Chemically amplified positive-type photosensitive composition, photosensitive dry film, method for producing photosensitive dry film, method for producing patterned resist film, and method for producing plated article

Abstract

To provide a chemically amplified positive photosensitive composition capable of forming a patterned resist film having a rectangular cross-sectional shape and excellent in crack resistance, a photosensitive dry film including a photosensitive layer composed of the chemically amplified positive photosensitive composition, a method for producing the photosensitive dry film, a method for producing a patterned resist film, and a method for producing a plated article.SOLUTION: The resist composition comprises (A) a resin having increased solubility in an alkali by the action of an acid and (B) an acid generator capable of generating an acid upon irradiation with actinic rays or radiation, wherein the resin (A) comprises two or more kinds of acrylic resins (A1). The acrylic resin (a1) has a phenolic hydroxyl group-containing unit (a1) having a specific structure, the ratio of the number of moles of the phenolic hydroxyl group-containing unit (a1) to the number of moles of all the structural units constituting the acrylic resin (a1) is 1 mol% or more and 20 mol% or less, and the resin (A) is a chemically amplified positive photosensitive composition.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a chemically amplified positive-working photosensitive composition, a photosensitive dry film, a method for producing a photosensitive dry film, a method for producing a patterned resist film, and a method for producing a plated object. [Background technology]

[0002] Currently, photofabrication is the mainstream of precision micromachining technology. Photofabrication is a general term for a technology for manufacturing various precision parts such as semiconductor packages, which involves applying a photoresist composition to the surface of a workpiece to form a photoresist layer, patterning the photoresist layer using photolithography technology, and then using the patterned photoresist layer (photoresist pattern) as a mask to perform chemical etching, electrolytic etching, or electroforming, which mainly involves electroplating.

[0003] Furthermore, in recent years, with the downsizing of electronic devices, high-density mounting technology for semiconductor packages has advanced, with efforts being made to increase mounting density through the adoption of multi-pin thin-film mounting for packages, miniaturization of package size, and two-dimensional mounting technology using the flip-chip method, as well as three-dimensional mounting technology. In such high-density mounting technology, connection terminals, such as protruding electrodes (mounting terminals) such as bumps protruding from the package, and metal posts that connect the mounting terminals to rewiring lines (RDL) extending from peripheral terminals on the wafer, are arranged with high precision on the substrate.

[0004] Photoresist compositions are used in the above-described photofabrication. Known examples of such photoresist compositions include chemically amplified photoresist compositions containing an acid generator. Chemically amplified photoresist compositions generate acid from the acid generator upon exposure to radiation, and heat treatment promotes the diffusion of the acid, causing an acid-catalyzed reaction with the base resin in the composition, which changes its alkali solubility.

[0005] Such chemically amplified photoresist compositions are used not only to form patterned insulating films and etching masks, but also to form plated objects such as bumps, metal posts, and Cu rewiring by plating processes. Specifically, a chemically amplified photoresist composition is used to form a photoresist layer of a desired thickness on a support such as a metal substrate, which is then exposed to light through a predetermined mask pattern and developed to form a photoresist pattern used as a mold from which portions from which plated objects will be formed are selectively removed (peeled off). Then, a conductor such as copper is embedded in these removed portions (non-resist portions) by plating, and the surrounding photoresist pattern is then removed to form plated objects such as bumps, metal posts, and Cu rewiring.

[0006] Patent Document 1 discloses a method for producing a plated object using a chemically amplified photoresist composition, the method comprising the steps of: preparing a substrate having a metal layer on its surface and the chemically amplified photoresist composition; applying the chemically amplified photoresist composition to the substrate to form a chemically amplified photoresist composition film; exposing the chemically amplified photoresist composition film; developing the exposed chemically amplified photoresist composition film to form a pattern that exposes at least a portion of the metal layer on the substrate; and forming a plated object using the pattern as a template. The chemically amplified photoresist composition contains a sulfur-containing compound and / or a nitrogen-containing compound, the sulfur-containing compound contains a sulfur atom that coordinates with the metal that constitutes the metal layer, and the nitrogen-containing compound contains a nitrogen atom that constitutes a nitrogen-containing aromatic heterocycle that coordinates with the metal that constitutes the metal layer. The method further comprises a step of ashing the surface of the exposed metal layer between the step of forming the pattern and the step of forming the plated object. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] Japanese Patent Publication No. 2020-034933 Summary of the Invention [Problem to be solved by the invention]

[0008] Generally, when forming a resist pattern (patterned resist film), it is often desirable for the cross-sectional shape to be rectangular. In particular, when forming connection terminals such as bumps and metal posts by the plating process, or when forming Cu rewiring, it is highly desirable for the non-resist portion of the resist pattern that serves as a mold to have a rectangular cross-sectional shape. In addition, the patterned resist film is also required to have excellent crack resistance.

[0009] The present invention has been made in view of the above-mentioned problems, and aims to provide a chemically amplified positive-type photosensitive composition capable of forming a patterned resist film having a rectangular cross-sectional shape and excellent crack resistance, a photosensitive dry film having a photosensitive layer made of the chemically amplified positive-type photosensitive composition, a method for manufacturing the photosensitive dry film, a method for manufacturing a patterned resist film using the aforementioned chemically amplified positive-type photosensitive composition, and a method for manufacturing a plated object using the aforementioned chemically amplified positive-type photosensitive composition. [Means for solving the problem]

[0010] As a result of extensive research into achieving the above object, the present inventors have discovered a polymerizable composition comprising a resin (A) whose solubility in alkali increases under the action of an acid and an acid generator (B) that generates an acid upon irradiation with actinic rays or radiation, wherein the resin (A) contains two or more acrylic resins (A1), and the acrylic resins (A1) are each a polymerizable compound having a structure of CH═CR 1 -R 2 -Ar-(OH) naThe present inventors have found that the above-mentioned problems can be solved by a chemically amplified positive-working photosensitive composition, which comprises an acrylic resin (A1) having phenolic hydroxyl group-containing units (a1) derived from an unsaturated compound represented by the formula: wherein the ratio of the number of moles of the phenolic hydroxyl group-containing units (a1) to the number of moles of all structural units constituting the acrylic resin (A1) is 1 mol % or more and 20 mol % or less, and the resin (A) contains a unit having an alkali-soluble group protected by an acid-dissociable group, and have completed the present invention. Specifically, the present invention provides the following.

[0011] A first aspect of the present invention is a composition comprising a resin (A) whose solubility in alkali increases under the action of an acid, and an acid generator (B) that generates an acid upon exposure to actinic rays or radiation, The resin (A) contains two or more acrylic resins (A1), The acrylic resin (A1) is represented by the following formula (a1-1): CH=CR 1 -R 2 -Ar-(OH) na ···(a1-1) (In formula (a1-1), R 1 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms which may have a substituent, and R 2 is a single bond or a divalent linking group, Ar is an aromatic hydrocarbon group having a valence of (na+1), and na is an integer of 1 or more and 4 or less. and (a1) a phenolic hydroxyl group-containing unit derived from an unsaturated compound represented by the formula: the acrylic resin (A1) is a resin in which the ratio of the number of moles of the phenolic hydroxyl group-containing unit (a1) to the number of moles of all structural units constituting the acrylic resin (A1) is 1 mol % or more and 20 mol % or less, The resin (A) is a chemically amplified positive-working photosensitive composition containing a unit having an alkali-soluble group protected by an acid-dissociable group.

[0012] A second aspect of the present invention is a photosensitive dry film having a base film and a photosensitive resin layer formed on the surface of the base film, wherein the photosensitive resin layer is made of the chemically amplified positive photosensitive composition according to the first aspect.

[0013] A third aspect of the present invention is a method for producing a photosensitive dry film, which includes applying the chemically amplified positive photosensitive composition according to the first aspect onto a substrate film to form a photosensitive resin layer.

[0014] A fourth aspect of the present invention provides a method for producing a photosensitive resin layer, comprising: a lamination step of laminating a photosensitive resin layer made of the chemically amplified positive photosensitive composition according to the first aspect on a substrate having a metal surface; an exposure step of position-selectively irradiating the photosensitive resin layer with actinic rays or radiation; and a developing step of developing the photosensitive resin layer after exposure.

[0015] A fifth aspect of the present invention provides a method for producing a photosensitive resin layer, comprising: a lamination step of laminating a photosensitive resin layer made of the chemically amplified positive photosensitive composition according to the first aspect on a substrate having a metal surface; an exposure step of irradiating the photosensitive resin layer with actinic rays or radiation; a development step of developing the exposed photosensitive resin layer to prepare a substrate with a mold for forming a plated object; and a step of plating the substrate with the mold to form a plated object within the mold. [Effects of the Invention]

[0016] According to the present invention, it is possible to provide a chemically amplified positive-type photosensitive composition capable of forming a patterned resist film having a rectangular cross-sectional shape and excellent crack resistance, a photosensitive dry film having a photosensitive layer made of the chemically amplified positive-type photosensitive composition, a method for manufacturing the photosensitive dry film, a method for manufacturing a patterned resist film using the aforementioned chemically amplified positive-type photosensitive composition, and a method for manufacturing a plated object using the aforementioned chemically amplified positive-type photosensitive composition. DETAILED DESCRIPTION OF THE INVENTION

[0017] <Chemically amplified positive-working photosensitive composition> The chemically amplified positive-working photosensitive composition (hereinafter also referred to as the photosensitive composition) contains a resin (A) (hereinafter also referred to as the resin (A)) whose solubility in alkali increases under the action of an acid, and an acid generator (B) (hereinafter also referred to as the acid generator (B)) that generates an acid upon exposure to actinic rays or radiation.

[0018] The resin (A) contains two or more acrylic resins (A1), and the acrylic resin (A1) has a phenolic hydroxyl group-containing unit (a1) derived from an unsaturated compound represented by the following formula (a1-1). CH=CR 1 -R 2 -Ar-(OH) na ···(a1-1)

[0019] In formula (a1-1), R 1 R is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, which may have a substituent. 2 is a single bond or a divalent linking group. Ar is an aromatic hydrocarbon group having a valence of (na+1), where na is an integer of 1 or more and 4 or less.

[0020] The acrylic resin (A1) contains phenolic hydroxyl group-containing units (a1) in an amount of 1 mol % to 20 mol % of the total molar amount of all structural units constituting the acrylic resin (A1). The resin (A) contains units having an alkali-soluble group protected by an acid-dissociable group.

[0021] Essential and optional components contained in the photosensitive composition and a method for producing the photosensitive composition will be described below.

[0022] <Resin (A)> The photosensitive composition contains two or more acrylic resins (A1) described below as resins (A) whose alkali solubility increases under the action of an acid. The resins (A) also contain units having alkali-soluble groups protected by acid-dissociable groups. The alkali-soluble groups are not particularly limited, but are typically phenolic hydroxyl groups and carboxyl groups.

[0023] The types and ratios of the structural units of the two or more acrylic resins (A1) contained in the resin (A) may be the same or different from one another. The molecular weights of the two or more acrylic resins (A1) contained in the resin (A) are preferably different from one another.

[0024] The maximum weight average molecular weight of two or more acrylic resins (A1) is Mw max The minimum weight average molecular weight is Mw min In this case, Mw max / Mw min The value of Mw is preferably 2 or more, more preferably 2.5 or more, and even more preferably 3 or more. max / Mw min There is no particular upper limit to the value of Mw. max / Mw min The value may be 30 or less, or 20 or less.

[0025] The mixing ratio of two or more acrylic resins (A1) is not particularly limited. For example, in a resin (A) containing two acrylic resins (A1), when the mass of a first acrylic resin (A1) is M1 and the mass of a second acrylic resin (A1) having a weight-average molecular weight greater than that of the first acrylic resin is M2, the ratio M1:M2 is preferably 1:99 to 99:1, more preferably 3:97 to 97:3, even more preferably 5:95 to 95:5, and particularly preferably 10:90 to 90:10. M1:M2 may be 20:80 to 80:20, 30:70 to 70:30, or 40:60 to 60:40.

[0026] When the photosensitive composition contains the resin (A) and the acid generator (B) that generates an acid upon irradiation with actinic rays or radiation, it is possible to form a resist film that has a rectangular cross-sectional shape and excellent crack resistance.

[0027] The resin (A) may contain only two or more acrylic resins (A1), or may contain two or more acrylic resins (A1) and an acrylic resin (A2) other than the acrylic resin (A1). The resin (A) may also contain any resin other than acrylic resins whose solubility in alkali increases under the action of an acid. However, the mass ratio of the acrylic resin (A1) to the mass of the resin (A) is preferably 40 mass% or more, more preferably 50 mass% or more.

[0028] The two or more acrylic resins (A1) are different from each other in at least one of their structural units and molecular weights. Preferably, the two or more acrylic resins (A1) are different in molecular weight, more preferably, the types of structural units constituting the acrylic resins are the same but the molecular weights are different, and more preferably, the types and ratios of structural units constituting the acrylic resins are the same but the molecular weights are different. The difference in molecular weight between two or more acrylic resins (A1) is Mw max -Mw min The value of Mw is preferably 30,000 or more, more preferably 80,000 or more. The upper limit of the difference in molecular weight between the two or more acrylic resins (A1) is not particularly limited, but may be 600,000 or less, 300,000 or less, 150,000 or less, or 120,000 or less. max , and Mw min As mentioned above,

[0029] The resin other than an acrylic resin whose solubility in alkali increases under the action of an acid, which may be contained in the resin (A), is not particularly limited, and examples thereof include a novolac resin (A3) and a polyhydroxystyrene resin (A4). In the novolak resin (A3) and the polyhydroxystyrene resin (A4), at least some of the phenolic hydroxyl groups are protected with acid-dissociable groups.

[0030] In this specification, "(meth)acrylic" means both "acrylic" and "methacrylic." "(meth)acrylate" means both "acrylate" and "methacrylate."

[0031] [Acrylic resin (A1)] The acrylic resin (A1) has a phenolic hydroxyl group-containing unit (a1) derived from an unsaturated compound represented by the following formula (a1-1). CH=CR 1 -R 2 -Ar-(OH) na ···(a1-1)

[0032] In formula (a1-1), R 1 R is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, which may have a substituent. 2 is a single bond or a divalent linking group. Ar is an aromatic hydrocarbon group having a valence of (na+1). na is an integer of 1 or more and 4 or less.

[0033] The ratio of the number of moles of the phenolic hydroxyl group-containing unit (a1) to the number of moles of all structural units constituting the acrylic resin (A1) is preferably from 1 mol% to 20 mol%, more preferably from 5 mol% to 20 mol%, and even more preferably from 10 mol% to 19 mol%.

[0034] In formula (a1-1), the phenolic hydroxyl group refers to a hydroxyl group (OH) directly bonded to a carbon atom constituting a six-membered aromatic ring. In a fused ring containing a six-membered aromatic ring, a hydroxyl group directly bonded to a carbon atom constituting the six-membered aromatic ring is also a phenolic hydroxyl group. As the six-membered aromatic ring, a benzene ring is preferred. In formula (a1-1), the structure having an unsaturated bond is preferably a structure containing an alkenyl group such as a vinyl group or an allyl group, and more preferably a structure containing a (meth)acryloyl group.

[0035] R in formula (a1-1) 1R is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, which may have a substituent. 1 Examples of the substituent that the alkyl group may have include a halogen atom, an alkoxy group having from 1 to 4 carbon atoms, an acyl group having from 2 to 4 carbon atoms, an acyloxy group having from 2 to 4 carbon atoms, and a cyano group. R 1 As the alkyl group, a hydrogen atom and an unsubstituted alkyl group having 1 to 10 carbon atoms are preferred, and a hydrogen atom and an unsubstituted alkyl group having 1 to 4 carbon atoms are more preferred. R 1 Preferred examples of the unsubstituted alkyl group as include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group. Among these, a methyl group and an ethyl group are more preferred, and a methyl group is even more preferred.

[0036] R 2 is a single bond or a divalent linking group.

[0037] R 2 Suitable examples of the divalent linking group as include a divalent hydrocarbon group which may have a substituent, and a divalent linking group containing a hetero atom.

[0038] Optionally substituted divalent hydrocarbon group The hydrocarbon group as a divalent linking group may be an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a combination of an aliphatic hydrocarbon group and an aromatic hydrocarbon group. The aliphatic hydrocarbon group may be a saturated aliphatic hydrocarbon group or an unsaturated aliphatic hydrocarbon group, and is preferably a saturated hydrocarbon group. Specific examples of the aliphatic hydrocarbon group include linear or branched aliphatic hydrocarbon groups and aliphatic hydrocarbon groups containing a ring in their structure.

[0039] The linear or branched aliphatic hydrocarbon group preferably has 1 or more and 10 or less carbon atoms, more preferably 1 or more and 8 or less carbon atoms, and even more preferably 1 or more and 5 or less carbon atoms.

[0040] The linear aliphatic hydrocarbon group is preferably a linear alkylene group, and specific examples of the linear alkylene group include a methylene group [-CH-], an ethylene group [-(CH)-], a trimethylene group [-(CH)-], a tetramethylene group [-(CH)-], and a pentamethylene group [-(CH)-].

[0041] The branched aliphatic hydrocarbon group is preferably a branched alkylene group. Specific examples of the branched alkylene group include alkylmethylene groups such as -CH(CH)-, -CH(CHCH)-, -C(CH)-, -C(CH)(CHCH)-, -C(CH)(CHCHCH)-, and -C(CHCH)-; alkylethylene groups such as -CH(CH)CH-, -CH(CH)CH(CH)-, -C(CH)CH-, -CH(CHCH)CH-, and -C(CHCH)-CH-; alkyltrimethylene groups such as -CH(CH)CHCH- and -CHCH(CH)CH-; and alkyltetramethylene groups such as -CH(CH)CHCHCHCH- and -CHCH(CH)CHCH-. The alkyl group in the alkylalkylene group is preferably a linear alkyl group having 1 to 5 carbon atoms.

[0042] The linear or branched aliphatic hydrocarbon group may have a substituent, specific examples of which include a fluorine atom, a fluorinated alkyl group having from 1 to 5 carbon atoms, and an oxo group (═O).

[0043] Examples of aliphatic hydrocarbon groups containing a ring in their structure include groups in which two hydrogen atoms have been removed from an aliphatic hydrocarbon ring, groups in which a cyclic aliphatic hydrocarbon group is bonded to the end of a linear or branched aliphatic hydrocarbon group, and groups in which a cyclic aliphatic hydrocarbon group is interposed in the middle of a linear or branched aliphatic hydrocarbon group. Examples of linear or branched aliphatic hydrocarbon groups include the same groups as described above.

[0044] The cyclic aliphatic hydrocarbon group preferably has 3 or more and 20 or less carbon atoms, and more preferably has 3 or more and 12 or less carbon atoms.

[0045] The cyclic aliphatic hydrocarbon group may be a polycyclic group or a monocyclic group. The monocyclic aliphatic hydrocarbon group is preferably a group obtained by removing two hydrogen atoms from a monocycloalkane. The monocycloalkane preferably has 3 or more and 6 or less carbon atoms. Specific examples of monocycloalkanes include cyclopentane and cyclohexane. The polycyclic aliphatic hydrocarbon group is preferably a group obtained by removing two hydrogen atoms from a polycycloalkane. The polycycloalkane preferably has 7 or more and 12 or less carbon atoms. Specific examples of polycycloalkanes include adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane.

[0046] The cyclic aliphatic hydrocarbon group may have a substituent, such as an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, or an oxo group (═O).

[0047] The alkyl group as a substituent is preferably an alkyl group having 1 to 5 carbon atoms, and more preferably a methyl group, an ethyl group, a propyl group, an n-butyl group, or a tert-butyl group.

[0048] The alkoxy group as a substituent is preferably an alkoxy group having from 1 to 5 carbon atoms, more preferably a methoxy group, an ethoxy group, an n-propyloxy group, an isopropyloxy group, an n-butyloxy group, or a tert-butyloxy group, and still more preferably a methoxy group or an ethoxy group.

[0049] Examples of the halogen atom as a substituent include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, with a fluorine atom being preferred.

[0050] Examples of the halogenated alkyl group as a substituent include the above alkyl groups in which some or all of the hydrogen atoms have been substituted with the above halogen atoms.

[0051] The aromatic hydrocarbon group as a divalent hydrocarbon group may have a substituent. The aromatic hydrocarbon group may be monocyclic or polycyclic. The number of carbon atoms in the aromatic ring is preferably 6 to 30, more preferably 6 to 20, and even more preferably 6 to 12. However, the number of carbon atoms does not include the number of carbon atoms in the substituent.

[0052] Specific examples of the aromatic ring constituting the aromatic hydrocarbon group include aromatic hydrocarbon rings such as a benzene ring, a naphthalene ring, an anthracene ring, and a phenanthrene ring.

[0053] Specific examples of aromatic hydrocarbon groups as divalent hydrocarbon groups include groups in which two hydrogen atoms have been removed from the above-mentioned aromatic hydrocarbon rings (arylene groups); groups in which one hydrogen atom of a group in which one hydrogen atom has been removed from the above-mentioned aromatic hydrocarbon rings (aryl groups) has been substituted with an alkylene group (for example, groups in which one hydrogen atom has been removed from the aryl group in an aralkyl group such as a benzyl group, a phenethyl group, a naphthalene-1-ylmethyl group, a naphthalene-2-ylmethyl group, a naphthalene-1-ylethyl group, and a naphthalene-2-ylethyl group); and the like.

[0054] The alkylene group bonded to the aryl group preferably has 1 or more and 4 or less carbon atoms, more preferably 1 or more and 2 or less carbon atoms, and particularly preferably 1 carbon atom.

[0055] The aromatic hydrocarbon group may have a substituent, such as an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, or a hydroxyl group.

[0056] The alkyl group as a substituent is preferably an alkyl group having 1 to 5 carbon atoms, and more preferably a methyl group, an ethyl group, an n-propyl group, an n-butyl group, or a tert-butyl group.

[0057] The alkoxy group as a substituent is preferably an alkoxy group having 1 to 5 carbon atoms, more preferably a methoxy group, an ethoxy group, an n-propyloxy group, an isopropyloxy group, an n-butyloxy group, or a tert-butyloxy group, and more preferably a methoxy group or an ethoxy group.

[0058] Examples of the halogen atom as a substituent include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, with a fluorine atom being preferred.

[0059] Examples of the halogenated alkyl group as a substituent include the above alkyl groups in which some or all of the hydrogen atoms have been substituted with the above halogen atoms.

[0060] Divalent linking groups containing heteroatoms Examples of the heteroatom in the divalent linking group containing a heteroatom include an oxygen atom, a nitrogen atom, a sulfur atom, and a halogen atom.

[0061] Specific examples of divalent linking groups containing a hetero atom include non-hydrocarbon linking groups such as -O-, -C(=O)-, -C(=O)-O-, -OC(=O)-O-, -S-, -S(=O)2-, -S(=O)2-O-, -NH-, -NH-C(=O)-, -NH-C(=NH)-, and =N-; combinations of at least one of these non-hydrocarbon linking groups with a divalent hydrocarbon group; divalent heterocyclic groups; and combinations of a divalent heterocyclic group with the above-mentioned non-hydrocarbon linking group and / or divalent hydrocarbon group. Examples of the divalent hydrocarbon group constituting the divalent linker containing a heteroatom include the same as the divalent hydrocarbon group that may have a substituent as described above, and linear or branched aliphatic hydrocarbon groups are preferred.

[0062] Of the above, -NH- in -C(=O)-NH-, -NH-, and H in -NH-C(=NH)- may each be substituted with a substituent such as an alkyl group or an acyl group. The number of carbon atoms in the substituent is preferably 1 or more and 10 or less, more preferably 1 or more and 8 or less, and particularly preferably 1 or more and 5 or less.

[0063] R 2 The divalent linking group as is preferably a linear alkylene group, a branched alkylene group, a cyclic aliphatic hydrocarbon group, or a divalent linking group containing a hetero atom.

[0064] R 2 When the divalent linking group as is a linear alkylene group or a branched alkylene group, the alkylene group preferably has 1 or more and 10 or less carbon atoms, more preferably 1 or more and 6 or less, even more preferably 1 or more and 4 or less, and particularly preferably 1 or more and 3 or less carbon atoms.

[0065] R 2 When the divalent linking group as represented by the formula (I) is a cyclic aliphatic hydrocarbon group, the cyclic aliphatic hydrocarbon group is preferably a group in which two hydrogen atoms have been removed from cyclopentane, cyclohexane, norbornane, isobornane, adamantane, tricyclodecane, or tetracyclododecane.

[0066] R 2 When the divalent linking group as the group represented by the formula (I) is a divalent linking group containing a hetero atom, -O-, -C(=O)-O-, -C(=O)-, -OC(=O)-O-, -C(=O)-NH-, -NH-, -S-, -S(=O)2-, -S(=O)2-O-, -Y 1a -OY 2a -, -[Y 1a -C(=O)-O] m’ -Y 2a - and -Y 1a -OC(=O)-Y 2a A group represented by - and the like are preferred as the divalent linking group. In the above formula, Y 1a , and Y 2aare each independently a divalent hydrocarbon group which may have a substituent. Examples of the divalent hydrocarbon group include the same groups as the divalent hydrocarbon groups which may have a substituent described above for the divalent linking group. m' is an integer of 0 to 3. Y 1a As the alkyl group, a linear aliphatic hydrocarbon group is preferred, a linear alkylene group is more preferred, a linear alkylene group having 1 to 5 carbon atoms is even more preferred, and a methylene group and an ethylene group are particularly preferred.

[0067] Y 2a As the alkyl group, a linear or branched aliphatic hydrocarbon group is preferred, and a methylene group, an ethylene group, or an alkylmethylene group is more preferred. As the alkyl group in the alkylmethylene group, a linear alkyl group having 1 to 5 carbon atoms is preferred, a linear alkyl group having 1 to 3 carbon atoms is more preferred, and a methyl group is particularly preferred.

[0068] -[Y 1a -C(=O)-O] m’ -Y 2a In -, m' is an integer of 0 to 3, preferably an integer of 0 to 2, more preferably 0 or 1, and particularly preferably 1. That is, -[Y 1a -C(=O)-O] m’ -Y 2a As a group represented by -, -Y 1a -C(=O)-OY 2a A group represented by -Y is preferred. 1a -C(=O)-OY 2a The group represented by - is -(CH2) a’ -C(=O)-O-(CH2) b’ A group represented by - is preferred. a' is an integer of 1 or more and 10 or less, preferably an integer of 1 or more and 8 or less, more preferably an integer of 1 or more and 5 or less, even more preferably 1 or 2, and most preferably 1. b' is an integer of 1 or more and 10 or less, preferably an integer of 1 or more and 8 or less, more preferably an integer of 1 or more and 5 or less, even more preferably 1 or 2, and most preferably 1.

[0069] R 2As the divalent linking group containing a hetero atom as -Y, an organic group consisting of a combination of at least one non-hydrocarbon group and a divalent hydrocarbon group is preferred. Among them, a linear group having an oxygen atom as a hetero atom is preferred, and a group containing an ether bond or an ester bond is more preferred. 1a -OY 2a -, a group represented by -[Y 1a -C(=O)-O] m’ -Y 2a -, and -Y 1a -OC(=O)-Y 2a A group represented by - is more preferred, and -[Y 1a -C(=O)-O] m’ -Y 2a -, and -Y 1a -OC(=O)-Y 2a A group represented by - is particularly preferred.

[0070] R 2 As the divalent linking group as , an alkylene group and a divalent linking group containing an ester bond (-C(=O)-O-) are preferred.

[0071] The alkylene group may be a straight-chain alkylene group or a branched-chain alkylene group. Preferred examples of the straight-chain alkylene group include a methylene group [-CH2-], an ethylene group [-(CH2)2-], a trimethylene group [-(CH2)3-], a tetramethylene group [-(CH2)4-], and a pentamethylene group [-(CH2)5-]. Suitable examples of the branched alkylene group include alkylmethylene groups such as -CH(CH3)-, -CH(CH2CH3)-, -C(CH3)2-, -C(CH3)(CH2CH3)-, -C(CH3)(CH2CH2CH3)-, and -C(CH2CH3)2-; alkylethylene groups such as -CH(CH3)CH2-, -CH(CH3)CH(CH3)-, -C(CH3)2CH2-, -CH(CH2CH3)CH2-, and -C(CH2CH3)2-CH2-; alkyltrimethylene groups such as -CH(CH3)CH2CH2- and -CH2CH(CH3)CH2-; and alkyltetramethylene groups such as -CH(CH3)CH2CH2CH2- and -CH2CH(CH3)CH2CH2-.

[0072] Examples of the divalent linking group containing an ester bond include -R 13a A group represented by -C(=O)-O- is preferred. R 13a is a divalent linking group. 13a As the divalent linking group as the aryl group, a linear or branched alkylene group, an aliphatic hydrocarbon group containing a ring in the structure, and a divalent linking group containing a heteroatom are preferred, and a linear or branched alkylene group and a divalent linking group containing an oxygen atom as a heteroatom are preferred.

[0073] In formula (a1-1), Ar is an aromatic hydrocarbon group having a valence of (na+1). The aromatic hydrocarbon group represented by Ar is preferably a group in which (na+1) hydrogen atoms have been removed from an aromatic hydrocarbon ring having from 6 to 30 carbon atoms. Examples of aromatic hydrocarbon rings having from 6 to 30 carbon atoms include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, and a biphenyl ring.

[0074] Suitable examples of the phenolic hydroxyl group-containing unit (a1) derived from the unsaturated compound represented by formula (a1-1) include the structural unit represented by the following formula (a1-1-1). [ka]

[0075] In the above formula (a1-1-1), R a01 represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, which may have a substituent. a02 represents a single bond or a divalent linking group. R a02 The divalent linking group as is not particularly limited.

[0076] R a01 The alkyl group having 1 to 10 carbon atoms, which may have a substituent, is represented by R 1 The alkyl group is the same as the alkyl group having 1 to 10 carbon atoms which may have a substituent as mentioned above. R a02 The divalent linking group represented by R 2 The same applies to the divalent linking group as defined above.

[0077] In formula (a1-1-1), the substitution position of the phenolic hydroxyl group on the benzene ring is not particularly limited. a02 is preferably in the para position or meta position relative to the carbon atom to which is bonded, and more preferably in the para position.

[0078] The structural unit represented by formula (a1-1-1) is preferably a structural unit represented by the following formula (a1-1-1a) or a structural unit derived from a hydroxystyrene-based monomer represented by the following formula (a1-1-1b). [ka]

[0079] In the above formula (a1-1-1a) and formula (a1-1-1b), Ra01 R represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms which may have a substituent. a03 represents a single bond or an alkylene group. R a03 The number of carbon atoms in the alkylene group as the alkylene group is not particularly limited, but is preferably 1 or more and 6 or less, and more preferably 1 or more and 4 or less. R a03 Specific examples of the alkylene group as include a methylene group, an ethane-1,2-diyl group, an ethane-1,1-diyl group, a propane-1,3-diyl group, and a butane-1,4-diyl group.

[0080] In the formula (a1-1-1a) and the formula (a1-1-1b), the substitution position of the phenolic hydroxyl group on the benzene ring is not particularly limited. a02 is preferably in the para position or meta position relative to the carbon atom to which is bonded, and more preferably in the para position.

[0081] At least a portion of the phenolic hydroxyl groups contained in the structural unit represented by formula (a1-1-1), the structural unit represented by formula (a1-1-1a), and the structural unit represented by formula (a1-1-1b) are protected with an acid-dissociable group.

[0082] The acid-dissociable group is preferably a group represented by the following formula (a1-I) or (a1-II), a linear alkyl group having from 1 to 6 carbon atoms, a branched alkyl group, a cycloalkyl group, a vinyloxyethyl group, a tetrahydropyranyl group, a tetrahydrofuranyl group, or a trialkylsilyl group.

[0083] [ka]

[0084] In formula (a1-I) and formula (a1-II), R 1A , R 2AR are each independently a hydrogen atom, a linear alkyl group having 1 to 6 carbon atoms, or a branched alkyl group having 1 to 6 carbon atoms. 3A R is a linear alkyl group having 1 to 10 carbon atoms, a branched alkyl group having 1 to 10 carbon atoms, or a cycloalkyl group having 3 to 10 carbon atoms. 4A is a linear alkyl group having from 1 to 6 carbon atoms, a branched alkyl group having from 1 to 6 carbon atoms, or a cycloalkyl group having from 3 to 6 carbon atoms. o represents 0 or 1.

[0085] Specific examples of the linear alkyl group and the branched alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, and a neopentyl group, etc. Specific examples of the cycloalkyl group include a cyclopentyl group and a cyclohexyl group, etc.

[0086] Specific examples of the acid-dissociable group represented by formula (AI) include a 1-methoxyethyl group, a 1-ethoxyethyl group, a 1-n-propoxyethyl group, a 1-isopropoxyethyl group, a 1-n-butoxyethyl group, a 1-isobutoxyethyl group, a 1-tert-butoxyethyl group, a 1-cyclohexyloxyethyl group, a 1-methoxypropyl group, a 1-ethoxypropyl group, a 1-methoxy-1-methylethyl group, and a 1-ethoxy-1-methylethyl group. Specific examples of the acid-dissociable group represented by formula (A-II) include a tert-butoxycarbonyl group, and a tert-butoxycarbonylmethyl group.

[0087] In the above trialkylsilyl group, the number of carbon atoms in the alkyl group bonded to the silicon atom is preferably from 1 to 6. The alkyl group bonded to the silicon atom may be either a linear alkyl group or a branched alkyl group. Specific examples of the trialkylsilyl group include a trimethylsilyl group and a tert-butyldimethylsilyl group.

[0088] The acrylic resin (A1) may contain a structural unit other than the aforementioned unit (a1). Examples of the structural unit other than the unit (a1) contained in the acrylic resin (A1) include a structural unit represented by the following formula (a1-2-1): [ka]

[0089] In formula (a1-2-1), R a04 represents a hydrogen atom, an alkyl group, a halogen atom, or a halogenated alkyl group; R a05 represents a monovalent organic group that does not have a phenolic hydroxyl group. R a04 Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, and a tert-butyl group. R a04 Examples of the halogen atom as the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. R a04 As the halogenated alkyl group, R a04 and groups in which some or all of the hydrogen atoms of the alkyl group have been substituted with the above-mentioned halogen atoms. R a05 Examples of the monovalent organic group include an alkyl group which may have a substituent, an aliphatic cyclic group which may have a substituent and may have a heteroatom, and a group in which two or more of these groups are linked via a heteroatom. Examples of the heteroatom include an oxygen atom and a sulfur atom.

[0090] Examples of the structural unit represented by formula (a1-2-1) include the structural unit (a1-3) derived from a (meth)acrylic acid ester containing an -SO- containing cyclic group or a lactone-containing cyclic group. When the acrylic resin contains these structural units, it is easy to form a patterned resist film having a desirable cross-sectional shape.

[0091] (-SO2-containing cyclic group) Here, the term "-SO2-containing cyclic group" refers to a cyclic group containing a ring containing -SO2- in its ring skeleton, specifically a cyclic group in which the sulfur atom (S) in -SO2- forms part of the ring skeleton of the cyclic group. The ring containing -SO2- in the ring skeleton is counted as the first ring, and if it contains only that ring, it is called a monocyclic group, and if it contains other ring structures, it is called a polycyclic group regardless of the structure. The -SO2- containing cyclic group may be monocyclic or polycyclic.

[0092] The -SO2- containing cyclic group is preferably a cyclic group containing -O-SO2- in its ring skeleton, i.e., a cyclic group containing a sultone ring in which -OS- in -O-SO2- forms part of the ring skeleton.

[0093] The number of carbon atoms in the —SO—-containing cyclic group is preferably from 3 to 30, more preferably from 4 to 20, even more preferably from 4 to 15, and particularly preferably from 4 to 12. The number of carbon atoms is the number of carbon atoms constituting the ring skeleton and does not include the number of carbon atoms in the substituents.

[0094] The -SO2- containing cyclic group may be an -SO2- containing aliphatic cyclic group or an -SO2- containing aromatic cyclic group, preferably an -SO2- containing aliphatic cyclic group.

[0095] Examples of the -SO2- containing aliphatic cyclic group include groups in which at least one hydrogen atom has been removed from an aliphatic hydrocarbon ring in which some of the carbon atoms constituting the ring skeleton have been substituted with -SO2- or -O-SO2-. More specifically, examples include groups in which at least one hydrogen atom has been removed from an aliphatic hydrocarbon ring in which -CH2- constituting the ring skeleton has been substituted with -SO2-, and groups in which at least one hydrogen atom has been removed from an aliphatic hydrocarbon ring in which -CH2-CH2- constituting the ring has been substituted with -O-SO2-.

[0096] The number of carbon atoms in the alicyclic hydrocarbon ring is preferably 3 to 20, more preferably 3 to 12. The alicyclic hydrocarbon ring may be polycyclic or monocyclic. The monocyclic alicyclic hydrocarbon group is preferably a group in which two hydrogen atoms have been removed from a monocycloalkane having 3 to 6 carbon atoms. Examples of the monocycloalkane include cyclopentane and cyclohexane. The polycyclic alicyclic hydrocarbon ring is preferably a group in which two hydrogen atoms have been removed from a polycycloalkane having 7 to 12 carbon atoms, and specific examples of the polycycloalkane include adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane.

[0097] The -SO2- containing cyclic group may have a substituent. Examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, an oxygen atom (=O), -COOR", -OC(=O)R", a hydroxyalkyl group, and a cyano group.

[0098] The alkyl group as the substituent is preferably an alkyl group having 1 to 6 carbon atoms. The alkyl group is preferably linear or branched. Specific examples include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, a neopentyl group, and an n-hexyl group. Of these, a methyl group or an ethyl group is preferred, and a methyl group is particularly preferred.

[0099] The alkoxy group as the substituent is preferably an alkoxy group having 1 to 6 carbon atoms. The alkoxy group is preferably linear or branched. Specific examples include groups in which the alkyl groups listed above as the alkyl groups as the substituent are bonded to an oxygen atom (—O—).

[0100] Examples of the halogen atom as the substituent include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, with a fluorine atom being preferred.

[0101] Examples of the halogenated alkyl group for the substituent include the above-mentioned alkyl groups in which some or all of the hydrogen atoms have been substituted with the above-mentioned halogen atoms.

[0102] Examples of the halogenated alkyl group as the substituent include the alkyl groups listed above as the alkyl groups for the substituent, in which some or all of the hydrogen atoms of the alkyl groups are substituted with the halogen atoms listed above. As the halogenated alkyl group, a fluorinated alkyl group is preferred, and a perfluoroalkyl group is particularly preferred.

[0103] R" in the above-mentioned -COOR" and -OC(=O)R" is either a hydrogen atom or a linear, branched, or cyclic alkyl group having 1 to 15 carbon atoms.

[0104] When R″ is a linear or branched alkyl group, the linear alkyl group preferably has 1 or more and 10 or less carbon atoms, more preferably 1 or more and 5 or less carbon atoms, and particularly preferably 1 or 2 carbon atoms.

[0105] When R" is a cyclic alkyl group, the cyclic alkyl group preferably has 3 or more and 15 or less carbon atoms, more preferably 4 or more and 12 or less carbon atoms, and particularly preferably 5 or more and 10 or less carbon atoms. Specific examples include groups in which one or more hydrogen atoms have been removed from monocycloalkanes, which may or may not be substituted with a fluorine atom or a fluorinated alkyl group, and polycycloalkanes such as bicycloalkanes, tricycloalkanes, and tetracycloalkanes. More specific examples include groups in which one or more hydrogen atoms have been removed from monocycloalkanes such as cyclopentane and cyclohexane, and polycycloalkanes such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane.

[0106] The hydroxyalkyl group as the substituent is preferably a hydroxyalkyl group having from 1 to 6 carbon atoms. Specific examples include groups in which at least one hydrogen atom of the alkyl groups listed above as the alkyl group as the substituent has been substituted with a hydroxyl group.

[0107] More specific examples of the —SO2—-containing cyclic group include groups represented by the following formulae (a1-3-1) to (a1-3-4). [ka] (In the formula, A′ represents an alkylene group having 1 to 5 carbon atoms which may contain an oxygen atom or a sulfur atom, an oxygen atom, or a sulfur atom; z represents an integer of 0 to 2; and R 10a is an alkyl group, an alkoxy group, a halogenated alkyl group, a hydroxyl group, -COOR", -OC(=O)R", a hydroxyalkyl group, or a cyano group, and R" is a hydrogen atom or an alkyl group.

[0108] In the above formulas (a1-3-1) to (a1-3-4), A' represents an alkylene group having from 1 to 5 carbon atoms, which may contain an oxygen atom (-O-) or a sulfur atom (-S-), an oxygen atom, or a sulfur atom. The alkylene group having from 1 to 5 carbon atoms in A' is preferably a linear or branched alkylene group, such as a methylene group, an ethylene group, an n-propylene group, or an isopropylene group.

[0109] When the alkylene group contains an oxygen atom or a sulfur atom, specific examples thereof include groups in which -O- or -S- is present at the terminal or between carbon atoms of the aforementioned alkylene group, such as -O-CH2-, -CH2-O-CH2-, -S-CH2-, -CH2-S-CH2-, etc. A' is preferably an alkylene group having from 1 to 5 carbon atoms or -O-, more preferably an alkylene group having from 1 to 5 carbon atoms, and most preferably a methylene group.

[0110] z may be any of 0, 1, and 2, and is most preferably 0. When z is 2, a plurality of R 10a may be the same or different.

[0111] R 10aExamples of the alkyl group, alkoxy group, halogenated alkyl group, -COOR", -OC(=O)R", and hydroxyalkyl group in the above formula include the same groups as those described above for the alkyl group, alkoxy group, halogenated alkyl group, -COOR", -OC(=O)R", and hydroxyalkyl group listed as the substituent that the -SO- containing cyclic group may have.

[0112] Specific examples of cyclic groups represented by the above formulae (a1-3-1) to (a1-3-4) are shown below, where "Ac" represents an acetyl group.

[0113] [ka]

[0114] [ka]

[0115] Of the above -SO2- containing cyclic groups, the group represented by the aforementioned formula (a1-3-1) is preferred, at least one selected from the group consisting of groups represented by any of the aforementioned chemical formulas (a1-3-1-1), (a1-3-1-18), (a1-3-3-1), and (a1-3-4-1) is more preferred, and the group represented by the aforementioned chemical formula (a1-3-1-1) is most preferred.

[0116] (lactone-containing cyclic group) A "lactone-containing cyclic group" refers to a cyclic group containing a ring (lactone ring) containing -OC(=O)- in its ring skeleton. The lactone ring is counted as the first ring, and a group consisting of only a lactone ring is called a monocyclic group. If a group further contains other ring structures, it is called a polycyclic group regardless of the structure. The lactone-containing cyclic group may be a monocyclic group or a polycyclic group.

[0117] The lactone-containing cyclic group in the structural unit (a1-3) is not particularly limited and any group can be used. Specific examples of lactone-containing monocyclic groups include groups in which one hydrogen atom has been removed from a 4- to 6-membered lactone, such as a group in which one hydrogen atom has been removed from β-propionolactone, a group in which one hydrogen atom has been removed from γ-butyrolactone, and a group in which one hydrogen atom has been removed from δ-valerolactone. Furthermore, examples of lactone-containing polycyclic groups include groups in which one hydrogen atom has been removed from a bicycloalkane, tricycloalkane, or tetracycloalkane having a lactone ring.

[0118] As for the structural unit (a1-3), there are no particular limitations on the structure of the other portions, so long as it contains an -SO- containing cyclic group or a lactone-containing cyclic group, but at least one structural unit selected from the group consisting of structural units (a1-3-S) derived from an acrylate ester in which the hydrogen atom bonded to the carbon atom at the α-position may be substituted with a substituent and which contain an -SO- containing cyclic group, and structural units (a1-3-L) derived from an acrylate ester in which the hydrogen atom bonded to the carbon atom at the α-position may be substituted with a substituent and which contain a lactone-containing cyclic group is preferred.

[0119] [Structural unit (a1-3-S)] More specific examples of the structural unit (a1-3-S) include structural units represented by the following formula (a1-3-S1).

[0120] [ka] (wherein R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms; R 11a is a -SO2- containing cyclic group, and R 12a is a single bond or a divalent linking group.

[0121] In formula (a1-3-S1), R is the same as defined above. R 11a is the same as the -SO2- containing cyclic group listed above. R 12a R may be either a single bond or a divalent linking group. 12a The divalent linking group represented by R 2 The same applies to the divalent linking group as defined above.

[0122] The structural unit (a1-3-S) is preferably a structural unit represented by the following formula (a1-3-S1-1).

[0123] [ka] (Wherein R and R 11a are the same as above, and R 13a is a divalent linking group.

[0124] R 13a The divalent linking group as R is not particularly limited. 13a The divalent linking group as R 12a The same applies to the divalent linking group as defined above. R 13a The divalent linking group as is preferably a linear or branched alkylene group, an aliphatic hydrocarbon group containing a ring in its structure, or a divalent linking group containing a heteroatom, and more preferably a linear or branched alkylene group or a divalent linking group containing an oxygen atom as a heteroatom.

[0125] The linear alkylene group is preferably a methylene group or an ethylene group, and more preferably a methylene group. The branched alkylene group is preferably an alkylmethylene group or an alkylethylene group, and more preferably -CH(CH3)-, -C(CH3)2-, or -C(CH3)2CH2-.

[0126] The divalent linking group containing an oxygen atom is preferably a divalent linking group containing an ether bond or an ester bond, and the above-mentioned -Y 1a -OY 2a -, -[Y 1a -C(=O)-O] m’ -Y 2a- or -Y 1a -OC(=O)-Y 2a - is more preferable. Y 1a , and Y 2a are each independently a divalent hydrocarbon group which may have a substituent, and m' is an integer of 0 to 3. 1a -OC(=O)-Y 2a - is preferred, -(CH2) c -OC(=O)-(CH2) d A group represented by the formula - is particularly preferred. c is an integer of 1 or more and 5 or less, preferably 1 or 2. d is an integer of 1 or more and 5 or less, preferably 1 or 2.

[0127] As the structural unit (a1-3-S), a structural unit represented by the following formula (a1-3-S1-11) or (a1-3-S1-12) is particularly preferred, with a structural unit represented by formula (a1-3-S1-12) being more preferred.

[0128] [ka] (In the formula, R, A', R 10a , z, and R 13a are the same as above.)

[0129] In formula (a1-3-S1-11), A' is preferably a methylene group, an oxygen atom (-O-), or a sulfur atom (-S-).

[0130] R 13a R is preferably a linear or branched alkylene group or a divalent linking group containing an oxygen atom. 13a Examples of the linear or branched alkylene group and the divalent linking group containing an oxygen atom in the formula (I) include the same as the linear or branched alkylene group and the divalent linking group containing an oxygen atom described above, respectively.

[0131] As the structural unit represented by formula (a1-3-S1-12), a structural unit represented by the following formula (a1-3-S1-12a) or (a1-3-S1-12b) is particularly preferred.

[0132] [ka] (In the formula, R and A' are the same as above, and c to e each independently represent an integer of 1 or more and 3 or less.)

[0133] [Structural unit (a1-3-L)] Examples of the structural unit (a1-3-L) include R 11a with a lactone-containing cyclic group, and more specific examples include structural units represented by the following formulae (a1-3-L1) to (a1-3-L5).

[0134] [ka] (In the formula, R is a hydrogen atom, an alkyl group having from 1 to 5 carbon atoms, or a halogenated alkyl group having from 1 to 5 carbon atoms; each R' is independently a hydrogen atom, an alkyl group, an alkoxy group, a halogenated alkyl group, a hydroxyl group, -COOR", -OC(=O)R", a hydroxyalkyl group, or a cyano group, and R" is a hydrogen atom or an alkyl group; R 12a represents a single bond or a divalent linking group, s″ represents an integer of 0 to 2, A″ represents an alkylene group having 1 to 5 carbon atoms which may contain an oxygen atom or a sulfur atom, an oxygen atom, or a sulfur atom, and r represents 0 or 1.

[0135] R in the formulae (a1-3-L1) to (a1-3-L5) is the same as described above. Examples of the alkyl group, alkoxy group, halogenated alkyl group, -COOR", -OC(=O)R", and hydroxyalkyl group for R' are the same as those described above for the alkyl group, alkoxy group, halogenated alkyl group, -COOR", -OC(=O)R", and hydroxyalkyl group listed as the substituent that the -SO- containing cyclic group may have, respectively.

[0136] Considering industrial availability and other factors, R' is preferably a hydrogen atom. The alkyl group in R'' may be linear, branched, or cyclic. When R″ is a linear or branched alkyl group, it preferably has 1 to 10 carbon atoms, and more preferably has 1 to 5 carbon atoms. When R" is a cyclic alkyl group, it preferably has 3 to 15 carbon atoms, more preferably 4 to 12 carbon atoms, and most preferably 5 to 10 carbon atoms. Specific examples include groups in which one or more hydrogen atoms have been removed from polycycloalkanes such as monocycloalkanes, bicycloalkanes, tricycloalkanes, and tetracycloalkanes, which may or may not be substituted with a fluorine atom or a fluorinated alkyl group. Specific examples include groups in which one or more hydrogen atoms have been removed from monocycloalkanes such as cyclopentane and cyclohexane, and polycycloalkanes such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane. Examples of A" include the same as A' in the above formula (3-1). A" is preferably an alkylene group having 1 to 5 carbon atoms, an oxygen atom (-O-), or a sulfur atom (-S-), and more preferably an alkylene group having 1 to 5 carbon atoms or -O-. As the alkylene group having 1 to 5 carbon atoms, a methylene group or a dimethylmethylene group is more preferable, and a methylene group is most preferable.

[0137] R 12a is the R in the above formula (a1-3-S1). 12a is the same as: In formula (a1-3-L1), s" is preferably 1 or 2. Specific examples of the structural units represented by the above formulas (a1-3-L1) to (a1-3-L3) are shown below. In each of the following formulas, R α represents a hydrogen atom, a methyl group, or a trifluoromethyl group.

[0138] [ka]

[0139] [ka]

[0140] [ka]

[0141] The structural unit (a1-3-L) is preferably at least one selected from the group consisting of structural units represented by the aforementioned formulas (a1-3-L1) to (a1-3-L5), more preferably at least one selected from the group consisting of structural units represented by the aforementioned formulas (a1-3-L1) to (a1-3-L3), and particularly preferably at least one selected from the group consisting of structural units represented by the aforementioned formula (a1-3-L1) or (a1-3-L3). Of these, at least one selected from the group consisting of structural units represented by the aforementioned formulas (a1-3-L1-1), (a1-3-L1-2), (a1-3-L2-1), (a1-3-L2-7), (a1-3-L2-12), (a1-3-L2-14), (a1-3-L3-1), and (a1-3-L3-5) is preferred.

[0142] Additionally, as the structural unit (a1-3-L), structural units represented by the following formulas (a1-3-L6) to (a1-3-L7) are also preferred. [ka] In formulas (a1-3-L6) and (a1-3-L7), R and R 12a is the same as above.

[0143] Examples of the structural unit represented by formula (a1-2-1) include structural units represented by the following formulae (a1-4) to (a1-6) that have an acid-dissociable group. The structural units represented by the following formulae (a1-4) to (a1-6) are structural units derived from (meth)acrylates that have an acid-dissociable group. The structural units represented by the following formulae (a1-4) to (a1-6) which have an acid-dissociable group increase the alkali solubility of the acrylic resin (A1) through the action of an acid.

[0144] [ka]

[0145] In the above formulas (a1-4) to (a1-6), R 14a , and R 18a ~R 23a each independently represents a hydrogen atom, a linear or branched alkyl group having from 1 to 6 carbon atoms, a fluorine atom, or a linear or branched fluorinated alkyl group having from 1 to 6 carbon atoms; R 15a ~R 17a each independently represents a linear or branched alkyl group having from 1 to 6 carbon atoms, a linear or branched fluorinated alkyl group having from 1 to 6 carbon atoms, an aliphatic cyclic group having from 5 to 20 carbon atoms, or an aromatic hydrocarbon group having from 6 to 15 carbon atoms; R 16a and R 17a may be bonded to each other to form a hydrocarbon ring having 5 to 20 carbon atoms together with the carbon atom to which they are bonded, and Y a represents an aliphatic cyclic group or alkyl group which may have a substituent; p represents an integer of 0 or more and 4 or less; and q represents 0 or 1.

[0146] Examples of the linear or branched alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, a neopentyl group, etc. A fluorinated alkyl group is an alkyl group in which some or all of the hydrogen atoms have been substituted with fluorine atoms. Specific examples of the aliphatic cyclic group include groups in which one or more hydrogen atoms have been removed from polycycloalkanes such as monocycloalkanes, bicycloalkanes, tricycloalkanes, and tetracycloalkanes. Specific examples include groups in which one hydrogen atom has been removed from monocycloalkanes such as cyclopentane, cyclohexane, cycloheptane, and cyclooctane, and polycycloalkanes such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane. Particularly preferred are groups in which one hydrogen atom has been removed from cyclohexane and adamantane (which may further have a substituent).

[0147] Above R 16a and R 17a When R 15a , R 16a , and R 17a In terms of high contrast, resolution, depth of focus, and the like, R is preferably a linear or branched alkyl group having 2 to 4 carbon atoms. 19a , R 20a , R 22a , R 23a is preferably a hydrogen atom or a methyl group.

[0148] Above R 16a and R 17a may form an aliphatic cyclic group having 5 to 20 carbon atoms together with the carbon atom to which they are bonded. Specific examples of such an aliphatic cyclic group include groups in which one or more hydrogen atoms have been removed from polycycloalkanes such as monocycloalkanes, bicycloalkanes, tricycloalkanes, and tetracycloalkanes. Specific examples include groups in which one or more hydrogen atoms have been removed from monocycloalkanes such as cyclopentane, cyclohexane, cycloheptane, and cyclooctane, and polycycloalkanes such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane. Particularly preferred are groups in which one or more hydrogen atoms have been removed from cyclohexane and adamantane (which may further have a substituent).

[0149] Furthermore, the above R16a and R 17a When the aliphatic cyclic group formed by the formula (I) has a substituent on its ring skeleton, examples of the substituent include polar groups such as a hydroxyl group, a carboxyl group, a cyano group, and an oxygen atom (=O), as well as linear or branched alkyl groups having from 1 to 4 carbon atoms. An oxygen atom (=O) is particularly preferred as the polar group.

[0150] Above Y a is an aliphatic cyclic group or an alkyl group, and examples thereof include groups in which one or more hydrogen atoms have been removed from polycycloalkanes such as monocycloalkanes, bicycloalkanes, tricycloalkanes, and tetracycloalkanes. Specific examples include groups in which one or more hydrogen atoms have been removed from monocycloalkanes such as cyclopentane, cyclohexane, cycloheptane, and cyclooctane, and groups in which one or more hydrogen atoms have been removed from polycycloalkanes such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane. Particularly preferred are groups in which one or more hydrogen atoms have been removed from adamantane (which may further have a substituent).

[0151] Furthermore, the above Y a When the aliphatic cyclic group has a substituent on its ring skeleton, examples of the substituent include polar groups such as a hydroxyl group, a carboxyl group, a cyano group, and an oxygen atom (=O), as well as linear or branched alkyl groups having from 1 to 4 carbon atoms. An oxygen atom (=O) is particularly preferred as the polar group.

[0152] Also, Y a When is an alkyl group, it is preferably a linear or branched alkyl group having from 1 to 20 carbon atoms, and more preferably from 6 to 15. Such an alkyl group is particularly preferably an alkoxyalkyl group, and examples of such an alkoxyalkyl group include a 1-methoxyethyl group, a 1-ethoxyethyl group, a 1-n-propoxyethyl group, a 1-isopropoxyethyl group, a 1-n-butoxyethyl group, a 1-isobutoxyethyl group, a 1-tert-butoxyethyl group, a 1-methoxypropyl group, a 1-ethoxypropyl group, a 1-methoxy-1-methylethyl group, and a 1-ethoxy-1-methylethyl group.

[0153] Preferred specific examples of the structural unit represented by the above formula (a1-4) include those represented by the following formulas (a1-4-1) to (a1-4-33).

[0154] [ka]

[0155] In the above formulas (a1-4-1) to (a1-4-33), R 24a represents a hydrogen atom or a methyl group.

[0156] Preferred specific examples of the structural unit represented by the above formula (a1-5) include those represented by the following formulas (a1-5-1) to (a1-5-26).

[0157] [ka]

[0158] In the above formulas (a1-5-1) to (a1-5-26), R 24a represents a hydrogen atom or a methyl group.

[0159] Preferred specific examples of the structural unit represented by the above formula (a1-6) include those represented by the following formulas (a1-6-1) to (a1-6-15).

[0160] [ka]

[0161] In the above formulas (a1-6-1) to (a1-6-15), R 24a represents a hydrogen atom or a methyl group.

[0162] Examples of the structural unit represented by formula (a1-2-1) include structural units derived from (meth)acrylic acid esters having an ether bond.

[0163] Examples of structural units derived from the (meth)acrylic acid ester having an ether bond include structural units derived from a (meth)acrylic acid derivative having an ether bond and an ester bond. Specific examples of (meth)acrylic acid derivatives having an ether bond and an ester bond include 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, methoxytriethylene glycol (meth)acrylate, 3-methoxybutyl (meth)acrylate, ethyl carbitol (meth)acrylate, phenoxypolyethylene glycol (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, methoxypolypropylene glycol (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, and (2-methyl-2-ethyl-1,3-dioxolan-4-yl)methyl (meth)acrylate. Furthermore, the (meth)acrylic acid derivative having an ether bond is preferably 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, or methoxytriethylene glycol (meth)acrylate. These (meth)acrylic acid derivatives may be used alone or in combination of two or more.

[0164] Examples of the structural unit represented by formula (a1-2-1) include structural units derived from methacrylic acid derivatives having a carboxy group and an ester bond, such as 2-methacryloyloxyethyl succinic acid, 2-methacryloyloxyethyl maleic acid, 2-methacryloyloxyethyl phthalic acid, and 2-methacryloyloxyethyl hexahydrophthalic acid; (meth)acrylic acid alkyl esters, such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, and cyclohexyl (meth)acrylate; (meth)acrylic acid hydroxyalkyl esters, such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate; and (meth)acrylic acid aryl esters, such as phenyl (meth)acrylate and benzyl (meth)acrylate.

[0165] Examples of the structural unit represented by formula (a1-2-1) include structural units derived from (meth)acrylic acid esters having an acid-non-dissociable aliphatic polycyclic group. As the acid-non-dissociable aliphatic polycyclic group, tricyclodecanyl, adamantyl, tetracyclododecanyl, isobornyl, norbornyl, and the like are particularly preferred because of their industrial availability. These aliphatic polycyclic groups may have a linear or branched alkyl group having from 1 to 5 carbon atoms as a substituent.

[0166] Specific examples of structural units derived from (meth)acrylic acid esters having an acid-non-dissociable aliphatic polycyclic group include those having structures of the following formulae (a1-7-1) to (a1-7-5).

[0167] [ka]

[0168] In the above formulas (a1-7-1) to (a1-7-5), R 25a represents a hydrogen atom or a methyl group.

[0169] Examples of the structural unit represented by formula (a1-2-1) include structural units derived from a (meth)acrylic acid derivative having a cyclic carbonate group and an ester bond. Examples of the cyclic carbonate group include a group in which one hydrogen atom has been removed from ethylene carbonate. Specific examples of structural units derived from a (meth)acrylic acid derivative having a cyclic carbonate group and an ester bond include the following formulae (a1-8-1) to (a1-8-4).

[0170] [ka]

[0171] In the above formulas (a1-8-1) to (a1-8-4), R 26a represents a hydrogen atom or a methyl group.

[0172] Furthermore, the acrylic resin (A1) may contain structural units derived from other polymerizable compounds in order to appropriately control the physical and chemical properties of the resin. Examples of such polymerizable compounds include known radically polymerizable compounds and anionically polymerizable compounds.

[0173] Examples of such polymerizable compounds include monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid; dicarboxylic acids such as maleic acid, fumaric acid, and itaconic acid; dicarboxylic acid diesters such as diethyl maleate and dibutyl fumarate; vinyl group-containing aromatic compounds such as styrene, α-methylstyrene, chlorostyrene, chloromethylstyrene, and vinyltoluene; vinyl group-containing aliphatic compounds such as vinyl acetate; conjugated diolefins such as butadiene and isoprene; nitrile group-containing polymerizable compounds such as acrylonitrile and methacrylonitrile; chlorine-containing polymerizable compounds such as vinyl chloride and vinylidene chloride; and amide bond-containing polymerizable compounds such as acrylamide and methacrylamide.

[0174] As described above, the acrylic resin (A1) may contain structural units derived from polymerizable compounds having a carboxy group, such as the monocarboxylic acids and dicarboxylic acids described above. The proportion of structural units derived from polymerizable compounds having a carboxy group in the acrylic resin (A1) is preferably 20 mol % or less, more preferably 15 mol % or less, and particularly preferably 5 mol % or less. In the acrylic resin (A1), an acrylic resin containing a relatively large amount of structural units derived from a polymerizable compound having a carboxy group is preferably used in combination with an acrylic resin containing only a small amount of or no structural units derived from a polymerizable compound having a carboxy group.

[0175] When the acrylic resin (A1) contains a structural unit (a1-3) containing an -SO2- containing cyclic group or a lactone-containing cyclic group, the content of the structural unit (a1-3) in the acrylic resin (A1) is preferably 5 mol% or more, more preferably 10 mol% or more, particularly preferably 10 mol% to 50 mol%, and most preferably 10 mol% to 30 mol%. When the photosensitive composition contains the structural unit (a1-3) in an amount within the above range, it is easy to achieve both good developability and good pattern shape.

[0176] The acrylic resin (A1) preferably contains 5 mol % or more, more preferably 10 mol % or more, and particularly preferably 10 mol % to 60 mol % of the structural units represented by the above formulas (a1-4) to (a1-6).

[0177] The acrylic resin (A1) preferably contains a structural unit derived from the (meth)acrylic acid ester having an ether bond. The content of the structural unit derived from the (meth)acrylic acid ester having an ether bond in the acrylic resin (A1) is preferably 0 mol % or more and 50 mol % or less, and more preferably 5 mol % or more and 40 mol % or less.

[0178] The acrylic resin (A1) preferably contains structural units derived from (meth)acrylic acid esters having an acid-non-dissociable aliphatic polycyclic group. The content of structural units derived from (meth)acrylic acid esters having an acid-non-dissociable aliphatic polycyclic group in the acrylic resin (A1) is preferably 0 mol % or more and 50 mol % or less, and more preferably 5 mol % or more and 30 mol % or less.

[0179] The content of structural units derived from a (meth)acrylic acid derivative having a cyclic carbonate group and an ester bond in the acrylic resin (A1) is preferably from 0 mol % to 50 mol %, more preferably from 5 mol % to 40 mol %.

[0180] As long as the photosensitive composition contains the acrylic resin (A1), an acrylic resin (A2) other than the acrylic resin (A1) described above can also be used as the resin (A). Such an acrylic resin (A2) other than the acrylic resin (A1) is not particularly limited as long as it is a resin that does not contain the phenolic hydroxyl group-containing unit (a1) derived from the unsaturated compound represented by formula (a1-1).

[0181] The polystyrene-equivalent weight average molecular weight of the resin (A) described above is preferably from 5,000 to 600,000, more preferably from 7,000 to 400,000, and even more preferably from 10,000 to 300,000. By setting the weight average molecular weight within this range, the photosensitive layer can maintain sufficient strength without reducing the releasability from the substrate, and furthermore, swelling of the profile and the occurrence of cracks during plating can be prevented.

[0182] The polydispersity of the resin (A) is preferably 1.05 or more. Here, the polydispersity is the value obtained by dividing the mass average molecular weight by the number average molecular weight. By achieving such a polydispersity, the desired stress resistance to plating can be achieved and the problem of the metal layer obtained by plating treatment being prone to swelling can be avoided.

[0183] The content of the resin (A) is preferably 5% by mass or more and 99% by mass or less based on the total solid content of the photosensitive composition.

[0184] [Novolac resin (A3)] As the novolak resin (A3), a resin containing a structural unit represented by the following formula (a3) ​​can be used.

[0185] [ka]

[0186] In the above formula (a-11), R 1a represents an acid-dissociable group. The acid-dissociable group is preferably a so-called acetal-type protecting group. R 1aThe acid-dissociable group as is the same as the acid-dissociable group described above for the structural unit represented by formula (a1-1-1), the structural unit represented by formula (a1-1-1a), and the structural unit represented by formula (a1-1-1b).

[0187] [Polyhydroxystyrene resin (A4)] As the polyhydroxystyrene resin (A4), a resin containing a structural unit represented by the following formula (a4) can be used.

[0188] [ka]

[0189] In the above formula (a4), R 8a represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R 9a represents an acid-dissociable group.

[0190] The alkyl group having from 1 to 6 carbon atoms is, for example, a linear, branched, or cyclic alkyl group having from 1 to 6 carbon atoms. Examples of the linear or branched alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, and a neopentyl group, and examples of the cyclic alkyl group include a cyclopentyl group and a cyclohexyl group.

[0191] R 9a Examples of the acid-dissociable, dissolution-inhibiting group as the structural unit represented by formula (a1-1-1), the structural unit represented by formula (a1-1-1a), and the structural unit represented by formula (a1-1-1b) include the acid-dissociable groups mentioned above for the structural unit represented by formula (a1-1-1), the structural unit represented by formula (a1-1-1a), and the structural unit represented by formula (a1-1-1b), as well as a tert-butyl group, a 1-ethylcyclohexyl group, a 1-ethylcyclopentyl group, a 1-propylcyclohexyl group, and a 1-propylcyclopentyl group.

[0192] Furthermore, the polyhydroxystyrene resin (A4) may contain other polymerizable compounds as structural units in order to appropriately control the physical and chemical properties. Examples of such polymerizable compounds include known radically polymerizable compounds and anionically polymerizable compounds. Examples of such polymerizable compounds include monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid; dicarboxylic acids such as maleic acid, fumaric acid, and itaconic acid; methacrylic acid derivatives having a carboxy group and an ester bond such as 2-methacryloyloxyethyl succinic acid, 2-methacryloyloxyethyl maleic acid, 2-methacryloyloxyethyl phthalic acid, and 2-methacryloyloxyethyl hexahydrophthalic acid; (meth)acrylic acid alkyl esters such as methyl (meth)acrylate, ethyl (meth)acrylate, and n-butyl (meth)acrylate; (meth)acrylic acid hydroxyalkyl esters such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate; and hydroxypropyl acrylate. Examples of suitable polymerizable compounds include (meth)acrylic acid aryl esters such as phenyl (meth)acrylate and benzyl (meth)acrylate; dicarboxylic acid diesters such as diethyl maleate and dibutyl fumarate; vinyl group-containing aromatic compounds such as styrene, α-methylstyrene, chlorostyrene, chloromethylstyrene, vinyltoluene, hydroxystyrene, α-methylhydroxystyrene, and α-ethylhydroxystyrene; vinyl group-containing aliphatic compounds such as vinyl acetate; conjugated diolefins such as butadiene and isoprene; nitrile group-containing polymerizable compounds such as acrylonitrile and methacrylonitrile; chlorine-containing polymerizable compounds such as vinyl chloride and vinylidene chloride; and amide bond-containing polymerizable compounds such as acrylamide and methacrylamide. These polymerizable compounds are preferably not acid-dissociable.

[0193] <Acid generator (B)> The acid generator (B) is a compound that generates an acid upon irradiation with actinic rays or radiation. As the acid generator (B), any photoacid generator that has been conventionally incorporated into various photosensitive compositions can be used without any particular limitation.

[0194] A suitable example of the acid generator (B) is a sulfonium salt composed of a sulfonium cation and an anion represented by the following formula (B1). Cf-SO2-N - -SO2-Cf···(B1) (In formula (B1), Cf represents a fluorine atom or a fluorinated alkyl group, and when two Cfs are both fluorinated alkyl groups, the two fluorinated alkyl groups may be bonded to each other to form a ring.)

[0195] In formula (B1), the fluorinated alkyl group represented by Cf is a linear or branched alkyl group in which at least one hydrogen atom is substituted with a fluorine atom. The number of carbon atoms in the alkyl group is preferably 1 to 10, more preferably 1 to 7, and particularly preferably 1 to 4. The two Cf's in formula (B1) may be the same or different, and are preferably the same.

[0196] Specific examples of the anion represented by formula (B1) include the following anions. [ka]

[0197] In the sulfonium salt composed of a sulfonium cation and an anion represented by formula (B1), the sulfonium cation is not particularly limited. The sulfonium cation is preferably a structure represented by the following formula (b1): [ka]

[0198] In the above formula (b1), R 1b , R 2b , R 3bAt least one of R represents a group represented by the following formula (b2), and the rest represent a linear or branched alkyl group having from 1 to 6 carbon atoms, a phenyl group which may have a substituent, or a linear or branched alkoxy group having from 1 to 6 carbon atoms. 1b , R 2b , R 3b One of the groups is a group represented by the following formula (b2), and the remaining two groups are each independently a linear or branched alkylene group having from 1 to 6 carbon atoms, and the ends of these groups may be bonded to form a ring. R 1b , R 2b , R 3b Specific examples of the linear or branched alkyl group having 1 to 6 carbon atoms as the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, and an n-hexyl group. R 1b , R 2b , R 3b Specific examples of the linear or branched alkoxy group having from 1 to 6 carbon atoms as the alkoxy group include a methoxy group, an ethoxy group, an n-propyloxy group, an isopropyloxy group, an n-butyloxy group, an isobutyloxy group, a sec-butyloxy group, a tert-butyloxy group, an n-pentyloxy group, and an n-hexyloxy group. R 1b , R 2b , R 3b When is a phenyl group which may have a substituent, preferred substituents include a hydroxyl group, a linear or branched alkoxy group having from 1 to 6 carbon atoms, and a linear or branched alkyl group having from 1 to 6 carbon atoms.

[0199] [ka]

[0200] In the above formula (b2), R 4b , R 5beach independently represents a hydroxyl group, a linear or branched alkoxy group having from 1 to 6 carbon atoms, or a linear or branched alkyl group having from 1 to 6 carbon atoms; R 6b represents a single bond or a linear or branched alkylene group having 1 to 6 carbon atoms, which may have a substituent. l and m each independently represent an integer of 0 to 2, and l+m is 3 or less. However, R 4b When there are multiple R, they may be the same or different. 5b When there are a plurality of, they may be the same or different. R 4b , and R 5b Specific examples of the linear or branched alkoxy group having from 1 to 6 carbon atoms as the alkoxy group include a methoxy group, an ethoxy group, an n-propyloxy group, an isopropyloxy group, an n-butyloxy group, an isobutyloxy group, a sec-butyloxy group, a tert-butyloxy group, an n-pentyloxy group, and an n-hexyloxy group. R 4a , and R 5a Specific examples of the linear or branched alkyl group having 1 to 6 carbon atoms as the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, and an n-hexyl group. R 6b Specific examples of the linear or branched alkylene group having 1 to 6 carbon atoms as the alkylene group include a methylene group, an ethane-1,2-diyl group (ethylene group), an ethane-1,1-diyl group, a propane-1,3-diyl group, a propane-1,2-diyl group, a propane-2,2-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, and a hexane-1,6-diyl group.

[0201] Above R 1b , R 2b , R 3bAmong these, the number of groups represented by the above formula (b2) is preferably one from the viewpoint of the stability of the compound, and the rest are linear or branched alkylene groups having from 1 to 6 carbon atoms, the ends of which may be bonded to form a ring. In this case, the two alkylene groups, including the sulfur atom, form a 3- to 9-membered ring. The number of atoms (including the sulfur atom) constituting the ring is preferably 5 to 6.

[0202] Furthermore, examples of the substituent that the alkylene group may have include an oxygen atom (which in this case forms a carbonyl group together with the carbon atom that constitutes the alkylene group), a hydroxyl group, and the like.

[0203] In addition, examples of the substituent that the phenyl group may have include a hydroxyl group, a linear or branched alkoxy group having 1 to 6 carbon atoms, and a linear or branched alkyl group having 1 to 6 carbon atoms.

[0204] Suitable examples of the sulfonium cation represented by formula (b1) include sulfonium cations represented by the following formulas: [ka]

[0205] In the sulfonium salt composed of a sulfonium cation and an anion represented by formula (B1), the sulfonium cation is preferably a cation represented by the following formula (b3). [ka]

[0206] In the above formula (b3), R 7b X each independently represents a group selected from the group consisting of a hydrogen atom, alkyl, hydroxy, alkoxy, alkylcarbonyl, alkylcarbonyloxy, alkyloxycarbonyl, a halogen atom, an aryl which may have a substituent, and an arylcarbonyl which may have a substituent. 1b is a structure represented by the following formula (b4). [ka]

[0207] In the above formula (b4), X 2b represents an alkylene group having 1 to 8 carbon atoms, an arylene group having 6 to 20 carbon atoms, or a divalent group of a heterocyclic compound having 8 to 20 carbon atoms; X 2b X may be substituted with at least one selected from the group consisting of alkyl having 1 to 8 carbon atoms, alkoxy having 1 to 8 carbon atoms, aryl having 6 to 10 carbon atoms, hydroxy, cyano, nitro, and halogen. 3b -O-, -S-, -SO-, -SO2-, -NH-, -NR 30b represents -, -CO-, -COO-, -CONH-, an alkylene group having 1 to 3 carbon atoms, or a phenylene group; h represents the number of repeating units of the structure in parentheses, and h represents an integer of 0 to 4; and h+1 X's 2b and h X's 3b may be the same or different. 30b is an alkyl group having 1 to 5 carbon atoms or an aryl group having 6 to 10 carbon atoms.

[0208] Specific examples of the sulfonium ion represented by the above formula (b3) include 4-(phenylthio)phenyldiphenylsulfonium, 4-(4-benzoyl-2-chlorophenylthio)phenylbis(4-fluorophenyl)sulfonium, 4-(4-benzoylphenylthio)phenyldiphenylsulfonium, phenyl[4-(4-biphenylthio)phenyl]4-biphenylsulfonium, phenyl[4-(4-biphenylthio)phenyl]3-biphenylsulfonium, [4-(4-acetophenylthio)phenyl]diphenylsulfonium, and diphenyl[4-(p-terphenylthio)phenyl]diphenylsulfonium.

[0209] Suitable examples of the sulfonium cation represented by formula (b3) include sulfonium cations represented by the following formulas: [ka]

[0210] The acid generator (B) also includes a sulfonium salt composed of a sulfonium cation and an anion other than the anion represented by the above formula (B1). The sulfonium cation in a sulfonium salt composed of a sulfonium cation and an anion other than the anion represented by formula (B1) above is the same as the sulfonium cation in the sulfonium salt composed of a sulfonium cation and an anion represented by formula (B1) above.

[0211] Examples of anions other than the anion represented by formula (B1) include the borate anion represented by the following formula (b5) and PF6 - Examples include: [ka]

[0212] In the above formula (b5), R 9b ~R 12b each independently represents a fluorine atom or a phenyl group, and some or all of the hydrogen atoms of the phenyl group may be substituted with at least one selected from the group consisting of a fluorine atom and a trifluoromethyl group.

[0213] A preferred example of the borate anion represented by the formula (b5) is tetrakis(pentafluorophenyl)borate ([B(C6F5)4] - ), tetrakis[(trifluoromethyl)phenyl]borate ([B(C6H4CF3)4] - ), difluorobis(pentafluorophenyl)borate ([(C6F5)2BF2] - ), trifluoro(pentafluorophenyl)borate ([(C6F5)BF3] - ), tetrakis(difluorophenyl)borate ([B(C6H3F2)4] -Among these, tetrakis(pentafluorophenyl)borate ([B(C6F5)4] - ) is particularly preferred.

[0214] Examples of anions other than the anion represented by formula (B1) include fluoroalkylsulfonate ions or arylsulfonate ions in which some or all of the hydrogen atoms have been fluorinated.

[0215] The alkyl group in the fluoroalkylsulfonate ion may be linear, branched, or cyclic and have from 1 to 20 carbon atoms, and preferably has from 1 to 10 carbon atoms in view of the bulkiness of the generated acid and its diffusion distance. Branched and cyclic groups are particularly preferred because they have a short diffusion distance. Furthermore, preferred groups include methyl, ethyl, propyl, butyl, and octyl groups because they can be synthesized inexpensively.

[0216] The aryl group in the arylsulfonate ion is an aryl group having from 6 to 20 carbon atoms, and examples thereof include an alkyl group, a phenyl group which may be substituted with a halogen atom, and a naphthyl group. In particular, an aryl group having from 6 to 10 carbon atoms is preferred because it can be synthesized inexpensively. Specific examples of preferred groups include a phenyl group, a toluenesulfonyl group, an ethylphenyl group, a naphthyl group, and a methylnaphthyl group.

[0217] In the above-mentioned fluoroalkylsulfonate ions or arylsulfonate ions, when some or all of the hydrogen atoms are fluorinated, the fluorination rate is preferably 10% or more and 100% or less, more preferably 50% or more and 100% or less, and in particular, those in which all the hydrogen atoms are substituted with fluorine atoms are preferred because they have a stronger acid strength. Specific examples of such fluorine ions include trifluoromethanesulfonate, perfluorobutanesulfonate, perfluorooctane sulfonate, and perfluorobenzenesulfonate.

[0218] Among these, preferred anions include those represented by the following formula (b6).

[0219] [ka]

[0220] In the above formula (b6), R 20b are groups represented by the following formulae (b7), (b8), and (b9).

[0221] [ka]

[0222] In the formula (b7), x represents an integer of 1 or more and 4 or less. In the formula (b8), R 21b represents a hydrogen atom, a hydroxyl group, a linear or branched alkyl group having from 1 to 6 carbon atoms, or a linear or branched alkoxy group having from 1 to 6 carbon atoms, and y represents an integer of from 1 to 3. Among these, trifluoromethanesulfonate and perfluorobutanesulfonate are preferred from the viewpoint of safety.

[0223] The acid generator (B) also includes a compound represented by the following formula (b10), which is a nonionic acid generator: The compound represented by the following formula (b10) generates a sulfonic acid when irradiated with actinic rays or radiation. [ka] (In formula (b10), R 22b is a monovalent organic group, and R 23b ~R 28b are each independently a hydrogen atom or a monovalent organic group, and R 23b and R 24b and R 24b and R 25b and R 25b and R 26b and R 26b and R 27b and, or R 27b and R 28bmay be bonded to each other to form a ring.

[0224] R 22b The organic group as the hydroxyl group is not particularly limited as long as it does not impair the object of the present invention. The organic group may be a hydrocarbon group or may contain heteroatoms such as O, N, S, P, or halogen atoms. The structure of the organic group may be linear, branched, cyclic, or a combination of these structures.

[0225] R 22b Suitable organic groups for the aryl group include an aliphatic hydrocarbon group having from 1 to 18 carbon atoms which may be substituted with a halogen atom and / or an alkylthio group, an aryl group having from 6 to 20 carbon atoms which may have a substituent, an aralkyl group having from 7 to 20 carbon atoms which may have a substituent, an alkylaryl group having from 7 to 20 carbon atoms which may have a substituent, a camphor-10-yl group, and a group represented by the following formula (b10a): -R 29b -(O) a -R 30b -(O) b -Y 1 -R 31b (b10a) (In formula (b10a), Y 1 R is a single bond or an alkanediyl group having 1 to 4 carbon atoms. 29b and R 30b R is an alkanediyl group having 2 to 6 carbon atoms which may be substituted with a halogen atom, or an arylene group having 6 to 20 carbon atoms which may be substituted with a halogen atom. 31b represents an alkyl group having from 1 to 18 carbon atoms which may be substituted with a halogen atom, an alicyclic hydrocarbon group having from 3 to 12 carbon atoms, an aryl group having from 6 to 20 carbon atoms which may be substituted with a halogen atom, or an aralkyl group having from 7 to 20 carbon atoms which may be substituted with a halogen atom. a and b each represent 0 or 1, and at least one of a and b is 1. Examples of the group include a group represented by the following formula:

[0226] R22b When the organic group has a halogen atom as a substituent, examples of the halogen atom include a chlorine atom, a bromine atom, an iodine atom, and a fluorine atom.

[0227] R 22b When the organic group is an alkyl group having 1 to 18 carbon atoms substituted with an alkylthio group, the alkylthio group preferably has 1 to 18 carbon atoms. Examples of the alkylthio group having 1 to 18 carbon atoms include a methylthio group, an ethylthio group, an n-propylthio group, an isopropylthio group, an n-butylthio group, a sec-butylthio group, a tert-butylthio group, an isobutylthio group, an n-pentylthio group, an isopentylthio group, a tert-pentylthio group, an n-hexylthio group, an n-heptylthio group, an isoheptylthio group, a tert-heptylthio group, an n-octylthio group, an isooctylthio group, a tert-octylthio group, a 2-ethylhexylthio group, an n-nonylthio group, an n-decylthio group, an n-undecylthio group, an n-dodecylthio group, an n-tridecylthio group, an n-tetradecylthio group, an n-pentadecylthio group, an n-hexadecylthio group, an n-heptadecylthio group, and an n-octadecylthio group.

[0228] R 22b When the organic group as the alkyl group is an aliphatic hydrocarbon group having 1 to 18 carbon atoms which may be substituted with a halogen atom and / or an alkylthio group, the aliphatic hydrocarbon group may contain an unsaturated double bond. The structure of the aliphatic hydrocarbon group is not particularly limited, and may be linear, branched, cyclic, or a combination of these structures.

[0229] R 22b When the organic group as is an alkenyl group, preferred examples include an allyl group and a 2-methyl-2-propenyl group.

[0230] R 22bWhen the organic group represented by is an alkyl group, preferred examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, an isobutyl group, an n-pentyl group, an isopentyl group, a tert-pentyl group, an n-hexyl group, an n-hexane-2-yl group, an n-hexane-3-yl group, an n-heptyl group, an n-heptan-2-yl group, an n-heptan-3-yl group, an isoheptyl group, a tert-heptyl group, an n-octyl group, an isooctyl group, a tert-octyl group, a 2-ethylhexyl group, an n-nonyl group, an isononyl group, an n-decyl group, an n-undecyl group, an n-dodecyl group, an n-tridecyl group, an n-tetradecyl group, an n-pentadecyl group, an n-hexadecyl group, an n-heptadecyl group, and an n-octadecyl group.

[0231] R 22b When the organic group is an alicyclic hydrocarbon group, examples of the alicyclic hydrocarbon constituting the main skeleton of the alicyclic hydrocarbon group include cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclodecane, bicyclo[2.1.1]hexane, bicyclo[2.2.1]heptane, bicyclo[3.2.1]octane, bicyclo[2.2.2]octane, and adamantane. As the alicyclic hydrocarbon group, a group in which one hydrogen atom has been removed from these alicyclic hydrocarbons is preferred.

[0232] R 22bWhen the organic group as the alkyl group is an aliphatic hydrocarbon group substituted with a halogen atom, preferred examples thereof include a trifluoromethyl group, a pentafluoroethyl group, a 2-chloroethyl group, a 2-bromoethyl group, a heptafluoro-n-propyl group, a 3-bromopropyl group, a nonafluoro-n-butyl group, a tridecafluoro-n-hexyl group, a heptadecafluoro-n-octyl group, a 2,2,2-trifluoroethyl group, a 1,1-difluoroethyl group, a 1,1-difluoro-n-propyl group, a 1,1,2,2-tetrafluoro-n-propyl group, a 3,3,3-trifluoro-n-propyl group, a 2,2,3,3,3-pentafluoro-n-propyl group, a 2-norbornyl-1,1-difluoroethyl group, a 2-norbornyltetrafluoroethyl group, and a 3-adamantyl-1,1,2,2-tetrafluoropropyl group.

[0233] R 22b When the organic group as the alkylthio group is an aliphatic hydrocarbon group substituted with an alkylthio group, preferred examples thereof include a 2-methylthioethyl group, a 4-methylthio-n-butyl group, and a 2-n-butylthioethyl group.

[0234] R 22b When the organic group as is an aliphatic hydrocarbon group substituted with a halogen atom and an alkylthio group, a suitable example thereof is a 3-methylthio-1,1,2,2-tetrafluoro-n-propyl group.

[0235] R 22b When the organic group as the alkyl group is an aryl group, preferred examples thereof include a phenyl group, a naphthyl group, and a biphenylyl group.

[0236] R 22b When the organic group as is an aryl group substituted with a halogen atom, preferred examples thereof include a pentafluorophenyl group, a chlorophenyl group, a dichlorophenyl group, and a trichlorophenyl group.

[0237] R 22bWhen the organic group as the alkylthio group is an aryl group substituted with an alkylthio group, preferred examples thereof include a 4-methylthiophenyl group, a 4-n-butylthiophenyl group, a 4-n-octylthiophenyl group, and a 4-n-dodecylthiophenyl group.

[0238] R 22b When the organic group as the alkyl group is an aryl group substituted with a halogen atom and an alkylthio group, preferred examples thereof include a 1,2,5,6-tetrafluoro-4-methylthiophenyl group, a 1,2,5,6-tetrafluoro-4-n-butylthiophenyl group, and a 1,2,5,6-tetrafluoro-4-n-dodecylthiophenyl group.

[0239] R 22b When the organic group as the alkyl group is an aralkyl group, preferred examples thereof include a benzyl group, a phenethyl group, a 2-phenylpropan-2-yl group, a diphenylmethyl group, and a triphenylmethyl group.

[0240] R 22b When the organic group as the alkyl group is an aralkyl group substituted with a halogen atom, preferred examples thereof include a pentafluorophenylmethyl group, a phenyldifluoromethyl group, a 2-phenyltetrafluoroethyl group, and a 2-(pentafluorophenyl)ethyl group.

[0241] R 22b When the organic group as is an aralkyl group substituted with an alkylthio group, a suitable example thereof is a p-methylthiobenzyl group.

[0242] R 22b When the organic group as is an aralkyl group substituted with a halogen atom and an alkylthio group, a suitable example thereof includes a 2-(2,3,5,6-tetrafluoro-4-methylthiophenyl)ethyl group.

[0243] R 22bWhen the organic group as the alkylaryl group is an alkylaryl group, preferred examples thereof include a 2-methylphenyl group, a 3-methylphenyl group, a 4-methylphenyl group, a 3-isopropylphenyl group, a 4-isopropylphenyl group, a 4-n-butylphenyl group, a 4-isobutylphenyl group, a 4-tert-butylphenyl group, a 4-n-hexylphenyl group, a 4-cyclohexylphenyl group, a 4-n-octylphenyl group, a 4-(2-ethyl-n-hexyl)phenyl group, a 2,3-dimethylphenyl group, a 2,4-dimethylphenyl group, a 2,5-dimethylphenyl group, a 2,6-dimethylphenyl group, Examples thereof include a 3,4-dimethylphenyl group, a 3,5-dimethylphenyl group, a 2,4-di-tert-butylphenyl group, a 2,5-di-tert-butylphenyl group, a 2,6-di-tert-butylphenyl group, a 2,4-di-tert-pentylphenyl group, a 2,5-di-tert-pentylphenyl group, a 2,5-di-tert-octylphenyl group, a 2-cyclohexylphenyl group, a 3-cyclohexylphenyl group, a 4-cyclohexylphenyl group, a 2,4,5-trimethylphenyl group, a 2,4,6-trimethylphenyl group, and a 2,4,6-triisopropylphenyl group.

[0244] The group represented by formula (b10a) is an ether group-containing group. In formula (b10a), Y 1 Examples of the alkanediyl group having 1 to 4 carbon atoms represented by the formula (I) include a methylene group, an ethane-1,2-diyl group, an ethane-1,1-diyl group, a propane-1,3-diyl group, a propane-1,2-diyl group, a butane-1,4-diyl group, a butane-1,3-diyl group, a butane-2,3-diyl group, and a butane-1,2-diyl group. In formula (b10a), R 29b or R 30bExamples of the alkanediyl group having 2 to 6 carbon atoms represented by the formula (I) include an ethane-1,2-diyl group, a propane-1,3-diyl group, a propane-1,2-diyl group, a butane-1,4-diyl group, a butane-1,3-diyl group, a butane-2,3-diyl group, a butane-1,2-diyl group, a pentane-1,5-diyl group, a pentane-1,3-diyl group, a pentane-1,4-diyl group, a pentane-2,3-diyl group, a hexane-1,6-diyl group, a hexane-1,2-diyl group, a hexane-1,3-diyl group, a hexane-1,4-diyl group, a hexane-2,5-diyl group, a hexane-2,4-diyl group, and a hexane-3,4-diyl group.

[0245] In formula (b10a), R 29b or R 30b is an alkanediyl group having from 2 to 6 carbon atoms substituted with a halogen atom, examples of the halogen atom include a chlorine atom, a bromine atom, an iodine atom, and a fluorine atom. Examples of the alkanediyl group substituted with a halogen atom include a tetrafluoroethane-1,2-diyl group, a 1,1-difluoroethane-1,2-diyl group, a 1-fluoroethane-1,2-diyl group, a 1,2-difluoroethane-1,2-diyl group, a hexafluoropropane-1,3-diyl group, a 1,1,2,2-tetrafluoropropane-1,3-diyl group, and a 1,1,2,2-tetrafluoropentane-1,5-diyl group.

[0246] In formula (b10a), R 29b or R 30bis an arylene group, examples of which include a 1,2-phenylene group, a 1,3-phenylene group, a 1,4-phenylene group, a 2,5-dimethyl-1,4-phenylene group, a biphenyl-4,4'-diyl group, a diphenylmethane-4,4'-diyl group, a 2,2-diphenylpropane-4,4'-diyl group, a naphthalene-1,2-diyl group, a naphthalene-1,3-diyl group, a naphthalene-1,4-diyl group, a naphthalene-1,5-diyl group, a naphthalene-1,6-diyl group, a naphthalene-1,7-diyl group, a naphthalene-1,8-diyl group, a naphthalene-2,3-diyl group, a naphthalene-2,6-diyl group, and a naphthalene-2,7-diyl group.

[0247] In formula (b10a), R 29b or R 30b is an arylene group substituted with a halogen atom, examples of which include a chlorine atom, a bromine atom, an iodine atom, and a fluorine atom. An example of an arylene group substituted with a halogen atom is a 2,3,5,6-tetrafluoro-1,4-phenylene group.

[0248] In formula (b10a), R 31b Examples of the alkyl group having 1 to 18 carbon atoms and which may have a branch, as represented by the formula (I), include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, an isobutyl group, an n-pentyl group, an isopentyl group, a tert-pentyl group, an n-hexyl group, an n-hexane-2-yl group, an n-hexane-3-yl group, an n-heptyl group, an n-heptan-2-yl group, an n-heptan-3-yl group, an isoheptyl group, a tert-heptyl group, an n-octyl group, an isooctyl group, a tert-octyl group, a 2-ethylhexyl group, an n-nonyl group, an isononyl group, an n-decyl group, an n-undecyl group, an n-dodecyl group, an n-tridecyl group, an n-tetradecyl group, an n-pentadecyl group, an n-hexadecyl group, an n-heptadecyl group, and an n-octadecyl group.

[0249] In formula (b10a), R 31bis an alkyl group having 1 to 18 carbon atoms substituted with a halogen atom, examples of the halogen atom include a chlorine atom, a bromine atom, an iodine atom, and a fluorine atom. Examples of the alkyl group substituted with a halogen atom include a trifluoromethyl group, a pentafluoroethyl group, a heptafluoro-n-propyl group, a nonafluoro-n-butyl group, a tridecafluoro-n-hexyl group, a heptadecafluoro-n-octyl group, a 2,2,2-trifluoroethyl group, a 1,1-difluoroethyl group, a 1,1-difluoro-n-propyl group, a 1,1,2,2-tetrafluoro-n-propyl group, a 3,3,3-trifluoro-n-propyl group, a 2,2,3,3,3-pentafluoro-n-propyl group, and a 1,1,2,2-tetrafluorotetradecyl group.

[0250] In formula (b10a), R 31b is an alicyclic hydrocarbon group having from 3 to 12 carbon atoms, examples of the alicyclic hydrocarbon constituting the main skeleton of the alicyclic hydrocarbon group include cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclodecane, bicyclo[2.1.1]hexane, bicyclo[2.2.1]heptane, bicyclo[3.2.1]octane, bicyclo[2.2.2]octane, and adamantane. As the alicyclic hydrocarbon group, a group in which one hydrogen atom has been removed from any of these alicyclic hydrocarbons is preferred.

[0251] In formula (b10a), R 31b is an aryl group, a halogenated aryl group, an aralkyl group, or a halogenated aralkyl group, suitable examples of these groups include R 22b is one of these groups.

[0252] Among the groups represented by formula (b10a), a suitable group is R 29b In the group represented by the formula (I), the carbon atom bonded to the sulfur atom is substituted with a fluorine atom. The number of carbon atoms in such a suitable group is preferably 2 or more and 18 or less.

[0253] R 22bAs R, a perfluoroalkyl group having 1 to 8 carbon atoms is preferred. In addition, a camphor-10-yl group is also preferred as R because it is easy to form a highly precise patterned resist film. 22b It is preferable as.

[0254] In equation (b10), R 23b ~R 28b is a hydrogen atom or a monovalent organic group. 23b and R 24b and R 24b and R 25b and R 25b and R 26b and R 26b and R 27b and, or R 27b and R 28b may be bonded to each other to form a ring. For example, R 25b and R 26b may be bonded to form a five-membered ring together with the naphthalene ring to form an acenaphthene skeleton.

[0255] The monovalent organic group is preferably an alicyclic hydrocarbon group, a heterocyclic group (heterocyclyl group), or an alkyl group or alkoxy group having 4 to 18 carbon atoms which may be substituted with a halogen atom and which may have a branched structure; a heterocyclyloxy group; an alicyclic hydrocarbon group, a heterocyclic group (heterocyclyl group), or an alkylthio group having 4 to 18 carbon atoms which may be substituted with a halogen atom and which may have a branched structure; or a heterocyclylthio group. Also preferred are groups in which a methylene group at any position not adjacent to the oxygen atom of the alkoxy group is substituted with -CO-. Also preferred are groups in which the alkoxy group is interrupted by an —O—CO— bond or an —O—CO—NH— bond, with the left end of the —O—CO— bond or —O—CO—NH— bond being closer to the naphthalic acid mother nucleus in the alkoxy group. Furthermore, an alicyclic hydrocarbon group, a heterocyclic group, or an alkylthio group having 4 to 18 carbon atoms which may be substituted with a halogen atom and which may have a branched structure may also be included in R. 23b ~R 28b It is preferable as. Also preferred is a group in which a methylene group at any position not adjacent to the sulfur atom of the alkylthio group is substituted with —CO—. Also preferred are alkylthio groups interrupted by an —O—CO— bond or an —O—CO—NH— bond, where the left end of the —O—CO— bond or the —O—CO—NH— bond is closer to the naphthalic acid mother nucleus in the alkylthio group.

[0256] R 23b ~R 28b As for R 24b is an organic group, and R 23b and R 25b ~R 28b is a hydrogen atom or R 25b is an organic group, and R 23b , R 24b and R 26b ~R 28b is preferably a hydrogen atom. 23b ~R 28b may all be hydrogen atoms.

[0257] R 23b ~R 28b is an unsubstituted alkyl group, examples of which include an n-butyl group, a sec-butyl group, a tert-butyl group, an isobutyl group, an n-pentyl group, an isopentyl group, a tert-pentyl group, an n-hexyl group, an n-heptyl group, an isoheptyl group, a tert-heptyl group, an n-octyl group, an isooctyl group, a tert-octyl group, a 2-ethylhexyl group, an n-nonyl group, an n-decyl group, an n-undecyl group, an n-dodecyl group, an n-tridecyl group, an n-tetradecyl group, an n-pentadecyl group, an n-hexadecyl group, an n-heptadecyl group, and an n-octadecyl group.

[0258] R 23b ~R 28bis an unsubstituted alkoxy group, examples of which include an n-butyloxy group, a sec-butyloxy group, a tert-butyloxy group, an isobutyloxy group, an n-pentyloxy group, an isopentyloxy group, a tert-pentyloxy group, an n-hexyloxy group, an n-heptyloxy group, an isoheptyloxy group, a tert-heptyloxy group, an n-octyloxy group, an isooctyloxy group, a tert-octyloxy group, a 2-ethylhexyl group, an n-nonyloxy group, an n-decyloxy group, an n-undecyloxy group, an n-dodecyloxy group, an n-tridecyloxy group, an n-tetradecyloxy group, an n-pentadecyloxy group, an n-hexadecyloxy group, an n-heptadecyloxy group, and an n-octadecyloxy group.

[0259] R 23b ~R 28b is an unsubstituted alkylthio group, examples of which include an n-butylthio group, a sec-butylthio group, a tert-butylthio group, an isobutylthio group, an n-pentylthio group, an isopentylthio group, a tert-pentylthio group, an n-hexylthio group, an n-heptylthio group, an isoheptylthio group, a tert-heptylthio group, an n-octylthio group, an isooctylthio group, a tert-octylthio group, a 2-ethylhexylthio group, an n-nonylthio group, an n-decylthio group, an n-undecylthio group, an n-dodecylthio group, an n-tridecylthio group, an n-tetradecylthio group, an n-pentadecylthio group, an n-hexadecylthio group, an n-heptadecylthio group, and an n-octadecylthio group.

[0260] R 23b ~R 28bis an alkyl group, alkoxy group, or alkylthio group substituted with an alicyclic hydrocarbon group, examples of the alicyclic hydrocarbon constituting the main skeleton of the alicyclic hydrocarbon group include cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclodecane, bicyclo[2.1.1]hexane, bicyclo[2.2.1]heptane, bicyclo[3.2.1]octane, bicyclo[2.2.2]octane, and adamantane. As the alicyclic hydrocarbon group, groups in which one hydrogen atom has been removed from these alicyclic hydrocarbons are preferred.

[0261] R 23b ~R 28b is an alkyl group, an alkoxy group, or an alkylthio group substituted with a heterocyclic group, or R 23a ~R 28a is a heterocyclyloxy group, examples of the heterocyclic ring constituting the main skeleton of the heterocyclic group or heterocyclyloxy group include pyrrole, thiophene, furan, pyran, thiopyran, imidazole, pyrazole, thiazole, isothiazole, oxazole, isoxazole, pyridine, pyrazine, pyrimidine, pyridazine, pyrrolidine, pyrazolidine, imidazolidine, isoxazolidine, isothiazolidine, piperidine, piperazine, morpholine, thiomorpholine, chroman, thiochroman, isochroman, isothiochroman, indoline, isoindoline, and pyrimidine. Examples of the heterocyclic ring include quinolizine, indolizine, indole, indazole, purine, quinolizine, isoquinoline, quinoline, naphthyridine, phthalazine, quinoxaline, quinazoline, cinnoline, pteridine, acridine, perimidine, phenanthroline, carbazole, carboline, phenazine, anthridine, thiadiazole, oxadiazole, triazine, triazole, tetrazole, benzimidazole, benzoxazole, benzothiazole, benzothiadiazole, benzofuroxan, naphthoimidazole, benzotriazole, and tetraazaindene. Among these heterocyclic rings, saturated heterocyclic rings in which a ring having a conjugated bond is hydrogenated are also preferred. As the heterocyclic group substituting an alkyl group, an alkoxy group or an alkylthio group, or the heterocyclic group contained in a heterocyclyloxy group, a group in which one hydrogen atom has been removed from the above heterocycle is preferred.

[0262] R 23b ~R 28b is an alkoxy group containing an alicyclic hydrocarbon group, examples of which include a cyclopentyloxy group, a methylcyclopentyloxy group, a cyclohexyloxy group, a fluorocyclohexyloxy group, a chlorocyclohexyloxy group, a cyclohexylmethyloxy group, a methylcyclohexyloxy group, a norbornyloxy group, an ethylcyclohexyloxy group, a cyclohexylethyloxy group, a dimethylcyclohexyloxy group, a methylcyclohexylmethyloxy group, a norbornylmethyloxy group, a trimethylcyclohexyloxy group, Examples of such groups include a cyclohexylbutyloxy group, an adamantyloxy group, a menthyloxy group, an n-butylcyclohexyloxy group, a tert-butylcyclohexyloxy group, a bornyloxy group, an isobornyloxy group, a decahydronaphthyloxy group, a dicyclopentadienoxy group, a 1-cyclohexylpentyloxy group, a methyladamantyloxy group, an adamantylmethyloxy group, a 4-pentylcyclohexyloxy group, a cyclohexylcyclohexyloxy group, an adamantylethyloxy group, and a dimethyladamantyloxy group.

[0263] R 23b ~R 28b When is a heterocyclyloxy group, examples thereof include a tetrahydrofuranyloxy group, a furfuryloxy group, a tetrahydrofurfuryloxy group, a tetrahydropyranyloxy group, a butyrolactonyloxy group, and an indolyloxy group.

[0264] R 23b ~R 28b When is an alkylthio group containing an alicyclic hydrocarbon group, examples thereof include a cyclopentylthio group, a cyclohexylthio group, a cyclohexylmethylthio group, a norbornylthio group, and an isonorbornylthio group.

[0265] R 23b ~R 28b When is a heterocyclylthio group, examples thereof include a furfurylthio group and a tetrahydrofuranylthio group.

[0266] R 23b ~R 28b However, examples of the alkoxy group in which a methylene group at any position not adjacent to the oxygen atom is substituted with -CO- include a 2-ketobutyl-1-oxy group, a 2-ketopentyl-1-oxy group, a 2-ketohexyl-1-oxy group, a 2-ketoheptyl-1-oxy group, a 2-ketooctyl-1-oxy group, a 3-ketobutyl-1-oxy group, a 4-ketopentyl-1-oxy group, a 5-ketohexyl-1-oxy group, a 6-ketoheptyl-1-oxy group, a 7-ketooctyl-1-oxy group, a 3-methyl-2-ketopentan-4-oxy group, a 2-ketopentan-4-oxy group, a 2-methyl-2-ketopentan-4-oxy group, a 3-ketoheptan-5-oxy group, and a 2-adamantanone-5-oxy group.

[0267] R 23b ~R 28b However, examples of alkylthio groups in which a methylene group at any position not adjacent to the sulfur atom is substituted with -CO- include 2-ketobutyl-1-thio, 2-ketopentyl-1-thio, 2-ketohexyl-1-thio, 2-ketoheptyl-1-thio, 2-ketooctyl-1-thio, 3-ketobutyl-1-thio, 4-ketopentyl-1-thio, 5-ketohexyl-1-thio, 6-ketoheptyl-1-thio, 7-ketooctyl-1-thio, 3-methyl-2-ketopentane-4-thio, 2-ketopentane-4-thio, 2-methyl-2-ketopentane-4-thio, and 3-ketoheptane-5-thio.

[0268] Specific examples of the compound represented by formula (b10) include the following compounds.

[0269] [ka]

[0270] [ka]

[0271] [ka]

[0272] [ka]

[0273] [ka]

[0274] [ka]

[0275] [ka]

[0276] [ka]

[0277] [ka]

[0278] [ka]

[0279] The acid generator (B) also includes a compound represented by the following formula (b11), which is a nonionic acid generator: The compound represented by the following formula (b11) generates a sulfonic acid when irradiated with actinic rays or radiation. [ka] In formula (b11), R b1 is a hydrocarbon group having 1 to 30 carbon atoms. R b1 When the hydrocarbon group as the alkyl group contains one or more methylene groups, at least a part of the methylene groups is -O-, -S-, -CO-, -CO-O-, -SO-, -SO2-, -CR b4 R b5 - and -NR b6 -, and optionally substituted with a group selected from the group consisting of -. R b1 When the hydrocarbon group as defined above contains a hydrocarbon ring, at least one of the carbon atoms constituting the hydrocarbon ring may be substituted with a heteroatom selected from the group consisting of N, O, P, S, and Se, or an atomic group containing such a heteroatom. R b4 and R b5 are each independently a hydrogen atom or a halogen atom, and R b4 and R b5 At least one of them is a halogen atom. R b6 is a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. R a1 , and R a2 each independently represents a hydrogen atom, an aliphatic hydrocarbon group having from 1 to 20 carbon atoms which may have a substituent, an aromatic group having from 5 to 20 ring atoms which may have a substituent, or -R a3 -R a4 It is a group represented by the following formula: R a1 , and R a2 is not a hydrogen atom at the same time. R a1 , or R a2 When the aliphatic hydrocarbon group as a5 -, and optionally substituted with a group selected from the group consisting of -. R a5 is a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. R a3 is a methylene group, -O-, -CO-, -CO-O-, -SO-, -SO2-, or -NR a6 -It is. R a6 is a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. R a4 is a heteroarylalkyl group containing an aromatic group having from 5 to 20 ring atoms which may have a substituent, a perfluoroalkyl group having from 1 to 6 carbon atoms, an aralkyl group having from 7 to 20 carbon atoms which may have a substituent, or an aromatic heterocyclic group having from 5 to 20 ring atoms which may have a substituent. Q 1 , and Q 2 are each independently a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms. L is an ester bond.

[0280] In formula (b11), R a1 and R a2 The aliphatic hydrocarbon group having 1 to 20 carbon atoms as the alkyl group may be linear, branched, cyclic, or a combination of these structures. The aliphatic hydrocarbon group is preferably an alkyl group. Specific preferred examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, a 2-ethylhexyl group, an n-nonyl group, and an n-decyl group. R a1 and R a2 Examples of the substituent that the aliphatic hydrocarbon group having 1 to 20 carbon atoms as R may have include a hydroxyl group, a mercapto group, an amino group, a halogen atom, an oxygen atom, a nitro group, and a cyano group. The number of substituents is optional. a1 and R a2Examples of the aliphatic hydrocarbon group having from 1 to 20 carbon atoms and having a substituent such as the above include perfluoroalkyl groups having from 1 to 6 carbon atoms. Specific examples thereof include CF3-, CF3CF2-, (CF3)2CF-, CF3CF2CF2-, CF3CF2CF2CF2-, (CF3)2CFCF2-, CF3CF2(CF3)CF-, and (CF3)3C-.

[0281] In formula (b11), R a1 and R a2 The aromatic group having 5 to 20 ring-constituting atoms which may have a substituent as described above may be an aromatic hydrocarbon group or an aromatic heterocyclic group. Examples of the aromatic group include aryl groups such as a phenyl group and a naphthyl group, and heteroaryl groups such as a furyl group and a thienyl group. The substituent that the aromatic group having 5 to 20 ring atoms may have is R a1 and R a2 The substituents are the same as those that may be contained in the aliphatic hydrocarbon group having 1 to 20 carbon atoms as the aryl group.

[0282] In formula (b11), R a4 The aromatic group having 5 to 20 ring atoms which may have a substituent as R a1 and R a2 The aromatic groups are the same as the aromatic groups having 5 to 20 ring-constituting atoms which may have a substituent, as described above. In formula (b11), R a4 The perfluoroalkyl group having 1 to 6 carbon atoms as R a1 and R a2 This is the same as the perfluoroalkyl group having 1 to 6 carbon atoms described above. In formula (b11), R a4 Specific examples of the aralkyl group having 7 to 20 carbon atoms, which may have a substituent as the aryl group, include a benzyl group, a phenethyl group, an α-naphthylmethyl group, a β-naphthylmethyl group, a 2-α-naphthylethyl group, and a 2-β-naphthylethyl group. In formula (b11), the heteroarylalkyl group is a group in which some of the carbon atoms constituting the aromatic hydrocarbon ring in the arylalkyl group are substituted with heteroatoms such as N, O, or S. a4 Specific examples of the heteroarylalkyl group containing an aromatic heterocyclic group having from 5 to 20 ring-constituting atoms, which may have a substituent as the heteroaryl group, include a pyridin-2-ylmethyl group, a pyridin-3-ylmethyl group, and a pyridin-4-ylmethyl group.

[0283] In formula (b11), R a5 The hydrocarbon group having 1 to 6 carbon atoms as the alkyl group may be an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a combination thereof. The aliphatic hydrocarbon group may be linear, branched, cyclic, or a combination of these structures. Examples of the aliphatic hydrocarbon group include alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, and n-hexyl. An example of the aromatic hydrocarbon group is a phenyl group.

[0284] In formula (b11), R a6 The hydrocarbon group having 1 to 6 carbon atoms as R a5 This is the same as the hydrocarbon group having 1 to 6 carbon atoms described above.

[0285] In formula (b11), R b1 The hydrocarbon group having 1 to 30 carbon atoms as the alkyl group may be an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a combination thereof. The aliphatic hydrocarbon group may be linear, branched, cyclic, or a combination of these structures. Examples of the aliphatic hydrocarbon group include chain aliphatic hydrocarbon groups such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, and an n-hexyl group, and cyclic aliphatic hydrocarbon groups (hydrocarbon rings) such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, an adamantyl group, and a norbornyl group. Examples of the aromatic hydrocarbon group include a phenyl group and a naphthyl group. Examples of groups in which an aliphatic hydrocarbon group and an aromatic hydrocarbon group are combined include a benzyl group, a phenethyl group, and a furylmethyl group. R b1 When the hydrocarbon group as defined above contains a hydrocarbon ring, examples of the atomic group containing a heteroatom substituting at least one carbon atom constituting the hydrocarbon ring include -CO-, -CO-O-, -SO-, -SO2-, -SO2-O-, -P(=O)-(OR b7 )3 is an example. b7 is a hydrocarbon group having 1 to 6 carbon atoms, and R a5 This is the same as the hydrocarbon group having 1 to 6 carbon atoms described above.

[0286] In formula (b11), R b4 and R b5 Specific examples of the halogen atom as include a chlorine atom, a fluorine atom, a bromine atom, and an iodine atom.

[0287] In formula (b11), R b6 The hydrocarbon group having 1 to 6 carbon atoms as R in formula (b11) a5 The carbon number of the hydrocarbon group is the same as that of the hydrocarbon group having 1 to 6 carbon atoms described above.

[0288] In formula (b11), Q 1 and Q 2 As the perfluoroalkyl group having 1 to 6 carbon atoms, R a1 and R a2 This is the same as the perfluoroalkyl group having 1 to 6 carbon atoms described above.

[0289] In the compound represented by formula (b11), the orientation of the ester bond as L is not particularly limited, and may be either -CO-O- or -O-CO-.

[0290] The compound represented by formula (b11) is preferably a compound represented by the following formula (b11-1). [ka] (R in formula (b11-1) b1 , R a1 , Q 1 , and Q 2 are the same as those in equation (b11).

[0291] R in formula (b11-1) a1 is an aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and R a1 When the aliphatic hydrocarbon group as a5 - is preferably a compound represented by formula (b11-1), which may be substituted with a group selected from the group consisting of:

[0292] The total content of the acid generator (B) is preferably from 0.01 to 20% by mass, more preferably from 0.03 to 10% by mass, and particularly preferably from 0.05 to 8% by mass, based on the total solid content of the photosensitive composition. In this specification, the solid content refers to components other than the organic solvent (S) and water.

[0293] <Alkali-soluble resin (D)> The photosensitive composition may further contain an alkali-soluble resin (D) to improve alkali solubility. Here, the alkali-soluble resin refers to a resin that dissolves to a depth of 0.01 μm or more when a 1 μm-thick resin film is formed on a substrate from a 20% by weight resin solution (solvent: propylene glycol monomethyl ether acetate) and the resulting film is immersed in a 2.38% by weight aqueous solution of TMAH (tetramethylammonium hydroxide) for 1 minute. This does not fall under the category of the aforementioned resin (A) (typically, this refers to a resin whose alkali solubility is substantially unchanged even under the action of acid). The alkali-soluble resin (D) is preferably at least one resin selected from the group consisting of novolac resins (D1), polyhydroxystyrene resins (D2), and acrylic resins (D3).

[0294] [Novolac resin (D1)] Novolak resins can be obtained, for example, by addition condensation of aromatic compounds having a phenolic hydroxyl group (hereinafter simply referred to as "phenols") with aldehydes in the presence of an acid catalyst.

[0295] Examples of the phenols include phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, o-butylphenol, m-butylphenol, p-butylphenol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol, 2,3,5-trimethylphenol, 3,4,5-trimethylphenol, p-phenylphenol, resorcinol, hydroquinone, hydroquinone monomethyl ether, pyrogallol, phloroglucinol, hydroxydiphenyl, bisphenol A, salicylic acid, gallic acid, gallic acid esters, α-naphthol, and β-naphthol. Examples of the aldehydes include formaldehyde, furfural, benzaldehyde, nitrobenzaldehyde, and acetaldehyde. The catalyst used in the addition condensation reaction is not particularly limited, but examples of acid catalysts that can be used include hydrochloric acid, nitric acid, sulfuric acid, formic acid, oxalic acid, and acetic acid.

[0296] The flexibility of novolak resins can be further improved by using o-cresol, substituting the hydrogen atoms of the hydroxyl groups in the resin with other substituents, or using bulky aldehydes.

[0297] The mass average molecular weight of the novolak resin (D1) is not particularly limited as long as it does not impair the object of the present invention, but is preferably 1,000 or more and 50,000 or less.

[0298] [Polyhydroxystyrene resin (D2)] Examples of the hydroxystyrene compound constituting the polyhydroxystyrene resin (D2) include p-hydroxystyrene, α-methylhydroxystyrene, and α-ethylhydroxystyrene. Furthermore, the polyhydroxystyrene resin (D2) is preferably a copolymer with a styrene resin. Examples of styrene-based compounds constituting such styrene resins include styrene, chlorostyrene, chloromethylstyrene, vinyltoluene, and α-methylstyrene.

[0299] The mass average molecular weight of the polyhydroxystyrene resin (D2) is not particularly limited as long as it does not impair the object of the present invention, but is preferably 1,000 or more and 50,000 or less.

[0300] [Acrylic resin (D3)] The acrylic resin (D3) preferably contains a structural unit derived from a polymerizable compound having an ether bond, and a structural unit derived from a polymerizable compound having a carboxy group.

[0301] Examples of the polymerizable compound having an ether bond include (meth)acrylic acid derivatives having an ether bond and an ester bond, such as 2-methoxyethyl (meth)acrylate, methoxytriethylene glycol (meth)acrylate, 3-methoxybutyl (meth)acrylate, ethyl carbitol (meth)acrylate, phenoxy polyethylene glycol (meth)acrylate, methoxypolypropylene glycol (meth)acrylate, and tetrahydrofurfuryl (meth)acrylate. The polymerizable compound having an ether bond is preferably 2-methoxyethyl acrylate or methoxytriethylene glycol acrylate. These polymerizable compounds may be used alone or in combination of two or more.

[0302] Examples of the polymerizable compound having a carboxy group include monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid; dicarboxylic acids such as maleic acid, fumaric acid, and itaconic acid; and compounds having a carboxy group and an ester bond such as 2-methacryloyloxyethyl succinic acid, 2-methacryloyloxyethyl maleic acid, 2-methacryloyloxyethyl phthalic acid, and 2-methacryloyloxyethyl hexahydrophthalic acid. The polymerizable compound having a carboxy group is preferably acrylic acid or methacrylic acid. These polymerizable compounds may be used alone or in combination of two or more.

[0303] The mass average molecular weight of the acrylic resin (D3) is not particularly limited as long as it does not impair the object of the present invention, but is preferably 50,000 or more and 800,000 or less.

[0304] The content of the alkali-soluble resin (D) is preferably 0 to 80 parts by mass, more preferably 5 to 70 parts by mass, based on 100 parts by mass of the total solid content of the photosensitive composition.

[0305] <Sulfur-containing compounds (E)> When the photosensitive composition is used for pattern formation on a metal substrate, the photosensitive composition preferably contains a sulfur-containing compound (E). The sulfur-containing compound (E) is a compound containing a sulfur atom capable of coordinating with a metal. Regarding a compound capable of generating two or more tautomers, if at least one tautomer contains a sulfur atom capable of coordinating with a metal constituting the surface of the metal substrate, the compound is considered to be a sulfur-containing compound. When a patterned resist film used as a plating mold is formed on a surface made of a metal such as Cu, defects in the cross-sectional shape such as footing are likely to occur. However, when the photosensitive composition contains a sulfur-containing compound (E), defects in the cross-sectional shape such as footing are easily suppressed even when a patterned resist film is formed on the metal surface of a substrate. Note that "footing" refers to a phenomenon in which the resist portion protrudes toward the non-resist portion near the contact surface between the substrate surface and the patterned resist film, resulting in the bottom width of the non-resist portion being narrower than the top width. When the photosensitive composition is used for pattern formation on a substrate other than a metal substrate, it is not particularly necessary for the photosensitive composition to contain a sulfur-containing compound. When the photosensitive composition is used for pattern formation on a substrate other than a metal substrate, it is preferable that the photosensitive composition does not contain a sulfur-containing compound (E) because the number of components in the photosensitive composition can be reduced, which makes it easier to produce the photosensitive composition and reduces the production cost of the photosensitive composition. Incidentally, there is no particular problem caused by the inclusion of the sulfur-containing compound (E) in a photosensitive composition used for forming a pattern on a substrate other than a metal substrate.

[0306] The sulfur atom capable of coordinating to a metal is contained in the sulfur-containing compound as, for example, a mercapto group (-SH), a thiocarboxy group (-CO-SH), a dithiocarboxy group (-CS-SH), a thiocarbonyl group (-CS-), and the like. The sulfur-containing compound preferably has a mercapto group, since this facilitates coordination with metals and provides an excellent effect of suppressing footing.

[0307] A preferred example of the sulfur-containing compound having a mercapto group is a compound represented by the following formula (e1). [ka] (In the formula, R e1 and R e2 each independently represents a hydrogen atom or an alkyl group, and R e3 represents a single bond or an alkylene group, and R e4 represents a u-valent aliphatic group which may contain atoms other than carbon, and u represents an integer of 2 or more and 4 or less.

[0308] R e1 and R e2 When R is an alkyl group, the alkyl group may be linear or branched, and is preferably linear. e1 and R e2 When R is an alkyl group, the number of carbon atoms in the alkyl group is not particularly limited as long as it does not impair the object of the present invention. The number of carbon atoms in the alkyl group is preferably 1 or more and 4 or less, more preferably 1 or 2, and most preferably 1. e1 and R e2 As a combination of the above, one is preferably a hydrogen atom and the other is an alkyl group, and particularly preferably one is a hydrogen atom and the other is a methyl group.

[0309] R e3 When R is an alkylene group, the alkylene group may be linear or branched, and is preferably linear. e3 When is an alkylene group, the number of carbon atoms of the alkylene group is not particularly limited as long as it does not impair the object of the present invention. The number of carbon atoms of the alkylene group is preferably 1 to 10, more preferably 1 to 5, particularly preferably 1 or 2, and most preferably 1.

[0310] R e4 R is a divalent to tetravalent aliphatic group which may contain atoms other than carbon. e4Examples of atoms other than carbon that may be contained in R include a nitrogen atom, an oxygen atom, a sulfur atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. e4 The structure of the aliphatic group may be linear, branched, or cyclic, or may be a combination of these structures.

[0311] Among the compounds represented by formula (e1), the compound represented by the following formula (e2) is more preferred. [ka] (In formula (e2), R e4 and u are the same as in formula (e1).

[0312] Among the compounds represented by the above formula (e2), the following compounds are preferred. [ka]

[0313] Compounds represented by the following formulae (e3-L1) to (e3-L7) are also preferred examples of the sulfur-containing compound having a mercapto group. [ka] (In formulas (e3-L1) to (e3-L7), R', s", A", and r are the same as those in formulas (a1-3-L1) to (a1-3-L5) described above for the acrylic resin (A1).)

[0314] Specific preferred examples of the mercapto compounds represented by the above formulae (e3-L1) to (e3-L7) include the following compounds. [ka]

[0315] Compounds represented by the following formulae (e3-1) to (e3-4) are also preferred examples of the sulfur-containing compound having a mercapto group. [ka] (The definitions of the abbreviations in formulas (e3-1) to (e3-4) are as described above for the acrylic resin (B3) and for formulas (3-1) to (3-4).)

[0316] Specific preferred examples of the mercapto compounds represented by the above formulae (e3-1) to (e3-4) include the following compounds.

[0317] [ka]

[0318] Furthermore, a suitable example of the compound having a mercapto group is a compound represented by the following formula (e4). [ka] (In formula (e4), R e5 is a group selected from the group consisting of a hydroxyl group, an alkyl group having from 1 to 4 carbon atoms, an alkoxy group having from 1 to 4 carbon atoms, an alkylthio group having from 1 to 4 carbon atoms, a hydroxyalkyl group having from 1 to 4 carbon atoms, a mercaptoalkyl group having from 1 to 4 carbon atoms, a halogenated alkyl group having from 1 to 4 carbon atoms, and a halogen atom; n1 is an integer of from 0 to 3, and n0 is an integer of from 0 to 3; when n1 is 2 or 3, R e5 may be the same or different.)

[0319] R e5 Specific examples of when is an alkyl group having from 1 to 4 carbon atoms which may have a hydroxyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group. Among these alkyl groups, a methyl group, a hydroxymethyl group, and an ethyl group are preferred.

[0320] R e5Specific examples of when is an alkoxy group having from 1 to 4 carbon atoms include a methoxy group, an ethoxy group, an n-propyloxy group, an isopropyloxy group, an n-butyloxy group, an isobutyloxy group, a sec-butyloxy group, and a tert-butyloxy group. Among these alkoxy groups, a methoxy group and an ethoxy group are preferred, and a methoxy group is more preferred.

[0321] R e5 Specific examples of when is an alkylthio group having from 1 to 4 carbon atoms include a methylthio group, an ethylthio group, an n-propylthio group, an isopropylthio group, an n-butylthio group, an isobutylthio group, a sec-butylthio group, and a tert-butylthio group. Among these alkylthio groups, a methylthio group and an ethylthio group are preferred, and a methylthio group is more preferred.

[0322] R e5 Specific examples of when is a hydroxyalkyl group having from 1 to 4 carbon atoms include a hydroxymethyl group, a 2-hydroxyethyl group, a 1-hydroxyethyl group, a 3-hydroxy-n-propyl group, and a 4-hydroxy-n-butyl group. Among these hydroxyalkyl groups, a hydroxymethyl group, a 2-hydroxyethyl group, and a 1-hydroxyethyl group are preferred, and a hydroxymethyl group is more preferred.

[0323] R e5 Specific examples of when is a mercaptoalkyl group having from 1 to 4 carbon atoms include a mercaptomethyl group, a 2-mercaptoethyl group, a 1-mercaptoethyl group, a 3-mercapto-n-propyl group, and a 4-mercapto-n-butyl group. Among these mercaptoalkyl groups, a mercaptomethyl group, a 2-mercaptoethyl group, and a 1-mercaptoethyl group are preferred, and a mercaptomethyl group is more preferred.

[0324] R e5 When R is a halogenated alkyl group having 1 to 4 carbon atoms, examples of the halogen atom contained in the halogenated alkyl group include fluorine, chlorine, bromine, and iodine.e5 Specific examples of when is a halogenated alkyl group having 1 to 4 carbon atoms include a chloromethyl group, a bromomethyl group, an iodomethyl group, a fluoromethyl group, a dichloromethyl group, a dibromomethyl group, a difluoromethyl group, a trichloromethyl group, a tribromomethyl group, a trifluoromethyl group, a 2-chloroethyl group, a 2-bromoethyl group, a 2-fluoroethyl group, a 1,2-dichloroethyl group, a 2,2-difluoroethyl group, a 1-chloro-2-fluoroethyl group, a 3-chloro-n-propyl group, a 3-bromo-n-propyl group, a 3-fluoro-n-propyl group, and a 4-chloro-n-butyl group. Among these halogenated alkyl groups, a chloromethyl group, a bromomethyl group, an iodomethyl group, a fluoromethyl group, a dichloromethyl group, a dibromomethyl group, a difluoromethyl group, a trichloromethyl group, a tribromomethyl group, and a trifluoromethyl group are preferred, and a chloromethyl group, a dichloromethyl group, a trichloromethyl group, and a trifluoromethyl group are more preferred.

[0325] R e5 When is a halogen atom, specific examples include fluorine, chlorine, bromine, and iodine.

[0326] In formula (e4), n1 is an integer of 0 to 3, and more preferably 1. When n1 is 2 or 3, a plurality of R e5 may be the same or different.

[0327] In the compound represented by formula (e4), R on the benzene ring e5 The substitution position of R on the benzene ring is not particularly limited. e5 The substitution position is -(CH2) n0 It is preferably in the meta or para position relative to the bonding position of --SH.

[0328] The compound represented by formula (e4) includes R e5 As R, a compound having at least one group selected from the group consisting of an alkyl group, a hydroxyalkyl group, and a mercaptoalkyl group is preferred. e5More preferred is a compound having one group selected from the group consisting of an alkyl group, a hydroxyalkyl group, and a mercaptoalkyl group as R e5 When the alkyl group has one group selected from the group consisting of an alkyl group, a hydroxyalkyl group, and a mercaptoalkyl group, the substitution position of the alkyl group, the hydroxyalkyl group, or the mercaptoalkyl group on the benzene ring is -(CH2) n0 The position is preferably meta or para relative to the bonding position of --SH, and more preferably para.

[0329] In formula (e4), n0 is an integer of 0 to 3. In terms of ease of preparation and availability of the compound, n0 is preferably 0 or 1, and more preferably 0.

[0330] Specific examples of the compound represented by formula (e4) include p-mercaptophenol, p-thiocresol, m-thiocresol, 4-(methylthio)benzenethiol, 4-methoxybenzenethiol, 3-methoxybenzenethiol, 4-ethoxybenzenethiol, 4-isopropyloxybenzenethiol, 4-tert-butoxybenzenethiol, 3,4-dimethoxybenzenethiol, 3,4,5-trimethoxybenzenethiol, 4-ethylbenzenethiol, 4-isopropylbenzenethiol, 4-n-butylbenzenethiol, 4 -tert-butylbenzenethiol, 3-ethylbenzenethiol, 3-isopropylbenzenethiol, 3-n-butylbenzenethiol, 3-tert-butylbenzenethiol, 3,5-dimethylbenzenethiol, 3,4-dimethylbenzenethiol, 3-tert-butyl-4-methylbenzenethiol, 3-tert-4-methylbenzenethiol, 3-tert-butyl-5-methylbenzenethiol, 4-tert-butyl-3-methylbenzenethiol, 4-mercaptobenzyl alcohol, 3-mercaptobenzyl alcohol phenol, 4-(mercaptomethyl)phenol, 3-(mercaptomethyl)phenol, 1,4-di(mercaptomethyl)phenol, 1,3-di(mercaptomethyl)phenol, 4-fluorobenzenethiol, 3-fluorobenzenethiol, 4-chlorobenzenethiol, 3-chlorobenzenethiol, 4-bromobenzenethiol, 4-iodobenzenethiol, 3-bromobenzenethiol, 3,4-dichlorobenzenethiol, 3,5-dichlorobenzenethiol, 3,4-difluorobenzenethiol, 3,5-difluorobenzene Examples of the thiol include 4-mercaptocatechol, 2,6-di-tert-butyl-4-mercaptophenol, 3,5-di-tert-butyl-4-methoxybenzenethiol, 4-bromo-3-methylbenzenethiol, 4-(trifluoromethyl)benzenethiol, 3-(trifluoromethyl)benzenethiol, 3,5-bis(trifluoromethyl)benzenethiol, 4-methylthiobenzenethiol, 4-ethylthiobenzenethiol, 4-n-butylthiobenzenethiol, and 4-tert-butylthiobenzenethiol.

[0331] Examples of the sulfur-containing compound having a mercapto group include a compound containing a nitrogen-containing aromatic heterocycle substituted with a mercapto group, and a tautomer of a compound containing a nitrogen-containing aromatic heterocycle substituted with a mercapto group. Specific preferred examples of the nitrogen-containing aromatic heterocycle include imidazole, pyrazole, 1,2,3-triazole, 1,2,4-triazole, oxazole, thiazole, pyridine, pyrimidine, pyridazine, pyrazine, 1,2,3-triazine, 1,2,4-triazine, 1,3,5-triazine, indole, indazole, benzimidazole, benzoxazole, benzothiazole, 1H-benzotriazole, quinoline, isoquinoline, cinnoline, phthalazine, quinazoline, quinoxaline, and 1,8-naphthyridine.

[0332] Specific examples of nitrogen-containing heterocyclic compounds suitable as sulfur-containing compounds and tautomers of nitrogen-containing heterocyclic compounds include the following compounds. [ka]

[0333] The content of the sulfur-containing compound (E) is preferably 0.001 to 5 parts by mass, more preferably 0.005 to 3 parts by mass, and particularly preferably 0.01 to 1 part by mass, relative to 100 parts by mass of the total mass of the resin (A) and the alkali-soluble resin (D).

[0334] <Acid diffusion controller (F)> The photosensitive composition may contain an acid diffusion controller (F). Examples of the acid diffusion controller (F) include a nitrogen-containing compound (F1), and if necessary, an organic carboxylic acid, a phosphorus oxoacid, or a derivative thereof (F2) may be further contained.

[0335] [Nitrogen-containing compounds (F1)] Examples of the nitrogen-containing compound (F1) include trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, tri-n-pentylamine, tribenzylamine, diethanolamine, triethanolamine, n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, ethylenediamine, N,N,N',N'-tetramethylethylenediamine, tetramethylenediamine, hexamethylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 4,4'-diaminobenzophenone, 4,4'-diaminodiphenylamine, formamide, N-methylformamide, N,N- Examples include dimethylformamide, acetamide, N-methylacetamide, N,N-dimethylacetamide, propionamide, benzamide, pyrrolidone, N-methylpyrrolidone, methylurea, 1,1-dimethylurea, 1,3-dimethylurea, 1,1,3,3-tetramethylurea, 1,3-diphenylurea, imidazole, benzimidazole, 4-methylimidazole, 8-oxyquinoline, acridine, purine, pyrrolidine, piperidine, 2,4,6-tri(2-pyridyl)-S-triazine, morpholine, 4-methylmorpholine, piperazine, 1,4-dimethylpiperazine, 1,4-diazabicyclo[2.2.2]octane, and pyridine. These may be used alone or in combination of two or more.

[0336] Alternatively, commercially available hindered amine compounds such as ADK STAB LA-52, ADK STAB LA-57, ADK STAB LA-63P, ADK STAB LA-68, ADK STAB LA-72, ADK STAB LA-77Y, ADK STAB LA-77G, ADK STAB LA-81, ADK STAB LA-82, and ADK STAB LA-87 (all manufactured by ADEKA CORPORATION), 4-hydroxy-1,2,2,6,6-pentamethylpiperidine derivatives, and pyridines substituted at the 2,6-positions with substituents such as hydrocarbon groups, such as 2,6-diphenylpyridine and 2,6-di-tert-butylpyridine, can also be used as the nitrogen-containing compound (F1).

[0337] The nitrogen-containing compound (F1) is preferably used in an amount of 5 parts by mass or less, more preferably 3 parts by mass or less, per 100 parts by mass of the total mass of the resin (A) and the alkali-soluble resin (D).

[0338] [Organic carboxylic acids, phosphorus oxoacids or their derivatives (F2)] Of the organic carboxylic acids or phosphorus oxoacids or derivatives thereof (F2), specific examples of suitable organic carboxylic acids include malonic acid, citric acid, malic acid, succinic acid, benzoic acid, and salicylic acid, with salicylic acid being particularly preferred.

[0339] Examples of phosphorus oxoacids or derivatives thereof include phosphoric acid, phosphoric acid di-n-butyl ester, phosphoric acid diphenyl ester, and other phosphoric acid and ester-like derivatives thereof; phosphonic acid, phosphonic acid dimethyl ester, phosphonic acid di-n-butyl ester, phenylphosphonic acid, phosphonic acid diphenyl ester, phosphonic acid dibenzyl ester, and other phosphonic acid and ester-like derivatives thereof; phosphinic acid, phenylphosphinic acid, and other phosphinic acid and ester-like derivatives thereof; and the like. Among these, phosphonic acid is particularly preferred. These may be used alone or in combination of two or more.

[0340] The organic carboxylic acid, or phosphorus oxoacid or its derivative (F2) is typically used in an amount of 0 to 5 parts by mass, and particularly preferably 0 to 3 parts by mass, per 100 parts by mass of the total mass of the resin (A) and the alkali-soluble resin (D) described below.

[0341] In order to form a stable salt, the organic carboxylic acid, or phosphorus oxoacid or derivative thereof (F2) is preferably used in an amount equivalent to that of the nitrogen-containing compound (F1).

[0342] <Organic solvent (S)> The photosensitive composition preferably contains an organic solvent (S) for the purpose of adjusting the coating properties. As the organic solvent (S), various organic solvents that have conventionally been added to various photosensitive compositions can be used.

[0343] Specific examples of the organic solvent (S) include ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl isoamyl ketone, and 2-heptanone; glycols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,3-butylene glycol, and hexylene glycol; polyols such as glycerin; polyacetates of polyols such as glycerin triacetate (triacetin); monools such as benzyl alcohol and terpineol; Monoacetates of glycols such as cholesteryl monoacetate, diethylene glycol monoacetate, triethylene glycol monoacetate, propylene glycol monoacetate, dipropylene glycol monoacetate, tripropylene glycol monoacetate, and 1,3-butylene glycol monoacetate; ethylene glycol diacetate, diethylene glycol diacetate, triethylene glycol diacetate, propylene glycol diacetate, dipropylene glycol diacetate, tripropylene glycol diacetate, and 1,Glycol diacetates such as 3-butylene glycol diacetate; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monophenyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monophenyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monopropyl ether, triethylene glycol monobutyl ether, triethylene glycol monophenyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether , propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol monophenyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monophenyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, tripropylene glycol monopropyl ether, tripropylene glycol monobutyl ether, tripropylene glycol monophenyl ether, 1,3-butylene glycol monomethyl ether, 1,3-butylene glycol monoethyl ether, 1,3-butylene glycol monopropyl ether, 1,3-butylene glycol monobutyl ether, and 1,Monoethers of glycols such as 3-butylene glycol monophenyl ether; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monophenyl ether acetate, triethylene glycol monomethyl ether acetate, triethylene glycol monoethyl ether acetate, triethylene glycol monopropyl ether acetate, triethylene glycol monobutyl ether acetate, triethylene glycol monophenyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol Glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, propylene glycol monophenyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol monopropyl ether acetate, dipropylene glycol monobutyl ether acetate, dipropylene glycol monophenyl ether acetate, tripropylene glycol monomethyl ether acetate, tripropylene glycol monoethyl ether acetate, tripropylene glycol monopropyl ether acetate, tripropylene glycol monobutyl ether acetate, tripropylene glycol monophenyl ether acetate, 1,3-butylene glycol monomethyl ether acetate (3-methoxybutyl acetate), 1,3-butylene glycol monoethyl ether acetate, 1,3-butylene glycol monopropyl ether acetate, 1,3-butylene glycol monobutyl ether acetate, 1,Monoether acetates of glycols such as 3-butylene glycol monophenyl ether acetate, 3-methyl-3-methoxybutyl acetate, 3-ethyl-3-methoxybutyl acetate, 2-methoxypentyl acetate, 3-methoxypentyl acetate, 4-methoxypentyl acetate, 2-methyl-3-methoxypentyl acetate, 3-methyl-3-methoxypentyl acetate, 3-methyl-4-methoxypentyl acetate, and 4-methyl-4-methoxypentyl acetate; ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether, ethylene glycol dibutyl ether, ethylene glycol diphenyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, diethylene glycol diphenyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, triethylene glycol diethyl ether, triethylene glycol diethyl ether, triethylene glycol dibutyl ether, triethylene glycol diphenyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ... Ethylene glycol dipropyl ether, triethylene glycol dibutyl ether, triethylene glycol diphenyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether, propylene glycol dibutyl ether, propylene glycol diphenyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol dipropyl ether, dipropylene glycol dibutyl ether, dipropylene glycol diphenyl ether, tripropylene glycol dimethyl ether, tripropylene glycol diethyl ether, tripropylene glycol dipropyl ether, tripropylene glycol dibutyl ether, tripropylene glycol diphenyl ether, 1,3-butylene glycol dimethyl ether, 1,3-butylene glycol diethyl ether, 1,3-butylene glycol dipropyl ether, 1,3-butylene glycol dibutyl ether, and 1,Examples of suitable diethers include glycols such as 3-butylene glycol diphenyl ether; ethers such as dioxane and dihexyl ether; esters such as ethyl formate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, benzyl acetate, ethyl benzoate, methyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl pyruvate, ethyl ethoxyacetate, methyl methoxypropionate, ethyl ethoxypropionate, methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, methyl 2-hydroxy-3-methylbutanoate, diethyl maleate, cyclohexanol acetate, and gamma-butyrolactone; and aromatic hydrocarbons such as toluene and xylene. These may be used alone or in combination.

[0344] When the photosensitive composition contains an organic solvent (S), the content of the organic solvent (S) is not particularly limited as long as it does not impair the object of the present invention. When the photosensitive composition is used to form a thick photosensitive layer having a film thickness of 5 μm or more, it is preferable to use the organic solvent (S) so that the solid content of the photosensitive composition is in the range of 20% by mass to 70% by mass.

[0345] <Other ingredients> The photosensitive composition may further contain a polyvinyl resin to improve plasticity. Specific examples of the polyvinyl resin include polyvinyl chloride, polystyrene, polyhydroxystyrene, polyvinyl acetate, polyvinyl benzoic acid, polyvinyl methyl ether, polyvinyl ethyl ether, polyvinyl alcohol, polyvinyl pyrrolidone, polyvinyl phenol, and copolymers thereof. The polyvinyl resin is preferably polyvinyl methyl ether because of its low glass transition temperature.

[0346] The photosensitive composition may further contain an adhesion promoter in order to improve the adhesion between a patterned resist film, such as a mold, formed using the photosensitive composition and a substrate.

[0347] The photosensitive composition may further contain a surfactant in order to improve coating properties, defoaming properties, leveling properties, etc. As the surfactant, for example, a fluorine-based surfactant or a silicone-based surfactant is preferably used. Specific examples of fluorine-based surfactants include commercially available fluorine-based surfactants such as BM-1000 and BM-1100 (all manufactured by BM Chemie), Megafac F142D, Megafac F172, Megafac F173, and Megafac F183 (all manufactured by Dainippon Ink and Chemicals, Inc.), Fluorad FC-135, Fluorad FC-170C, Fluorad FC-430, and Fluorad FC-431 (all manufactured by Sumitomo 3M Limited), Surflon S-112, Surflon S-113, Surflon S-131, Surflon S-141, and Surflon S-145 (all manufactured by Asahi Glass Co., Ltd.), SH-28PA, SH-190, SH-193, SZ-6032, and SF-8428 (all manufactured by Toray Silicones, Inc.), but are not limited to these. As the silicone surfactant, unmodified silicone surfactants, polyether-modified silicone surfactants, polyester-modified silicone surfactants, alkyl-modified silicone surfactants, aralkyl-modified silicone surfactants, reactive silicone surfactants, and the like can be preferably used. The silicone surfactant may be a commercially available silicone surfactant, and specific examples of commercially available silicone surfactants include Paintad M (manufactured by Dow Corning Toray Co., Ltd.), Topika K1000, Topika K2000, and Topika K5000 (all manufactured by Takachiho Sangyo Co., Ltd.), XL-121 (a polyether-modified silicone surfactant manufactured by Clariant), and BYK-310 (a polyester-modified silicone surfactant manufactured by BYK-Chemie).

[0348] The photosensitive composition may further contain an acid or an acid anhydride in order to finely adjust the solubility in the developer.

[0349] Specific examples of acids and acid anhydrides include monocarboxylic acids such as acetic acid, propionic acid, n-butyric acid, isobutyric acid, n-valeric acid, isovaleric acid, benzoic acid, and cinnamic acid; hydroxymonocarboxylic acids such as lactic acid, 2-hydroxybutyric acid, 3-hydroxybutyric acid, salicylic acid, m-hydroxybenzoic acid, p-hydroxybenzoic acid, 2-hydroxycinnamic acid, 3-hydroxycinnamic acid, 4-hydroxycinnamic acid, 5-hydroxyisophthalic acid, and syringic acid; and oxalic acid, succinic acid, glutaric acid, adipic acid, maleic acid, itaconic acid, hexahydrophthalic acid, phthalic acid, isophthalic acid, terephthalic acid, 1,2-cyclohexanedicarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid, butanetetracarboxylic acid, and trimellitic acid. Examples of suitable acid anhydrides include polycarboxylic acids such as itaconic anhydride, pyromellitic anhydride, cyclopentanetetracarboxylic acid, butanetetracarboxylic acid, and 1,2,5,8-naphthalenetetracarboxylic acid; and acid anhydrides such as itaconic anhydride, succinic anhydride, citraconic anhydride, dodecenylsuccinic anhydride, tricarbanilic anhydride, maleic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, himic anhydride, 1,2,3,4-butanetetracarboxylic anhydride, cyclopentanetetracarboxylic dianhydride, phthalic anhydride, pyromellitic anhydride, trimellitic anhydride, benzophenonetetracarboxylic anhydride, ethylene glycol bistrimellitate anhydride, and glycerin tristrimellitate anhydride.

[0350] The photosensitive composition may further contain a polymerization inhibitor. Known cage compounds can be used as the polymerization inhibitor. Examples of the polymerization inhibitor include compounds having a phenolic hydroxyl group, nitroso compounds, N-oxide compounds, quinone compounds, N-oxyl compounds, and phenothiazine compounds. More specifically, Irganox 1010, Irganox 1035, Irganox 1098, Irganox 1135, Irganox 245, Irganox 259, Irganox 3114 (all manufactured by BASF Japan), 2,6-di-tert-butyl-p-cresol, and 4-methoxyphenol are preferred, with Irganox 1010, 2,6-di-tert-butyl-p-cresol, and 4-methoxyphenol being more preferred.

[0351] The photosensitive composition may further contain a sensitizer to improve sensitivity. The photosensitive composition may further contain a dye or a pigment.

[0352] <Method for preparing chemically amplified positive-working photosensitive composition> The chemically amplified positive-working photosensitive composition is prepared by mixing and stirring the above components by a conventional method. Examples of devices that can be used to mix and stir the above components include a dissolver, a homogenizer, and a three-roll mill. After the above components are mixed uniformly, the resulting mixture may be further filtered using a mesh, a membrane filter, or the like.

[0353] <Photosensitive dry film> The photosensitive dry film has a substrate film and a photosensitive layer formed on the surface of the substrate film, and the photosensitive layer is made of the above-mentioned photosensitive composition.

[0354] The substrate film is preferably a light-transmitting film, specifically, a polyethylene terephthalate (PET) film, a polypropylene (PP) film, a polyethylene (PE) film, etc., but a polyethylene terephthalate (PET) film is preferred because of its excellent balance between light transmittance and breaking strength.

[0355] The photosensitive dry film is produced by applying the above-mentioned photosensitive composition onto a substrate film to form a photosensitive layer. When forming a photosensitive layer on a substrate film, the photosensitive composition is applied to the substrate film using an applicator, bar coater, wire bar coater, roll coater, curtain flow coater, or the like so that the thickness of the photosensitive layer is preferably 0.5 μm or more and 300 μm or less, more preferably 1 μm or more and 300 μm or less, and particularly preferably 3 μm or more and 100 μm or less, and then dried as necessary.

[0356] The photosensitive dry film may further have a protective film on the photosensitive layer, such as a polyethylene terephthalate (PET) film, a polypropylene (PP) film, or a polyethylene (PE) film.

[0357] <Method for producing patterned resist film and method for producing substrate with mold> There are no particular limitations on the method for forming a patterned resist film on a substrate using the photosensitive composition described above. Such a patterned resist film is suitably used as a mold for forming a plated object. The photosensitive composition described above can form a patterned resist film that has a rectangular cross-sectional shape and is suppressed from footing. Therefore, by using such a patterned resist film as a mold, a plated object can be formed that has a rectangular cross-sectional shape and is suppressed from biting into the substrate near its interface. A preferred method is a lamination step of laminating a photosensitive layer made of a photosensitive composition on a substrate; an exposure step of exposing the photosensitive layer to actinic rays or radiation in a position-selective manner; a development step of developing the exposed photosensitive layer; The method for producing a patterned resist film includes the steps of: The method for manufacturing a mold-attached substrate equipped with a mold for forming a plated object is similar to the method for manufacturing a patterned resist film, except that it includes a step of laminating a photosensitive layer on the metal surface of a substrate having a metal surface, and a development step of producing a mold for forming a plated object by development.

[0358] The substrate on which the photosensitive layer is laminated is not particularly limited, and any conventionally known substrate can be used, such as a substrate for electronic components, a substrate on which a predetermined wiring pattern is formed, etc. The substrate can also be a silicon substrate, a glass substrate, etc. When producing a template-mounted substrate having a template for forming a plated object, a substrate having a metal surface is used as the substrate. The metal species constituting the metal surface is preferably copper, gold, or aluminum, and more preferably copper.

[0359] The photosensitive layer is laminated on the substrate, for example, as follows: A liquid photosensitive composition is applied to the substrate, and the solvent is removed by heating as necessary to form a photosensitive layer of the desired thickness. Alternatively, the photosensitive layer may be laminated on the substrate using the aforementioned photosensitive dry film. The thickness of the photosensitive layer is not particularly limited as long as it can form a patterned resist film serving as a mold with a desired film thickness. The film thickness of the photosensitive layer is not particularly limited, but is preferably 0.5 μm or more, more preferably 0.5 μm to 300 μm, particularly preferably 1 μm to 150 μm, and most preferably 3 μm to 100 μm.

[0360] The photosensitive composition can be applied to a substrate by spin coating, slit coating, roll coating, screen printing, applicator, or other methods. The photosensitive layer is preferably prebaked. Prebaking conditions vary depending on the type and blending ratio of each component in the photosensitive composition, the coating film thickness, and other factors, but are typically between 70°C and 200°C, preferably between 80°C and 150°C, for between 2 and 120 minutes.

[0361] The photosensitive layer formed as described above is selectively irradiated (exposed) with actinic rays or radiation, for example, ultraviolet rays or visible light having a wavelength of 300 nm or more and 500 nm or less, such as g-rays (wavelength 436 nm), h-rays (wavelength 405 nm), or i-rays (wavelength 365 nm), through a mask having a predetermined pattern.

[0362] Examples of radiation sources that can be used include low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, and argon gas lasers. Examples of radiation include microwaves, infrared rays, visible light, ultraviolet rays, X-rays, gamma rays, electron beams, proton beams, neutron beams, and ion beams. The radiation dose varies depending on the composition of the photosensitive composition and the film thickness of the photosensitive layer, but is typically 100 J / m 2 More than 10000J / m 2 Radiation also includes light rays that activate the acid generator (B) to generate an acid.

[0363] After exposure, the photosensitive layer is heated by a known method to promote diffusion of the acid, thereby changing the alkali solubility of the photosensitive layer in the exposed areas of the layer.

[0364] The exposed photosensitive layer is then developed by a conventional method to dissolve and remove unnecessary portions, thereby forming a resist film having a predetermined pattern, a mold for forming a plated object, etc. In this case, an alkaline aqueous solution is used as the developer.

[0365] Examples of the developer that can be used include aqueous solutions of alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide (tetramethylammonium hydroxide), tetraethylammonium hydroxide, pyrrole, piperidine, 1,8-diazabicyclo[5,4,0]-7-undecene, and 1,5-diazabicyclo[4,3,0]-5-nonane. Alternatively, an aqueous solution prepared by adding an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant to the above-mentioned aqueous solution of alkalis can also be used as the developer.

[0366] The development time varies depending on the composition of the photosensitive composition, the film thickness of the photosensitive layer, etc., but is usually between 1 minute and 30 minutes. The development method may be any of a puddle method, a dipping method, a puddle method, a spray development method, etc.

[0367] After development, the substrate is washed with running water for 30 to 90 seconds and then dried using an air gun, oven, or the like. In this manner, a resist film patterned into a desired shape is formed on the surface of the substrate. In addition, in this manner, a mold-attached substrate can be produced, which has a patterned resist film serving as a mold on the metal surface of a substrate having a metal surface.

[0368] The thickness of the patterned resist film formed using the photosensitive composition is not particularly limited, and can be applied to both thick and thin films. The photosensitive composition is preferably used to form a thick patterned resist film. Specifically, the thickness of the patterned resist film formed using the photosensitive composition is preferably 0.5 μm or more, more preferably 0.5 μm or more and 300 μm or less, even more preferably 0.5 μm or more and 200 μm or less, and particularly preferably 0.5 μm or more and 150 μm or less. The upper limit of the film thickness may be, for example, 100 μm or less, and the lower limit of the film thickness may be, for example, 1 μm or more, or 3 μm or more.

[0369] <Method for manufacturing plated objects> By embedding a conductor such as a metal by plating into the non-resist portion (the portion removed by the developer) in the mold of the mold-attached substrate formed by the above method, it is possible to form plated objects such as connection terminals such as bumps and metal posts, and Cu rewiring. The plating method is not particularly limited, and various conventionally known methods can be used. Suitable plating solutions include solder plating, copper plating, gold plating, and nickel plating solutions. Finally, the remaining mold is removed using a stripping solution or the like according to conventional methods.

[0370] When producing a plated object, it is preferable to perform an ashing treatment on the exposed metal surface in the non-patterned portion of the patterned resist film that serves as a mold for forming the plated object. This is because, when a plated object is formed using a pattern formed using a photosensitive composition containing a sulfur-containing compound (E) as a mold, the adhesion of the plated object to the metal surface may be easily impaired.

[0371] The ashing process is not particularly limited as long as it is a method that does not cause damage to the patterned resist film that serves as a mold for forming a plated object to an extent that it is not possible to form a plated object of the desired shape. A preferred ashing method is a method using oxygen plasma. In order to ash a metal surface on a substrate using oxygen plasma, oxygen plasma is generated using a known oxygen plasma generator, and the metal surface on the substrate is irradiated with the oxygen plasma.

[0372] The gas used to generate oxygen plasma can be mixed with various gases that have been used in plasma treatments together with oxygen, such as nitrogen gas, hydrogen gas, and CF4 gas, within the scope of the present invention. The conditions for ashing using oxygen plasma are not particularly limited as long as they do not impair the object of the present invention, but the processing time is, for example, in the range of 10 seconds to 20 minutes, preferably in the range of 20 seconds to 18 minutes, and more preferably in the range of 30 seconds to 15 minutes. By setting the treatment time with oxygen plasma within the above range, it becomes easier to achieve the effect of improving the adhesion of the plated object without causing any change in the shape of the patterned resist film.

[0373] As described above, the present inventors provide the following (1) to (11). (1) A composition comprising a resin (A) whose solubility in alkali increases under the action of an acid, and an acid generator (B) that generates an acid upon exposure to actinic rays or radiation, The resin (A) contains two or more acrylic resins (A1), The acrylic resin (A1) is represented by the following formula (a1-1): CH=CR 1 -R 2 -Ar-(OH) na ···(a1-1) (In formula (a1-1), R 1 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms which may have a substituent, and R 2 is a single bond or a divalent linking group, Ar is an aromatic hydrocarbon group having a valence of (na+1), and na is an integer of 1 or more and 4 or less. and (a1) a phenolic hydroxyl group-containing unit derived from an unsaturated compound represented by the formula: the acrylic resin (A1) is a resin in which the ratio of the number of moles of the phenolic hydroxyl group-containing unit (a1) to the number of moles of all structural units constituting the acrylic resin (A1) is 1 mol % or more and 20 mol % or less, The resin (A) is a chemically amplified positive-working photosensitive composition containing a unit having an alkali-soluble group protected by an acid-dissociable group. (2) The resin (A) is composed of two or more kinds of acrylic resins (A1) alone, or two or more kinds of acrylic resins (A1) and an acrylic resin (A2) other than the acrylic resin (A1), The chemically amplified positive photosensitive composition according to (1), wherein the acrylic resin (A1) and the acrylic resin (A2) are copolymers of monomers each composed of two or more compounds selected from the group consisting of (meth)acrylic acid, (meth)acrylic acid esters, and (meth)acrylic acid amides. (3) The two or more acrylic resins (A1) each contain two or more structural units, The chemically amplified positive photosensitive composition according to (1) or (2), wherein the combinations of the two or more structural units constituting the two or more acrylic resins (A1) are the same as each other. (4) The chemically amplified positive photosensitive composition according to any one of (1) to (3), wherein the molecular weights of the two or more acrylic resins (A1) are different from each other. (5) The chemically amplified positive photosensitive composition according to any one of (1) to (4), wherein at least one of the two or more acrylic resins (A1) has a structural unit derived from a (meth)acrylic acid ester having an oxygen-containing aliphatic ring containing an oxygen atom as a ring-constituting atom. (6) The chemically amplified positive photosensitive composition according to any one of (1) to (5), wherein at least one of the two or more acrylic resins (A1) has a structural unit derived from a (meth)acrylic acid ester having an aliphatic hydrocarbon ring. (7) Among the weight average molecular weights of two or more kinds of acrylic resins (A1), the largest weight average molecular weight is Mw max The minimum weight average molecular weight is Mw min In this case, Mw max / Mw min The chemically amplified positive photosensitive composition according to any one of (1) to (6), wherein the value of is 2 or more. (8) A photosensitive dry film having a substrate film and a photosensitive resin layer formed on the surface of the substrate film, the photosensitive resin layer being made of the chemically amplified positive photosensitive composition according to any one of (1) to (7). (9) A method for producing a photosensitive dry film, comprising applying the chemically amplified positive photosensitive composition according to any one of (1) to (7) onto a substrate film to form a photosensitive resin layer. (10) A lamination step of laminating a photosensitive resin layer made of the chemically amplified positive photosensitive composition according to any one of (1) to (7) on a substrate having a metal surface; an exposure step of position-selectively irradiating the photosensitive resin layer with actinic rays or radiation; and a developing step of developing the photosensitive resin layer after exposure. (11) A lamination step of laminating a photosensitive resin layer made of the chemically amplified positive photosensitive composition according to any one of (1) to (7) on a substrate having a metal surface; an exposure step of irradiating the photosensitive resin layer with actinic rays or radiation; a development step of developing the exposed photosensitive resin layer to prepare a substrate with a mold for forming a plated object; and a step of plating the substrate with the mold to form a plated object within the mold. [Example]

[0374] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[0375] In the examples and comparative examples, the following P1 and P2 were used as the acid generator (B). [ka]

[0376] In the examples and comparative examples, the following resins A1 to A13 (acrylic resin (A1)), R1 to R4 (acrylic resin (A2) other than acrylic resin (A1)), and PHS-1 (polyhydroxystyrene resin (A4)) were used as resins (resin (A)) whose solubility in alkali increases under the action of acid. The numbers in the parentheses to the right of each structural unit in the following structural formulas indicate the content (mol %) of the structural unit in the resin. The weight-average molecular weights (Mw) of resins A1 to A13, R1 to R4, and PHS-1 are as follows. Furthermore, the polydispersity (Mw / Mn) of resins A1 to A13 and R1 to R4 is all 2.8. The polydispersity (Mw / Mn) of PHS-1 is 1.0. (Weight average molecular weight (Mw) of resin (A)) Resin A1: 40000 Resin A2:120000 Resin A3: 7000 Resin A4:40000 Resin A5: 120,000 Resin A6:40000 Resin A7:120000 Resin A8:40000 Resin A9:120000 Resin A10: 40000 Resin A11: 120000 Resin A12: 40000 Resin A13: 120000 Resin R1:40000 Resin R2:120000 Resin R3: 40000 Resin R4: 120000 Resin PHS-1:10000

[0377] [ka]

[0378] [ka]

[0379] [ka]

[0380] [ka]

[0381] In the examples and comparative examples, the following resin N-1 was used as the alkali-soluble resin (D). N-1 (novolac resin (D1)) had a weight average molecular weight Mw of 6500 and a dispersity (Mw / Mn) of 5.0. [ka]

[0382] In the examples and comparative examples, the following T1 and T2 were used as the sulfur-containing compound (E). [ka]

[0383] In the examples and comparative examples, the following Q1 was used as the acid diffusion inhibitor (F). Q1: Transesterification product of 1,2,3,4-butanetetracarboxylic acid tetramethyl ester with 1,2,2,6,6-pentamethyl-4-piperidinol and β,β,β',β'-tetramethyl-2,4,8,10-tetraoxaspiro[5.5]undecane-3.9-diethanol.

[0384] [Examples 1 to 12 and Comparative Examples 1 to 4] The resin (A) and alkali-soluble resin (D), each having the type and mass part shown in Table 1, the acid generator (B), the sulfur-containing compound (E), the acid diffusion controller (F), and 0.05 mass part of a surfactant (BYK310, manufactured by BYK-Chemie KK), were dissolved in a mixed solvent of 3-methoxybutyl acetate (MA) and propylene glycol monomethyl ether acetate (PGMEA) (MA / PGMEA = 6 / 4 (volume ratio)) to a solids concentration of 50 mass%, thereby obtaining photosensitive compositions of Examples 1 to 12 and Comparative Examples 1 to 4.

[0385] The photosensitive compositions obtained in each of the Examples and Comparative Examples were evaluated for rectangularity and crack resistance by the following methods. The results are shown in Table 1.

[0386] [Rectangularity evaluation] The photosensitive compositions of the Examples and Comparative Examples were applied to an 8-inch diameter silicon wafer (copper substrate) on the surface of which a copper sputtered film was formed, to form a 50 μm-thick photosensitive layer. The photosensitive layer was then post-applied baked (PAB) at 150°C for 450 seconds. After PAB, the layer was subjected to pattern exposure with i-line light using a mask with a 20 μm diameter hole pattern and an exposure system FPA-5510iV (Canon Inc.) (NA 0.18). The exposure dose was calculated as the hole width (width of the non-resist portion) at the middle of the substrate thickness direction in the cross section of the resist pattern (cross section perpendicular to the surface direction of the resist pattern): CD middle The exposure dose was set to give a thickness of 20 μm. The substrate was then placed on a hot plate and subjected to post-exposure baking (PEB) at 100°C for 90 seconds. A 2.38 wt% aqueous solution of tetramethylammonium hydroxide (developer, NMD-3, manufactured by Tokyo Ohka Kogyo Co., Ltd.) was then dropped onto the exposed photosensitive layer, followed by leaving the layer at 23°C for 60 seconds. This procedure was repeated four times. The resist pattern surface was then washed with running water and then nitrogen was blown to obtain a resist pattern. The cross-sectional shape of this resist pattern was observed with a scanning electron microscope, and the rectangularity was evaluated for each of the examples and comparative examples. Specifically, the cross section of the resist pattern (cross section perpendicular to the surface direction of the resist pattern) was observed using a scanning electron microscope, and the maximum value CD of the hole width (width of the non-resist portion) was calculated. max and minimum CD min was measured. max -CD min The rectangularity was evaluated based on the CD value according to the following criteria: max -CD min The closer the value is to 0, the better the cross-sectional shape of the hole is rectangular. <Evaluation criteria for rectangularity> A: 0 μm or more and less than 1 μm B: 1 μm or more and less than 3 μm C: 3μm or more

[0387] [Crack resistance evaluation] The resist pattern (RP1) obtained in the above [Evaluation of rectangularity] and the resist pattern (RP2) obtained in the same manner as in the above [Evaluation of rectangularity] except that the PEB temperature was changed to 160°C were observed under an optical microscope to check for cracks on the film surface or inside. 200 μm square RP1 and RP2 were each observed under an optical microscope, and crack resistance was evaluated according to the following criteria. <Crack resistance evaluation criteria> A: No cracks in either RP1 or RP2 B: RP1 no crack, RP2 crack C: Both RP1 and RP2 have cracks

[0388] [Table 1]

[0389] Table 1 shows that a chemically amplified positive resist composition containing a resin (A) and an acid generator (B), wherein the resin (A) contains two or more types of acrylic resin (A1) and contains a unit having an alkali-soluble group protected by an acid-dissociable group, can form a patterned resist film having a rectangular cross-sectional shape and excellent crack resistance.

Claims

1. The composition comprises a resin (A) whose solubility in alkali increases under the action of an acid, and an acid generator (B) that generates an acid when exposed to actinic rays or radiation, The resin (A) contains two or more acrylic resins (A1), The acrylic resin (A1) is represented by the following formula (a1-1): CH=CR １ -R ２ -Ar-(OH) ｎａ ・・・(a1-1) (In formula (a1-1), R １ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms which may have a substituent, and R ２ represents a single bond or a divalent linking group, Ar represents an aromatic hydrocarbon group having a valence of (na+1), and na represents an integer of 1 or more and 4 or less. and (a1) a phenolic hydroxyl group-containing unit derived from an unsaturated compound represented by the formula: the acrylic resin (A1) contains the phenolic hydroxyl group-containing unit (a1) in an amount of 1 mol % or more and 20 mol % or less of the number of moles of all structural units constituting the acrylic resin (A1), The resin (A) is a chemically amplified positive-working photosensitive composition containing a unit having an alkali-soluble group protected by an acid-dissociable group.

2. the resin (A) consists of two or more of the acrylic resins (A1) alone, or two or more of the acrylic resins (A1) and an acrylic resin (A2) other than the acrylic resin (A1); 2. The chemically amplified positive-working photosensitive composition according to claim 1, wherein the acrylic resin (A1) and the acrylic resin (A2) are each a copolymer of monomers composed of two or more compounds selected from the group consisting of (meth)acrylic acid, (meth)acrylic acid esters, and (meth)acrylic acid amides.

3. the two or more acrylic resins (A1) each contain two or more structural units, 3. The chemically amplified positive photosensitive composition according to claim 2, wherein the combinations of the two or more structural units constituting the two or more acrylic resins (A1) are the same as each other.

4. 4. The chemically amplified positive photosensitive composition according to claim 3, wherein the two or more types of acrylic resins (A1) have molecular weights different from each other.

5. 2. The chemically amplified positive-working photosensitive composition according to claim 1, wherein at least one of the two or more acrylic resins (A1) has a structural unit derived from a (meth)acrylic acid ester having an oxygen-containing aliphatic ring containing an oxygen atom as a ring-constituting atom.

6. 2. The chemically amplified positive photosensitive composition according to claim 1, wherein at least one of the two or more acrylic resins (A1) has a structural unit derived from a (meth)acrylic acid ester having an aliphatic hydrocarbon ring.

7. The largest weight average molecular weight among the weight average molecular weights of the two or more acrylic resins (A1) is Mw ｍａｘ The minimum weight average molecular weight is Mw ｍｉｎ In this case, Mw ｍａｘ / Mw ｍｉｎ 2. The chemically amplified positive photosensitive composition according to claim 1, wherein the value of is 2 or more.

8. A photosensitive dry film having a base film and a photosensitive resin layer formed on the surface of the base film, wherein the photosensitive resin layer is made of the chemically amplified positive photosensitive composition according to any one of claims 1 to 7.

9. A method for producing a photosensitive dry film, comprising applying the chemically amplified positive photosensitive composition according to any one of claims 1 to 7 onto a substrate film to form a photosensitive resin layer.

10. a lamination step of laminating a photosensitive resin layer made of the chemically amplified positive photosensitive composition according to any one of claims 1 to 7 on a substrate having a metal surface; an exposure step of position-selectively irradiating the photosensitive resin layer with actinic rays or radiation; a developing step of developing the photosensitive resin layer after exposure.

11. a lamination step of laminating a photosensitive resin layer made of the chemically amplified positive photosensitive composition according to any one of claims 1 to 7 on a substrate having a metal surface; an exposure step of irradiating the photosensitive resin layer with actinic rays or radiation; a development step of developing the photosensitive resin layer after exposure to light to prepare a substrate with a mold for forming a plated object; and a step of plating the substrate with the mold to form a plated object within the mold.

Images