Photosensitive resin composition and transfer film

Abstract

The invention provides a photosensitive resin composition capable of forming a photosensitive resin layer, wherein the pattern forming performance of the photosensitive resin layer does not easily change with time after the photosensitive resin composition is transferred to an object to be transferred. Also provided are a transfer film and a method for producing a laminate having a conductor pattern. A photosensitive resin composition containing an alkali-soluble resin, a polymerizable compound, a photopolymerization initiator, and a surfactant, the photosensitive resin composition being characterized in that the value of [Delta] HSP1 calculated by formula (F1) is 6.0 MPa 0.5 or less. Formula (F1): [delta] HSP1 = (4 ([delta] DM-[delta] DS) 2 + ([delta] HM-[delta] HS) 2 + ([delta] PM-[delta] PS) 2) 0.5

Description

Technical Field

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

[0002] Since the number of steps for obtaining a predetermined pattern is small, a pattern forming method is widely used in which a photosensitive resin layer is disposed on an arbitrary substrate using a transfer film and the photosensitive resin is exposed and developed via a mask.

[0003] The photosensitive resin layer of the transfer film is typically formed by coating using a photosensitive resin composition, and often contains a surfactant for improving the surface properties (e.g., reducing the unevenness of the film and suppressing composition fluctuations) during coating. For example, Patent Document 1 discloses a photosensitive film comprising: a support film; a positive photosensitive resin layer containing a fluorine-based surfactant; and a protective layer.

[0004] Patent Document 1: Japanese Patent Application Publication No. 2012-226148

[0005] The present inventors have conducted various studies on transfer films having a negative photosensitive resin layer containing a fluorine-based surfactant, with reference to the transfer film having a positive photosensitive resin layer containing a fluorine-based surfactant described in Patent Document 1. The results have clarified that when pattern formation on a transfer object is performed using a transfer film that has been stored for a long period of time, there is a possibility that the pattern forming performance is reduced due to a decrease in adhesion to the transfer object, etc. Summary of the invention

[0006] Therefore, an object of the present invention is to provide a photosensitive resin composition capable of forming a photosensitive resin layer whose pattern forming performance after transfer to a transfer target is unlikely to change over time.

[0007] Furthermore, another object of the present invention is to provide a transfer film.

[0008] The present inventors have conducted intensive studies to solve the above-mentioned problems, and have found that the above-mentioned problems can be solved by the following configuration.

[0009] [1] A photosensitive resin composition comprising an alkali-soluble resin, a polymerizable compound, a photopolymerization initiator and a surfactant,

[0010] The value of ΔHSP1 calculated by the formula (F1) described later of the photosensitive resin composition is δ.0 MPa 0.5 the following.

[0011] [2] A photosensitive resin composition comprising an alkali-soluble resin, a polymerizable compound, a photopolymerization initiator and a surfactant,

[0012] The surfactant is a resin having a first repeating unit containing an atom selected from silicon atoms and fluorine atoms and a second repeating unit containing neither silicon atoms nor fluorine atoms,

[0013] The value of ΔHSP2 of the photosensitive resin composition calculated by the formula (F2) described later was 4.0 MPa. 0.5 the following.

[0014] When at least one selected from 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.

[0015] [3] A photosensitive resin composition comprising an alkali-soluble resin, a polymerizable compound, a photopolymerization initiator and a surfactant,

[0016] At least one selected from the alkali-soluble resin and the polymerizable compound and the surfactant each have an aromatic ring structure in the molecule.

[0017] [4] A photosensitive resin composition comprising an alkali-soluble resin, a polymerizable compound, a photopolymerization initiator and a surfactant,

[0018] At least one selected from 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.

[0019] [5] The photosensitive resin composition according to any one of [1] to [4], wherein

[0020] The above-mentioned surfactant does not have a fluorine atom.

[0021] v6) The photosensitive resin composition according to any one of [1] to [5], wherein

[0022] The surfactant is a resin having at least one repeating unit selected from the repeating unit represented by the formula (A-1) described below and the repeating unit represented by the formula (A-2) described below.

[0023] [7] The photosensitive resin composition according to any one of [1] to [6], wherein

[0024] The polymerizable compound includes a compound represented by formula (P1) described below.

[0025] [8] The photosensitive resin composition according to any one of [1] to [7], wherein

[0026] The alkali-soluble resin includes a resin having one or more selected from a repeating unit represented by the formula (R1) described below and a repeating unit represented by the formula (R2) described below.

[0027] [9] The photosensitive resin composition according to any one of [1] to [8], wherein

[0028] The photopolymerization initiator includes at least one selected from acridine-based photopolymerization initiator, oxime ester-based photopolymerization initiator, biimidazole-based photopolymerization initiator, alkylphenone-based photopolymerization initiator, acetophenone-based photopolymerization initiator, and acylphosphine oxide-based photopolymerization initiator.

[0029]

[10] A transfer film comprising: 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 in this order.

[0030]

[11] The transfer film according to

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

[0031]

[12] The transfer film according to

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

[0032] Effects of the Invention

[0033] According to the present invention, it is possible to provide a photosensitive resin composition capable of forming a photosensitive resin layer whose pattern forming performance after transfer to a transfer target is unlikely to change over time.

[0034] Furthermore, according to the present invention, a transfer film can also be provided. BRIEF DESCRIPTION OF THE DRAWINGS

[0035] Figure 1 It is a schematic diagram for explaining the form of the transfer film. DETAILED DESCRIPTION

[0036] Hereinafter, the present invention will be described in detail.

[0037] In the present specification, a numerical range expressed using "to" means a range including the numerical values ​​described before and after "to" as the lower limit and the upper limit.

[0038] In this specification, in the numerical range recorded in stages, the upper limit or lower limit recorded in a certain numerical range can be replaced by the upper limit or lower limit of other numerical ranges recorded in stages. In addition, in the numerical range recorded in this specification, the upper limit or lower limit recorded in a certain numerical range can also be replaced by the value shown in the embodiment.

[0039] In the present 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 can be achieved.

[0040] In this specification, unless otherwise specified, "transparent" means that the average transmittance of visible light with a wavelength of 400 to 700 nm is 80% or more, preferably 90% or more.

[0041] 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.

[0042] In this specification, unless otherwise specified, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are values ​​converted using polystyrene of the standard substance measured by a gel permeation chromatography (GPC) analyzer using TSKgel GMHxL, TSKgel G4000HxL or TSKgel G2000HxL (all product names manufactured by TOSOH Corporation) as a column, THF (tetrahydrofuran) as an eluent, a differential refractometer as a detector, and polystyrene as a standard substance.

[0043] In addition, in this specification, unless otherwise specified, the molecular weight of a compound having a molecular weight distribution is a weight average molecular weight (Mw).

[0044] In this specification, unless otherwise specified, the content of a metal element is a value measured using an inductively coupled plasma (ICP: Inductively Coupled Plasma) spectrometer.

[0045] In this specification, “(meth)acrylic acid” is a concept including both acrylic acid and methacrylic acid, “(meth)acryloyloxy” is a concept including both acryloxy and methacryloyloxy, “(meth)acrylamide” is a concept including both acrylamide and methacrylamide, “(meth)acrylate” is a concept including both acrylate and methacrylate, and (meth)acrylonitrile is a concept including both acrylonitrile and methacrylonitrile.

[0046] In the present specification, "alkali-soluble" means that the solubility in 100 g of a 1 mass % sodium carbonate aqueous 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 solubility condition.

[0047] In this specification, "water-soluble" means that the solubility in 100 g of water with a pH of 7.0 at 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 condition.

[0048] In this specification, the "solid content" of the composition refers to the components that form the composition layer (e.g., photosensitive resin layer) formed using the composition, and when the composition contains a solvent (e.g., an organic solvent and water, etc.), it refers to all components other than the solvent. In addition, if it is a component that forms the composition layer, the liquid component is also regarded as a solid component.

[0049] In this specification, the thickness of each layer is calculated as an average value of five arbitrary points measured by cross-sectional observation using a SEM (Scanning Electron Microscope).

[0050] [Photosensitive resin composition according to the first embodiment]

[0051] The photosensitive resin composition of the first embodiment (hereinafter also referred to as "first composition") is a photosensitive resin composition containing an alkali-soluble resin, a polymerizable compound, a photopolymerization initiator, and a surfactant, wherein:

[0052] The value of ΔHSP1 calculated by the formula (F1) described below is 6.0 MPa 0.5 the following.

[0053] When the transfer film having the photosensitive resin layer formed of the first composition having the above-mentioned constitution is stored for a long period of time and then transferred to a transfer object to form a pattern, the pattern forming performance is unlikely to change over time. That is, even when the transfer film having the photosensitive resin layer formed of the first composition is stored for a long period of time and then transferred to a transfer object to form a pattern, the transfer film exhibits the same pattern forming performance as when the transfer film is transferred to a transfer object immediately after production and subjected to pattern formation.

[0054] The mechanism of action by which the first composition can achieve the above-mentioned effects is not clear, but the present inventors speculate as follows.

[0055] As the reason why the pattern forming performance changes over time when the transfer film after long-term storage is used to form a pattern on the transfer object in the prior art, it is speculated that the surfactant has poor compatibility with the alkali-soluble resin and polymerizable compound equivalent to the matrix component of the photosensitive resin layer, so the surfactant overflows due to environmental changes such as temperature changes during the storage of the transfer film and is concentrated on the surface of the photosensitive resin layer, thereby reducing the adhesion between the photosensitive resin layer and the transfer object after transfer. In addition, it is speculated that as a result, the part with weak adhesion is easily peeled off during development, so that the pattern forming performance formed on the transfer object may change.

[0056] On the other hand, since the HSP distance (value of ΔHSP1) between the surfactant of the first composition and the alkali-soluble resin and polymerizable compound corresponding to the matrix component of the photosensitive resin layer is close to 6.0 MPa, 0.5 Therefore, it is estimated that even when the pattern is formed by transferring the transferred material to the transfer object after long-term storage, the pattern forming performance is unlikely to change.

[0057] In addition, when the transfer film having the photosensitive resin layer formed of the first composition is used after long-term storage and transferred onto a transfer object to form a pattern, changes in pattern forming performance are further suppressed, which is also referred to as "the effect of the present invention is more excellent".

[0058] Hereinafter, the first composition will be described in detail.

[0059] From the viewpoint of further improving the effect of the present invention, the value of ΔHSP1 calculated by the following formula (F1) of the first composition is 6.0 MPa 0.5 Below, preferably 5.7MPa 0.5 Below, more preferably 5.5MPa 0.5 Below, more preferably 5.0 MPa 0.5 In addition, as a lower limit, it is only necessary to be 0.0 MPa 0.5 Above, 3.0MPa 0.5 The above situations are more common.

[0060] Formula (F1): ΔHSP1=(4(δDM-δDS) 2 +(δHM-δHS) 2 +(δPM-δPS) 2 ) 0.5

[0061] In formula (F1), δDM represents the weighted average of the dispersion term of the Hansen solubility parameters of the alkali-soluble resin and the dispersion term of the Hansen solubility parameters of the polymerizable compound calculated by the following formula (F1A). δHM represents the weighted average of the hydrogen bonding term of the Hansen solubility parameters of the alkali-soluble resin and the hydrogen bonding term of the Hansen solubility parameters of the polymerizable compound calculated by the following formula (F1B). δPM represents the weighted average of the polarity term of the Hansen solubility parameters of the alkali-soluble resin and the polarity term of the Hansen solubility parameters of the polymerizable compound calculated by the following formula (F1C). δDS represents the dispersion term of the Hansen solubility parameters of the surfactant. δHS represents the hydrogen bonding term of the Hansen solubility parameters of the surfactant. δPS represents the polarity term of the Hansen solubility parameters of the surfactant.

[0062] Formula (F1A): δDM=δDb×Wb / (Wb+Wm)+δDm×Wm / (Wb+Wm)

[0063] Formula (F1B): δHM=δHb×Wb / (Wb+Wm)+δHm×Wm / (Wb+Wm)

[0064] Formula (F1C): δPM=δPb×Wb / (Wb+Wm)+δPm×Wm / (Wb+Wm)

[0065] In formula (F1A), 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.

[0066] In formula (F1B), δHb represents the hydrogen bonding term of the Hansen solubility parameter of the alkali-soluble resin, and δHm represents the hydrogen bonding term of the Hansen solubility parameter of the polymerizable compound.

[0067] 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.

[0068] In formula (F1A) to formula (F1C), Wb represents the mass fraction of the alkali-soluble resin relative to the total solid content in the first composition. Wm represents the mass fraction of the polymerizable compound relative to the total solid content in the first composition.

[0069] The dispersion term δDb, hydrogen bonding term δHb and polar term δPb of the Hansen solubility parameters of the alkali-soluble resin, the dispersion term δDm, hydrogen bonding term δHm and polar term δPm of the Hansen solubility parameters of the polymerizable compound, and the dispersion term δDS, hydrogen bonding term δHS and polar term δPS of the Hansen solubility parameters of the surfactant were calculated using the commercially available software "HSPiP (developed by www.hansen-solubility.com)" for Windows.

[0070] In addition, in the first composition, only one surfactant may be used, or two or more surfactants may be used in combination. When only one surfactant is contained in the first composition, the dispersion term δDS, hydrogen bonding term δHS, and polarity term δPS of the Hansen solubility parameter of the surfactant in formula (F1) respectively represent the dispersion term δDS, hydrogen bonding term δHS, and polarity term δPS of the Hansen solubility parameter of the single surfactant contained in the above-mentioned first composition. When two or more surfactants are contained in the first composition, the dispersion term δDS, hydrogen bonding term δHS, and polarity term δPS of the Hansen solubility parameter of the surfactant in formula (F1) respectively represent the weighted average of the dispersion terms of the Hansen solubility parameters of the two or more surfactants, the weighted average of the hydrogen bonding terms of the Hansen solubility parameters of the two or more surfactants, and the weighted average of the polarity terms of the Hansen solubility parameters of the two or more surfactants.

[0071] When two or more surfactants are included in the first composition, the weighted average of the dispersion terms of the Hansen solubility parameters of the two or more surfactants is calculated by the following formula (S1).

[0072] Formula (S1): δDS=δDS1×WS1+δDS2×WS2+…δDS n ×WS n

[0073] Among them, δDS1~δDS n The value of the dispersion term representing the Hansen solubility parameters of the n surfactants contained in the first composition, WS n The content of each surfactant (the content (mass fraction) of each surfactant relative to the total content of n types of surfactants) is represented. That is, for example, when the first composition contains two surfactants in equal amounts, it is represented by δDS=δDS1×0.5+δDS2×0.5.

[0074] Furthermore, the weighted average value of the hydrogen bonding term and the weighted average value of the polar term of the Hansen solubility parameters of two or more surfactants can also be obtained by the same method as described above.

[0075] In the first composition, only one type of alkali-soluble resin may be used, or two or more types may be used in combination.

[0076] When only one alkali-soluble resin is included in the first composition, the dispersion term δDb, hydrogen bonding 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 bonding term δHb and polar term δPb of the Hansen solubility parameter of the single alkali-soluble resin contained in the first composition. When two or more alkali-soluble resins are included in the first composition, the "δDb" part in formula (F1A) is replaced by "δDb1×Wb1+δDb2×Wb2+……δDb n ×Wb n "And find out. Among them, δDb1~δDb n The values ​​of the dispersion terms of the Hansen solubility parameters of the n alkali-soluble resins contained in the first composition, Wb1 to Wb n The content (mass fraction) of each alkali-soluble resin relative to the total content of n alkali-soluble resins in the first composition. That is, when two alkali-soluble resins are contained in the first composition, the "δDb" part in formula (F1A) is replaced by "δDb1×Wb1+δDb2×Wb2" and calculated.

[0077] When two or more alkali-soluble resins are included in the first composition, the "δHb" part in formula (F1B) is replaced by "δHb1×Wb1+δHb2×Wb2+...δHb n ×Wb n " and the same method as in formula (F1A) is used to obtain (where δHb1 to δHb n The values ​​of the hydrogen bonding terms of the Hansen solubility parameters of the n alkali-soluble resins contained in the first composition, Wb1 to Wb n The content (mass fraction) of each alkali-soluble resin relative to the total content of the n alkali-soluble resins in the first composition. ). In addition, the "δPb" part in formula (F1C) is replaced by "δPb1×Wb1+δPb2×Wb2+……δPb n ×Wb n " and the same method as in formula (F1A) is used to obtain (where δPb1 to δPb n The values ​​of the polar terms of the Hansen solubility parameters of the n alkali-soluble resins contained in the first composition, Wb1 to Wb2 n It 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. ).

[0078] In the first composition, only one polymerizable compound may be used, or two or more polymerizable compounds may be used in combination.

[0079] When only one polymerizable compound is included in the first composition, the dispersion term δDm, hydrogen bonding 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 bonding term δHm and polar term δPm of the Hansen solubility parameter of the single polymerizable compound contained in the first composition. When two or more polymerizable compounds are included in the first composition, the "δDm" part in formula (F1A) is replaced by "δDm1×Wm1+δDm2×Wm2+……δDm n ×Wm n "And find out. Among them, δDm1~δDm n The values ​​of the dispersion terms of the Hansen solubility parameters of the n polymerizable compounds contained in the first composition, Wm1 to Wm2 n The content (mass fraction) of each polymerizable compound relative to the total content of n polymerizable compounds in the first composition. That is, when two polymerizable compounds are contained in the first composition, the "δDm" part in formula (F1A) is replaced by "δDm1×Wm1+δDm2×Wm2" and calculated.

[0080] When two or more polymerizable compounds are contained in the first composition, the "δHm" part in formula (F1B) is replaced by "δHm1×Wm1+δHm2×Wm2+...δHm n ×Wmn" and calculated using the same method as formula (F1A) (where δHm1 to δHm n =Wm1 to Wm2 represent the values ​​of the hydrogen bonding terms of the Hansen solubility parameters of the n polymerizable compounds contained in the first composition. n represents the content (mass fraction) of each polymerizable compound relative to the total content of n polymerizable compounds in the first composition). In addition, the "δPm" part in formula (F1C) is replaced by "δPm1×Wm1+δPm2×Wm2+……δPm n ×Wm n " and the same method as in formula (F1A) is used to obtain (where δPm1 to δPm n =Wm1 to Wm2 represent the polar terms of the Hansen solubility parameters of the n polymerizable compounds contained in the first composition. n It represents the content (mass fraction) of each polymerizable compound relative to the total content of n types of polymerizable compounds in the first composition.

[0081] 〔Various ingredients〕

[0082] Hereinafter, various components that may be contained in the first composition will be described in detail.

[0083] The first composition includes an alkali-soluble resin, a polymerizable compound, a photopolymerization initiator, and a surfactant.

[0084] <Alkali-soluble resin>

[0085] As a preferable aspect of the alkali-soluble resin, a (meth)acrylic resin is mentioned from the point which is excellent in alkali developability and film-forming property.

[0086] In the present specification, (meth)acrylic resin refers to a resin having repeating units derived from (meth)acrylic compounds. The content of repeating units derived from (meth)acrylic compounds is preferably 30% by mass or more, more preferably 40% by mass or more, relative to all repeating units of the (meth)acrylic resin.

[0087] The (meth)acrylic resin may be composed of repeating units derived from a (meth)acrylic compound alone, or may have repeating units derived from a polymerizable monomer other than a (meth)acrylic compound. That is, the upper limit of the content of repeating units derived from a (meth)acrylic compound relative to all repeating units of the (meth)acrylic resin is 100% by mass or less.

[0088] As a (meth)acrylic acid compound, (meth)acrylic acid, (meth)acrylic acid ester, (meth)acrylamide, and (meth)acrylonitrile are mentioned, for example.

[0089] Examples of the (meth)acrylate include alkyl (meth)acrylates, tetrahydrofuran (meth)acrylates, dimethylaminoethyl (meth)acrylates, diethylaminoethyl (meth)acrylates, glycidyl (meth)acrylates, 2,2,2-trifluoroethyl (meth)acrylates, 2,2,3,3-tetrafluoropropyl (meth)acrylates, and (meth)acrylates having an aromatic ring structure represented by formula (A) (e.g., benzyl (meth)acrylate, etc.). Among them, alkyl (meth)acrylates or (meth)acrylates having an aromatic ring structure represented by formula (A) are preferred.

[0090] Formula (A): CH=C(R 1 )-COO-L-Ar

[0091] 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.

[0092] Examples of the divalent linking group represented by L include -O-, -S-, -CO-, -NR T -, alkylene, and a divalent connecting group in a combination thereof, etc.

[0093] The alkylene group is preferably linear or branched. The number of carbon atoms in the alkylene group is preferably 1 to 20, more preferably 1 to 12, and even more preferably 1 to 6.

[0094] The number of atoms other than hydrogen atoms in the divalent linking group represented by L is preferably 1 to 20, more preferably 1 to 12, and even more preferably 1 to 6.

[0095] R T It represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and is preferably a hydrogen atom.

[0096] As the aromatic ring constituting the aromatic ring group represented by Ar, an aromatic hydrocarbon ring is preferred, and a benzene ring or a naphthalene ring is more preferred.

[0097] The substituent that Ar may have is not particularly limited, and examples thereof include an alkyl group.

[0098] Examples of the alkyl (meth)acrylate include alkyl (meth)acrylates 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.

[0099] As the (meth)acrylate, an alkyl (meth)acrylate having an alkyl group having 1 to 4 carbon atoms is preferred, and methyl (meth)acrylate or ethyl (meth)acrylate is more preferred.

[0100] Moreover, as (meth)acrylamide, acrylamides, such as diacetone acrylamide, are mentioned, for example.

[0101] In addition, the (meth)acrylic resin also preferably contains repeating units derived from alkyl (meth)acrylate. The content of alkyl (meth)acrylate in the (meth)acrylic resin is, for example, preferably 10 to 90% by mass, more preferably 15 to 70% by mass, and further preferably 15 to 40% by mass relative to all repeating units of the (meth)acrylic resin.

[0102] The (meth)acrylic resin may have a repeating unit other than the repeating unit derived from the (meth)acrylic compound.

[0103] The polymerizable monomer forming the above-mentioned repeating unit is not particularly limited as long as it is a compound other than the (meth)acrylic acid compound that can be copolymerized with the (meth)acrylic acid compound. For example, there can be mentioned styrene compounds which 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, maleic anhydride, maleic acid monoesters such as monomethyl maleate, monoethyl maleate and monoisopropyl maleate, fumaric acid, cinnamic acid, α-cyanocinnamic acid, itaconic acid and crotonic acid.

[0104] These polymerizable monomers may be used alone or in combination of two or more.

[0105] Furthermore, from the viewpoint of further improving alkali developability, the (meth)acrylic resin preferably contains a repeating unit having an acid group. Examples of the acid group include a carboxyl group, a sulfone group, a phosphoric acid group, and a phosphonic acid group.

[0106] Among them, as the repeating unit having an acid group, a repeating unit having a carboxyl group is preferred, and a repeating unit derived from (meth)acrylic acid is more preferred.

[0107] When the (meth)acrylic resin contains repeating units having an acid group, the content of the repeating units having an acid group is preferably 10% by mass or more relative to all repeating units of the resin from the perspective of better developability. The upper limit is not particularly limited, but is preferably 50% by mass or less, more preferably 40% by mass or less from the perspective of excellent alkali resistance.

[0108] As the (meth)acrylic resin, a resin having both a repeating unit derived from (meth)acrylic acid and a repeating unit derived from an alkyl (meth)acrylate is also preferred.

[0109] Furthermore, as a preferred embodiment of the alkali-soluble resin, a styrene-acrylic acid copolymer can also be mentioned.

[0110] In addition, in this specification, styrene-acrylic acid copolymer refers to a resin having repeating units derived from styrene compounds and repeating units derived from (meth)acrylic acid compounds. The total content of repeating units derived from styrene compounds and repeating units derived from (meth)acrylic acid compounds is preferably 30% by mass or more, more preferably 50% by mass or more, relative to all repeating units of the copolymer.

[0111] Furthermore, the content of the repeating unit derived from the styrene compound is preferably 1% by mass or more, more preferably 5% by mass or more, and further preferably 5 to 80% by mass, based on all the repeating units of the copolymer.

[0112] The content of the repeating unit derived from the (meth)acrylic acid compound is preferably 5% by mass or more, more preferably 10% by mass or more, and further preferably 20 to 95% by mass, based on all the repeating units of the copolymer.

[0113] The alkali-soluble resin also preferably contains a repeating unit having a reactive group.

[0114] As the reactive group, a radical polymerizable group is preferred, an ethylenically unsaturated group is more preferred, and an allyl group or a (meth)acryloyloxy group is further preferred.

[0115] From the perspective of further improving the compatibility with the surfactant and achieving more excellent effects of the present invention, it is also preferred 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. As the aromatic ring structure, an aromatic hydrocarbon ring structure is more preferred, and a benzene ring structure or a naphthalene ring structure is further preferred.

[0116] Among them, the alkali-soluble resin preferably contains a resin including one or more repeating units selected from the repeating units represented by the following formula (R1) and the repeating units represented by the following formula (R2) (hereinafter also referred to as "repeating units A").

[0117] [Chemical formula 1]

[0118]

[0119] 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)acrylate having an aromatic ring structure represented by formula (A).

[0120] The content of the repeating unit (preferably repeating unit A) containing an aromatic ring structure in the resin is preferably 5 to 90% by mass, more preferably 10 to 80% by mass, and further preferably 20 to 70% by mass relative to all repeating units in the resin. The resin may contain only one repeating unit (repeating unit A) containing an aromatic ring structure, or may contain two or more. When the resin contains two or more repeating units (preferably repeating unit A) containing an aromatic ring structure, the above content is preferably the total content.

[0121] From the viewpoint of more excellent effects of the present invention, 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.

[0122] The acid value of the alkali-soluble resin is preferably 10 to 200 mgKOH / g, more preferably 60 to 200 mgKOH / g, further preferably 60 to 150 mgKOH / g, and particularly preferably 60 to 130 mgKOH / g. The acid value of the alkali-soluble resin is a value measured by the method described in JIS K0070:1992.

[0123] The first composition may contain one type of alkali-soluble resin alone, or may contain two or more types of alkali-soluble resin.

[0124] From the viewpoint of achieving more excellent effects of the present invention, the content of the alkali-soluble resin is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, and even more preferably 30 to 70% by mass based on the total solid content of the first composition.

[0125] <Polymerizable Compound>

[0126] The first composition contains a polymerizable compound.

[0127] The polymerizable compound is a compound having a polymerizable group. Examples of the polymerizable group include radical polymerizable groups and cation polymerizable groups, and radical polymerizable groups are preferred.

[0128] The polymerizable compound preferably contains a radical polymerizable compound having an ethylenically unsaturated group (hereinafter, also simply referred to as an "ethylenically unsaturated compound").

[0129] As the ethylenically unsaturated group, a (meth)acryloyloxy group is preferred.

[0130] The number of ethylenically unsaturated groups in the ethylenically unsaturated compound is not particularly limited as long as it is 1 or more, but is preferably 1 to 6, more preferably 1 to 3, and still more preferably 2 to 3.

[0131] In addition, 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.

[0132] The ethylenically unsaturated compound may have an alkyleneoxy group.

[0133] The alkylene group is preferably an ethyleneoxy group or a propyleneoxy group, and more preferably an ethyleneoxy group. The number of alkyleneoxy groups added to the polymerizable compound is preferably 2 to 60, more preferably 2 to 30, and further preferably 2 to 20 per molecule.

[0134] Polymerizable compound B1

[0135] From the viewpoint of achieving more excellent effects of the present invention, the first composition preferably contains a polymerizable compound having an aromatic ring structure in its molecule. Among them, the polymerizable compound having an aromatic ring structure in its molecule preferably contains a polymerizable compound B1 having an aromatic ring and two ethylenically unsaturated groups.

[0136] Examples of the aromatic ring possessed by the polymerizable compound B1 include aromatic hydrocarbon rings such as a benzene ring, a naphthalene ring, and an anthracene ring; aromatic heterocyclic rings 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, preferably an aromatic hydrocarbon ring, more preferably a benzene ring. The above aromatic rings may have a substituent.

[0137] The polymerizable compound B1 may have one or two or more aromatic rings.

[0138] From the viewpoint of improving the resolution by suppressing the swelling of the first composition by the developer, the polymerizable compound B1 preferably has a bisphenol structure.

[0139] 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), and a bisphenol A structure is preferred.

[0140] 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.

[0141] The two ends of the bisphenol structure may be directly bonded to the two polymerizable groups or may be bonded via one or more alkyleneoxy groups. As the alkyleneoxy groups added to the two ends of the bisphenol structure, ethyleneoxy or propyleneoxy is preferred, and ethyleneoxy is more preferred. The number of alkyleneoxy groups (preferably ethyleneoxy) added to the bisphenol structure is preferably 2 to 60 per molecule, more preferably 2 to 30, and further preferably 2 to 20.

[0142] Examples of the polymerizable compound B1 having a bisphenol structure include paragraphs

[0072] to

[0080] of JP-A-2016-224162, and the contents thereof are incorporated herein.

[0143] As the polymerizable compound B1, a bifunctional ethylenically unsaturated compound having a bisphenol A structure is preferred, and 2,2-bis(4-((meth)acryloyloxypolyalkoxy)phenyl)propane is more preferred.

[0144] Examples of 2,2-bis(4-((meth)acryloxypolyalkoxy)phenyl)propane include 2,2-bis(4-(methacryloxydiethoxy)phenyl)propane (FA-324M, manufactured by Hitachi Chemical Co., Ltd.), ethoxylated bisphenol A dimethacrylates such as 2,2-bis(4-(methacryloxyethoxypropoxy)phenyl)propane and 2,2-bis(4-(methacryloxypentaethoxy)phenyl)propane (BPE series, manufactured by Shin-Nakamura Chemical Co., Ltd.), 2,2-bis(4-(methacryloxydodecyltetrapropoxy)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.).

[0145] As the polymerizable compound B1, a compound represented by the following formula (P1) is preferred.

[0146] [Chemical formula 2]

[0147]

[0148] 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. In addition, the arrangement of the repeating units of -(A-0)- and -(B-0)- may be random or block. When arranged in a block, either -(A-0)- or -(B-0)- may be on the biphenyl side.

[0149] n1+n2+n3+n4 is preferably 2 to 20, more preferably 2 to 16, and still more preferably 2 to 12. n2+n4 is preferably 0 to 10, and more preferably 0 to 4.

[0150] From the perspective of better resolution, the content of the polymerizable compound B1 is preferably 10% by mass or more, more preferably 20% by mass or more, and further preferably 25% by mass or more relative to the total solid content of the first composition. From the perspective of transferability and edge melting (phenomenon in which the first composition oozes out from the end of the transfer film), the upper limit is preferably 90% by mass or less, and more preferably 70% by mass or less.

[0151] From the perspective of better resolution, the content of the polymerizable compound B1 is preferably 40% by mass or more, more preferably 50% by mass or more, further preferably 55% by mass or more, and particularly preferably 60% by mass or more, relative to the total mass of the polymerizable compound. From the perspective of peelability, the upper limit is preferably 100% by mass or less, more preferably 99% by mass or less, and further preferably 95% by mass or less, relative to the total mass of the polymerizable compound.

[0152] Other ethylenically unsaturated compounds other than polymerizable compound B1

[0153] There are no particular restrictions on other ethylenically unsaturated compounds other than the polymerizable compound B1, and examples thereof include compounds having one ethylenically unsaturated group in the molecule (monofunctional ethylenically unsaturated compounds), bifunctional ethylenically unsaturated compounds having no aromatic ring, and trifunctional or higher ethylenically unsaturated compounds.

[0154] Examples of the monofunctional ethylenically unsaturated compound 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.

[0155] Examples of the bifunctional ethylenically unsaturated compound having no aromatic ring include alkylene glycol di(meth)acrylate, polyalkylene glycol di(meth)acrylate, urethane di(meth)acrylate, and trimethylolpropane diacrylate.

[0156] Examples of the alkylene glycol di(meth)acrylate 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.

[0157] Examples of the polyalkylene glycol di(meth)acrylate 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.).

[0158] As urethane di(meth)acrylate, for example, propylene oxide modified urethane di(meth)acrylate and ethylene oxide and propylene oxide modified urethane di(meth)acrylate can be cited. And as commercially available products of urethane di(meth)acrylate, for example, 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.) can be cited.

[0159] Examples of trifunctional or higher 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, glycerol tri(meth)acrylate, and alkylene oxide-modified products thereof.

[0160] “(Tri / tetra / penta / hexa) (meth)acrylate” is a concept including tri(meth)acrylate, tetra(meth)acrylate, penta(meth)acrylate and hexa(meth)acrylate. Also, “(tri / tetra) (meth)acrylate” is a concept including tri(meth)acrylate and tetra(meth)acrylate.

[0161] Examples of the alkylene oxide-modified products of trifunctional or higher ethylenic 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., etc.), 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., EBECRYL (registered trademark) 135 manufactured by DAICEL-ALLNEX LTD., etc.), ethoxylated glyceryl triacrylate (A-GLY-9E manufactured by Shin-Nakamura Chemical Co., Ltd., etc.), ARONIX (registered trademark) TO-2349 (TOAGOSEI CO., LTD.), ARONIX M-520 (manufactured by TOAGOSEI CO., LTD.), ARONIX M-510 (manufactured by TOAGOSEI CO., LTD.) and SR454 (manufactured by TOMOE Engineering Co., Ltd.).

[0162] The polymerizable compound may be an ethylenically unsaturated compound having an acid group (eg, a carboxyl group, etc.). The acid group may form an acid anhydride group.

[0163] Examples of the ethylenically unsaturated compound 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.).

[0164] Examples of the ethylenically unsaturated compound having an acid group include polymerizable compounds described in paragraphs

[0025] to

[0030] of JP-A-2004-239942.

[0165] The polymerizable compound may be used alone or in combination of two or more.

[0166] The content of the polymerizable compound is preferably 10 to 70% by mass, more preferably 15 to 70% by mass, and further preferably 20 to 70% by mass, relative to the total solid content of the first composition.

[0167] The content of the ethylenically unsaturated compound is preferably 10 to 70% by mass, more preferably 15 to 70% by mass, and further preferably 20 to 70% by mass, relative to the total solid content of the first composition.

[0168] <Photopolymerization initiator>

[0169] The first composition contains a photopolymerization initiator.

[0170] The photopolymerization initiator is a compound that receives activating light such as ultraviolet rays, visible rays, and X-rays to initiate polymerization of a polymerizable compound. As the photopolymerization initiator, known photopolymerization initiators can be cited. As the photopolymerization initiator, among them, photoradical polymerization initiators and photocationic polymerization initiators can be cited, preferably photoradical polymerization initiators, more preferably selected from one or more of acridine photopolymerization initiators, oxime ester photopolymerization initiators, biimidazole photopolymerization initiators, alkylphenone-based photopolymerization initiators, acetophenone-based photopolymerization initiators, and acylphosphine oxide-based photopolymerization initiators.

[0171] The photopolymerization initiator may be used alone or in combination of two or more.

[0172] The content of the photopolymerization initiator is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, relative to the total solid content of the first composition. The upper limit is preferably 20% by mass or less, more preferably 15% by mass or less, and further preferably 10% by mass or less, relative to the total solid content of the first composition.

[0173] <Surfactant>

[0174] The first composition includes a surfactant.

[0175] As the surfactant, nonionic surfactants, fluorine-based surfactants and silicone-based surfactants can be cited, among which silicone-based surfactants are preferred. As the silicone-based surfactant, for example, linear polymers formed by siloxane bonds and modified siloxane polymers having organic groups introduced into the side chains and / or the ends can be cited.

[0176] Furthermore, as the surfactant, a cross-linked resin is also preferred, such as a resin having a repeating unit represented by the formula (B-3) and the formula (B-4) described later.

[0177] As the surfactant, a known surfactant can be used.

[0178] As the surfactant, it is also preferred that the surfactant has no fluorine atom, since ΔHSP1 can be easily adjusted within a predetermined range and the effect of the present invention is more excellent.

[0179] As a surfactant, from the perspective of easily adjusting ΔHSP1 within a specified range and achieving a more excellent effect of the present invention, a resin containing at least one repeating unit selected from the repeating unit represented by the following formula (A-1) and the repeating unit represented by the following formula (A-2) (hereinafter also referred to as "repeating unit α") is preferred.

[0180] [Chemical formula 3]

[0181]

[0182] 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. 1 represents an integer of 5 to 100.

[0183] In formula (A-2), R4 represents a hydrogen atom or a methyl group. R5 represents an alkylene group having 1 to 10 carbon atoms. L represents a trimethylsilyl group or a tris(trimethylsiloxy)silyl group.

[0184] In the above-mentioned resin, the content of repeating unit α is preferably 20 to 90% by mass, more preferably 30 to 90% by mass, and further preferably 40 to 80% by mass relative to all repeating units of the resin. In the above-mentioned resin, only one repeating unit α may be included, or two or more repeating units α may be included. In addition, when two or more repeating units α are included, the above-mentioned content is preferably the total content of repeating units α.

[0185] As the surfactant, from the viewpoint that ΔHSP1 can be easily adjusted within a predetermined range and the effect of the present invention is more excellent, a resin having a first repeating unit (polar part) containing an atom selected from silicon atoms and fluorine atoms and a second repeating unit (non-polar part) containing neither silicon atoms nor fluorine atoms is preferred. Among them, the resin having a first repeating unit containing silicon atoms and the second repeating unit is more preferred.

[0186] Specific examples of the first repeating unit include repeating units represented by the above formula (A-1) or formula (A-2).

[0187] As a specific example of the second repeating unit, as long as any one of the silicon atom and the fluorine atom is not included, it is not particularly limited, but from the aspect of the more excellent effect of the present invention, it is preferred to have a repeating unit with an aromatic ring structure. As the second repeating unit, for example, the repeating unit represented by the following formula (B-1) to formula (B-4) can be enumerated.

[0188] [Chemical formula 4]

[0189]

[0190] In formula (B-1), RB11 represents a hydrogen atom or a methyl group. B11 Represents a single bond or -COO-. L B12 represents a single bond or a divalent linking group. B12 It represents a monovalent aromatic ring group which may have a substituent.

[0191] As L B12 The divalent linking group represented by may be selected from -O-, -S-, -CO-, -NR T -, alkylene, and a divalent connecting group in a combination thereof, etc.

[0192] The alkylene group is preferably in a chain (straight chain or branched chain) form. The number of carbon atoms in the alkylene group is preferably 1 to 30, more preferably 1 to 20, further preferably 1 to 10, and particularly preferably 1 to 6.

[0193] As L B12 The number of atoms other than hydrogen atoms in the divalent linking group represented is preferably 1-30, more preferably 1-20, and even more preferably 1-10.

[0194] RT represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and is preferably a hydrogen atom.

[0195] As L B12 An example of a divalent linking group represented by may include -AL1-, -(AL2-0)p- and -(AL2-0)n-CO-. AL1 and AL2 represent an alkylene group. p represents an integer of 1 to 10 (preferably 1 to 6). The number of carbon atoms of the alkylene group represented by AL2 is preferably 2 to 6, more preferably 2 to 4. AL1 and AL2 may have a substituent such as a hydroxyl group. Furthermore, when a plurality of p and n are present, the plurality of AL2 present may be the same or different.

[0196] As R B12 The monovalent aromatic ring group represented by is preferably a monovalent aromatic hydrocarbon ring group, and more preferably a phenyl group or a naphthyl group.

[0197] The monovalent aromatic ring group may further have a substituent. The substituent is not particularly limited, and examples thereof include hydroxyl, alkyl, alkoxy, alkoxycarbonyl, and monovalent aromatic ring groups (for example, monovalent aromatic hydrocarbon ring groups such as phenyl).

[0198] Furthermore, examples of the substituent that the monovalent aromatic ring group may have include monovalent groups represented by the following formula (M1).

[0199] Formula (M1): *-L M1-( A M1 -L M2 ) q -RM1

[0200] Where, L M1 and L M2 Examples include a single bond, a -O-, -S-, -CO-, -NR T - and a divalent linking group in a combination thereof, for example, -O-, -CO-, and -COO-. T It represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and is preferably a hydrogen atom.

[0201] A M1 represents 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.

[0202] Furthermore, the substituents that the divalent aromatic ring group and the divalent alicyclic group may have are not particularly limited, and examples thereof include hydroxyl groups, alkyl groups (straight-chain, branched, and cyclic), alkoxy groups, alkoxycarbonyl groups, and monovalent aromatic ring groups (for example, monovalent aromatic hydrocarbon ring groups such as phenyl), and the like.

[0203] q represents an integer of 1-6, and preferably 1-3.

[0204] R M1 represents a hydrogen atom or a substituent. M1 The substituent represented is not particularly limited, and examples thereof include hydroxyl, alkyl (straight-chain, branched, and cyclic), alkoxy, alkoxycarbonyl, cyano, primary and tertiary amino, and acylamino groups.

[0205] R M1 The number of carbon atoms of the alkyl part in the alkyl group, alkoxy group and alkoxycarbonyl group represented is, for example, preferably 1 to 10, more preferably 1 to 6.

[0206] Examples of primary to tertiary amino groups include -NH2, -NHR Y and-NR Y 2 etc. R Y represents an alkyl group. Examples of the acylamino group include -NHCOR Y and-NR Y COR Y Etc. R Y represents an alkyl group.

[0207] As in R Y The alkyl group mentioned in the above is preferably linear or branched, and has, for example, 1 to 10 carbon atoms, and more preferably 1 to 6 carbon atoms.

[0208] R in formula (B-1) B12 The substituents that the monovalent aromatic ring group represented by and R in formula (M1) may have M1 The substituent represented is also preferably an electron accepting group or an electron donating group, wherein an electron donating group is preferred. Examples of the electron donating group include unsubstituted or substituted amino, substituted or unsubstituted acylamino, nitro, cyano, halogen-substituted saturated or unsaturated hydrocarbon groups (e.g., halogen-substituted alkyl, halogen-substituted alkenyl, halogen-substituted aromatic hydrocarbon ring groups), nitrogen-containing heterocyclic groups, oxygen-containing heterocyclic groups, and sulfur-containing heterocyclic groups.

[0209] Examples of the unsubstituted or substituted amino group include -NH2, -NHR Y and-NR Y 2 etc. R Y represents an alkyl group.

[0210] Examples of the substituted or unsubstituted acylamino group include -NHCOR Y and-NR Y COR Y Etc. R Y represents an alkyl group.

[0211] As in R Y The alkyl group mentioned in the above is preferably linear or branched, and has, for example, 1 to 10 carbon atoms, and more preferably 1 to 6 carbon atoms.

[0212] Examples of the electron accepting group include an acid group, and specific examples thereof include a carboxyl group, a phenolic hydroxyl group (a hydroxyl group substituted on an aromatic ring corresponds to this), a sulfonic acid group, and a phosphoric acid group.

[0213] [Chemical formula 5]

[0214]

[0215] In formula (B-2), R B21 represents a hydrogen atom or a methyl group. B21 Represents a single bond or -COO-. L B22 represents a single bond or a divalent linking group. B22 represents a hydrogen atom or a substituent other than an aromatic group.

[0216] As L B22 The divalent linking group represented by may be selected from -O-, -S-, -CO-, -NR T -, alkylene, and a divalent connecting group in a combination thereof, etc.

[0217] The alkylene group is preferably in a chain (straight chain or branched chain) form. The number of carbon atoms in the alkylene group is preferably 1 to 100, more preferably 1 to 50, and even more preferably 1 to 30.

[0218] As L B22 The number of atoms other than hydrogen atoms in the divalent linking group represented is preferably 1-100, more preferably 1-50, and even more preferably 1-30.

[0219] R T It represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and is preferably a hydrogen atom.

[0220] As L B22 An example of a divalent linking group represented by can include -AL1- and -(AL2-O)q-. AL1 and AL2 represent alkylene groups. q represents an integer of 1 to 60 (preferably 1 to 20). The number of carbon atoms of the alkylene group represented by AL2 is preferably 2 to 6, more preferably 2 to 4. AL1 and AL2 may have a substituent such as a hydroxyl group. Furthermore, when there are multiple q, the multiple AL2s may be the same or different.

[0221] As R B22 The substituents other than the aromatic group represented by the above are not particularly limited, and examples thereof include hydroxyl, alkyl, alkoxy, alkoxycarbonyl, and unsubstituted or substituted amino (-NH2, -NHR Y and-NR Y 2) etc. Y represents an alkyl group.

[0222] As the above alkyl group and the above R Y The number of carbon atoms of the alkyl group represented by and the number of carbon atoms of the alkyl part (preferably linear or branched) in the alkoxy group and the alkoxycarbonyl group are preferably 1 to 10, more preferably 1 to 6. Y The alkyl group, the alkoxy group, and the alkoxycarbonyl group represented by the above-mentioned group may have a substituent such as a hydroxyl group.

[0223] R in formula (B-2) B22 The substituents other than the aromatic group represented are also preferably electron accepting groups or electron donating groups, and among them, electron donating groups are preferred. Specific examples of the electron accepting groups and electron donating groups are as described above.

[0224] [Chemical formula 6]

[0225]

[0226] In formula (B-3), R B31 and R B34 Each independently represents a hydrogen atom or a methyl group.B31 and L B33 Each independently represents a single bond or a divalent linking group. B32 Represents 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.

[0227] As L B31 and L B33 The divalent linking group represented by is not particularly limited, and examples thereof include -O-, -S-, -CO-, -NR T- , alkylene groups, and divalent connecting groups in combinations thereof.

[0228] The alkylene group is preferably in a chain (straight chain or branched chain) form. The number of carbon atoms in the alkylene group is preferably 1 to 100, more preferably 1 to 50, and even more preferably 1 to 30.

[0229] As L B31 and L B33 The number of atoms other than hydrogen atoms in the divalent linking group represented is preferably 1-100, more preferably 1-50, and even more preferably 1-30.

[0230] R T It represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and is preferably a hydrogen atom.

[0231] As L B31 and L B33 An example of a divalent linking group represented by can 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 number of carbon atoms of the alkylene group represented by AL is preferably 2 to 6, more preferably 2 to 4. AL may have a substituent such as a hydroxyl group. Furthermore, when there are multiple r, the multiple ALs may be the same or different.

[0232] As R w Examples of the monovalent organic group represented by include an alkyl group and a monovalent aromatic ring group.

[0233] The alkyl group is preferably a chain (straight chain or branched chain). The number of carbon atoms in the alkyl group is preferably 1 to 6, more preferably 1 to 3.

[0234] The monovalent aromatic ring group is preferably a monovalent aromatic hydrocarbon ring group, and preferably a phenyl group.

[0235] The monovalent aromatic ring group may further have a substituent. The substituent is not particularly limited, and examples thereof include hydroxyl, alkyl, alkoxy, alkoxycarbonyl, and monovalent aromatic ring groups (for example, monovalent aromatic hydrocarbon ring groups such as phenyl).

[0236] As Ar B11 and Ar B12 The divalent aromatic ring group represented by is preferably a divalent aromatic hydrocarbon ring group (preferably having 6 to 10 carbon atoms), and more preferably a phenylene group.

[0237] The above-mentioned divalent aromatic ring group may further have a substituent. The substituent is not particularly limited, and examples thereof include hydroxyl, alkyl, alkoxy, alkoxycarbonyl, and monovalent aromatic ring groups (for example, monovalent aromatic hydrocarbon ring groups such as phenyl).

[0238] [Chemical formula 7]

[0239]

[0240] In formula (B-4), R B41 and R B42 Each 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 greater than 1. When p represents an integer greater than 2, there are a plurality of Ar B41 Each other and multiple L B42 They can be the same or different.

[0241] As L B41 ~L B43 The divalent linking group represented by is not particularly limited, and examples thereof include B31 and L B33 The divalent linking group represented by is the same linking group. B42 The divalent linking group represented by is preferably -O-, -S-, -CO-, -CO-O-, -O-CO-O-, -CO-NR T -or -OCH2-, etc.

[0242] As Ar B41 The divalent aromatic ring group represented by is preferably a divalent aromatic hydrocarbon ring group (preferably having 6 to 10 carbon atoms), and more preferably a phenylene group.

[0243] The above-mentioned divalent aromatic ring group may further have a substituent. The substituent is not particularly limited, and examples thereof include hydroxyl, alkyl, alkoxy, alkoxycarbonyl, and monovalent aromatic ring groups (for example, monovalent aromatic hydrocarbon ring groups such as phenyl).

[0244] In the above-mentioned resin, the content of the first repeating unit relative to all repeating units of the resin is preferably 20 to 90 mass %, more preferably 30 to 90 mass %, and further preferably 40 to 80 mass %. In the above-mentioned resin, only one first repeating unit may be included, or two or more first repeating units may be included. In addition, when two or more first repeating units are included, the above-mentioned content is preferably the total content of the first repeating unit.

[0245] In the above-mentioned resin, the content of the second repeating unit relative to all repeating units of the resin is preferably 10 to 80% by mass, more preferably 20 to 70% by mass, and further preferably 20 to 60% by mass. In the above-mentioned resin, only one second repeating unit may be included, or two or more may be included. In addition, when two or more second repeating units are included, the above-mentioned content is preferably the total content of the second repeating units.

[0246] The weight average molecular weight (Mw) of the surfactant is preferably 500 or more, more preferably 1,000 or more, further preferably 10,000 or more, particularly preferably 15,000 or more, and most preferably 18,000 or more. The upper limit is preferably 100,000 or less, and more preferably 80,000 or less.

[0247] The content of the surfactant is preferably 0.01 to 5% by mass, more preferably 0.01 to 3% by mass, and further preferably 0.05 to 1% by mass, relative to the total solid content of the first composition.

[0248] Specific examples of the surfactant are given below, but the surfactant is not limited thereto.

[0249] [Chemical formula 8]

[0250]

[0251] [Chemical formula 9]

[0252]

[0253] [Chemical formula 10]

[0254]

[0255] [Chemical formula 11]

[0256]

[0257]

[0258] [Chemical formula 12]

[0259]

[0260] [Chemical formula 13]

[0261]

[0262] [Chemical formula 14]

[0263]

[0264]

[0265] <Other additives>

[0266] The first composition may contain other additives in addition to the above-mentioned various components.

[0267] Examples of other additives include triazole, benzotriazole, tetrazole and derivatives thereof, aliphatic thiol compounds, thermal crosslinking compounds, polymerization inhibitors, hydrogen donating compounds, solvents, impurities, plasticizers, sensitizers and alkoxysilane compounds.

[0268] Examples of triazole, benzotriazole, tetrazole, and derivatives thereof, aliphatic thiol compounds, thermally crosslinkable compounds, polymerization inhibitors, and hydrogen donating compounds include those described in International Publication No. 2022 / 039027.

[0269] As a plasticizer, a sensitizer, and an alkoxysilane compound, the description of paragraphs 0097 to 0119 of International Publication No. 2018 / 179640 can be mentioned, for example.

[0270] The solvent is not particularly limited as long as it can dissolve or disperse various components that may be contained in the photosensitive resin composition other than the solvent.

[0271] 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 and N-ethylpyrrolidone), lactone solvents, and mixed solvents containing two or more thereof.

[0272] The solvent may be used alone or in combination of two or more.

[0273] 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, based on 100 parts by mass of the total solid content of the photosensitive resin composition.

[0274] The first composition may contain impurities.

[0275] As impurities, for example, sodium, potassium, magnesium, calcium, iron, manganese, copper, aluminum, titanium, chromium, cobalt, nickel, zinc, tin, halogen and ions thereof can be cited. Halide ions, sodium ions and potassium ions are easily mixed as impurities, so it is preferably set to the following content.

[0276] The content of impurities is preferably 80 mass ppm or less, more preferably 10 mass ppm or less, and further preferably 2 mass ppm or less relative to the total solid content of the first composition. In many cases, the lower limit is 0 mass ppb or more relative to the total solid content of the first composition, and may be 1 mass ppb or more, or 0.1 mass ppm or more.

[0277] Examples of methods for adjusting the content of impurities include a method of using raw materials with a low impurity content as raw materials for various components that may be included in the first composition, a method of purifying various components that may be included in the first composition, and a method of preventing impurities from being mixed in when preparing the first composition.

[0278] The content of impurities can be measured by a known method such as ICP (Inductively Coupled Plasma) emission spectrometry, atomic absorption spectrometry, and ion chromatography.

[0279] In the first composition, the content of compounds such as benzene, formaldehyde, trichloroethylene, 1,3-butadiene, carbon tetrachloride, chloroform and hexane is preferably small. Specifically, the content of these compounds is preferably 100 mass ppm or less, more preferably 20 mass ppm or less, and further preferably 4 mass ppm or less relative to the total solid content of the first composition. The lower limit may be 10 mass ppb or more, or 100 mass ppb or more relative to the total solid content of the first composition.

[0280] The content of these compounds can be adjusted by the same method as the above-mentioned impurities, and the content of these compounds can be measured by a known measurement method.

[0281] [Preferred embodiment of the first composition]

[0282] From the viewpoint of achieving more excellent effects of the present invention, the first composition preferably includes the following aspects (1A) to (1C).

[0283] The surfactant (1A) is a resin having a first repeating unit (polar part) containing an atom selected from silicon atoms and fluorine atoms and a second repeating unit (non-polar part) containing neither silicon atoms nor fluorine atoms (hereinafter also referred to as a "specific surfactant"), and the value of ΔHSP2 calculated by the formula (F2) described later as the composition of the second composition is 4.0 MPa 0.5 Herein, when at least one selected from 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.

[0284] (1B) At least one 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.

[0285] (1C) At least one selected from 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.

[0286] In the above (1A), as a specific example of a resin having a first repeating unit (polar part) containing atoms selected from silicon atoms and fluorine atoms and a second repeating unit (non-polar part) containing neither silicon atoms nor fluorine atoms, the same surfactant as the specific surfactant described in the second composition in the latter section can be used.

[0287] In the above (1A) and (1C), examples of the electron-donating group include unsubstituted or substituted amino groups, substituted or unsubstituted acylamino groups, nitro groups, cyano groups, saturated or unsaturated hydrocarbon groups substituted by halogens (for example, alkyl groups substituted by halogens, alkenyl groups substituted by halogens, aromatic hydrocarbon ring groups substituted by halogens), nitrogen-containing heterocyclic groups, oxygen-containing heterocyclic groups, and sulfur-containing heterocyclic groups.

[0288] Examples of the unsubstituted or substituted amino group include -NH2, -NHR Y and-NR Y 2 etc. R Y represents an alkyl group.

[0289] Examples of the substituted or unsubstituted acylamino group include -NHCOR Y and-NR Y COR Y Etc. R Y represents an alkyl group.

[0290] As in R YThe alkyl group mentioned in the above is preferably linear or branched, and has, for example, 1 to 10 carbon atoms, and more preferably 1 to 6 carbon atoms.

[0291] Examples of the electron accepting group include an acid group, and specific examples thereof include a carboxyl group, a phenolic hydroxyl group (a hydroxyl group substituted on an aromatic ring corresponds to this), a sulfonic acid group, and a phosphoric acid group.

[0292] In (1B) above, the aromatic ring constituting the aromatic ring structure may be a monocyclic or polycyclic ring. Furthermore, the aromatic ring constituting the aromatic ring structure may be 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.

[0293] [Photosensitive resin composition according to the second embodiment]

[0294] The photosensitive resin composition of the second embodiment (hereinafter also referred to as "second composition") is a photosensitive resin composition comprising an alkali-soluble resin, a polymerizable compound, a photopolymerization initiator, and a surfactant, wherein:

[0295] The surfactant is a resin having a first repeating unit (polar part) containing an atom selected from silicon atoms and fluorine atoms and a second repeating unit (non-polar part) containing neither silicon atoms nor fluorine atoms (hereinafter also referred to as a "specific surfactant"),

[0296] The value of ΔHSP2 calculated by the formula (F2) described below is 4.0 MPa 0.5 the following.

[0297] When at least one selected from 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.

[0298] When the transfer film having the photosensitive resin layer formed of the second composition having the above-mentioned structure is transferred to a transfer object after long-term storage to form a pattern, the pattern forming performance is unlikely to change over time. That is, even when the transfer film having the photosensitive resin layer formed of the second composition is transferred to a transfer object to form a pattern after long-term storage, the transfer film exhibits the same pattern forming performance as when it is transferred to a transfer object immediately after production and subjected to pattern formation.

[0299] The mechanism of action by which the second composition can achieve the above-mentioned effects is not clear, but the present inventors speculate as follows.

[0300] As the reason why the pattern forming performance changes over time when the transfer film after long-term storage is used to form a pattern on the transfer object in the prior art, it is speculated that the surfactant has poor compatibility with the alkali-soluble resin and polymerizable compound equivalent to the matrix component of the photosensitive resin layer, so the surfactant overflows due to environmental changes such as temperature changes during the storage of the transfer film and is concentrated on the surface of the photosensitive resin layer, thereby reducing the adhesion between the photosensitive resin layer and the transfer object after transfer. In addition, it is speculated that as a result, the part with weak adhesion is easily peeled off during development, so that the pattern forming performance formed on the transfer object may change.

[0301] In contrast, the second composition contains a specific surfactant, and the HSP distance (ΔHSP2 value) between the nonpolar part of the specific surfactant described below and the alkali-soluble resin and polymerizable compound corresponding to the matrix component of the photosensitive resin layer is close to 4.0 MPa. 0.5 In addition, it is speculated that at the interface of the photosensitive resin layer, the specific surfactant is oriented in a state where the polar part described later is oriented toward the outside of the layer and the non-polar part described later is oriented toward the inside of the layer, and the non-polar part described later of the specific surfactant is oriented toward the HSP distance of the alkali-soluble resin and polymerizable compound of the photosensitive resin layer corresponding to the matrix component is close to each other, so that the surfactant can be suppressed from overflowing. Therefore, it is speculated that even in the case of transferring to a transfer object to form a pattern after long-term storage, the pattern forming performance is not likely to change.

[0302] In addition, when the transfer film having the photosensitive resin layer formed of the second composition is used after long-term storage and transferred onto a transfer object to form a pattern, changes in pattern forming performance are further suppressed, which is also referred to as "the effect of the present invention is more excellent".

[0303] The second composition is described in detail below. First, the specific surfactant contained in the second composition is described below. In addition, the various components (alkali-soluble resin, polymerizable compound, photopolymerization initiator and other additives) and their contents other than the specific surfactant that the second composition may contain are the same as the various components and their contents of the first composition described above, and the preferred embodiments are also the same.

[0304] Among them, when at least one of the above-mentioned alkali-soluble resin and the above-mentioned polymerizable compound has one of the electron accepting group and the electron donating group, the specific surfactant does not have the other of the electron accepting group and the electron donating group. Here, as the electron donating group, specifically, unsubstituted or substituted amino, substituted or unsubstituted acylamino, nitro, cyano, halogen-substituted saturated or unsaturated hydrocarbon group (for example, halogen-substituted alkyl, halogen-substituted alkenyl, halogen-substituted aromatic hydrocarbon ring group), nitrogen-containing heterocyclic group, oxygen-containing heterocyclic group and sulfur-containing heterocyclic group can be cited. As the electron accepting group, the acid group is equivalent to this, and specifically, a carboxyl group, a phenolic hydroxyl group (the hydroxyl group substituted on the aromatic ring is equivalent to this.), a sulfonic acid group and a phosphoric acid group can be cited.

[0305] 〔Specific surfactant〕

[0306] The second composition contains a resin (specific surfactant) having a first repeating unit (polar part) containing an atom selected from silicon atoms and fluorine atoms and a second repeating unit (non-polar part) containing neither silicon atoms nor fluorine atoms.

[0307] Among them, the specific surfactant is more preferably a resin having a first repeating unit containing a silicon atom and the second repeating unit.

[0308] Specific examples of the first repeating unit include the repeating unit represented by the formula (A-1) or (A-2) described above with respect to the first composition.

[0309] As a specific example of the second repeating unit, as long as any one of the silicon atom and the fluorine atom is not included, it is not limited, but from the aspect of the more excellent effect of the present invention, it is preferably a repeating unit with an aromatic ring structure. As the second repeating unit, for example, the repeating unit represented by the formula (B-1) to the formula (B-4) described in the first composition can be cited.

[0310] In the specific surfactant, the content of the first repeating unit is preferably 20 to 90% by mass, more preferably 30 to 90% by mass, and further preferably 40 to 80% by mass relative to all repeating units of the resin (specific surfactant). In the specific surfactant, only one first repeating unit may be included, or two or more may be included. In addition, when two or more first repeating units are included, the above content is preferably the total content of the first repeating unit.

[0311] In the specific surfactant, the content of the second repeating unit is preferably 10 to 80% by mass, more preferably 20 to 70% by mass, and further preferably 20 to 60% by mass relative to all repeating units of the resin (specific surfactant). It can contain only one second repeating unit or two or more. In addition, when containing two or more second repeating units, the above content is preferably the total content of the second repeating units.

[0312] Specific examples of the specific surfactant are the same compounds as those exemplified as the surfactant compounds in the first composition.

[0313] The weight average molecular weight (Mw) of the specific surfactant is preferably 500 or more, more preferably 1,000 or more, further preferably 10,000 or more, particularly preferably 15,000 or more, and most preferably 18,000 or more. The upper limit is preferably 100,000 or less, and more preferably 80,000 or less.

[0314] The content of the specific surfactant is preferably 0.01 to 5% by mass, more preferably 0.01 to 3% by mass, and further preferably 0.05 to 1% by mass, relative to the total solid content of the second composition.

[0315] 〔ΔHSP2〕

[0316] The value of ΔHSP2 calculated by the following formula (F2) for the second composition was 4.0 MPa. 0.5 From the viewpoint of more excellent effects of the present invention, 3.5 MPa is preferred. 0.5 Below, more preferably 3.0 MPa 0.5 Below, 2.8 MPa is more preferred 0.5 In addition, as a lower limit, it is only necessary to be 0.0 MPa 0.5 Above 0.5MPa 0.5 The above situations are more common.

[0317] Formula (F2): ΔHSP2=(4(δDM-δDSs) 2 +(δHM-δHSs) 2 +(δPM-δPSs) 2 ) 0.5

[0318] 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 bonding term of the Hansen solubility parameter of the alkali-soluble resin and the hydrogen bonding 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 of the non-polar part of the specific surfactant, and when the specific surfactant has only one second repeating unit, it represents the dispersion term of the Hansen solubility parameter of the second repeating unit, and when the specific surfactant has two or more second repeating units, it represents the weighted average of the dispersion terms of the Hansen solubility parameters of the two or more second repeating units. δHSs is the hydrogen bonding term of the Hansen solubility parameter of the non-polar part of the specific surfactant. When the specific surfactant has only one second repeating unit, it represents the hydrogen bonding term of the Hansen solubility parameter of the second repeating unit. When the specific surfactant has two or more second repeating units, it represents the weighted average of the hydrogen bonding terms of the Hansen solubility parameters of the two or more second repeating units. δPSs is the polar term of the Hansen solubility parameter of the non-polar part of the specific surfactant. When the specific surfactant has only one second repeating unit, it represents the polar term of the Hansen solubility parameter of the second repeating unit. When the specific surfactant has two or more second repeating units, it represents the weighted average of the polar terms of the Hansen solubility parameters of the two or more second repeating units.

[0319] Formula (F2A): δDM=δDb×Wb / (Wb+Wm)+δDm×Wm / (Wb+Wm)

[0320] Formula (F2B): δHM=δHb×Wb / (Wb+Wm)+δHm×Wm / (Wb+Wm)

[0321] Formula (F2C): δPM=δPb×Wb / (Wb+Wm)+δPm×Wm / (Wb+Wm)

[0322] 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.

[0323] In formula (F2B), δHb represents the hydrogen bonding term of the Hansen solubility parameter of the alkali-soluble resin, and δHm represents the hydrogen bonding term of the Hansen solubility parameter of the polymerizable compound.

[0324] 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.

[0325] In formula (F2A) to formula (F2C), Wb represents the mass fraction of the alkali-soluble resin relative to the total solid content in the second composition. Wm represents the mass fraction of the polymerizable compound relative to the total solid content in the second composition.

[0326] The dispersion term δDb, hydrogen bonding term δHb and polar term δP of the Hansen solubility parameters of the alkali-soluble resin, the dispersion term δDm, hydrogen bonding term δHm and polar term δm of the Hansen solubility parameters of the polymerizable compound, and the dispersion term δDSs, hydrogen bonding term δHSs and polar term δSs of the Hansen solubility parameters in the non-polar part of the specific surfactant were calculated using the commercially available software "HSPiP (developed by www.hansen-solubility.com)" for Windows.

[0327] In the above formula (F2), when the specific surfactant has two or more second repeating units, δDSs represents the weighted average of the dispersion terms of the Hansen solubility parameters of the two or more second repeating units. Here, the weighted average is calculated by the following formula (S2).

[0328] Formula (S2): δDSs=δDSs1×WSs1+δDSs2×WSs2+····δDSs n ×WS n

[0329] Among them, δDSs1~δDSs n The values ​​of the dispersion terms representing the Hansen solubility parameters of the n second repeating units contained in the specific surfactant, WSs1 to WSs N It represents the content of each second repeating unit (the content (mass fraction) of each second repeating unit relative to the total content of the second repeating units of the specific surfactant). That is, for example, when the specific surfactant includes two types of repeating units, it is represented by δDSs=δDSs1×WSs1+δDSs2×WSs2.

[0330] Furthermore, the weighted average value of the hydrogen bonding term and the weighted average value of the polar term of each Hansen solubility parameter of the specific surfactant having two or more second repeating units are also determined by the same method as described above.

[0331] In addition, in the second composition, only one specific surfactant may be used, or two or more specific surfactants may be used in combination. When only one specific surfactant is contained in the second composition, the dispersion term δDSs, hydrogen bonding term δHSs, and polar term δPSs of the Hansen solubility parameter of the non-polar part of the specific surfactant in formula (F2) respectively represent the dispersion term δDSs, hydrogen bonding 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 included in the second composition, the dispersion term δDSs, hydrogen bonding term δHSs and polar term δPSs of the Hansen solubility parameters of the non-polar part of the specific surfactant in formula (F2) respectively represent the value obtained by weighted averaging the dispersion terms of the Hansen solubility parameters of the non-polar parts of each of the two or more specific surfactants, the value obtained by weighted averaging the hydrogen bonding terms of the Hansen solubility parameters of the non-polar parts of each of the two or more specific surfactants, and the value obtained by weighted averaging the polar terms of the Hansen solubility parameters of the non-polar parts of each of the two or more specific surfactants.

[0332] When two or more specific surfactants are included in the second composition, a value obtained by weighted averaging the dispersion terms of the Hansen solubility parameters of the nonpolar sites of the two or more specific surfactants is determined by the following formula (S3).

[0333] Formula (S3): δDSs=δDSs1×WSs1+δDSs2×WSs2+…δDSs n ×WS n

[0334] Among them, δDSs1~δDSs n = The value of the dispersion term representing the Hansen solubility parameter of the nonpolar part in the n specific surfactants contained in the second composition, WS s1 ~WS sn Indicates 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 two specific surfactants in equal amounts, it is represented by δDSs=δDSs1×0.5+δDSs2×0.5.

[0335] Furthermore, the value obtained by weighted averaging the hydrogen bonding terms of the Hansen solubility parameters of the respective non-polar parts of two or more specific surfactants and the value obtained by weighted averaging the polarities of the Hansen solubility parameters of the respective non-polar parts of two or more specific surfactants can also be calculated by the same method as described above.

[0336] In the second composition, only one type of alkali-soluble resin may be used, or two or more types may be used in combination.

[0337] When only one alkali-soluble resin is included in the second composition, the dispersion term δDb, hydrogen bonding 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 bonding term δHb and polar term δPb of the Hansen solubility parameter of the single alkali-soluble resin contained in the above-mentioned second composition. When two or more alkali-soluble resins are included in the second composition, the "δDb" part in formula (F2A) is replaced by "δDb1×Wb1+δDb2×Wb2+……δDb n ×Wb n "And find out. Among them, δDb1~δDb n The values ​​of the dispersion terms of the Hansen solubility parameters of the n alkali-soluble resins contained in the second composition, Wb1 to Wb n The content (mass fraction) of each alkali-soluble resin relative to the total content of n alkali-soluble resins in the second composition. That is, when two alkali-soluble resins are included in the second composition, the "δDb" part in formula (F2A) is replaced by "δDb1×Wb1+δDb2×Wb2" and calculated.

[0338] When two or more alkali-soluble resins are included in the second composition, the "δHb" part in formula (F2B) is replaced by "δHb1×Wb1+δHb2×Wb2+...δHb n ×Wb n " and the same method as in formula (F2A) is used to obtain (where δHb1 to δHb n Wb1 to Wb2 represent the values ​​of the hydrogen bonding terms of the Hansen solubility parameters of the n alkali-soluble resins contained in the second composition. n The content (mass fraction) of each alkali-soluble resin relative to the total content of the n alkali-soluble resins in the second composition. ). In addition, the "δPb" part in formula (F2C) is replaced by "δPb1×Wb1+δPb2×Wb2+……δPb n ×Wb n " and the same method as in formula (F2A) is used to obtain (where δPb1 to δPb n The values ​​of the polar terms of the Hansen solubility parameters of the n alkali-soluble resins contained in the second composition, Wb1 to Wb n It 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. ).

[0339] In the second composition, only one polymerizable compound may be used, or two or more polymerizable compounds may be used in combination.

[0340] When only one polymerizable compound is included in the second composition, the dispersion term δDm, hydrogen bonding 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 bonding term δHm and polar term δPm of the Hansen solubility parameter of the single polymerizable compound contained in the second composition. When two or more polymerizable compounds are included in the second composition, the "δDm" part in formula (F2A) is replaced by "δDm1×Wm1+δDm2×Wm2+……δDm n ×Wm n "And find out. Among them, δDm1~δDm n =Wm1 to Wm2 represent the values ​​of the dispersion terms of the Hansen solubility parameters of the n polymerizable compounds contained in the second composition. n The content (mass fraction) of each polymerizable compound relative to the total content of n polymerizable compounds in the second composition. That is, when the second composition contains two polymerizable compounds, the "δDm" part in formula (F2A) is replaced by "δDm1×Wm1+δDm2×Wm2" and calculated.

[0341] When the second composition contains two or more polymerizable compounds, the "δHm" part in formula (F2B) is replaced by "δHm1×Wm1+δHm2×Wm2+...δHm n ×Wmn" and calculated using the same method as formula (F2A) (where δHm1 to δHm n =Wm1 to Wm2 represent the values ​​of the hydrogen bonding terms of the Hansen solubility parameters of the n polymerizable compounds contained in the second composition. n The content (mass fraction) of each polymerizable compound relative to the total content of n polymerizable compounds in the second composition). In addition, the "δPm" part in formula (F2C) is replaced by "δPm1×Wm1+δPm2×Wm2+……δPm n ×Wm n " and the same method as in formula (F2A) is used to obtain (where δPm1 to δPm n =Wm1 to Wm2 represent the polar terms of the Hansen solubility parameters of the n polymerizable compounds contained in the second composition. n It represents the content (mass fraction) of each polymerizable compound relative to the total content of n types of polymerizable compounds in the second composition.

[0342] [Preferred embodiment of the second composition]

[0343] As the second composition, it is also preferred that the second composition has each of the following aspects (2A) to (2B) from the viewpoint of achieving more excellent effects of the present invention.

[0344] (2A) The value of ΔHSP1 calculated by the formula (F1) described in the upper part as the composition of the first composition is 6.0 MPa. 0.5 the following.

[0345] (2B) At least one 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 the aromatic ring structure is as described in the embodiment (1B) of the first composition.

[0346] [Photosensitive resin composition according to the third embodiment]

[0347] The photosensitive resin composition of the third embodiment (hereinafter also referred to as "third composition") is a photosensitive resin composition containing an alkali-soluble resin, a polymerizable compound, a photopolymerization initiator, and a surfactant, wherein:

[0348] At least one selected from the alkali-soluble resin and the polymerizable compound and the surfactant each have an aromatic ring structure in the molecule.

[0349] When the transfer film having the photosensitive resin layer formed of the third composition having the above-mentioned constitution is stored for a long period of time and then transferred to a transfer object to form a pattern, the pattern forming performance is unlikely to change over time. That is, even when the transfer film having the photosensitive resin layer formed of the third composition is stored for a long period of time and then transferred to a transfer object to form a pattern, the transfer film exhibits the same pattern forming performance as when the transfer film is transferred to a transfer object immediately after production and subjected to pattern formation.

[0350] The mechanism of action by which the third composition can achieve the above-mentioned effects is not clear, but the present inventors speculate as follows.

[0351] As the reason why the pattern forming performance changes over time when the transfer film after long-term storage is used to form a pattern on the transfer object in the prior art, it is speculated that the surfactant has poor compatibility with the alkali-soluble resin and polymerizable compound equivalent to the matrix component of the photosensitive resin layer, so the surfactant overflows due to environmental changes such as temperature changes during the storage of the transfer film and is concentrated on the surface of the photosensitive resin layer, thereby reducing the adhesion between the photosensitive resin layer and the transfer object after transfer. In addition, it is speculated that as a result, the part with weak adhesion is easily peeled off during development, so that the pattern forming performance formed on the transfer object may change.

[0352] In contrast, in the third composition, at least one selected from an alkali-soluble resin and a polymerizable compound and the surfactant each have an aromatic ring structure in the molecule, thereby improving the compatibility of the components and preventing the surfactant from overflowing. Therefore, it is estimated that even when the pattern is formed by transferring to a transfer object after long-term storage, the pattern forming performance is unlikely to change.

[0353] In addition, when the transfer film having the photosensitive resin layer formed of the third composition is used after long-term storage and transferred onto a transfer object to form a pattern, changes in pattern forming performance are further suppressed, which is also referred to as "the effect of the present invention is more excellent".

[0354] Hereinafter, the third composition will be described in detail.

[0355] In the third composition, 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.

[0356] The aromatic ring in the aromatic ring structure may be a monocyclic or polycyclic aromatic ring.

[0357] The aromatic ring constituting the aromatic ring structure may be any of an aromatic hydrocarbon ring and an aromatic heterocyclic ring, but is preferably an aromatic hydrocarbon ring, and more preferably a benzene ring or a naphthalene ring.

[0358] Among them, from the viewpoint of more excellent effects of the present invention, it is preferred that both the alkali-soluble resin and the polymerizable compound have an aromatic ring structure in the molecule. In other words, the third composition preferably contains an alkali-soluble resin having an aromatic ring structure and a polymerizable compound having an aromatic ring structure.

[0359] The alkali-soluble resin, polymerizable compound and surfactant contained in the third composition are described below. In addition, the various components (photopolymerization initiator and other additives) and their contents other than the above components that the third composition may contain are the same as the various components and their contents of the first composition described above, and the preferred embodiments are also the same.

[0360] 〔Alkali soluble resin〕

[0361] The third composition contains an alkali-soluble resin. Examples of the alkali-soluble resin include the same alkali-soluble resins as those that may be contained in the first composition.

[0362] From the perspective of achieving a more excellent effect of the present invention, it is preferred 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 described in the first composition, which contains one or more repeating units selected from the repeating units represented by the formula (R1) and the repeating units represented by the formula (R2) (hereinafter also referred to as "repeating unit A"), is more preferred.

[0363] The content of the repeating unit (repeating unit A) containing an aromatic ring structure in the resin is preferably 20 to 90% by mass, more preferably 30 to 90% by mass, and further preferably 40 to 80% by mass relative to all repeating units in the resin. The resin may contain only one repeating unit (repeating unit A) containing an aromatic ring structure, or may contain two or more. When the resin contains two or more repeating units (repeating units A) containing an aromatic ring structure, the above content is preferably the total content.

[0364] From the viewpoint of more excellent effects of the present invention, 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.

[0365] The acid value of the alkali-soluble resin is preferably 10 to 200 mgKOH / g, more preferably 60 to 200 mgKOH / g, further preferably 60 to 150 mgKOH / g, and particularly preferably 60 to 130 mgKOH / g. The acid value of the alkali-soluble resin is a value measured by the method described in JIS K0070:1992.

[0366] The third composition may contain one type of alkali-soluble resin alone, or may contain two or more types of alkali-soluble resin.

[0367] From the viewpoint of achieving more excellent effects of the present invention, the content of the alkali-soluble resin is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, and even more preferably 30 to 70% by mass based on the total solid content of the third composition.

[0368] From the viewpoint of achieving more excellent effects of the present invention, the content of the alkali-soluble resin having an aromatic structure in the molecule is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, and further preferably 30 to 70% by mass, based on the total solid content of the third composition.

[0369] 〔Polymerizable compounds〕

[0370] The third composition contains a polymerizable compound. Examples of the polymerizable compound include the same polymerizable compounds as those that may be contained in the first composition.

[0371] From the perspective of achieving a more excellent effect of the present invention, it is preferred 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 described in the first composition is more preferred.

[0372] The polymerizable compound may be used alone or in combination of two or more.

[0373] The content of the polymerizable compound is preferably 10 to 70% by mass, more preferably 15 to 70% by mass, and even more preferably 20 to 70% by mass, relative to the total solid content of the third composition.

[0374] The content of the polymerizable compound containing an aromatic ring structure in the molecule is preferably 10 to 70% by mass, more preferably 15 to 70% by mass, and further preferably 20 to 70% by mass, based on the total solid content of the third composition.

[0375] 〔Surfactant〕

[0376] The third composition contains a surfactant. Examples of the surfactant include the same surfactants as those that may be contained in the first composition.

[0377] From the viewpoint of further improving the effects of the present invention, it is preferred that at least one of the surfactants contained in the third composition is a surfactant containing an aromatic ring structure in its molecule.

[0378] As a surfactant containing an aromatic ring structure in the molecule, it is preferably a structure in which a resin has a first repeating unit containing atoms selected from silicon atoms and fluorine atoms and a second repeating unit containing neither silicon atoms nor fluorine atoms, and at least one of the first repeating unit and the second repeating unit contains an aromatic ring structure. It is more preferably a structure in which a resin has a first repeating unit containing silicon atoms and the second repeating unit, and at least one of the first repeating unit and the second repeating unit contains an aromatic ring structure.

[0379] Specific examples of the first repeating unit include the repeating unit represented by the formula (A-1) or (A-2) described above with respect to the first composition.

[0380] As a specific example of the second repeating unit, from the perspective of achieving a more excellent effect of the present invention, a repeating unit having an aromatic ring structure is preferred, and examples thereof include repeating units represented by formula (B-1), formula (B-3) and formula (B-4) described in the first composition.

[0381] In the surfactant containing an aromatic ring structure in the molecule, the content of the first repeating unit is preferably 20 to 90% by mass, more preferably 30 to 90% by mass, and further preferably 40 to 80% by mass relative to all repeating units of the resin. In the surfactant containing an aromatic ring structure in the molecule, only one first repeating unit may be included, or two or more first repeating units may be included. In addition, when two or more first repeating units are included, the above content is preferably the total content of the first repeating unit.

[0382] In the surfactant containing an aromatic ring structure in the molecule, the content of the second repeating unit is preferably 10 to 80% by mass, more preferably 20 to 70% by mass, and further preferably 20 to 60% by mass relative to all repeating units of the resin. In the surfactant containing an aromatic ring structure in the molecule, only one second repeating unit may be included, or two or more second repeating units may be included. In addition, when two or more second repeating units are included, the above content is preferably the total content of the second repeating units.

[0383] The weight average molecular weight (Mw) of the surfactant is preferably 500 or more, more preferably 1,000 or more, further preferably 10,000 or more, particularly preferably 15,000 or more, and most preferably 18,000 or more. The upper limit is preferably 100,000 or less, and more preferably 80,000 or less.

[0384] The content of the surfactant is preferably 0.01 to 5% by mass, more preferably 0.01 to 3% by mass, and further preferably 0.05 to 1% by mass, relative to the total solid content of the third composition.

[0385] The content of the surfactant containing an aromatic ring structure in the molecule is preferably 0.01 to 5% by mass, more preferably 0.01 to 3% by mass, and further preferably 0.05 to 1% by mass, based on the total solid content of the third composition.

[0386] [Preferred embodiment of the third composition]

[0387] As the third composition, it is also preferable to have each of the following aspects (3A) to (3C) from the viewpoint of further improving the effects of the present invention.

[0388] (3A) The value of ΔHSP3 calculated by the following formula (F3) is 10.0 MPa 0.5 the following.

[0389] Formula (F3): ΔHSP3=(4(δDM-δDS) 2 +(δHM-δHS) 2 +(δPM-δPS) 2 ) 0.5

[0390] In formula (F1), δDM represents the weighted average of the dispersion term of the Hansen solubility parameters of the alkali-soluble resin and the dispersion term of the Hansen solubility parameters of the polymerizable compound calculated by the following formula (F3A). δHM represents the weighted average of the hydrogen bonding term of the Hansen solubility parameters of the alkali-soluble resin and the hydrogen bonding term of the Hansen solubility parameters of the polymerizable compound calculated by the following formula (F3B). δPM represents the weighted average of the polarity term of the Hansen solubility parameters of the alkali-soluble resin and the polarity term of the Hansen solubility parameters of the polymerizable compound calculated by the following formula (F3C). δDS represents the dispersion term of the Hansen solubility parameters of the surfactant. δHS represents the hydrogen bonding term of the Hansen solubility parameters of the surfactant. δPS represents the polarity term of the Hansen solubility parameters of the surfactant.

[0391] Formula (F3A): δDM=δDb×Wb / (Wb+Wm)+δDm×Wm / (Wb+Wm)

[0392] Formula (F3B): δHM=δHb×Wb / (Wb+Wm)+δHm×Wm / (Wb+Wm)

[0393] Formula (F3C): δPM=δPb×Wb / (Wb+Wm)+δPm×Wm / (Wb+Wm)

[0394] 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.

[0395] In formula (F3B), δHb represents the hydrogen bonding term of the Hansen solubility parameter of the alkali-soluble resin, and δHm represents the hydrogen bonding term of the Hansen solubility parameter of the polymerizable compound.

[0396] 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.

[0397] In formula (F3A) to formula (F3C), Wb represents the mass fraction of the alkali-soluble resin relative to the total solid content in the third composition. Wm represents the mass fraction of the polymerizable compound relative to the total solid content in the third composition.

[0398] The surfactant (3B) is a resin having a first repeating unit (polar part) containing an atom selected from silicon atoms and fluorine atoms and a second repeating unit (non-polar part) containing neither silicon atoms nor fluorine atoms (hereinafter also referred to as a "specific surfactant"), and the value of ΔHSP4 calculated by the following formula (F4) is 15.0 MPa 0.5 the following.

[0399] Formula (F4): ΔHSP4=(4(δDM-δDSs) 2 +(δHM-δHSs) 2 +(δPM-δPSs) 2 ) 0.5

[0400] In formula (F4), 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 (F4A). δHM represents the weighted average of the hydrogen bonding term of the Hansen solubility parameter of the alkali-soluble resin and the hydrogen bonding term of the Hansen solubility parameter of the polymerizable compound calculated by the following formula (F4B). 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 (F4C). δDSs is the dispersion term of the Hansen solubility parameter of the non-polar part of the surfactant, and when the above-mentioned surfactant has only one kind of the above-mentioned second repeating unit, it represents the dispersion term of the Hansen solubility parameter of the above-mentioned second repeating unit, and when the above-mentioned surfactant has two or more kinds of the above-mentioned second repeating units, it represents the weighted average of the dispersion terms of the Hansen solubility parameters of the two or more kinds of the above-mentioned second repeating units. δHSs is the hydrogen bonding term of the Hansen solubility parameter of the non-polar part of the surfactant. When the surfactant has only one type of the second repeating unit, it represents the hydrogen bonding term of the Hansen solubility parameter of the second repeating unit. When the surfactant has two or more types of the second repeating units, it represents the weighted average of the hydrogen bonding terms of the Hansen solubility parameters of the two or more second repeating units. δPss is the polar term of the Hansen solubility parameter of the non-polar part of the surfactant. When the surfactant has only one type of the second repeating unit, it represents the polar term of the Hansen solubility parameter of the second repeating unit. When the surfactant has two or more types of the second repeating units, it represents the weighted average of the polar terms of the Hansen solubility parameters of the two or more second repeating units.

[0401] Formula (F4A): δDM=δDb×Wb / (Wb+Wm)+δDm×Wm / (Wb+Wm)

[0402] Formula (F4B): δHM=δHb×Wb / (Wb+Wm)+δHm×Wm / (Wb+Wm)

[0403] Formula (F4C): δPM=δPb×Wb / (Wb+Wm)+δPm×Wm / (Wb+Wm)

[0404] In formula (F4A), 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.

[0405] In formula (F4B), δHb represents the hydrogen bonding term of the Hansen solubility parameter of the alkali-soluble resin, and δHm represents the hydrogen bonding term of the Hansen solubility parameter of the polymerizable compound.

[0406] 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.

[0407] In formula (F4A) to formula (F4C), Wb represents the mass fraction of the alkali-soluble resin relative to the total solid content in the third composition. Wm represents the mass fraction of the polymerizable compound relative to the total solid content in the third composition.

[0408] (3C) At least one selected from 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. The electron accepting group and the electron donating group are as described in the embodiment (1C) of the first composition.

[0409] (Regarding (3A) above)

[0410] In the above (3A), the value of ΔHSP3 calculated by formula (F3) is preferably 10.0 MPa. 0.5 Below, more preferably 9.0 MPa 0.5 Below, more preferably 8.0 MPa 0.5 In addition, as a lower limit, it is only necessary to be 0.0 MPa 0.5 Above 5.0MPa 0.5 The above situations are more common.

[0411] The dispersion term δDb, hydrogen bonding term δHb and polar term δPb of the Hansen solubility parameters of the alkali-soluble resin, the dispersion term δDm, hydrogen bonding term δHm and polar term δPm of the Hansen solubility parameters of the polymerizable compound, and the dispersion term δDS, hydrogen bonding term δHS and polar term δPS of the Hansen solubility parameters of the surfactant were calculated using the commercially available software "HSPiP (developed by www.hansen-solubility.com)" for Windows.

[0412] In addition, in the third composition, only one surfactant may be used, or two or more surfactants may be used in combination. When only one surfactant is included in the third composition, the dispersion term δDS, hydrogen bonding term δHS, and polarity term δPS of the Hansen solubility parameter of the surfactant in formula (F3) respectively represent the dispersion term δDS, hydrogen bonding term δHS, and polarity term δPS of the Hansen solubility parameter of the single surfactant contained in the third composition. When two or more surfactants are included in the third composition, the dispersion term δDS, hydrogen bonding term δHS, and polarity term δPS of the Hansen solubility parameter of the surfactant in formula (F3) respectively represent the weighted average of the dispersion terms of the Hansen solubility parameters of the two or more surfactants, the weighted average of the hydrogen bonding terms of the Hansen solubility parameters of the two or more surfactants, and the weighted average of the polarity terms of the Hansen solubility parameters of the two or more surfactants.

[0413] When two or more surfactants are included in the third composition, the weighted average of the dispersion terms of the Hansen solubility parameters of the two or more surfactants is calculated by the following formula (S1).

[0414] Formula (S1): δDS=δDS1×WS1+δDS2×WS2+…δDS n ×WS n

[0415] Among them, δDS1~δDS n The value of the dispersion term representing the Hansen solubility parameters of the n surfactants contained in the third composition, WS n The content of each surfactant (the content (mass fraction) of each surfactant relative to the total content of n types of surfactants) is represented. That is, for example, when the third composition contains two surfactants in equal amounts, it is represented by δDS=δDS1×0.5+δDS2×0.5.

[0416] Furthermore, the weighted average value of the hydrogen bonding term and the weighted average value of the polar term of the Hansen solubility parameters of two or more surfactants can also be obtained by the same method as described above.

[0417] In the third composition, only one type of alkali-soluble resin may be used, or two or more types may be used in combination.

[0418] When only one alkali-soluble resin is included in the third composition, the dispersion term δDb, hydrogen bonding 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 bonding term δHb and polar term δPb of the Hansen solubility parameter of the single alkali-soluble resin contained in the third composition. When two or more alkali-soluble resins are included in the third composition, the "δDb" part in formula (F3A) is replaced by "δDb1×Wb1+δDb2×Wb2+……δDb n ×Wb n "And find out. Among them, δDb1~δDb n The values ​​of the dispersion terms of the Hansen solubility parameters of the n alkali-soluble resins contained in the third composition, Wb1 to Wb n The content (mass fraction) of each alkali-soluble resin relative to the total content of n alkali-soluble resins in the third composition. That is, when two alkali-soluble resins are included in the third composition, the "δDb" part in formula (F3A) is replaced by "δDb1×Wb1+δDb2×Wb2" and calculated.

[0419] When two or more alkali-soluble resins are included in the third composition, the "δHb" part in formula (F3B) is replaced by "δHb1×Wb1+δHb2×Wb2+...δHb n ×Wb n " and the same method as in formula (F3A) is used to obtain (where δHb1 to δHb n The values ​​of the hydrogen bonding terms of the Hansen solubility parameters of the n alkali-soluble resins contained in the third composition, Wb1 to Wb n The content (mass fraction) of each alkali-soluble resin relative to the total content of the n alkali-soluble resins in the third composition. ). In addition, the "δPb" part in formula (F3C) is replaced by "δPb1×Wb1+δPb2×Wb2+……δPb n ×Wb n " and the same method as in formula (F3A) is used to obtain (where δPb1 to δPb n The values ​​of the polar terms of the Hansen solubility parameters of the n alkali-soluble resins contained in the third composition, Wb1 to Wb n It 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. ).

[0420] In the third composition, only one polymerizable compound may be used, or two or more polymerizable compounds may be used in combination.

[0421] When only one polymerizable compound is included in the third composition, the dispersion term δDm, hydrogen bonding 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 bonding term δHm and polar term δPm of the Hansen solubility parameter of the single polymerizable compound contained in the third composition. When two or more polymerizable compounds are included in the third composition, the "δDm" part in formula (F3A) is replaced by "δDm1×Wm1+δDm2×Wm2+……δDm n ×Wm n "And find out. Among them, δDm1~δDm n The values ​​of the dispersion terms of the Hansen solubility parameters of the n polymerizable compounds contained in the third composition, Wm1 to Wm2 n The content (mass fraction) of each polymerizable compound relative to the total content of n polymerizable compounds in the third composition. That is, when the third composition contains two polymerizable compounds, the "δDm" part in formula (F3A) is replaced by "δDm1×Wm1+δDm2×Wm2" and calculated.

[0422] When two or more polymerizable compounds are included in the third composition, the "δHm" portion in formula (F3B) is replaced by "δHm1×Wm1+δHm2×Wm2+...δHm n ×Wmn" and calculated using the same method as formula (F3A) (where δHm1 to δHm n Wm1 to Wm2 represent the values ​​of the hydrogen bonding terms of the Hansen solubility parameters of the n polymerizable compounds contained in the third composition. n The content (mass fraction) of each polymerizable compound relative to the total content of n polymerizable compounds in the third composition). In addition, the "δPm" part in formula (F3C) is replaced by "δPm1×Wm1+δPm2×Wm2+……δPm n ×Wm n " and the same method as in formula (F3A) is used to obtain (where δPm1 to δPm n =Wm1 to Wm2 represent the polar terms of the Hansen solubility parameters of the n polymerizable compounds contained in the third composition. n It represents the content (mass fraction) of each polymerizable compound relative to the total content of n types of polymerizable compounds in the third composition.

[0423] (Regarding (3B) above)

[0424] In the above (3B), as a specific example of a resin (specific surfactant) having a first repeating unit (polar part) containing atoms selected from the group consisting of silicon atoms and fluorine atoms and a second repeating unit (non-polar part) containing neither silicon atoms nor fluorine atoms, the same surfactant as the specific surfactant described in the second composition can be used.

[0425] Furthermore, in the above (3B), the value of ΔHSP4 calculated by formula (F4) is preferably 15.0 MPa. 0.5 Below, more preferably 14.5MPa 0.5 Below, more preferably 14.0 MPa 0.5 In addition, as a lower limit, it is only necessary to be 0.0 MPa 0.5 Above, 7.0MPa 0.5 The above situations are more common.

[0426] The dispersion term δDb, hydrogen bonding term δHb and polar term δPb of the Hansen solubility parameters of the alkali-soluble resin, the dispersion term δDm, hydrogen bonding term δHm and polar term δPm of the Hansen solubility parameters of the polymerizable compound, and the dispersion term δDSs, hydrogen bonding term δHSs and polar term δPSs of the Hansen solubility parameters of the non-polar part of the specific surfactant were calculated using the commercially available software "HSPiP (developed by www.hansen-solubility.com)" for Windows.

[0427] In the above formula (F4), when the specific surfactant has two or more second repeating units, δDSs represents the weighted average of the dispersion terms of the Hansen solubility parameters of the two or more second repeating units. Here, the weighted average is calculated by the following formula (S2).

[0428] Formula (S2): δDSs=δDSs1×WSs1+δDSs2×WSs2+…δDSs n ×WS n

[0429] Among them, δDSs1~δDSs n The values ​​of the dispersion terms representing the Hansen solubility parameters of the n second repeating units contained in the specific surfactant, WSs1 to WSs n It represents the content of each second repeating unit (the content (mass fraction) of each second repeating unit relative to the total content of the second repeating units of the specific surfactant). That is, for example, when the specific surfactant includes two types of repeating units, it is represented by δDSs=δDSs1×WSs1+δDSs2×WSs2.

[0430] Furthermore, the weighted average value of the hydrogen bonding term and the weighted average value of the polar term of each Hansen solubility parameter of the specific surfactant having two or more second repeating units are also determined by the same method as described above.

[0431] In addition, in the third composition, only one specific surfactant may be used, or two or more specific surfactants may be used in combination. When only one specific surfactant is contained in the third composition, the dispersion term δDSs, hydrogen bonding term δHSs, and polar term δPSs of the Hansen solubility parameter of the non-polar part of the specific surfactant in formula (F4) respectively represent the dispersion term δDSs, hydrogen bonding 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 included in the third composition, the dispersion term δDSs, hydrogen bonding term δHSs and polar term δPSs of the Hansen solubility parameters of the non-polar part of the specific surfactant in formula (F4) respectively represent the value obtained by weighted averaging the dispersion terms of the Hansen solubility parameters of the non-polar parts of each of the two or more specific surfactants, the value obtained by weighted averaging the hydrogen bonding terms of the Hansen solubility parameters of the non-polar parts of each of the two or more specific surfactants, and the value obtained by weighted averaging the polar terms of the Hansen solubility parameters of the non-polar parts of each of the two or more specific surfactants.

[0432] When two or more specific surfactants are included in the third composition, a value obtained by weighted averaging the dispersion terms of the Hansen solubility parameters of the nonpolar sites of the two or more specific surfactants is determined by the following formula (S3).

[0433] Formula (S3): δDSs=δDSs1×WSs1+δDSs2×WSs2+…δDSs n ×WS n

[0434] Here, δDSs1~δDSs n The value of the dispersion term representing the Hansen solubility parameter of the nonpolar part in the n specific surfactants contained in the third composition, WS s1 ~WS sn Indicates 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 third composition contains two specific surfactants in equal amounts, it is represented by δDSs=δDSs1×0.5+δDSs2×0.5.

[0435] Furthermore, the value obtained by weighted averaging the hydrogen bonding terms of the Hansen solubility parameters of the respective non-polar parts of two or more specific surfactants and the value obtained by weighted averaging the polarities of the Hansen solubility parameters of the respective non-polar parts of two or more specific surfactants can also be calculated by the same method as described above.

[0436] In the third composition, only one type of alkali-soluble resin may be used, or two or more types may be used in combination.

[0437] When only one alkali-soluble resin is included in the third composition, the dispersion term δDb, hydrogen bonding 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 bonding term δHb and polar term δPb of the Hansen solubility parameter of the single alkali-soluble resin contained in the third composition. When two or more alkali-soluble resins are included in the third composition, the "δDb" part in formula (F4A) is replaced by "δDb1×Wb1+δDb2×Wb2+……δDb n ×Wb n "And find out. Among them, δDb1~δDb n The values ​​of the dispersion terms of the Hansen solubility parameters of the n alkali-soluble resins contained in the third composition, Wb1 to Wb n The content (mass fraction) of each alkali-soluble resin relative to the total content of n alkali-soluble resins in the third composition. That is, when two alkali-soluble resins are included in the third composition, the "δDb" part in formula (F4A) is replaced by "δDb1×Wb1+δDb2×Wb2" and calculated.

[0438] When two or more alkali-soluble resins are included in the third composition, the "δHb" part in formula (F4B) is replaced by "δHb1×Wb1+δHb2×Wb2+...δHb N ×Wb N " and the same method as in formula (F4A) is used to obtain (where δHb1 to δHb n The values ​​of the hydrogen bonding terms of the Hansen solubility parameters of the n alkali-soluble resins contained in the third composition, Wb1 to Wb n The content (mass fraction) of each alkali-soluble resin relative to the total content of the n alkali-soluble resins in the third composition. ). In addition, the "δPb" part in formula (F4C) is replaced by "δPb1×Wb1+δPb2×Wb2+……δPb n ×Wb n " and the same method as in formula (F4A) is used to obtain (where δPb1 to δPb nThe values ​​of the polar terms of the Hansen solubility parameters of the n alkali-soluble resins contained in the third composition, Wb1 to Wb n It 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. ).

[0439] In the third composition, only one polymerizable compound may be used, or two or more polymerizable compounds may be used in combination.

[0440] When only one polymerizable compound is included in the third composition, the dispersion term δDm, hydrogen bonding 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 bonding term δHm and polar term δPm of the Hansen solubility parameter of the single polymerizable compound contained in the third composition. When two or more polymerizable compounds are included in the third composition, the "δDm" part in formula (F4A) is replaced by "δDm1×Wm1+δDm2×Wm2+……δDm n ×Wm n "And find out. Among them, δDm1~δDm n The values ​​of the dispersion terms of the Hansen solubility parameters of the n polymerizable compounds contained in the third composition, Wm1 to Wm2 n The content (mass fraction) of each polymerizable compound relative to the total content of n polymerizable compounds in the third composition. That is, when the third composition contains two polymerizable compounds, the "δDm" part in formula (F4A) is replaced by "δDm1×Wm1+δDm2×Wm2" and calculated.

[0441] When two or more polymerizable compounds are included in the third composition, the "δHm" portion in formula (F4B) is replaced by "δHm1×Wm1+δHm2×Wm2+...δHm n ×Wmn” and calculated using the same method as formula (F4A) (where δHm1 to δHm n Wm1 to Wm2 represent the values ​​of the hydrogen bonding terms of the Hansen solubility parameters of the n polymerizable compounds contained in the third composition. n represents the content (mass fraction) of each polymerizable compound relative to the total content of n polymerizable compounds in the third composition). In addition, the "δPm" part in formula (F4C) is replaced by "δPm1×Wm1+δPm2×Wm2+……δPm n ×Wm n " and the same method as in formula (F4A) is used to obtain (where δPm1 to δPm n=Wm1 to Wm2 represent the polar terms of the Hansen solubility parameters of the n polymerizable compounds contained in the third composition. n It represents the content (mass fraction) of each polymerizable compound relative to the total content of n types of polymerizable compounds in the third composition.

[0442] [Photosensitive resin composition according to the fourth embodiment]

[0443] The photosensitive resin composition of the fourth embodiment (hereinafter also referred to as "the fourth composition") is a photosensitive resin composition comprising an alkali-soluble resin, a polymerizable compound, a photopolymerization initiator, and a surfactant, wherein:

[0444] 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.

[0445] When the transfer film having the photosensitive resin layer formed of the fourth composition having the above-mentioned constitution is stored for a long period of time and then transferred to a transfer object to form a pattern, the pattern forming performance is unlikely to change over time. That is, even when the transfer film having the photosensitive resin layer formed of the fourth composition is transferred to a transfer object to form a pattern after being stored for a long period of time, the transfer film exhibits the same pattern forming performance as when the transfer film is transferred to a transfer object immediately after production and subjected to pattern formation.

[0446] The mechanism of action by which the fourth composition can achieve the above-mentioned effects is not clear, but the present inventors speculate as follows.

[0447] As the reason why the pattern forming performance changes over time when the transfer film after long-term storage is used to form a pattern on the transfer object in the prior art, it is speculated that the surfactant has poor compatibility with the alkali-soluble resin and polymerizable compound equivalent to the matrix component of the photosensitive resin layer, so the surfactant overflows due to environmental changes such as temperature changes during the storage of the transfer film and is concentrated on the surface of the photosensitive resin layer, thereby reducing the adhesion between the photosensitive resin layer and the transfer object after transfer. In addition, it is speculated that as a result, the part with weak adhesion is easily peeled off during development, so that the pattern forming performance formed on the transfer object may change.

[0448] In contrast, in the fourth composition, at least one selected from 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, thereby improving the compatibility of the components through electronic interaction, and the surfactant is less likely to overflow. Therefore, it is estimated that even if the pattern is formed by transferring to a transfer object after long-term storage, the pattern forming performance is less likely to change.

[0449] In addition, when the transfer film having the photosensitive resin layer formed of the fourth composition is used after long-term storage and transferred onto a transfer object to form a pattern, changes in pattern forming performance are further suppressed, which is also referred to as "the effect of the present invention is more excellent".

[0450] Hereinafter, the fourth composition will be described in detail.

[0451] In the fourth composition, at least one selected from 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.

[0452] Specific examples of the electron-donating group include unsubstituted or substituted amino groups, substituted or unsubstituted acylamino groups, nitro groups, cyano groups, saturated or unsaturated hydrocarbon groups substituted by halogen (e.g., alkyl groups substituted by halogen, alkenyl groups substituted by halogen, aromatic hydrocarbon ring groups substituted by halogen), nitrogen-containing heterocyclic groups, oxygen-containing heterocyclic groups, and sulfur-containing heterocyclic groups.

[0453] Examples of the unsubstituted or substituted amino group include -NH2, -NHR Y and-NR Y 2 etc. R Y represents an alkyl group.

[0454] Examples of the substituted or unsubstituted acylamino group include -NHCOR Y and-NR Y COR Y Etc. R Y represents an alkyl group.

[0455] As in R Y The alkyl group mentioned in the above is preferably linear or branched, and has, for example, 1 to 10 carbon atoms, and more preferably 1 to 6 carbon atoms.

[0456] Examples of the electron accepting group include acid groups, specifically, carboxyl groups, phenolic hydroxyl groups (the hydroxyl group substituted on an aromatic ring corresponds to this), sulfonic acid groups, and phosphoric acid groups. Among them, carboxyl groups are preferred.

[0457] Among them, from the viewpoint of more excellent effects of the present invention, an embodiment in which 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 is preferred.

[0458] Furthermore, from the perspective of achieving a more excellent effect of the present invention, it is also preferred that the alkali-soluble resin contains a repeating unit having an electron accepting group and the surfactant contains a repeating unit having an electron donating group. In other words, the fourth composition preferably contains an alkali-soluble resin containing a repeating unit having an electron accepting group and a surfactant containing a repeating unit having an electron donating group.

[0459] The alkali-soluble resin, polymerizable compound and surfactant contained in the fourth composition are described below. In addition, the various components (photopolymerization initiator and other additives) and their contents other than the above components that the fourth composition may contain are the same as the various components and their contents of the first composition described above, and the preferred embodiments are also the same.

[0460] (Alkali soluble resin)

[0461] The fourth composition contains an alkali-soluble resin. Examples of the alkali-soluble resin include the same alkali-soluble resins as those that may be contained in the first composition.

[0462] From the viewpoint of achieving more excellent effects of the present invention, at least one of the alkali-soluble resins contained in the fourth composition is preferably a resin having an electron accepting group (preferably a carboxyl group), and more preferably a resin containing a repeating unit having an electron accepting group (preferably a carboxyl group).

[0463] The content of the repeating unit having an electron accepting group in the resin is preferably 1 to 50% by mass, more preferably 2 to 40% by mass, and further preferably 3 to 30% by mass, based on all the repeating units in the resin.

[0464] The resin may contain only one type of repeating unit having an electron accepting group, or may contain 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.

[0465] From the viewpoint of more excellent effects of the present invention, 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.

[0466] The acid value of the alkali-soluble resin is preferably 10 to 200 mgKOH / g, more preferably 60 to 200 mgKOH / g, further preferably 60 to 150 mgKOH / g, and particularly preferably 60 to 130 mgKOH / g. The acid value of the alkali-soluble resin is a value measured by the method described in JIS K0070:1992.

[0467] The fourth composition may contain one type of alkali-soluble resin alone, or may contain two or more types of alkali-soluble resin.

[0468] From the viewpoint of achieving more excellent effects of the present invention, the content of the alkali-soluble resin is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, and even more preferably 30 to 70% by mass based on the total solid content of the fourth composition.

[0469] From the viewpoint of further improving the effects of the present invention, the content of the alkali-soluble resin having an electron accepting group is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, and further preferably 30 to 70% by mass based on the total solid content of the fourth composition.

[0470] 〔Polymerizable compounds〕

[0471] The fourth composition contains a polymerizable compound. Examples of the polymerizable compound include the same polymerizable compounds as those that may be contained in the first composition.

[0472] From the viewpoint of further improving the 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.

[0473] The number of groups selected from the electron accepting group and the electron donating group in the polymerizable compound may be 1 or more, and more preferably 2 or more. The upper limit is, for example, 6 or less.

[0474] The polymerizable compound may be used alone or in combination of two or more.

[0475] The content of the polymerizable compound is preferably 10 to 70% by mass, more preferably 15 to 70% by mass, and even more preferably 20 to 70% by mass, relative to the total solid content of the fourth composition.

[0476] The content of the polymerizable compound containing a group selected from electron accepting groups and electron donating groups is preferably 10 to 70% by mass, more preferably 15 to 70% by mass, and further preferably 20 to 70% by mass, based on the total solid content of the fourth composition.

[0477] 〔Surfactant〕

[0478] The fourth composition contains a surfactant. Examples of the surfactant include the same surfactants as those that may be contained in the first composition.

[0479] From the viewpoint of further improving the effects of the present invention, at least one of the surfactants contained in the fourth composition is preferably a surfactant containing at least one of an electron accepting group and an electron donating group, and more preferably a surfactant containing an electron donating group.

[0480] As a surfactant containing an electron-donating group in the molecule, it is preferred to have a resin having a first repeating unit (polar part) containing an atom selected from silicon atoms and fluorine atoms and a second repeating unit (non-polar part) containing neither silicon atoms nor fluorine atoms, and at least one of the first repeating unit and the second repeating unit contains a group selected from electron-accepting groups and electron-donating groups. It is more preferred to have a resin having a first repeating unit containing silicon atoms and the second repeating unit, and at least one of the first repeating unit and the second repeating unit contains a group selected from electron-accepting groups and electron-donating groups. It is further preferred to have a resin having a first repeating unit containing silicon atoms and the second repeating unit, and the second repeating unit contains an electron-donating group.

[0481] Specific examples of the first repeating unit include the repeating unit represented by the formula (A-1) or (A-2) described above with respect to the first composition.

[0482] Specific examples of the second repeating unit include, from the viewpoint of further improving the effect of the present invention, the repeating unit represented by the formula (B-1) described in the first composition, wherein R in the formula (B-1) is B12 The substituent that the monovalent aromatic ring group represented by represents an electron-donating group, is a repeating unit represented by formula (B-1) and R in formula (B-1) B12 The monovalent aromatic ring group represented by further has a substituent represented by formula (M1) and R in formula (M1) M1 The substituent represented by represents an electron-donating group and is a repeating unit represented by formula (B-2) and R in the formula B22 Substituents other than aromatic groups shown here represent electron-donating groups.

[0483] In the surfactant comprising at least one of an electron accepting group and an electron donating group, the content of the first repeating unit relative to all repeating units of the resin is preferably 20 to 90% by mass, more preferably 30 to 90% by mass, and further preferably 40 to 80% by mass. In the surfactant comprising at least one of an electron accepting group and an electron donating group, only one first repeating unit may be included, or two or more may be included. In addition, when two or more first repeating units are included, the above content is preferably the total content of the first repeating unit.

[0484] In the surfactant comprising 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% by mass, more preferably 20 to 70% by mass, and further preferably 20 to 60% by mass relative to all repeating units of the surfactant comprising at least one of an electron accepting group and an electron donating group. In the surfactant comprising at least one of an electron accepting group and an electron donating group, only one second repeating unit may be included, or two or more may be included. In addition, when two or more second repeating units are included, the above content is preferably the total content of the second repeating units.

[0485] The weight average molecular weight (Mw) of the surfactant is preferably 500 or more, more preferably 1,000 or more, further preferably 10,000 or more, particularly preferably 15,000 or more, and most preferably 18,000 or more. The upper limit is preferably 100,000 or less, and more preferably 80,000 or less.

[0486] The content of the surfactant is preferably 0.01 to 5% by mass, more preferably 0.01 to 3% by mass, and even more preferably 0.05 to 1% by mass, relative to the total solid content of the fourth composition.

[0487] 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 further preferably 0.05 to 1 mass % based on the total solid content of the fourth composition.

[0488] [Preferred embodiment of the fourth composition]

[0489] As the fourth composition, it is also preferred that the composition has each of the following aspects (4A) to (4C) from the viewpoint of achieving more excellent effects of the present invention.

[0490] (4A) The value of ΔHSP1 calculated by the formula (F1) described in the upper part as the composition of the first composition is 6.0 MPa. 0.5 the following.

[0491] The surfactant (4B) is a resin having a first repeating unit (polar part) containing an atom selected from silicon atoms and fluorine atoms and a second repeating unit (non-polar part) containing neither silicon atoms nor fluorine atoms (hereinafter also referred to as a "specific surfactant"), and the value of ΔHSP4 calculated by the formula (F4) described as the composition of the third composition is 15.0 MPa. 0.5 In addition, the value of ΔHSP4 is preferably 14.5 MPa 0.5 Below, more preferably 14.0 MPa 0.5 Below, more preferably 12.0 MPa 0.5 As the lower limit, it is only necessary to be 0.0 MPa. 0.5 Above, can be 5.0MPa 0.5 above.

[0492] (4C) At least one 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 the aromatic ring structure is as described in the embodiment (1B) of the first composition.

[0493] In the above (4B), as a specific example of a resin (specific surfactant) having a first repeating unit (polar part) containing atoms selected from silicon atoms and fluorine atoms and a second repeating unit (non-polar part) containing neither silicon atoms nor fluorine atoms, the same surfactant as the specific surfactant described in the second composition in the previous paragraph can be used.

[0494] [Transfer film]

[0495] The transfer film of the present invention comprises: a temporary support; a photosensitive resin layer formed of a photosensitive resin composition (a composition selected from the first to fourth compositions); and a protective layer (cover film).

[0496] The transfer film may have other composition layers except the photosensitive resin layer. As other composition layers, thermoplastic resin layers and intermediate layers can be cited. When the transfer film has a thermoplastic resin layer and an intermediate layer, between the temporary support and the photosensitive resin layer, it is preferred to have an intermediate layer and a thermoplastic resin layer in order from the photosensitive resin layer side.

[0497] Figure 1 It is a schematic cross-sectional view showing an example of an embodiment of the transfer film.

[0498] Figure 1 The transfer film 10 shown includes 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.

[0499] in addition, Figure 1The transfer film 10 shown is in a form in which the thermoplastic resin layer 3 and the intermediate layer 5 are arranged, but the thermoplastic resin layer 3 and the intermediate layer 5 may not be arranged.

[0500] Furthermore, the transfer film may be in a form without the protective film 9 .

[0501] Hereinafter, each component of the transfer film will be described in detail.

[0502] Temporary support

[0503] The transfer film has a temporary support.

[0504] The temporary support is a member that supports a composition layer such as a photosensitive resin layer, and is finally removed by a peeling treatment.

[0505] The temporary support may have a single-layer structure or a multi-layer structure.

[0506] The temporary support is preferably a film, more preferably a resin film.

[0507] As the temporary support, a film that is flexible and does not undergo significant deformation, shrinkage, or stretching under pressure or under pressure and heating is also preferred. Examples of the above-mentioned film include polyethylene terephthalate film (e.g., biaxially stretched polyethylene terephthalate film, etc.), polymethyl methacrylate film, cellulose triacetate film, polystyrene film, polyimide film, and polycarbonate film, preferably polyethylene terephthalate film. In addition, the temporary support is also preferably free of deformation such as wrinkles and scratches.

[0508] From the aspect of being able to carry out pattern exposure across the temporary support, the temporary support preferably has high transparency. Specifically, the transmittance at any of the preferred wavelengths 313nm, 365nm, 405nm and 436nm is 60% or more, more preferably 70% or more, further preferably 80% or more, and particularly preferably 90% or more. The upper limit is preferably less than 100%. As the preferred value of the transmittance at any of the above-mentioned wavelengths, for example, 87%, 92% and 98% can be cited.

[0509] From the perspective of pattern formation during pattern exposure through the temporary support and the transparency of the temporary support, the temporary support preferably has a small haze. Specifically, the haze value of the temporary support is preferably 2% or less, more preferably 0.5% or less, and further preferably 0.1% or less. The lower limit is preferably 0% or more.

[0510] From the perspective of pattern formation during pattern exposure through the temporary support and the transparency of the temporary support, it is preferred that the number of particles, foreign matter and defects contained in the temporary support is small. Specifically, the number of particles, foreign matter and defects with a diameter of 1 μm or more in the temporary support is preferably 50 / mm 2 Below, more preferably 10 / mm 2 Below, more preferably 3 pieces / mm 2 Below, especially preferably 0 / mm 2 .

[0511] As a specific example of the number of particles, foreign matter and defects with a diameter of 1 μm or more in the temporary support, 2 particles / mm 2 and 0 / mm 2 .

[0512] The thickness of the temporary support is preferably 5 to 200 μm, more preferably 5 to 150 μm, further preferably 5 to 50 μm, and particularly preferably 5 to 35 μm from the viewpoint of ease of handling and versatility.

[0513] The thickness of the temporary support body was set as an average value of arbitrary five points measured by cross-sectional observation using SEM.

[0514] The surface of the temporary support in contact with the composition layer may be surface-modified by UV irradiation, corona discharge, plasma, or the like, from the viewpoint of improving the adhesion between the temporary support and the photosensitive resin layer.

[0515] When surface modification is performed by UV irradiation, the exposure amount of UV irradiation is preferably 10 to 2000 mJ / cm 2 , more preferably 50 to 1000 mJ / cm 2 .

[0516] Examples of the light source for UV irradiation include low-pressure mercury lamps, high-pressure mercury lamps, ultrahigh-pressure mercury lamps, carbon arc lamps, metal halide lamps, xenon lamps, chemical lamps, electrodeless discharge lamps, and light-emitting diodes that emit light in a wavelength region of 150 to 450 nm.

[0517] Lamp output and illumination can be adjusted appropriately.

[0518] Examples of the temporary support include a biaxially stretched polyethylene terephthalate film having a film thickness of 16 μm, a biaxially stretched polyethylene terephthalate film having a film thickness of 12 μm, and a biaxially stretched polyethylene terephthalate film having a film thickness of 9 μm.

[0519] The temporary support may be a recycled product. As a recycled product, for example, a used film or the like is washed and cut and the obtained material is filmized. As a commercially available product of the recycled product, for example, the Ecouse series (manufactured by TORAY INDUSTRIES, INC.) can be cited.

[0520] As a temporary support body, for example, the records in paragraphs 0017 to 0018 of Japanese Patent Publication No. 2014-085643, paragraphs 0019 to 0026 of Japanese Patent Publication No. 2016-027363, paragraphs 0041 to 0057 of International Publication No. 2012 / 081680, and paragraphs 0029 to 0040 of International Publication No. 2018 / 179370 can be cited, and the contents of these publications are incorporated into this specification.

[0521] From the perspective of providing handleability, the temporary support may have a layer containing fine particles (lubricant layer) on one or both surfaces of the temporary support. 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.

[0522] Commercially available products of temporary supports include, for example, lumirror16FB40, lumirror16KS40, lumirror#38-U48, lumirror#75-U34 and lumirror#25T60 (all manufactured by TORAY INDUSTRIES, INC.); COSMOSHINEA4100, COSMOSHINEA4160, COSMOSHINEA4300, COSMOSHINEA4360 and COSMOSHINEA8300 (all manufactured by TOYOBO CO., LTD.).

[0523] [Photosensitive resin layer]

[0524] The photosensitive resin layer is a layer formed using the photosensitive resin composition described above.

[0525] The various components that may be contained in the photosensitive resin layer have the same meanings as, for example, the various components that may be contained in the photosensitive resin composition, and preferred aspects are also the same.

[0526] The preferred numerical range of the content of each component in the photosensitive resin layer is the same as the preferred range obtained by rewriting the above-mentioned "content (mass %) of each component relative to the total solid content of the photosensitive resin composition" as "content (mass %) of each component relative to the total mass of the photosensitive resin layer". For example, the description "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" is rewritten as "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".

[0527] <Thickness of Photosensitive Resin Layer>

[0528] The average thickness of the photosensitive resin layer is preferably 0.5 to 40 μm, more preferably 0.5 to 25 μm, and further preferably 3 to 20 μm. When the average thickness of the photosensitive resin layer is 40 μm or less, it is preferred from the perspective of excellent pattern resolution, and when the average thickness of the photosensitive resin layer is 0.5 μm or more, it is preferred from the perspective of excellent pattern reliability.

[0529] 〔Other layers〕

[0530] The transfer film may include other layers (hereinafter also referred to as “other layers”) other than the above-mentioned layers. Examples of the other layers include the above-mentioned intermediate layer and thermoplastic resin layer, and known layers can be appropriately adopted.

[0531] The intermediate layer is preferably a water-soluble resin layer containing a water-soluble resin.

[0532] Examples of the intermediate layer (water-soluble resin layer) and the thermoplastic resin layer include the descriptions in paragraphs 0164 to 0204 of International Publication No. 2021 / 166719, and these contents are incorporated into the present specification.

[0533] Furthermore, 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.

[0534] 〔Protective layer〕

[0535] The transfer film has a protective layer (protective film).

[0536] As the protective film, for example, a resin film having heat resistance and solvent resistance can be cited. Specifically, polyolefin films such as polypropylene films and polyethylene films, polyester films such as polyethylene terephthalate films, polycarbonate films, and polystyrene films can be cited. In addition, as the protective film, a resin film made of the same material as the above-mentioned temporary support can also be used. In addition, for example, the records of paragraphs 0083 to 0087 and paragraph 0093 of Japanese Patent Publication No. 2006-259138 can be cited, and these contents are incorporated into this specification.

[0537] As the protective film, among them, a polyolefin film or a polyester film is preferred, and a polypropylene film or a polyethylene terephthalate film is more preferred.

[0538] The thickness of the protective film is preferably 1 to 100 μm, more preferably 5 to 50 μm, further preferably 5 to 40 μm, and particularly preferably 15 to 30 μm.

[0539] The thickness of the protective film is preferably 1 μm or more from the viewpoint of excellent mechanical strength, and is preferably 100 μm or less from the viewpoint of relatively low cost.

[0540] The number of fisheyes with a diameter of 80 ∑m or more contained in the protective film is preferably 5 / m 2 The lower limit is preferably 0 pieces / m 2 above.

[0541] "Fish eyes" refer to the parts formed when foreign matter, undissolved matter, oxidative degradation products, etc. of the material are introduced into the film when the material is hot-melted, kneaded, extruded, biaxially stretched, casted, etc. to produce a film.

[0542] The number of particles with a diameter of 3 μm or more contained in the protective film is preferably 30 particles / mm 2 Below, more preferably 10 / mm 2 Below, more preferably 5 / mm 2 The lower limit is preferably 0 pieces / mm 2 In the case of the above range, it is possible to suppress defects caused by the transfer of the unevenness due to the particles contained in the protective film to the photosensitive resin layer or the conductive layer.

[0543] From the perspective of providing windability, the arithmetic mean roughness Ra of the surface opposite to the surface in contact with the photosensitive resin layer of the protective film or the surface in contact with the photosensitive resin layer is preferably 0.01 μm or more, more preferably 0.02 μm or more, and further preferably 0.03 μm or more. The upper limit is preferably less than 0.50 μm, more preferably 0.40 μm or less, and further preferably 0.30 μm or less.

[0544] 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.), Cerapeel (registered trademark) 25WZ (manufactured by Toray Advanced Film Co., Ltd.), and lumirror (registered trademark) 16QS62 (16KS40) (manufactured by TORAY INDUSTRIES, INC.).

[0545] The protective film may also be a recycled product. As a recycled product, for example, a used film is washed and cut and the obtained material is film-formed. As a commercially available product of the recycled product, for example, the Ecouse series (manufactured by TORAY INDUSTRIES, INC.) can be cited.

[0546] [Method for producing transfer film]

[0547] The method for producing the transfer film is not particularly limited as long as it is a method for producing the transfer film using the photosensitive resin composition described above.

[0548] The method for producing the transfer film is preferably performed by coating the above-described photosensitive resin composition on a temporary support to form a photosensitive resin layer.

[0549] For example, as Figure 1 The method for producing the transfer film 10 shown in the figure may include the following steps: after sequentially forming the thermoplastic resin layer 3 and the intermediate layer 5 on the surface of the temporary support 1, coating the surface of the intermediate layer 5 with a photosensitive resin composition to form a coating film, and further drying the coating film to form a photosensitive resin layer 7. Then, a protective film is pressed onto the photosensitive resin layer 7 of the transfer film 10 produced by the above-mentioned production method to produce the transfer film 10. Figure 1 The transfer film 10 is shown.

[0550] Furthermore, it can be manufactured Figure 1 The transfer film 1 shown is then wound up and stored as a roll-shaped transfer film 1. The roll-shaped transfer film 1 can be used in a step of laminating the transfer film 1 to a substrate in a roll-to-roll method without changing its form.

[0551] 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.

[0552] Examples of the composition for forming an intermediate layer and the method for forming an intermediate layer, and the composition for forming a thermoplastic resin layer and the method for forming a thermoplastic resin layer include paragraphs 0133 to 0136 and 0143 to 0144 of International Publication No. 2021 / 033451, and these contents are incorporated into this specification.

[0553] [Method for forming photosensitive resin layer]

[0554] As a method for forming the photosensitive resin layer, for example, a known method can be mentioned.

[0555] Specifically, the formation method of applying and drying the photosensitive resin composition described above can be mentioned.

[0556] Examples of the coating method include slit coating, spin coating, curtain coating, and inkjet coating.

[0557] The photosensitive resin composition used in the method for forming a photosensitive resin layer preferably contains a solvent. The solvent has the same meaning as the solvent that may be contained in the photosensitive resin composition described above, and the preferred embodiment is also the same.

[0558] 〔use〕

[0559] The pattern (cured film) obtained from the photosensitive resin layer formed using the above-mentioned transfer film can be applied to various purposes. For example, it can be used as a resist film in the process of forming a circuit on a semiconductor substrate by plating and in the process of forming a circuit on a metal substrate or a resin substrate with a metal layer by etching. In addition, it can be used as a resist film in the manufacture of a metal mask. As a metal mask, a vapor deposition mask for manufacturing OLEDs, etc. can be cited. As an example of a vapor deposition mask, the vapor deposition mask described in paragraphs 0245 to 0257 of Japanese Patent Gazette No. 2022-168819 can be cited.

[0560] As a method for producing a laminated body having a metal pattern layer using the above-mentioned transfer film, it is preferable to have the following steps, for example.

[0561] Step X1: A step of laminating the transfer film and the substrate so that the surface exposed by peeling off the protective layer of the transfer film contacts the metal layer of the substrate having the metal layer on the surface.

[0562] Step X2: Exposure step of pattern-exposing the photosensitive resin layer

[0563] Step X3: A developing step of developing the exposed photosensitive resin layer using a developer to form a resist pattern

[0564] Step X4: an etching step (step X4-1) of etching the metal layer in the region where the resist pattern is not provided, or a plating step (step X4-2) of plating the metal layer

[0565] Step X5: Resist stripping step of stripping the resist pattern

[0566] Step X6: When the plating treatment step (step X4-2) is included in step X4, a step of removing the metal layer exposed by the resist stripping step and forming a metal pattern layer on the substrate

[0567] Step X7: Step of peeling off the temporary support between the laminating step and the exposure step or between the exposure step and the development step

[0568] Hereinafter, each step will be described in detail.

[0569] [Process X1 (bonding process)]

[0570] During the lamination, it is preferred that the surface of the transfer film on the side opposite to the temporary support body side is brought into contact with the metal layer on the substrate and pressure-bonded. In addition, the protective layer is peeled off before lamination.

[0571] Examples of the pressure-bonding method include known transfer methods and lamination methods, and a method in which the surface of the transfer film opposite to the temporary support side is superimposed on the substrate and pressure and heating are performed using a roller or the like.

[0572] Examples of the lamination method include a method using a known laminator such as a vacuum laminator and an automatic cutting laminator.

[0573] The lamination temperature is preferably 70 to 130°C.

[0574] A substrate having a metal layer on the surface (substrate with a metal layer) includes a substrate and a metal layer disposed on the surface of the substrate.

[0575] The substrate with a metal layer may have any layer other than the above-mentioned metal layer formed on the substrate as required. 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.

[0576] As the substrate, for example, a resin substrate, a glass substrate, a ceramic substrate and a semiconductor substrate can be cited, and the substrate described in paragraph

[0140] of International Publication No. 2018 / 155193 is preferred.

[0577] As a material of the resin substrate, polyethylene terephthalate, cycloolefin polymer or polyimide is preferable.

[0578] The thickness of the resin substrate is preferably 5 to 200 μm, more preferably 10 to 100 μm.

[0579] The metal layer is a layer containing a metal, and the metal is not particularly limited, and a known metal can be used. The metal layer is preferably a conductive layer.

[0580] Examples of the main component of the metal layer (so-called main metal) include copper, chromium, lead, nickel, gold, silver, tin, and zinc. The main component refers to the metal with the largest content among the metals contained in the metal layer.

[0581] The thickness of the metal layer is not particularly limited, but is preferably 50 nm or more, more preferably 100 nm or more. The upper limit is not particularly limited, but is preferably 2 μm or less.

[0582] The method for forming the metal layer is not particularly limited, and examples thereof include a method of applying a dispersion in which metal fine particles are dispersed and calcining the coating, a sputtering method, a vapor deposition method, and other well-known methods.

[0583] One or more metal layers may be arranged on the substrate.

[0584] When two or more metal layers are configured, the two or more metal layers may be the same as or different from each other, and are preferably metal layers of different materials.

[0585] Examples of the metal contained in the metal layer include gold, silver, copper, molybdenum, aluminum, titanium, chromium, zinc, manganese, and alloys of these. Copper, molybdenum, aluminum, or titanium is preferred, and copper is more preferred.

[0586] [Process X2 (exposure process)]

[0587] The exposure step is a step of pattern-exposing the photosensitive resin layer.

[0588] “Pattern exposure” means exposure in a pattern-like form in which exposed areas and non-exposed areas exist.

[0589] The positional relationship between the exposure portion (exposure region) and the non-exposure portion (non-exposure region) in pattern exposure can be adjusted as appropriate.

[0590] The exposure direction may be from the photosensitive resin layer side or the side opposite to the photosensitive resin layer side (substrate side).

[0591] Typically, the exposure step is a step of performing pattern exposure via a photomask. In the exposure step, the photomask may or may not be in contact with the laminated body as the object to be exposed to light.

[0592] In the case of the exposure process of the pattern exposure, a curing reaction of the components contained in the photosensitive resin layer may occur in the exposure area of ​​the photosensitive resin layer (corresponding to the area of ​​the opening of the photomask). By performing a development process after the exposure, the non-exposed area of ​​the photosensitive resin layer is removed, thereby forming a pattern.

[0593] The method of the present invention also preferably includes a photomask peeling step of peeling off the photomask used in the exposure step between the exposure step and the development treatment.

[0594] As the photomask peeling step, for example, a known peeling step can be mentioned.

[0595] The light source for pattern exposure may be any light source capable of irradiating at least a wavelength region capable of curing the photosensitive resin layer (eg, 365 nm and 405 nm), preferably 365 nm. The "dominant wavelength" refers to a wavelength with the highest intensity.

[0596] Examples of the light source include various lasers, light emitting diodes (LEDs), ultrahigh pressure mercury lamps, high pressure mercury lamps, and metal halide lamps.

[0597] The exposure dose is preferably 5 to 200 mJ / cm 2 , more preferably 10 to 200 mJ / cm 2 .

[0598] As light sources, exposure amounts, and exposure methods, for example, paragraphs

[0146] to

[0147] of International Publication No. 2018 / 155193 can be cited, and these contents are incorporated into this specification.

[0599] In addition, as an exposure method, in the case of contact exposure, the contact exposure method can be appropriately selected and applied, and in the case of non-contact exposure, a proximity exposure method, a projection exposure method of a lens system or a reflector system, and a direct exposure (direct drawing exposure) method using an exposure laser or the like can be appropriately selected and applied. In the case of projection exposure of a lens system or a reflector system, an exposure machine with an appropriate lens aperture number (NA) can be used according to the required resolution and depth of focus. In the case of a direct exposure method, drawing can be performed directly on the photosensitive resin layer, or reduced projection exposure can be performed on the photosensitive resin layer via a lens. In addition, exposure can be performed not only in the atmosphere, but also under reduced pressure or in a vacuum, and exposure can be performed with a liquid such as water interposed between the light source and the transfer layer.

[0600] From the viewpoint of resolution, it is preferred that the transfer layer be brought into contact with a mask and the exposure in step X2 be performed by contact exposure.

[0601] Furthermore, from the viewpoint of being able to reduce the influence on the mask and the photosensitive resin layer, it is also preferable to perform the exposure in the step X2 by direct drawing exposure or projection exposure.

[0602] [Step X7 (temporary support peeling step)]

[0603] The temporary support peeling step is performed between the laminating step and the exposure step or between the exposure step and the development step. Among them, it is more preferable to have a temporary support peeling step between the laminating step and the exposure step.

[0604] The temporary support peeling step is a step of peeling the temporary support from the laminate of the transfer film and the substrate with the metal layer.

[0605] As a method for peeling the temporary support, for example, a known peeling method can be cited. Specifically, a cover film peeling mechanism described in paragraphs

[0161] to

[0162] of Japanese Patent Application Laid-Open No. 2010-072589 can be cited.

[0606] [Step X3 (Development Step)]

[0607] The development step is a step of developing the exposed photosensitive resin layer with a developer to form a pattern. By developing with the developer, the non-exposed region of the photosensitive resin layer is removed, thereby forming a resist pattern with the opening of the photomask as a convex portion.

[0608] As the developer, an alkaline aqueous solution containing an alkali metal salt is preferred.

[0609] The alkali metal salt contained in the developer is preferably a compound that dissolves in water and exhibits alkalinity.

[0610] Examples of the alkali metal salt include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, and potassium hydrogen carbonate.

[0611] The developer may contain a compound other than the alkali metal salt that is dissolved in water and exhibits alkalinity. Examples of such compounds include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, and choline (2-hydroxyethyltrimethylammonium hydroxide).

[0612] In the developer, the content of water 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, relative to the total mass of the developer.

[0613] In the developer, the content of the alkali metal salt is preferably 0.01 to 20% by mass, more preferably 0.1 to 10% by mass, based on the total mass of the developer.

[0614] As the developing method, for example, a well-known developing method can be mentioned.

[0615] Specifically, there can be mentioned spin immersion development, shower development, spin development and immersion development.

[0616] As the development method, the development method described in paragraph

[0195] of International Publication No. 2015 / 093271 is preferred.

[0617] It is also preferable to perform a rinsing treatment to remove the developer remaining on the substrate with the metal layer after the development and before the next step. Water or the like can be used for the rinsing treatment.

[0618] After the development and / or rinsing process, a drying process may be performed to remove excess liquid from the substrate with the metal layer.

[0619] [Process XA (post-exposure process) and process XB (post-drying process)]

[0620] The above-mentioned manufacturing method may include a step of further exposing the resist pattern obtained on the substrate with the metal layer (hereinafter also referred to as "step XA" or "post-exposure step") and / or a heating step (hereinafter also referred to as "step XB" or "post-drying step") between the development step and the etching step described later.

[0621] When the above-mentioned manufacturing method has both a post-exposure step and a post-baking step, it is preferable to perform the post-baking step after performing the post-exposure step.

[0622] The exposure dose in the post-exposure step is preferably 100 to 5000 mJ / cm 2 , more preferably 200 to 3000 mJ / cm 2 .

[0623] The temperature of the post-drying in the post-drying step is preferably 80 to 250°C, more preferably 90 to 160°C.

[0624] The time of post-drying in the post-drying step is preferably 1 to 180 minutes, more preferably 10 to 60 minutes.

[0625] [Step X4-1 (etching step)]

[0626] The etching step is a step of etching the metal layer in a region where the resist pattern is not provided.

[0627] Specifically, in the etching step, the metal layer is etched using the resist pattern obtained up to the above steps as an etching resist.

[0628] When the etching step is performed, the metal layer is removed in the opening of the resist pattern, so that the metal layer has the same pattern shape as the resist pattern.

[0629] The etching process may be a known method. As the etching process, for example, wet etching and dry etching (for example, plasma etching) may be cited. As the etching process, for example, the method described in paragraphs 0209 to 0210 of Japanese Patent Publication No. 2017-120435 and the method described in paragraphs 0048 to 0054 of Japanese Patent Publication No. 2010-152155 may also be cited.

[0630] The etching treatment is preferably wet etching. In wet etching, an etching solution is generally used. The type of etching solution can be selected from an acidic or alkaline etching solution according to the etching object. As an acidic etching solution, for example, an aqueous solution containing at least one acidic component selected from hydrochloric acid, sulfuric acid, nitric acid, acetic acid, hydrofluoric acid, oxalic acid and phosphoric acid can be cited. As an acidic etching solution, for example, a mixed aqueous solution of the above-mentioned acidic component and at least one salt selected from ferric chloride, ammonium fluoride and potassium permanganate can also be cited. The acidic component can also be a component composed of a combination of multiple acidic components. As an alkaline etching solution, for example, an aqueous solution containing at least one alkaline component selected from sodium hydroxide, potassium hydroxide, ammonia, organic amines and salts of organic amines (tetramethylammonium hydroxide, etc.) can be cited. As an alkaline etching solution, for example, a mixed aqueous solution of the above-mentioned alkaline component and a salt (for example, potassium permanganate) can also be cited. The alkaline component can also be a component composed of a combination of multiple alkaline components.

[0631] 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, through holes penetrating the metal substrate are formed by the etching process.

[0632] (Through hole)

[0633] A plurality of through holes may be formed. The depth of the through hole corresponds to the thickness of the metal substrate. The through hole is usually defined by the inner surface of the metal substrate. The through hole may be defined by one or more than two surfaces. The surface defining the through hole observed in cross-section may be a straight line or a curve. The number, shape and configuration of the through holes are determined, for example, according to the target pattern. The through hole extending from the first surface to the second surface forms an opening on the first surface, and an opening is formed on the second surface. The diameter of the opening formed on the first surface corresponds to the diameter of the through hole in the first surface described later, and the diameter of the opening formed on the second surface corresponds to the diameter of the through hole in the second surface described later. As the shape of the through hole (specifically the opening) observed in a top view, for example, a circular shape, an elliptical shape and a quadrilateral shape may be cited. The shape of the through hole observed in a top view is preferably a quadrilateral, more preferably a square or a rectangle. When the shape of the through hole observed in a top view is a polygon (for example, a quadrilateral), part or all of the multiple corners of the polygon may be rounded.

[0634] The average diameter of the through holes formed on the first surface of the metal substrate (hereinafter, sometimes referred to as "the average diameter D1 of the through holes") is preferably 15 μm to 100 μm, more preferably 20 μm to 50 μm, and further 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 "the average diameter D2 of the through holes") is preferably 25 μm or less, more preferably 20 μm or less, and further preferably 10 μm or less. The lower limit of the average diameter D2 of the through holes is not limited.

[0635] The average diameter of the through-holes is calculated as the arithmetic average of the diameters of 10 through-holes measured based on an image obtained using a scanning electron microscope (SEM).

[0636] [Step X4-2 (plating step)]

[0637] The plating step is a step of forming a plated layer by plating treatment on the metal layer located in a region where the resist pattern is not arranged (the metal layer exposed to the surface by the development step).

[0638] Examples of the plating method include electrolytic plating and electroless plating. From the viewpoint of productivity, electrolytic plating is preferred.

[0639] When the plating step is performed, a plated layer having the same pattern shape as that of a region (opening of the resist pattern) where the resist pattern is not arranged is obtained on the substrate with the metal layer.

[0640] As a component of the plating solution used in electroplating, for example, a water-soluble copper salt can be mentioned. As a water-soluble copper salt, a water-soluble copper salt commonly used as a component of the plating solution can be used. As a water-soluble copper salt, for example, it is preferably selected from at least one of an inorganic copper salt, an alkanesulfonic acid copper salt, an alkanesulfonic acid copper salt and an organic acid copper salt. As an inorganic copper salt, for example, copper sulfate, copper oxide, copper chloride and copper carbonate can be mentioned. As an alkanesulfonic acid copper salt, for example, copper methanesulfonate and copper propanesulfonate can be mentioned. As an alkanesulfonic acid copper salt, for example, copper hydroxyethyl sulfonate and copper propanesulfonate can be mentioned. As an organic acid copper salt, for example, copper acetate, copper citrate and copper tartrate can be mentioned.

[0641] Furthermore, as a component of the plating solution used in the electroplating, a salt of another corresponding metal may be used instead of the copper mentioned above.

[0642] The plating solution may contain sulfuric acid. When the plating solution contains sulfuric acid, the pH and sulfate ion concentration of the plating solution can be adjusted.

[0643] The method and conditions of electroplating are not limited. For example, by supplying the laminated body after the development process to a plating tank filled with a plating solution, a metal pattern can be formed on the metal layer in the area where the resin pattern is not arranged. In plating, for example, the metal pattern can be formed by controlling the current density and the conveying speed of the substrate.

[0644] The temperature of the plating solution used in the plating is preferably 70° C. or lower, more preferably 10 to 40° C. The current density during the plating is preferably 0.1 to 100 A / dm 2 , more preferably 0.5 to 20 A / dm 2 By increasing the current density, the productivity of the conductor pattern can be improved. By reducing the current density, the uniformity of the thickness of the metal pattern can be improved.

[0645] Examples of the metal contained in the plating layer include well-known metals.

[0646] Specific examples include metals such as copper, chromium, lead, nickel, gold, silver, tin, and zinc, and alloys of these metals.

[0647] Among them, from the viewpoint of further improving the conductivity of the conductive pattern, the plating layer preferably contains copper or its alloy. Also, from the viewpoint of further improving the conductivity of the conductive pattern, the plating layer preferably contains copper as a main component.

[0648] 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.

[0649] [Step X1-C (Protective layer forming step)]

[0650] The above-mentioned production method also preferably includes a protective layer forming step between the plating step and the resist stripping step described later.

[0651] The protective layer forming step is a step of forming a protective layer on the plated layer.

[0652] As the material of the protective layer, it is preferred that the material has resistance to the stripping solution and / or etching solution in the resist stripping process and / or the removal process. For example, metals such as nickel, chromium, tin, zinc, magnesium, gold, and silver, their alloys, and resins can be cited. Among them, as the material of the protective layer, nickel or chromium is preferred.

[0653] Examples of the method for forming the protective layer include electroless plating and electroplating, and electroplating is preferred.

[0654] The lower limit of the thickness of the protective layer is not particularly limited, but is preferably 0.3 μm or more, more preferably 0.5 μm or more, and the upper limit is not particularly limited, but is preferably 3.0 μm or less, more preferably 2.0 μm or less.

[0655] <Step X5 (resist stripping step)>

[0656] The resist stripping step is a step of removing a resist pattern remaining after the etching step of step X4-1 or a step of removing a resist pattern remaining after the plating step or the protective layer forming step of step X4-2.

[0657] As a method of removing the remaining resist pattern, for example, a method of removing by chemical treatment can be mentioned, and a method of removing using a stripping liquid is preferred.

[0658] As a method of removing the remaining resist pattern, for example, there can be mentioned a method of removing by a known method such as a spray method, a shower method, or a spin immersion method using a stripping liquid.

[0659] Examples of the removal liquid include a removal liquid containing an inorganic base component or an organic base component and water, dimethyl sulfoxide, N-methylpyrrolidone, or a mixed solvent thereof. Examples of the inorganic base component include sodium hydroxide and potassium hydroxide. Examples of the organic base component include primary amine compounds, secondary amine compounds, tertiary amine compounds, and quaternary ammonium salt compounds.

[0660] The resist pattern can be removed by immersing the laminate including the resin pattern in a removal liquid. The temperature of the removal liquid 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 removal liquid may be stirred.

[0661] The resist pattern can be removed by, for example, a spray method, a shower method, or a spin immersion method using a removal liquid.

[0662] When the resist stripping step is performed, the remaining resist pattern is removed from the substrate, whereby the metal layer existing between the substrate and the resist pattern is exposed to the surface.

[0663] [Process X6 (removal process)]

[0664] The removal process is a process of removing the metal layer exposed by the resist stripping process to obtain a metal layer pattern.

[0665] In the removal step, the plated layer formed in the plating step is used as an etching resist to perform etching treatment on the metal layer located in the non-pattern formation region (in other words, the region not protected by the plated layer).

[0666] The method for removing a part of the metal layer is not particularly limited, but a known etching solution is preferably used.

[0667] As one form of the known etching solution, for example, there can be mentioned a ferric chloride solution, a cupric chloride solution, an ammoniacal alkali solution, a sulfuric acid-hydrogen peroxide mixed solution, and a phosphoric acid-hydrogen peroxide mixed solution.

[0668] Furthermore, as a method of removing a part of the metal layer, dry etching is also preferably performed.

[0669] If the removal process is performed, the metal layer exposed on the surface is removed from the substrate, and the plating layer having a pattern shape remains.

[0670] <Other Processes>

[0671] The manufacturing method may include any steps (other steps) other than the above steps. Other steps include, for example, electroless plating, sputtering, seed layer imparting, seed layer etching, but are not limited to these steps.

[0672] Example

[0673] Below, the present invention is further described in detail according to examples. The material, usage, ratio, processing content and processing sequence etc. shown in the following examples can be appropriately changed as long as they do not depart from the purpose of the present invention. Therefore, the scope of the present invention should not be interpreted restrictively by the examples shown below.

[0674] In addition, below, "part" and "%" respectively mean "part by mass" and "mass %" unless otherwise specified.

[0675] [Production of transfer film]

[0676] Hereinafter, various compositions used for preparing each transfer film shown in the latter section will be described in detail.

[0677] [Preparation of thermoplastic resin layer composition]

[0678] The thermoplastic resin layer composition was prepared by mixing the various components shown below.

[0679] Propylene glycol monomethyl ether acetate solution of a copolymer of benzyl methacrylate / methacrylic acid / acrylic acid (solid content concentration: 30.0% by mass, ratio of each monomer: 65% by mass / 28% by mass / 7% by mass, weight average molecular weight (Mw): 30,000, acid value: 153 mgKOH / g): 42.85 parts by mass

[0680] NK Ester A-DCP (manufactured by Shin-Nakamura Chemical Co., Ltd.): 4.33 parts by mass

[0681] 8UX-015A (manufactured by Taisei Fine Chemical Co., Ltd.): 2.31 parts by mass

[0682] ARONIX TO-2349 (manufactured by TOAGOSEI CO., LTD.): 0.77 parts by mass

[0683] MEGAFACE F-552 (fluorine-based surfactant, manufactured by DIC Corporation): 0.03 parts by mass

[0684] Methyl ethyl ketone (manufactured by SANKYO CHEMICAL Co., Ltd.): 39.80 parts by mass

[0685] Propylene glycol monomethyl ether acetate (manufactured by Resonac Corporation): 9.51 parts by mass

[0686] [Preparation of water-soluble resin layer composition]

[0687] The various components shown below were mixed to prepare a water-soluble resin layer composition.

[0688] KURARAY POVAL PVA-205 (polyvinyl alcohol, manufactured by Kuraray Co., Ltd.): 3.22 parts by mass

[0689] Polyvinylpyrrolidone K-30 (manufactured by NIPPON SHOKUBAI CO., LTD.): 1.49 parts by mass

[0690] MEGAFACE F-444 (fluorine-based surfactant, manufactured by DIC Corporation): 0.0015 parts by mass

[0691] Ion exchange water: 38.12 parts by mass

[0692] Methanol (manufactured by Mitsubishi Gas Chemical Company, Inc.): 57.17 parts by mass

[0693] [Preparation of photosensitive resin composition 1]

[0694] The photosensitive resin composition 1 was prepared by mixing the various components shown below.

[0695] Propylene glycol monomethyl ether acetate solution of a copolymer of styrene / methacrylic acid / methyl methacrylate (solid content concentration: 30.0% by mass, ratio of each monomer: 60% by mass / 20% by mass / 20% by mass, Mw: 50,000. Equivalent to an alkali-soluble resin): 23.4 parts by mass

[0696] BPE-100 (ethoxylated bisphenol A dimethacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd., equivalent to a polymerizable compound): 4.1 parts by mass

[0697] B-CIM (2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, manufactured by KUROGANE KASEIC Co., Ltd.. Corresponding to a photopolymerization initiator): 0.25 parts by mass

[0698] SB-PI 701 (4,4'-bis(diethylamino)benzophenone, obtained from Sanyo Trading Co., Ltd., corresponding to a sensitizer): 0.04 parts by mass

[0699] TDP-G (phenothiazine, manufactured by Kawaguchi Chemical Industry Co., Ltd.): 0.0175 parts by mass

[0700] 1-Phenyl-3-pyrazolidinone (manufactured by FUJIFILM Wako Pure Chemical Corporation): 0.0011 parts by mass

[0701] Leuco crystal violet (manufactured by Tokyo Chemical Industry Co., Ltd.): 0.051 parts by mass

[0702] N-phenylcarbamoylmethyl-N-carboxymethylaniline (manufactured by FUJIFILM Wako Pure Chemical Corporation): 0.02 parts by mass

[0703] CBT-1 (benzotriazole rust inhibitor, manufactured by JOHOKU CHEMICAL CO., LTD.): 0.75 parts by mass

[0704] Methyl ethyl ketone (manufactured by SANKYO CHEMICAL Co., Ltd.): 40.4 parts by mass

[0705] Propylene glycol monomethyl ether acetate (manufactured by Resonac Corporation): 26.7 parts by mass

[0706] Surfactant listed in Table 2 (molecular weight 18,000): 0.05 parts by mass

[0707] [Preparation of photosensitive resin compositions 2 to 9, 10 to 12, R1 and R2]

[0708] Except having changed the surfactant into the composition shown in Table 2 and Table 3, it carried out similarly to the photosensitive resin composition 1, and prepared the photosensitive resin compositions 2-9, R1, and R2.

[0709] Furthermore, except having changed the surfactant into the composition shown in Table 5, it carried out similarly to the photosensitive resin composition 1, and prepared the photosensitive resin compositions 10-12.

[0710] The structures of the surfactants shown in Table 2 and Table 3 are shown in the following Table 1. In addition, the structures of the surfactants shown in Table 5 are shown in Table 4 described later.

[0711] [Table 1]

[0712]

[0713] The following lists the repeating units (A-1 to A-2, B-1 to B-12) described in Table 1 and Table 4 described later.

[0714] [Chemical formula 15]

[0715]

[0716] [Chemical formula 16]

[0717]

[0718] (Calculation of ΔHSP1 and ΔHSP2)

[0719] By calculation using the commercially available Windows software "HSPiP (developed by www.hansen-solubility.com)", three vectors of the Hansen solubility parameters of the alkali-soluble resins used in the photosensitive resin compositions 1 to 7, R1 and R2 (dispersion term of the Hansen solubility parameters of the alkali-soluble resin: δDb, hydrogen bonding term of the Hansen solubility parameters of the alkali-soluble resin: δHb, polar term of the Hansen solubility parameters of the alkali-soluble resin: δP) were obtained. The respective values ​​are shown in Table 2.

[0720] Furthermore, by the same method, three vectors of the Hansen solubility parameters of the alkali-soluble resins used in the photosensitive resin compositions 10 to 12 (dispersion term of the Hansen solubility parameters of the alkali-soluble resin: δDb, hydrogen bonding term of the Hansen solubility parameters of the alkali-soluble resin: δHb, polar term of the Hansen solubility parameters of the alkali-soluble resin: δP) were obtained. The respective values ​​are shown in Table 5.

[0721] Furthermore, by the same method, three vectors of the Hansen solubility parameters of the polymerizable compounds used in the photosensitive resin compositions 1 to 7, R1, and R2 (dispersion term of the Hansen solubility parameters of the polymerizable compounds: δDm, hydrogen bonding term of the Hansen solubility parameters of the polymerizable compounds: δHm, polar term of the Hansen solubility parameters of the polymerizable compounds: δPm) were obtained. The respective values ​​are shown in Table 2.

[0722] Furthermore, by the same method, three vectors of the Hansen solubility parameters of the polymerizable compounds used in the photosensitive resin compositions 10 to 12 (dispersion term of the Hansen solubility parameters of the polymerizable compounds: δDm, hydrogen bonding term of the Hansen solubility parameters of the polymerizable compounds: δHm, polar term of the Hansen solubility parameters of the polymerizable compounds: δPm) were obtained. The respective values ​​are shown in Table 5.

[0723] Furthermore, by the same method, three vectors of the Hansen solubility parameters of the surfactants used in the photosensitive resin compositions 1 to 7, R1, and R2 (dispersion term of the Hansen solubility parameters of the surfactant: δDS, hydrogen bonding term of the Hansen solubility parameters of the surfactant: δHS, polar term of the Hansen solubility parameters of the surfactant: δPS) were obtained. The respective values ​​are shown in Table 2.

[0724] Furthermore, by the same method, three vectors of Hansen solubility parameters of the surfactants used in the photosensitive resin compositions 10 to 12 (dispersion term of Hansen solubility parameters of surfactants: δDS, hydrogen bonding term of Hansen solubility parameters of surfactants: δHS, polar term of Hansen solubility parameters of surfactants: δPS) were obtained. The respective values ​​are shown in Table 5.

[0725] Furthermore, by the same method, three vectors of the Hansen solubility parameters of the nonpolar part of the surfactant used in the photosensitive resin compositions 1 to 7, R1 and R2 (dispersion term of the Hansen solubility parameters of the nonpolar part of the surfactant: δDSs, hydrogen bonding term of the Hansen solubility parameters of the nonpolar part of the surfactant: δHSs, polar term of the Hansen solubility parameters of the nonpolar part of the surfactant: δPSs) were obtained. The respective values ​​are shown in Table 2.

[0726] Furthermore, by the same method, three vectors of the Hansen solubility parameters of the nonpolar part of the surfactant used in the photosensitive resin compositions 10 to 12 (dispersion term of the Hansen solubility parameters of the nonpolar part of the surfactant: δDSs, hydrogen bonding term of the Hansen solubility parameters of the nonpolar part of the surfactant: δHSs, polar term of the Hansen solubility parameters of the nonpolar part of the surfactant: δPSs) were obtained. The respective values ​​are shown in Table 5.

[0727] In addition, in surfactants 1 to 14, the repeating unit that does not contain silicon atoms and fluorine atoms (the second repeating unit. Repeating units 2 and 3 in Tables 1 and 4 are equivalent to this.) corresponds to the non-polar part. For surfactants containing only one second repeating unit, the dispersion term, hydrogen bonding term, and polarity term of the Hansen solubility parameter in the second repeating unit are set to δDSs, δHSs, and δPSs, respectively. On the other hand, for surfactants containing two or more second repeating units (surfactants 7 and 10 are equivalent to this), the dispersion term, hydrogen bonding term, and polarity term of the Hansen solubility parameter of each repeating unit equivalent to the second repeating unit are respectively calculated, and the weighted average value of each repeating unit is used, and it is set to δDSs, δHSs, and δPSs. The values ​​are shown in Tables 2 and 5.

[0728] Furthermore, using the various numerical values ​​calculated in the upper section, and according to the above formulas (F1A) to (F1C), the weighted average value (δDM) of the dispersion term of each Hansen solubility parameter of the alkali-soluble resin and the polymerizable compound, the weighted average value (δHM) of the hydrogen bonding term of each Hansen solubility parameter of the alkali-soluble resin and the polymerizable compound, and the weighted average value (δPM) of the polar term of each Hansen solubility parameter of the alkali-soluble resin and the polymerizable compound were obtained, and ΔHSP1 was calculated according to the above formula (F1). The results are shown in Tables 2 and 5.

[0729] In addition, the numerical values ​​obtained by the formula (F3A) to the formula (F3C) of the upper part are obtained in the same manner as above. The numerical values ​​obtained by the formula (F3A) to the formula (F3C) are the same as the numerical values ​​obtained by the formula (F1A) to the formula (F1C).

[0730] Furthermore, using the various numerical values ​​calculated in the upper section, and according to the above formulas (F2A) to (F2C), the weighted average value (δDM) of the dispersion term of each Hansen solubility parameter of the alkali-soluble resin and the polymerizable compound, the weighted average value (δHM) of the hydrogen bonding term of each Hansen solubility parameter of the alkali-soluble resin and the polymerizable compound, and the weighted average value (δPM) of the polar term of each Hansen solubility parameter of the alkali-soluble resin and the polymerizable compound were obtained, and ΔHSP2 was calculated according to the above formula (F2). The results are shown in Tables 2 and 5.

[0731] In addition, the numerical values ​​obtained by the formula (F4A) to the formula (F4C) of the upper part are obtained in the same manner as above. The numerical values ​​obtained by the formula (F4A) to the formula (F4C) are the same as the numerical values ​​obtained by the formula (F2A) to the formula (F2C).

[0732] [Preparation and evaluation of transfer films 1 to 7]

[0733] <Production of transfer film 1>

[0734] The thermoplastic resin layer composition was applied onto a temporary support (polyethylene terephthalate film, thickness: 16 μm) using a slit nozzle to a thickness of 3.0 μm after drying. The resulting coating of the thermoplastic resin composition was dried at 80° C. for 40 seconds to form a thermoplastic resin layer.

[0735] The water-soluble resin layer composition was applied onto the surface of the formed thermoplastic resin layer using a slit nozzle to a layer thickness of 1.0 μm after drying. The coating of the water-soluble resin layer composition was dried at 90° C. for 180 seconds to form a water-soluble resin layer.

[0736] The photosensitive resin composition 1 was applied onto the surface of the formed water-soluble resin layer using a slit nozzle so that the layer thickness after drying was 3.0 μm, and dried at 100° C. for 2 minutes to form a photosensitive resin layer.

[0737] A protective film (polypropylene film, thickness: 12 μm) was bonded onto the photosensitive resin layer as a protective layer, thereby producing a transfer film 1 .

[0738] <Adhesion Evaluation>

[0739] (Preparation of transfer film for adhesion evaluation)

[0740] The produced transfer film 1 was wrapped and sealed with a metal-laminated polyethylene sheet, and subjected to a heat treatment in a drying oven at 40° C. for 80 hours (accelerated test).

[0741] (Adhesion Evaluation)

[0742] For the transfer film that had been heated and the transfer film that had not been heated, the protective film was peeled off and then the transfer film with the protective film peeled off was laminated onto a glass substrate sputtered with copper to a thickness of 100 nm under lamination conditions of a roller temperature of 100° C., a linear pressure of 0.8 MPa, and a linear speed of 3.0 m / min.

[0743] Then, after peeling off the temporary support from the attached transfer film, a glass mask having an isolated wiring pattern with a line width of 1.5 to 5 μm and a scale of 0.5 μm or 0.25 μm (in the case of "B" evaluation or above, the mask is evaluated with a scale change of 0.25 μm) was attached to the temporary support and exposed using an exposure machine (M-1S, manufactured by MIKASA CO., LTD.). The exposure amount was adjusted so that the width of the resin pattern after development was 1.8 to 2.2 μm for a 2 μm designed pattern.

[0744] The above patterning was performed at 10 locations on the heat-treated and untreated transfer films, and the residual minimum width pattern was compared to see if it changed. If the minimum width pattern changes, it means that the state of the surfactant has changed due to the heat treatment (for example, overflow and condensation, etc.), which has changed the close fit between the transfer film and the substrate. The heat treatment has the effect of accelerating the movement of the surfactant in the film. When the minimum width pattern changes due to the heat treatment, the same performance problem will occur over time during long-term storage.

[0745] Evaluation was performed based on the following criteria: As the transfer film, D or higher is preferred.

[0746] A: The minimum width pattern does not change before and after heating

[0747] B: The minimum width of the pattern changes by less than 0.5 μm before and after heating

[0748] C: The minimum width of the pattern changes by more than 0.5 μm and less than 1 μm before and after heating

[0749] D: The minimum width of the pattern changes by more than 1.0 μm and less than 1.5 μm before and after heating

[0750] E: The minimum width of the pattern changes by more than 1.5 μm before and after heating

[0751] <Production and Evaluation of Transfer Films 2 to 7, R1, and R2>

[0752] Except changing the photosensitive resin composition 1 to the photosensitive resin compositions 2 to 7, R1, and R2 according to the composition of Table 2, the transfer films 2 to 7, R1, and R2 were prepared and evaluated for adhesion by the same method as the transfer film 1.

[0753] Table 2 is shown below.

[0754] In addition, “the presence or absence of an aromatic ring structure” in Tables 2 and 3 indicates whether or not the surfactant has an aromatic ring structure.

[0755] 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 one of the electron accepting groups or the electron donating groups possessed by at least one of the alkali-soluble resin and the polymerizable compound. In addition, the alkali-soluble resin used in the examples has a carboxyl group (electron accepting group). In addition, the dialkylamino group in surfactant 7 corresponds to an electron donating group.

[0756] [Table 2]

[0757]

[0758] It is clear from the results in Table 2 that the photosensitive resin composition of the example can form a photosensitive resin layer whose pattern forming performance is unlikely to change over time after being transferred to a transfer object.

[0759] Furthermore, according to the comparison between Example 1, Example 2 and Example 4, it was confirmed that when the weight average molecular weight of the surfactant was 10,000 or more, the pattern forming performance was less likely to change over time.

[0760] On the other hand, it was found that the photosensitive resin composition of the comparative example could not obtain the expected effect.

[0761] [Production and evaluation of transfer films 8 to 9]

[0762] Except having changed the photosensitive resin composition 1 into the photosensitive resin compositions 8-9 according to the composition of Table 3, the transfer films 8-9 were prepared and evaluated for adhesion by the same method as the transfer film 1.

[0763] Table 3 is shown below.

[0764] In addition, the "presence or absence of an aromatic ring structure" in Table 3 indicates whether the surfactant has an aromatic ring structure. Furthermore, the "presence or absence of an interactive group" indicates whether the surfactant has an electron accepting group or an electron donating group that can interact with one of the electron accepting groups or the electron donating groups possessed by at least one of the alkali-soluble resin and the polymerizable compound.

[0765] [Table 3]

[0766]

[0767] It is clear from the results in Table 3 that the photosensitive resin composition of the example can form a photosensitive resin layer whose pattern forming performance is unlikely to change over time after being transferred to a transfer object.

[0768] [Production and evaluation of transfer films 10 to 12]

[0769] Transfer films 10 to 12 were prepared and evaluated for adhesion by the same method as transfer film 1, except that the surfactants listed in Table 4 were used and the photosensitive resin composition 1 was changed to photosensitive resin compositions 10 to 12 according to the compositions of Table 5. The specific structures of the repeating units of the surfactants listed in Table 4 are as described above.

[0770] [Table 4]

[0771]

[0772] [Table 5]

[0773]

[0774] The results in Table 5 indicate that the following phenomena occurred: In Example 10, ΔHSP2 was larger than that in Example 1, at 7.8, but since the cyano group contained in the surfactant 10 is an electron-donating group, it is estimated that the adhesion was better than that in Example 1.

[0775] In Example 11, ΔHSP2 was increased to 5.6 compared with Example 1 or 5, but ΔHSP1 was decreased to 4.8, and since the amide group contained in the surfactant 11 was an electron-donating group, it was estimated that the adhesion was better than that of Example 1 or 7.

[0776] In Example 12, since ΔHSP2 is the same as that in Example 1, it is estimated that the adhesion is of the same degree.

[0777] [Production and evaluation of transfer films 13 to 18]

[0778] [Preparation of thermoplastic resin layer composition]

[0779] Thermoplastic resin layer compositions A1 to A3 were prepared by mixing the various components shown below. The thermoplastic resin layer compositions A1 to A3 differ only in the type of surfactant contained in the thermoplastic resin layer composition. The numbers of the surfactants shown in Table 6 correspond to the numbers of the surfactants shown in Table 1 or Table 4. Furthermore, the thermoplastic resin layer compositions A1 to A3 are equivalent to thermoplastic resin layer compositions in which MEGAFACE F-552 (a fluorine-based surfactant manufactured by DIC Corporation) is replaced with the surfactants shown in Table 6 in the thermoplastic resin layer composition for forming the thermoplastic resin layer contained in the transfer film 1 described above.

[0780] Propylene glycol monomethyl ether acetate solution of a copolymer of benzyl methacrylate / methacrylic acid / acrylic acid (solid content concentration: 30.0% by mass, ratio of each monomer: 65% by mass / 28% by mass / 7% by mass, weight average molecular weight (Mw): 30,000, acid value: 153 mgKOH / g): 42.85 parts by mass

[0781] NK Ester A-DCP (manufactured by Shin-Nakamura Chemical Co., Ltd.): 4.33 parts by mass

[0782] 8UX-015A (manufactured by Taisei Fine Chemical Co., Ltd.): 2.31 parts by mass

[0783] ARONIX TO-2349 (manufactured by TOAGOSEI CO., LTD.): 0.77 parts by mass

[0784] Methyl ethyl ketone (manufactured by SANKYO CHEMICAL Co., Ltd.): 39.80 parts by mass

[0785] Propylene glycol monomethyl ether acetate (manufactured by Resonac Corporation): 9.51 parts by mass

[0786] Surfactant listed in Table 6: 0.03 parts by mass

[0787] [Preparation of water-soluble resin layer composition]

[0788] The water-soluble resin layer compositions B1 and B2 were prepared by mixing the various components shown below. The water-soluble resin layer compositions B1 and B2 differ only in the type of surfactant contained in the water-soluble resin layer composition. Furthermore, the water-soluble resin layer compositions B1 and B2 are equivalent to water-soluble resin layer compositions in which MEGAFACE F-444 (a fluorine-based surfactant manufactured by DIC Corporation) is replaced with the surfactant shown in Table 6 in the water-soluble resin layer composition used to form the water-soluble resin layer contained in the transfer film 1 described above.

[0789] KURARAY POVAL PVA-205 (polyvinyl alcohol, manufactured by Kuraray Co., Ltd.): 3.22 parts by mass

[0790] Polyvinylpyrrolidone K-30 (manufactured by NIPPON SHOKUBAI CO., LTD.): 1.49 parts by mass

[0791] Ion exchange water: 38.12 parts by mass

[0792] Methanol (manufactured by Mitsubishi Gas Chemical Company, Inc.): 57.17 parts by mass

[0793] Surfactant listed in Table 6: 0.0015 parts by mass

[0794] In addition, b1 and b2 among the surfactants described in Table 6 are shown below.

[0795] b1: BYK-345 (manufactured by BYK Japan KK)

[0796] b2: MEGAFACE EFS-801 (manufactured by DIC Corporation)

[0797] Using the thermoplastic resin layer compositions A1 to A3, water-soluble resin layer compositions B1 to B2, and photosensitive resin compositions 1, 9, and 11 prepared in the upper section, transfer films 13 to 18 were prepared so as to have the layer structures described in Table 6. The preparation method was the same as that of transfer film 1. For each of the prepared transfer films, the adhesion was evaluated in the same manner as that of transfer film 1. The results are collectively shown in Table 6.

[0798] [Table 6]

[0799]

[0800] According to the results of Table 6, by changing the surfactant of the thermoplastic resin layer and the water-soluble resin layer, the adhesion of the photosensitive resin layer will change. The reason is not yet very clear, but it is inferred that when the photosensitive resin layer is coated on the thermoplastic resin layer and the water-soluble resin layer, the surfactant of the thermoplastic resin layer and the water-soluble resin layer is extracted and transferred to the photosensitive resin layer, so the adhesion of the photosensitive resin layer may change. According to the above results, it is believed that according to the surfactant used in the thermoplastic resin layer and the water-soluble resin layer, it is possible to further improve the adhesion. For example, by using the surfactant used in the photosensitive resin layer as the surfactant of the thermoplastic resin layer and the water-soluble resin layer, even if the surfactant of the thermoplastic resin layer and the water-soluble resin layer is transferred to the photosensitive resin layer when the coating is formed, the photosensitive resin layer is not easy to have a decrease in high adhesion, thereby being able to further improve the adhesion of the photosensitive resin layer.

[0801] Explanation of symbols

[0802] 1-temporary support, 3-thermoplastic resin layer, 5-intermediate layer, 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 of the photosensitive resin composition calculated by the following formula (F1) was 6.0 MPa. 0.5 the following, 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 bonding term of the Hansen solubility parameter of the alkali-soluble resin and the hydrogen bonding term of the Hansen solubility parameter of the polymerizable compound calculated by the following formula (F1B), δPM represents the weighted average value of the polarity term of the Hansen solubility parameter of the alkali-soluble resin and the polarity 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 bonding term of the Hansen solubility parameter of the surfactant, and δPS represents the polarity 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 dispersion term of the Hansen solubility parameter of the alkali-soluble resin, δDm represents the dispersion term of the Hansen solubility parameter of the polymerizable compound, In formula (F1B), δHb represents the hydrogen bonding term of the Hansen solubility parameter of the alkali-soluble resin, δHm represents the hydrogen bonding 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, δPm represents the polar term of the Hansen solubility parameter of the polymerizable compound, In formula (F1A) to formula (F1C), Wb represents the mass fraction of the alkali-soluble resin relative to the total solid content in the photosensitive resin composition, and Wm represents the mass fraction of the polymerizable compound relative 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 silicon atoms and fluorine atoms and a second repeating unit containing neither silicon atoms nor fluorine atoms, The value of ΔHSP2 of the photosensitive resin composition calculated by the following formula (F2) was 4.0 MPa. 0.5 the following, in, When at least one selected from 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 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 bonding term of the Hansen solubility parameter of the alkali-soluble resin and the hydrogen bonding 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 represents the dispersion term of the Hansen solubility parameter of the non-polar part of the surfactant, when the surfactant has only one type of the second repeating unit, represents the dispersion term of the Hansen solubility parameter of the second repeating unit, when the surfactant has two or more types of the second repeating units, represents is the weighted average of the dispersion terms of the Hansen solubility parameters of the two or more second repeating units, δHSs is the hydrogen bonding term of the Hansen solubility parameter of the non-polar part of the surfactant, when the surfactant has only one type of the second repeating unit, it represents the hydrogen bonding term of the Hansen solubility parameter of the second repeating unit, when the surfactant has two or more types of the second repeating units, it represents the weighted average of the hydrogen bonding terms of the Hansen solubility parameters of the two or more second repeating units, δPSs is the polar term of the Hansen solubility parameter of the non-polar part of the surfactant, when the surfactant has only one type of the second repeating unit, it represents the polar term of the Hansen solubility parameter of the second repeating unit, when the surfactant has two or more types of the second repeating units, it represents the weighted average of the polar terms of the Hansen solubility parameters of the two or more second repeating 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, δDm represents the dispersion term of the Hansen solubility parameter of the polymerizable compound, In formula (F2B), δHb represents the hydrogen bonding term of the Hansen solubility parameter of the alkali-soluble resin, δHm represents the hydrogen bonding 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, δPm represents the polar term of the Hansen solubility parameter of the polymerizable compound, In formula (F2A) to formula (F2C), Wb represents the mass fraction of the alkali-soluble resin relative to the total solid content in the photosensitive resin composition, and Wm represents the mass fraction of the polymerizable compound relative 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, At least one selected from the alkali-soluble resin and the polymerizable compound and the surfactant each have an aromatic ring structure in a 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 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 repeating unit represented by the following formula (A-1) and the repeating unit represented by the following formula (A-2), 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 l represents an integer of 5 to 100. 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.

7. The photosensitive resin composition according to any one of claims 1 to 4, wherein The polymerizable compound includes a compound represented by the following formula (P1): 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. In addition, the arrangement of the repeating units of -(AO)- and -(BO)- is optionally random or block. When arranged in a block, either -(AO)- or -(BO)- is on the biphenyl side.

8. The photosensitive resin composition according to any one of claims 1 to 4, wherein The alkali-soluble resin includes one or more resins 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), In formula (R1) and formula (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 includes at least one selected from acridine photopolymerization initiator, oxime ester photopolymerization initiator, biimidazole photopolymerization initiator, alkylphenone photopolymerization initiator, acetophenone photopolymerization initiator and acylphosphine oxide photopolymerization initiator. 10 . A transfer film comprising: a temporary support; a photosensitive resin layer formed from the photosensitive resin composition according to claim 1 ; and a protective layer in this order. 11 . The transfer film according to claim 10 , which is used in a process of 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 on a metal substrate or a resin substrate with a metal layer by etching.

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