping solution. The remaining resist pattern can be removed by a known method such as a spray method, a shower method, or a puddle method using a stripping solution.

[0252] Examples of the removal solution include a removal solution containing an inorganic or organic alkaline component and water, dimethyl sulfoxide, N-methylpyrrolidone, or a mixed solvent thereof. Examples of the inorganic alkaline component include sodium hydroxide and potassium hydroxide. Examples of the organic alkaline component include primary amine compounds, secondary amine compounds, tertiary amine compounds, and quaternary ammonium salt compounds.

[0253] The resist pattern may be removed by immersing the laminate including the resin pattern in a remover. The temperature of the remover is preferably 30°C to 80°C, more preferably 50°C to 80°C. The immersion time is preferably 1 minute to 30 minutes. In the immersion method, the remover may be stirred.

[0254] The resist pattern may be removed by, for example, a spray method, a shower method, or a puddle method using a remover.

[0255] When the resist stripping step is carried out, the resist pattern remaining on the substrate is removed, thereby exposing the metal layer that was present between the substrate and the resist pattern to the surface.

[0256] [Process X6 (removal process)] The removal step is a step of removing the metal layer exposed by the resist stripping step to obtain a metal layer pattern. In the removal process, the plating layer formed in the plating process is used as an etching resist, and the metal layer located in the non-pattern formation area (in other words, the area not protected by the plating layer) is etched.

[0257] The method for removing a portion of the metal layer is not particularly limited, but it is preferable to use a known etching solution. Examples of known etching solutions include ferric chloride solution, cupric chloride solution, ammonia alkali solution, sulfuric acid-hydrogen peroxide mixed solution, and phosphoric acid-hydrogen peroxide mixed solution. Furthermore, a method for removing a portion of the metal layer is preferably performed by dry etching.

[0258] When the removal step is carried out, the metal layer exposed on the surface of the substrate is removed, and the plating layer having the pattern shape remains.

[0259] <Other processes> The above manufacturing method may include any other steps (other steps) in addition to the steps described above, such as, but not limited to, an electroless plating step, a sputtering step, a seed layer application step, a seed layer etching step, etc. [Example]

[0260] The present invention will be described in more detail below with reference to the following examples. The materials, amounts used, ratios, treatment details, treatment 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 construed as being limited by the following examples. In the following, "parts" and "%" mean "parts by mass" and "% by mass", respectively, unless otherwise specified.

[0261] [Creating transfer film] The various compositions used to prepare the transfer films shown below will be described in detail below.

[0262] [Preparation of Thermoplastic Resin Layer Composition] A thermoplastic resin layer composition was prepared by mixing the various components shown below.

[0263] 42.85 parts by mass of propylene glycol monomethyl ether acetate solution of benzyl methacrylate / methacrylic acid / acrylic acid copolymer (solid concentration: 30.0% by mass, monomer ratio: 65% by mass / 28% by mass / 7% by mass, weight average molecular weight (Mw): 30,000, acid value: 153 mg KOH / g) NK Ester A-DCP (manufactured by Shin-Nakamura Chemical Co., Ltd.): 4.33 parts by mass 8UX-015A (manufactured by Taisei Fine Chemical Co., Ltd.): 2.31 parts by mass Aronix TO-2349 (manufactured by Toagosei Co., Ltd.): 0.77 parts by mass Megafac F-552 (fluorine-based surfactant, manufactured by DIC Corporation): 0.03 parts by mass Methyl ethyl ketone (manufactured by Sankyo Chemical Co., Ltd.): 39.80 parts by mass Propylene glycol monomethyl ether acetate (manufactured by Resonac Co., Ltd.): 9.51 parts by mass

[0264] [Preparation of Water-Soluble Resin Layer Composition] A water-soluble resin layer composition was prepared by mixing the various components shown below.

[0265] Kuraray Poval PVA-205 (Polyvinyl alcohol, manufactured by Kuraray Co., Ltd.): 3.22 parts by mass Polyvinylpyrrolidone K-30 (manufactured by Nippon Shokubai Co., Ltd.): 1.49 parts by mass Megafac F-444 (fluorine-based surfactant, manufactured by DIC Corporation): 0.0015 parts by mass Ion-exchanged water: 38.12 parts by mass Methanol (manufactured by Mitsubishi Gas Chemical Company, Inc.): 57.17 parts by mass

[0266] [Preparation of Photosensitive Resin Composition 1] Photosensitive resin composition 1 was prepared by mixing the following components.

[0267] Propylene glycol monomethyl ether acetate solution of styrene / methacrylic acid / methyl methacrylate copolymer (solid concentration: 30.0% by mass, monomer ratio: 60% by mass / 20% by mass / 20% by mass, Mw: 50,000. Corresponding to alkali-soluble resin): 23.4 parts by mass BPE-100 (ethoxylated bisphenol A dimethacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd., which corresponds to a polymerizable compound): 4.1 parts by mass B-CIM (2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, manufactured by Kurogane Chemical Co., Ltd., a photopolymerization initiator): 0.25 parts by mass SB-PI 701 (4,4'-bis(diethylamino)benzophenone, obtained from Sanyo Trading Co., Ltd., which corresponds to a sensitizer): 0.04 parts by mass TDP-G (phenothiazine, manufactured by Kawaguchi Chemical Industry Co., Ltd.): 0.0175 parts by mass 1-Phenyl-3-pyrazolidone (Fujifilm Wako Pure Chemical Industries, Ltd.): 0.0011 parts by mass Leuco Crystal Violet (Tokyo Chemical Industry Co., Ltd.): 0.051 parts by mass N-phenylcarbamoylmethyl-N-carboxymethylaniline (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.): 0.02 parts by mass CBT-1 (benzotriazole-based rust inhibitor, manufactured by Johoku Chemical Industry Co., Ltd.): 0.75 parts by mass Methyl ethyl ketone (manufactured by Sankyo Chemical Co., Ltd.): 40.4 parts by mass Propylene glycol monomethyl ether acetate (manufactured by Resonac Co., Ltd.): 26.7 parts by mass Surfactant listed in Table 2 (molecular weight 18,000): 0.05 parts by mass

[0268] [Preparation of Photosensitive Resin Compositions 2 to 9, 10 to 12, R1, and R2] Photosensitive resin compositions 2 to 9, R1, and R2 were prepared in the same manner as in the preparation of photosensitive resin composition 1, except that the surfactants were changed to the compositions shown in Tables 2 and 3. In addition, photosensitive resin compositions 10 to 12 were prepared in the same manner as photosensitive resin composition 1, except that the surfactant was changed to the composition shown in Table 5.

[0269] Table 1 below shows the structures of the surfactants shown in Tables 2 and 3. The structures of the surfactants shown in Table 5 are shown in Table 4 below.

[0270] [Table 1]

[0271] The repeating units (A-1 to A-2, B-1 to B-12) shown in Table 1 and Table 4 below are shown below.

[0272] [ka]

[0273] [ka]

[0274] [Calculation of ΔHSP1 and ΔHSP2] Using the commercially available Windows software "HSPiP (developed by www.hansen-solubility.com)," calculations were performed to determine the three vectors of the Hansen solubility parameters of the alkali-soluble resins used in photosensitive resin compositions 1 to 7, R1, and R2 (the dispersion term of the Hansen solubility parameter of the alkali-soluble resin: δDb, the hydrogen bond term of the Hansen solubility parameter of the alkali-soluble resin: δHb, and the polar term of the Hansen solubility parameter of the alkali-soluble resin: δP). Table 2 shows the respective values. In addition, using the same method, three vectors of the Hansen solubility parameters of the alkali-soluble resins used in photosensitive resin compositions 10 to 12 (dispersion term of the Hansen solubility parameter of the alkali-soluble resin: δDb, hydrogen bond term of the Hansen solubility parameter of the alkali-soluble resin: δHb, polar term of the Hansen solubility parameter of the alkali-soluble resin: δP) were determined. Table 5 shows the respective values.

[0275] In addition, using a similar method, three vectors of the Hansen solubility parameters of the polymerizable compounds used in photosensitive resin compositions 1 to 7, R1, and R2 (dispersion term of the Hansen solubility parameter of the polymerizable compound: δDm, hydrogen bond term of the Hansen solubility parameter of the polymerizable compound: δHm, polar term of the Hansen solubility parameter of the polymerizable compound: δPm) were determined. Table 2 shows the respective values. In addition, using a similar method, three vectors of the Hansen solubility parameters of the polymerizable compounds used in photosensitive resin compositions 10 to 12 (dispersion term of the Hansen solubility parameter of the polymerizable compound: δDm, hydrogen bond term of the Hansen solubility parameter of the polymerizable compound: δHm, polar term of the Hansen solubility parameter of the polymerizable compound: δPm) were determined. Table 5 shows the respective values.

[0276] Using the same method, three vectors of the Hansen solubility parameters of the surfactants used in photosensitive resin compositions 1 to 7, R1, and R2 (dispersion term of the Hansen solubility parameter of the surfactant: ΔDS, hydrogen bond term of the Hansen solubility parameter of the surfactant: ΔHS, polar term of the Hansen solubility parameter of the surfactant: ΔPS) were also determined. Table 2 shows the respective values. In addition, using a similar method, three vectors of the Hansen solubility parameters of the surfactants used in photosensitive resin compositions 10 to 12 (dispersion term of the Hansen solubility parameter of the surfactant: ΔDS, hydrogen bond term of the Hansen solubility parameter of the surfactant: ΔHS, polar term of the Hansen solubility parameter of the surfactant: ΔPS) were determined. Table 5 shows the respective values.

[0277] Using the same method, three vectors of the Hansen solubility parameters in the non-polar portion of the surfactants used in photosensitive resin compositions 1 to 7, R1, and R2 were also calculated (the dispersion term of the Hansen solubility parameter in the non-polar portion of the surfactant: ΔDSs, the hydrogen bond term of the Hansen solubility parameter in the non-polar portion of the surfactant: ΔHSs, and the polar term of the Hansen solubility parameter in the non-polar portion of the surfactant: ΔPSs). Table 2 shows the respective values. In addition, using a similar method, three vectors of the Hansen solubility parameters in the non-polar portion of the surfactants used in photosensitive resin compositions 10 to 12 (dispersion term of the Hansen solubility parameter in the non-polar portion of the surfactant: ΔDSs, hydrogen bond term of the Hansen solubility parameter in the non-polar portion of the surfactant: ΔHSs, polar term of the Hansen solubility parameter in the non-polar portion of the surfactant: ΔPSs) were determined. Table 5 shows the respective values. In surfactants 1 to 14, the repeating unit that does not contain a silicon atom or a fluorine atom (the second repeating unit, which corresponds to repeating units 2 and 3 in Table 1) corresponds to the non-polar moiety. For surfactants containing only one type of second repeating unit, the dispersion term, hydrogen bond term, and polar term of the Hansen solubility parameter for the second repeating unit are designated as δDSs, δHSs, and δPSs, respectively. On the other hand, for surfactants containing two or more types of second repeating units (such as surfactants 7 and 10), the dispersion term, hydrogen bond term, and polar term of the Hansen solubility parameter for each repeating unit corresponding to the second repeating unit are calculated, and the weighted average values ​​for each repeating unit are taken, which are designated as δDSs, δHSs, and δPSs. The respective values ​​are shown in Tables 2 and 5.

[0278] In addition, using the various values ​​calculated in the upper part, based on the above formulas (F1A) to (F1C), the weighted average value of the dispersion term of each Hansen solubility parameter of the alkali-soluble resin and polymerizable compound (δDM), the weighted average value of the hydrogen bond term of each Hansen solubility parameter of the alkali-soluble resin and polymerizable compound (δHM), and the weighted average value of the polarity term of each Hansen solubility parameter of the alkali-soluble resin and polymerizable compound (δPM) were calculated, and ΔHSP1 was calculated based on the above formula (F1). The results are shown in Tables 2 and 5. The values ​​calculated from the formulas (F3A) to (F3C) in the upper part were calculated in the same manner as above. The values ​​calculated from the formulas (F3A) to (F3C) are the same as the values ​​calculated from the formulas (F1A) to (F1C), respectively.

[0279] In addition, using the various values ​​calculated in the upper part, based on the above formulas (F2A) to (F2C), the weighted average value of the dispersion term of each Hansen solubility parameter of the alkali-soluble resin and polymerizable compound (δDM), the weighted average value of the hydrogen bond term of each Hansen solubility parameter of the alkali-soluble resin and polymerizable compound (δHM), and the weighted average value of the polarity term of each Hansen solubility parameter of the alkali-soluble resin and polymerizable compound (δPM) were calculated, and ΔHSP2 was calculated based on the above formula (F2). The results are shown in Tables 2 and 5. The values ​​calculated from the formulas (F4A) to (F4C) in the upper part were calculated in the same manner as above. The values ​​calculated from the formulas (F4A) to (F4C) are the same as the values ​​calculated from the formulas (F2A) to (F2C), respectively.

[0280] [Preparation and evaluation of transfer films 1 to 7] <Preparation of transfer film 1> The thermoplastic resin layer composition was applied onto a temporary support (polyethylene terephthalate film, thickness: 16 μm) using a slit nozzle so that the layer thickness after drying would be 3.0 μm. The formed coating of the thermoplastic resin composition was dried at 80° C. for 40 seconds to form a thermoplastic resin layer. The water-soluble resin layer composition was applied to the surface of the formed thermoplastic resin layer using a slit nozzle so that the layer thickness after drying would be 1.0 μm. The coating of the water-soluble resin layer composition was dried at 90° C. for 180 seconds to form a water-soluble resin layer. The above-mentioned photosensitive resin composition 1 was applied to the surface of the formed water-soluble resin layer using a slit nozzle so that the layer thickness after drying would be 3.0 μm, and the layer was dried at 100°C for 2 minutes to form a photosensitive resin layer. A protective film (polypropylene film, thickness: 12 μm) was attached as a protective layer onto the photosensitive resin layer to prepare transfer film 1.

[0281] <Adhesion evaluation> (Preparation of transfer film for adhesion evaluation) The prepared transfer film 1 was wrapped and sealed in a metal-laminated polyethylene sheet, and subjected to a heat treatment (accelerated test) in a dry oven at 40°C for 80 hours.

[0282] (Adhesion evaluation) The protective films were removed from the heat-treated and unheated transfer films, and the transfer films with the protective films removed were then bonded to a glass substrate on which copper had been sputtered to a thickness of 100 nm under lamination conditions of a roll temperature of 100°C, a linear pressure of 0.8 MPa, and a linear speed of 3.0 m / min. The temporary support was then peeled off from the laminated transfer film, and a glass mask bearing an isolated wiring pattern with line widths of 1.5 to 5 μm in 0.5 μm or 0.25 μm increments (for evaluations of "B" or higher, the mask was changed in 0.25 μm increments) was attached to the temporary support, and exposure was performed using an exposure machine (M-1S, manufactured by Mikasa Co., Ltd.) The exposure dose was adjusted so that the resin pattern width after development would be 1.8 to 2.2 μm for a 2 μm design pattern. The above pattern creation was performed on 10 samples each for heat-treated and untreated transfer films, and a comparison was made to see if the remaining minimum width pattern had changed. If the minimum width pattern had changed, this suggests that the heat treatment had changed the state of the surfactant (for example, by causing it to weep and aggregate), changing the adhesion between the transfer film and the substrate. Heat treatment has the effect of accelerating the mass transfer of surfactants within the film, and if the minimum width pattern had changed due to heat treatment, similar performance issues would occur over long periods of storage.

[0283] The evaluation was carried out according to the following criteria: D or higher is preferable for a transfer film. A: The minimum width pattern remains unchanged before and after heating. B: The minimum width pattern changes by less than 0.5 μm before and after heating C: The minimum width pattern changes by 0.5 μm or more and less than 1 μm before and after heating D: The minimum width pattern changes by 1.0 μm or more and less than 1.5 μm before and after heating E: The minimum width pattern changes by 1.5 μm or more before and after heating

[0284] <Preparation and evaluation of transfer films 2 to 7, R1, and R2> Transfer films 2 to 7, R1, and R2 were prepared and their adhesion evaluated in the same manner as transfer film 1, except that photosensitive resin composition 1 was replaced with photosensitive resin compositions 2 to 7, R1, and R2 according to the compositions in Table 2.

[0285] Table 2 is shown below. In Tables 2 and 3, "presence or absence of aromatic ring structure" indicates whether the surfactant has an aromatic ring structure. In addition, the "presence or absence of an interactive group" in Tables 2 and 3 indicates whether the surfactant has an electron-accepting group or an electron-donating group that can interact with either the electron-accepting group or the electron-donating group possessed by at least one of the alkali-soluble resin and the polymerizable compound. The alkali-soluble resin used in the examples has a carboxyl group (electron-accepting group). The dialkylamino group in Surfactant 7 corresponds to the electron-donating group.

[0286] [Table 2]

[0287] From the results in Table 2, it is clear that the photosensitive resin compositions of the examples can form photosensitive resin layers that are less susceptible to changes over time in pattern forming performance after being transferred to a transfer target. Furthermore, a comparison of Examples 1, 2, and 4 confirmed that when the weight-average molecular weight of the surfactant is 10,000 or more, the pattern forming performance is less likely to change over time.

[0288] On the other hand, it is clear that the photosensitive resin compositions of the comparative examples do not provide the desired effects.

[0289] [Preparation and evaluation of transfer films 8 and 9] Transfer films 8 to 9 were produced and their adhesion evaluated in the same manner as for transfer film 1, except that photosensitive resin composition 1 was changed to photosensitive resin compositions 8 to 9 according to the formulations in Table 3.

[0290] Table 3 is shown below. In Table 3, "presence or absence of aromatic ring structure" indicates whether the surfactant has an aromatic ring structure, and "presence or absence of interactive group" indicates whether the surfactant has an electron-accepting group or an electron-donating group that can interact with the other of the electron-accepting group or the electron-donating group contained in at least one of the alkali-soluble resin and the polymerizable compound.

[0291] [Table 3]

[0292] From the results in Table 3, it is clear that the photosensitive resin compositions of the examples can form photosensitive resin layers that are less susceptible to changes over time in pattern forming performance after being transferred to a transfer target.

[0293] [Preparation and Evaluation of Transfer Films 10 to 12] Transfer films 10 to 12 were produced and their adhesion evaluated in the same manner as for transfer film 1, except that the surfactants shown in Table 4 were used and photosensitive resin compositions 10 to 12 were used instead of photosensitive resin composition 1 according to the compositions in Table 5. The specific structures of the repeating units of the surfactants shown in Table 4 are as described above.

[0294] [Table 4]

[0295] [Table 5]

[0296] From the results in Table 5, it is considered that the following phenomenon occurred: In Example 10, although ΔHSP2 was larger at 7.8 compared to Example 1, it is presumed that the adhesion was better than that of Example 1 because the cyano group contained in Surfactant 10 is an electron-donating group. In Example 11, ΔHSP2 is larger at 5.6 compared to Examples 1 and 5, but ΔHSP1 is smaller at 4.8. In addition, since the amide group contained in surfactant 11 is an electron-donating group, it is estimated that the adhesion was lower than that of Examples 1 and 7. In Example 12, ΔHSP2 was equivalent to that of Example 1, and therefore it is presumed that the adhesion was at the same level.

[0297] [Preparation and evaluation of transfer films 13 to 18] [Preparation of Thermoplastic Resin Layer Composition] Thermoplastic resin layer compositions A1 to A3 were prepared by mixing the various components shown below. The only difference between thermoplastic resin layer compositions A1 to A3 is the type of surfactant contained in the thermoplastic resin layer composition. The surfactant numbers shown in Table 6 correspond to the surfactant numbers shown in Table 1 or Table 4. Thermoplastic resin layer compositions A1 to A3 correspond to the thermoplastic resin layer composition for forming the thermoplastic resin layer contained in the previously described transfer film 1, except that Megafac F-552 (a fluorine-based surfactant, manufactured by DIC Corporation) is replaced with the surfactant shown in Table 6.

[0298] 42.85 parts by mass of propylene glycol monomethyl ether acetate solution of benzyl methacrylate / methacrylic acid / acrylic acid copolymer (solid concentration: 30.0% by mass, monomer ratio: 65% by mass / 28% by mass / 7% by mass, weight average molecular weight (Mw): 30,000, acid value: 153 mg KOH / g) NK Ester A-DCP (manufactured by Shin-Nakamura Chemical Co., Ltd.): 4.33 parts by mass 8UX-015A (manufactured by Taisei Fine Chemical Co., Ltd.): 2.31 parts by mass Aronix TO-2349 (manufactured by Toagosei Co., Ltd.): 0.77 parts by mass Methyl ethyl ketone (manufactured by Sankyo Chemical Co., Ltd.): 39.80 parts by mass Propylene glycol monomethyl ether acetate (manufactured by Resonac Co., Ltd.): 9.51 parts by mass Surfactant listed in Table 6: 0.03 parts by mass

[0299] [Preparation of Water-Soluble Resin Layer Composition] Water-soluble resin layer compositions B1 and B2 were prepared by mixing the various components shown below. The only difference between water-soluble resin layer compositions B1 and B2 is the type of surfactant contained in the water-soluble resin layer composition. Water-soluble resin layer compositions B1 and B2 correspond to the water-soluble resin layer composition for forming the water-soluble resin layer contained in the previously described transfer film 1, except that Megafac F-444 (a fluorine-based surfactant, manufactured by DIC Corporation) was replaced with the surfactants shown in Table 6.

[0300] Kuraray Poval PVA-205 (Polyvinyl alcohol, manufactured by Kuraray Co., Ltd.): 3.22 parts by mass Polyvinylpyrrolidone K-30 (manufactured by Nippon Shokubai Co., Ltd.): 1.49 parts by mass Ion-exchanged water: 38.12 parts by mass Methanol (manufactured by Mitsubishi Gas Chemical Company, Inc.): 57.17 parts by mass Surfactant listed in Table 6: 0.0015 parts by mass

[0301] Among the surfactants listed in Table 6, b1 and b2 represent the following: b1: BYK-345 (BYK Japan Co., Ltd.) b2: MEGAFACE EFS-801 (DIC Corporation)

[0302] Transfer films 13 to 19 were produced using the thermoplastic resin layer compositions A1 to A3, water-soluble resin layer compositions B1 and B2, and photosensitive resin compositions 1, 9, and 11 prepared in the upper section to have the layer configurations shown in Table 6. The production method was the same as for transfer film 1. Each of the produced transfer films was evaluated for adhesion in the same manner as for transfer film 1. The results are also shown in Table 6.

[0303] [Table 6]

[0304] The results in Table 6 show that changing the surfactants in the thermoplastic resin layer and the water-soluble resin layer can change the adhesion of the photosensitive resin layer. While the cause of this is not fully understood, it is presumed that when the photosensitive resin layer is coated on top of the thermoplastic resin layer and the water-soluble resin layer, the surfactants in the thermoplastic resin layer and the water-soluble resin layer are extracted and migrate to the photosensitive resin layer, thereby changing the adhesion of the photosensitive resin layer. Based on these results, it is believed that depending on the surfactant used in the thermoplastic resin layer and the water-soluble resin layer, adhesion can be further improved. For example, by using the surfactant used in the photosensitive resin layer as the surfactant for the thermoplastic resin layer and the water-soluble resin layer, even if the surfactants in the thermoplastic resin layer and the water-soluble resin layer migrate to the photosensitive resin layer during coating and formation, the high adhesion of the photosensitive resin layer is less likely to be reduced, and the adhesion of the photosensitive resin layer can be further improved. [Explanation of symbols]

[0305] 1 Temporary support 3 Thermoplastic resin layer 5. Middle class 7 Photosensitive resin layer 9 Protective film 10 Transfer film

Claims

1. A photosensitive resin composition comprising an alkali-soluble resin, a polymerizable compound, a photopolymerization initiator, and a surfactant, The value of ΔHSP1 calculated by the following formula (F1) is 6.0 MPa ０．５ A photosensitive resin composition comprising: Formula (F1): ΔHSP1=(4(δDM-δDS) ２ + (δHM-δHS) ２ + (δPM-δPS) ２ ) ０．５ In formula (F1), δDM represents a weighted average value of the dispersion term of the Hansen solubility parameter of the alkali-soluble resin and the dispersion term of the Hansen solubility parameter of the polymerizable compound, calculated by the following formula (F1A). δHM represents a weighted average value of the hydrogen bond term of the Hansen solubility parameter of the alkali-soluble resin and the hydrogen bond term of the Hansen solubility parameter of the polymerizable compound, calculated by the following formula (F1B). δPM represents a weighted average value of the polar term of the Hansen solubility parameter of the alkali-soluble resin and the polar term of the Hansen solubility parameter of the polymerizable compound, calculated by the following formula (F1C). δDS represents the dispersion term of the Hansen solubility parameter of the surfactant. δHS represents the hydrogen bond term of the Hansen solubility parameter of the surfactant. δPS represents the polar term of the Hansen solubility parameter of the surfactant. Formula (F1A): δDM=δDb×Wb / (Wb+Wm)+δDm×Wm / (Wb+Wm) Formula (F1B): δHM=δHb×Wb / (Wb+Wm)+δHm×Wm / (Wb+Wm) Formula (F1C): δPM=δPb×Wb / (Wb+Wm)+δPm×Wm / (Wb+Wm) In formula (F1A), δDb represents the variance term of the Hansen solubility parameter of the alkali-soluble resin, and δDm represents the variance term of the Hansen solubility parameter of the polymerizable compound. In formula (F1B), δHb represents the hydrogen bond term of the Hansen solubility parameter of the alkali-soluble resin, and δHm represents the hydrogen bond term of the Hansen solubility parameter of the polymerizable compound. In formula (F1C), δPb represents the polar term of the Hansen solubility parameter of the alkali-soluble resin, and δPm represents the polar term of the Hansen solubility parameter of the polymerizable compound. In formulae (F1A) to (F1C), Wb represents a mass fraction of the alkali-soluble resin with respect to the total solid content in the photosensitive resin composition, and Wm represents a mass fraction of the polymerizable compound with respect to the total solid content in the photosensitive resin composition.

2. A photosensitive resin composition comprising an alkali-soluble resin, a polymerizable compound, a photopolymerization initiator, and a surfactant, the surfactant is a resin having a first repeating unit containing an atom selected from the group consisting of a silicon atom and a fluorine atom, and a second repeating unit containing neither a silicon atom nor a fluorine atom, The value of ΔHSP2 calculated by the following formula (F2) is 4.0 MPa ０．５ A photosensitive resin composition as set forth below, provided that when at least one selected from the group consisting of the alkali-soluble resin and the polymerizable compound has one of an electron-accepting group and an electron-donating group, the surfactant does not have the other of the electron-accepting group and the electron-donating group. Formula (F2): ΔHSP2=(4(δDM-δDSs) ２ +(δHM-δHSs) ２ +(δPM-δPSs) ２ ) ０．５ In formula (F2), δDM represents a weighted average value of the variance term of the Hansen solubility parameter of the alkali-soluble resin and the variance term of the Hansen solubility parameter of the polymerizable compound, calculated by the following formula (F2A). δHM represents a weighted average value of the hydrogen bond term of the Hansen solubility parameter of the alkali-soluble resin and the hydrogen bond term of the Hansen solubility parameter of the polymerizable compound, calculated by the following formula (F2B). δPM represents a weighted average value of the polar term of the Hansen solubility parameter of the alkali-soluble resin and the polar term of the Hansen solubility parameter of the polymerizable compound, calculated by the following formula (F2C). δDSs is the dispersion term of the Hansen solubility parameter in the non-polar portion of the surfactant, and when the surfactant has only one type of the second repeat unit, it represents the dispersion term of the Hansen solubility parameter of the second repeat unit, and when the surfactant has two or more types of the second repeat unit, it represents the weighted average value of the dispersion term of each of the Hansen solubility parameters of the two or more second repeat units. δHSs is the hydrogen bond term of the Hansen solubility parameter in the non-polar portion of the surfactant, and when the surfactant has only one type of the second repeat unit, it represents the hydrogen bond term of the Hansen solubility parameter of the second repeat unit, and when the surfactant has two or more types of the second repeat unit, it represents the weighted average value of the hydrogen bond term of each of the Hansen solubility parameters of the two or more second repeat units. δPSs is the polar term of the Hansen solubility parameter at the non-polar portion of the surfactant. When the surfactant has only one type of the second repeat unit, it represents the polar term of the Hansen solubility parameter of the second repeat unit. When the surfactant has two or more types of the second repeat unit, it represents the weighted average value of the polar terms of the Hansen solubility parameters of each of the two or more types of the second repeat units. Formula (F2A): δDM=δDb×Wb / (Wb+Wm)+δDm×Wm / (Wb+Wm) Formula (F2B): δHM=δHb×Wb / (Wb+Wm)+δHm×Wm / (Wb+Wm) Formula (F2C): δPM=δPb×Wb / (Wb+Wm)+δPm×Wm / (Wb+Wm) In formula (F2A), δDb represents the variance term of the Hansen solubility parameter of the alkali-soluble resin, and δDm represents the variance term of the Hansen solubility parameter of the polymerizable compound. In formula (F2B), δHb represents the hydrogen bond term of the Hansen solubility parameter of the alkali-soluble resin, and δHm represents the hydrogen bond term of the Hansen solubility parameter of the polymerizable compound. In formula (F2C), δPb represents the polar term of the Hansen solubility parameter of the alkali-soluble resin, and δPm represents the polar term of the Hansen solubility parameter of the polymerizable compound. In formulae (F2A) to (F2C), Wb represents a mass fraction of the alkali-soluble resin with respect to the total solid content in the photosensitive resin composition, and Wm represents a mass fraction of the polymerizable compound with respect to the total solid content in the photosensitive resin composition.

3. A photosensitive resin composition comprising an alkali-soluble resin, a polymerizable compound, a photopolymerization initiator, and a surfactant, the at least one compound selected from the group consisting of the alkali-soluble resin and the polymerizable compound, and the surfactant, each of which has an aromatic ring structure in its molecule.

4. A photosensitive resin composition comprising an alkali-soluble resin, a polymerizable compound, a photopolymerization initiator, and a surfactant, at least one selected from the group consisting of the alkali-soluble resin and the polymerizable compound has one of an electron accepting group and an electron donating group, and the surfactant has the other of the electron accepting group and the electron donating group.

5. The photosensitive resin composition according to any one of claims 1 to 4, wherein the surfactant does not have a fluorine atom.

6. The photosensitive resin composition according to any one of claims 1 to 4, wherein the surfactant is a resin having at least one repeating unit selected from the group consisting of a repeating unit represented by the following formula (A-1) and a repeating unit represented by the following formula (A-2): 【Chemistry 1】 In formula (A-1), 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 l represents an integer of 5 to 100. In formula (A-2), R ４ represents a hydrogen atom or a methyl group. ５ represents an alkylene group having 1 to 10 carbon atoms. L represents a trimethylsilyl group or a tris(trimethylsiloxy)silyl group.

7. The photosensitive resin composition according to any one of claims 1 to 4, wherein the polymerizable compound comprises a compound represented by the following formula (P1): 【Chemistry 2】 In the formula, R １ and R ２ Each of A and B independently represents a hydrogen atom or a methyl group. ２ H ４ B represents -C ３ H ６ - represents n １ and n ３ Each independently represents an integer from 1 to 39, and １ +n ３ represents an integer from 2 to 40. ２ and n ４ Each independently represents an integer of 0 to 29, and ２ +n ４ represents an integer of 0 to 30. The arrangement of the repeating units -(A-O)- and -(B-O)- may be random or block. When the arrangement is block, either -(A-O)- or -(B-O)- may be on the bisphenyl group side.

8. The photosensitive resin composition according to any one of claims 1 to 4, wherein the alkali-soluble resin comprises a resin having one or more repeating units selected from the group consisting of a repeating unit represented by the following formula (R1) and a repeating unit represented by the following formula (R2): 【Chemistry 3】 In formulae (R1) and (R2), R1 represents a hydrogen atom or a methyl group, and L represents a single bond or a divalent linking group.

9. The photosensitive resin composition according to any one of claims 1 to 4, wherein the photopolymerization initiator comprises at least one selected from the group consisting of an acridine-based photopolymerization initiator, an oxime ester-based photopolymerization initiator, a biimidazole-based photopolymerization initiator, an alkylphenone-based photopolymerization initiator, an acetophenone-based photopolymerization initiator, and an acylphosphine oxide-based photopolymerization initiator.

10. A transfer film comprising, in this order, a temporary support, a photosensitive resin layer formed from the photosensitive resin composition according to any one of claims 1 to 4, and a protective layer.

11. The transfer film according to claim 10, which is used in a process for forming a circuit on a semiconductor substrate by plating.

12. The transfer film according to claim 10, which is used in a process of forming a circuit by etching on a metal substrate or a resin substrate with a metal layer.

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