Chemically amplified positive-type photosensitive composition, photosensitive dry film, method for producing photosensitive dry film, method for producing patterned resist film, method for producing substrate with template, 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 suppressed footing, a photosensitive dry film including a photosensitive layer, a method for manufacturing the photosensitive dry film, a method for manufacturing a patterned resist film, a method for manufacturing a substrate with a mold, and a method for manufacturing a plated article.SOLUTION: An actinic ray-sensitive or radiation-sensitive resin composition includes an acid generator (A) that generates an acid upon irradiation with actinic rays or radiation, a resin (B) whose solubility in alkali increases under the action of an acid, and a sulfur-containing compound (E), wherein the acid generator (A) includes a sulfonium salt composed of a sulfonium cation and an anion represented by the formula (A1): The sulfur-containing compound (E) comprises a compound represented by formula (E1): X e - (- R1e - SH) n e (E1).SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a chemically amplified positive-tone photosensitive composition, a photosensitive dry film having a photosensitive layer made of the chemically amplified positive-tone photosensitive composition, a method for manufacturing the photosensitive dry film, a method for manufacturing a patterned resist film using the chemically amplified positive-tone photosensitive composition, a method for manufacturing a substrate with a mold, and a method for manufacturing 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. According to Patent Document 1, it is possible to form a plated object with good adhesion to the metal surface on the substrate using the above-mentioned mold, while suppressing footing, which occurs when the resist portion at the contact surface between the substrate surface and the resist pattern protrudes toward the non-resist portion, resulting in the bottom width of the non-resist portion being narrower than the top width. [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. It is also highly desirable to further suppress footing.

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

[0010] As a result of extensive research to achieve the above object, the present inventors have discovered that the above problems can be solved by a chemically amplified positive-working photosensitive composition comprising an acid generator (A) that generates an acid upon exposure to actinic rays or radiation, a resin (B) whose solubility in alkali increases due to the action of acid, and a sulfur-containing compound (E), wherein the acid generator (A) comprises a sulfonium salt composed of a sulfonium cation and an anion represented by the following formula (A1), and the sulfur-containing compound (E) comprises a compound represented by the following formula (E1), thereby completing the present invention. Specifically, the present invention provides the following:

[0011] [1] A composition comprising an acid generator (A) that generates an acid upon exposure to actinic rays or radiation, a resin (B) whose solubility in alkali increases under the action of an acid, and a sulfur-containing compound (E), The acid generator (A) is a compound represented by the following formula (A1): Cf-SO2-N - -SO2-Cf···(A1) (In formula (A1), 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.) and an anion represented by the formula: The sulfur-containing compound (E) is represented by the following formula (E1): X e -(-R 1e -SH) ne (E1) (In formula (E1), X e is an aromatic group-containing group with a valence of ne, and R 1e is an alkylene group, and X e and n e is an integer of 2 or more and 4 or less. A chemically amplified positive photosensitive composition comprising a compound represented by the formula:

[0012] [2] R in the formula (E1) 1e The chemically amplified positive photosensitive composition according to the above [1], wherein the alkylene group as

[0013] [3] X in the formula (E1) e The chemically amplified positive photosensitive composition according to the above [1] or [2], wherein the ne-valent aromatic group-containing group as the aromatic group-containing group is an ne-valent aromatic hydrocarbon group which may have a substituent.

[0014] [4] The chemically amplified positive photosensitive composition according to the above [3], wherein the aromatic hydrocarbon group having a valence of ne as Xe in formula (E1) is a phenylene group, a benzenetriyl group, or a benzenetetrayl group, each of which may have a substituent.

[0015] [5] A photosensitive dry film having a base film and a photosensitive layer formed on the surface of the base film, the photosensitive layer being made of the chemically amplified positive photosensitive composition described in any one of [1] to [4] above.

[0016] [6] A method for producing a photosensitive dry film, comprising applying the chemically amplified positive photosensitive composition described in any one of [1] to [4] above onto a substrate film to form a photosensitive layer.

[0017] [7] a lamination step of laminating a photosensitive layer made of the chemically amplified positive photosensitive composition described in any one of [1] to [4] above on a substrate; an exposure step of position-selectively irradiating the photosensitive layer with actinic rays or radiation; a developing step of developing the photosensitive layer after exposure.

[0018] [8] a lamination step of laminating a photosensitive layer made of the chemically amplified positive photosensitive composition described in any one of [1] to [4] above on a substrate; an exposure step of position-selectively irradiating the photosensitive layer with actinic rays or radiation; and a development step of developing the photosensitive layer after exposure to produce a mold for forming a plated object.

[0019] [9] A method for producing a plated object, comprising the step of plating the mold-equipped substrate produced by the mold-equipped substrate production method described in [8] above, to form a plated object within the mold. [Effects of the Invention]

[0020] According to the present invention, it is possible to provide a chemically amplified positive-working photosensitive composition capable of forming a patterned resist film having a rectangular cross-sectional shape and suppressing footing, a photosensitive dry film having a photosensitive layer made of the chemically amplified positive-working photosensitive composition, a method for manufacturing the photosensitive dry film, a method for manufacturing a patterned resist film using the aforementioned chemically amplified positive-working photosensitive composition, a method for manufacturing a mold-equipped substrate using the aforementioned chemically amplified positive-working photosensitive composition, and a method for manufacturing a plated object using the aforementioned chemically amplified positive-working photosensitive composition. [Brief explanation of the drawings]

[0021] [Figure 1] FIG. 2 is a diagram schematically showing a cross section of a resist pattern observed when measuring the amount of footing in a non-resist portion in the resist pattern in Examples and Comparative Examples. DETAILED DESCRIPTION OF THE INVENTION

[0022] <Chemically amplified positive-working photosensitive composition> The chemically amplified positive-working photosensitive composition (hereinafter also referred to as the photosensitive composition) contains an acid generator (A) (hereinafter also referred to as the acid generator (A)) that generates an acid upon exposure to actinic rays or radiation, a resin (B) (hereinafter also referred to as the resin (B)) whose solubility in alkali increases due to the action of the acid, and a sulfur-containing compound (E). The acid generator (A) contains a sulfonium salt composed of a sulfonium cation and an anion represented by the above formula (A1). The sulfur-containing compound (E) includes a compound represented by the above formula (E1). The photosensitive composition may contain components such as an alkali-soluble resin (D) and an acid diffusion controller (F), if necessary.

[0023] Essential and optional components contained in the photosensitive composition and a method for producing the photosensitive composition will be described below.

[0024] <Acid generator (A)> The acid generator (A) is a compound that generates an acid when irradiated with actinic rays or radiation, and is a compound that generates an acid directly or indirectly when irradiated with light. The acid generator (A) contains a sulfonium salt composed of a sulfonium cation and an anion represented by the following formula (A1). Cf-SO2-N - -SO2-Cf···(A1) (In formula (A1), 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.)

[0025] The photosensitive composition contains, as the acid generator (A), a sulfonium salt composed of a sulfonium cation and an anion represented by formula (A1), and also contains a compound represented by formula (E1) described below, so that a patterned resist film having a rectangular cross-sectional shape and suppressed footing can be formed. "Footing" is 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, causing the bottom width of the non-resist portion to become narrower than the top width.

[0026] In formula (A1), 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 (A1) may be the same or different, and are preferably the same.

[0027] Specific examples of the anion represented by formula (A1) include the following anions. [ka]

[0028] In the sulfonium salt composed of a sulfonium cation and an anion represented by formula (A1), the sulfonium cation is not particularly limited. The sulfonium cation is preferably a structure represented by the following formula (a1): [ka]

[0029] In the above formula (a1), R 1a , R 2a , R 3a At least one of R represents a group represented by the following formula (a2), 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. 1a , R 2a , R 3a One of the groups is a group represented by the following formula (a2), 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 1a , R 2a , R 3a 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 1a , R 2a , R 3a 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 1a , R 2a , R 3aWhen 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.

[0030] [ka]

[0031] In the above formula (a2), R 4a , R 5a each 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 6a 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 4a When there are multiple R, they may be the same or different. 5a When there are a plurality of, they may be the same or different. R 4a , and R 5a 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 6aSpecific 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.

[0032] Above R 1a , R 2a , R 3a Among these, the number of groups represented by the above formula (a2) is preferably one from the viewpoint of compound stability, 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.

[0033] 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.

[0034] 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.

[0035] Suitable examples of the sulfonium cation represented by formula (a1) include sulfonium cations represented by the following formulas: [ka]

[0036] In the sulfonium salt composed of a sulfonium cation and an anion represented by formula (A1), the sulfonium cation is preferably a cation represented by the following formula (a4). [ka]

[0037] In the above formula (a4), R 7a X each independently represents a group selected from the group consisting of a hydrogen atom, an alkyl group, a hydroxy group, an alkoxy group, an alkylcarbonyl group, an alkylcarbonyloxy group, an alkyloxycarbonyl group, a halogen atom, an aryl group which may have a substituent, and an arylcarbonyl group. 1a is a structure represented by the following formula (a5). [ka]

[0038] In the above formula (a5), X 2a 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 2a 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. 3a -O-, -S-, -SO-, -SO2-, -NH-, -NR 30a 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 2a and h X's 3a may be the same or different. 30a is an alkyl group having 1 to 5 carbon atoms or an aryl group having 6 to 10 carbon atoms.

[0039] Specific examples of the sulfonium ion represented by the above formula (a4) 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.

[0040] Suitable examples of the sulfonium cation represented by formula (a4) include sulfonium cations represented by the following formulas: [ka]

[0041] The acid generator (A) may contain only a sulfonium salt formed from a sulfonium cation and an anion represented by formula (A1), or may contain an acid generator other than a sulfonium salt formed from a sulfonium cation and an anion represented by formula (A1) in addition to the sulfonium salt formed from a sulfonium cation and an anion represented by formula (A1). However, the ratio of the mass of the sulfonium salt formed from a sulfonium cation and an anion represented by formula (A1) to the mass of the acid generator (A) is preferably 60 mass% or more, and more preferably 80 mass% or more. As the acid generator other than the sulfonium salt composed of a sulfonium cation and an anion represented by formula (A1), any photoacid generator that has conventionally been incorporated into various photosensitive compositions can be used without any particular limitation.

[0042] Acid generators other than the sulfonium salt formed from a sulfonium cation and an anion represented by formula (A1) (hereinafter also referred to as "other acid generators") include sulfonium salts formed from a sulfonium cation and an anion other than the anion represented by formula (A1). The sulfonium cation in a sulfonium salt composed of a sulfonium cation and an anion other than the anion represented by formula (A1) above is the same as the sulfonium cation in the sulfonium salt composed of a sulfonium cation and an anion represented by formula (A1) above.

[0043] Examples of anions other than the anion represented by formula (A1) include a borate anion represented by the following formula (a7) and PF6 - Examples include: [ka]

[0044] In the above formula (a7), R 9a ~R 12a 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.

[0045] A preferred example of the borate anion represented by the formula (a7) 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.

[0046] Examples of anions other than the anion represented by formula (A1) include fluoroalkylsulfonate ions or arylsulfonate ions in which some or all of the hydrogen atoms have been fluorinated.

[0047] 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.

[0048] 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.

[0049] 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.

[0050] Among these, preferred anions include those represented by the following formula (a8).

[0051] [ka]

[0052] In the above formula (a8), R 20a are groups represented by the following formulae (a9), (a10), and (a11).

[0053] [ka]

[0054] In the formula (a9), x represents an integer of 1 or more and 4 or less. In the formula (a10), R 21a 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.

[0055] Other examples of the acid generator include a compound represented by the following formula (a12), which is a nonionic acid generator: The compound represented by the following formula (a12) generates a sulfonic acid when irradiated with actinic rays or radiation. [ka] (In formula (a12), R 22a is a monovalent organic group, and R 23a ~R 28a are each independently a hydrogen atom or a monovalent organic group, and R 23a and R 24a and R 24a and R 25a and R 25a and R 26a and R 26a and R 27a and, or R 27a and R 28a may be bonded to each other to form a ring.

[0056] R 22aThe 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.

[0057] R 22a 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 (a12a): -R 29a -(O) a -R 30a -(O) b -Y 1 -R 31a ···(a12a) (In formula (a12a), Y 1 R is a single bond or an alkanediyl group having 1 to 4 carbon atoms. 29a and R 30a 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. 31a represents an alkyl group having 1 to 18 carbon atoms which may be substituted with a halogen atom, an alicyclic hydrocarbon group having 3 to 12 carbon atoms, an aryl group having 6 to 20 carbon atoms which may be substituted with a halogen atom, or an aralkyl group having 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:

[0058] R 22aWhen 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.

[0059] R 22a 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.

[0060] R 22a 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.

[0061] R 22a When the organic group as is an alkenyl group, preferred examples include an allyl group and a 2-methyl-2-propenyl group.

[0062] R 22aWhen 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.

[0063] R 22a 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.

[0064] R 22aWhen 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.

[0065] R 22a 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.

[0066] R 22a 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.

[0067] R 22a 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.

[0068] R 22a 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.

[0069] R 22aWhen 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.

[0070] R 22a 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.

[0071] R 22a 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.

[0072] R 22a 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.

[0073] R 22a When the organic group as is an aralkyl group substituted with an alkylthio group, a suitable example thereof is a p-methylthiobenzyl group.

[0074] R 22a 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.

[0075] R 22aWhen 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.

[0076] The group represented by formula (a12a) is an ether group-containing group. In formula (a12a), 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 (a12a), R 29a or R 30aExamples 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.

[0077] In formula (a12a), R 29a or R 30a 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.

[0078] In formula (a12a), R 29a or R 30ais 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.

[0079] In formula (a12a), R 29a or R 30a 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.

[0080] In formula (a12a), R 31a 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.

[0081] In formula (a12a), R 31ais 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.

[0082] In formula (a12a), R 31a 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.

[0083] In formula (a12a), R 31a is an aryl group, a halogenated aryl group, an aralkyl group, or a halogenated aralkyl group, suitable examples of these groups include R 22a is one of these groups.

[0084] Among the groups represented by formula (a12a), a suitable group is R 29a 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.

[0085] R 22aAs 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. 22a It is preferable as.

[0086] In formula (a12), R 23a ~R 28a is a hydrogen atom or a monovalent organic group. 23a and R 24a and R 24a and R 25a and R 25a and R 26a and R 26a and R 27a and, or R 27a and R 28a may be bonded to each other to form a ring. For example, R 25a and R 26a may be bonded to form a five-membered ring together with the naphthalene ring to form an acenaphthene skeleton.

[0087] 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. 23a ~R 28a 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.

[0088] R 23a ~R 28a As for R 24a is an organic group, and R 23a and R 25a ~R 28a is a hydrogen atom or R 25a is an organic group, and R 23a , R 24a and R 26a ~R 28a is preferably a hydrogen atom. 23a ~R 28a may all be hydrogen atoms.

[0089] R 23a ~R 28a 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.

[0090] R 23a ~R 28ais 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.

[0091] R 23a ~R 28a 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.

[0092] R 23a ~R 28ais 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.

[0093] R 23a ~R 28a 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.

[0094] R 23a ~R 28a 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.

[0095] R 23a ~R 28a 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.

[0096] R 23a ~R 28a 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.

[0097] R 23a ~R 28a When is a heterocyclylthio group, examples thereof include a furfurylthio group and a tetrahydrofuranylthio group.

[0098] R 23a ~R 28a 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.

[0099] R 23a ~R 28a 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.

[0100] Specific examples of the compound represented by formula (a12) include the following compounds.

[0101] [ka]

[0102] [ka]

[0103] [ka]

[0104] [ka]

[0105] [ka]

[0106] [ka]

[0107] [ka]

[0108] [ka]

[0109] [ka]

[0110] [ka]

[0111] Other examples of the acid generator include a compound represented by the following formula (a13), which is a nonionic acid generator: The compound represented by the following formula (a13) generates a sulfonic acid when irradiated with actinic rays or radiation. [ka] In equation (a13), 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.

[0112] In formula (a13), 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-.

[0113] In formula (a13), 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.

[0114] In formula (a13), 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 (a13), 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 (a13), 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 (a13), 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, include a pyridin-2-ylmethyl group, a pyridin-3-ylmethyl group, and a pyridin-4-ylmethyl group.

[0115] In formula (a13), 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.

[0116] In formula (a13), 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.

[0117] In formula (a13), 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, or cyclic, or may be 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.

[0118] In formula (a13), 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.

[0119] In formula (a13), R b6 The hydrocarbon group having 1 to 6 carbon atoms as R in formula (a13) 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.

[0120] In formula (a13), Q 1 and Q 2 As the perfluoroalkyl group having 1 to 6 carbon atoms, R in formula (a13) a1 and R a2 This is the same as the perfluoroalkyl group having 1 to 6 carbon atoms described above.

[0121] In the compound represented by formula (a13), the orientation of the ester bond as L is not particularly limited, and may be either -CO-O- or -O-CO-.

[0122] The compound represented by formula (a13) is preferably a compound represented by the following formula (a13-1): [ka] In formula (a13-1), R b1 , R a1 , Q 1 , and Q 2 are the same as those in equation (a13).

[0123] R in formula (a13-1) 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 A compound represented by formula (a13-1) which may be substituted with a group selected from the group consisting of - is preferred.

[0124] The total content of the acid generator (A) 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.

[0125] <Resin (B)> The resin (B) whose solubility in alkali increases under the action of an acid is not particularly limited, and any resin whose solubility in alkali increases under the action of an acid can be used. Among them, it is preferable to contain at least one resin selected from the group consisting of novolak resins (B1), polyhydroxystyrene resins (B2), and acrylic resins (B3). In the novolak resin (B1) and the polyhydroxystyrene resin (B2), at least some of the phenolic hydroxyl groups are protected with acid-dissociable, dissolution-inhibiting groups. The acrylic resin (B3) also contains a structural unit derived from a (meth)acrylate having an acid-dissociable group.

[0126] [Novolac resin (B1)] As the novolac resin (B1), a resin containing a structural unit represented by the following formula (b-11) can be used.

[0127] [ka]

[0128] In the above formula (b-11), R 1b represents an acid dissociable, dissolution inhibiting group. The acid dissociable, dissolution inhibiting group is preferably a so-called acetal-type protecting group. R 2b , R 3b each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

[0129] Above R 1b The acid dissociable, dissolution inhibiting group represented by the formula (b-12) is preferably a group represented by the formula (b-13) below, a linear, branched, or cyclic alkyl group having from 1 to 6 carbon atoms, a vinyloxyethyl group, a tetrahydropyranyl group, a tetrahydrofuranyl group, or a trialkylsilyl group.

[0130] [ka]

[0131] In the above formulas (b-12) and (b-13), R 4b , R 5b each independently represents a hydrogen atom or a linear or branched alkyl group having 1 to 6 carbon atoms; R 6b represents a linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms; R 7brepresents a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms; o represents 0 or 1.

[0132] 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. Examples of the cyclic alkyl group include a cyclopentyl group, a cyclohexyl group, etc.

[0133] Specific examples of the acid-dissociable, dissolution-inhibiting group represented by formula (b-12) include 1-methoxyethyl, 1-ethoxyethyl, 1-n-propoxyethyl, 1-isopropoxyethyl, 1-n-butoxyethyl, 1-isobutoxyethyl, 1-tert-butoxyethyl, 1-cyclohexyloxyethyl, 1-methoxypropyl, 1-ethoxypropyl, 1-methoxy-1-methylethyl, and 1-ethoxy-1-methylethyl groups. Specific examples of the acid-dissociable, dissolution-inhibiting group represented by formula (b-13) include tert-butoxycarbonyl and tert-butoxycarbonylmethyl groups. Examples of the trialkylsilyl group include trimethylsilyl and tri-tert-butyldimethylsilyl groups, each of which has 1 to 6 carbon atoms in the alkyl group.

[0134] [Polyhydroxystyrene resin (B2)] As the polyhydroxystyrene resin (B2), a resin containing a structural unit represented by the following formula (b4) can be used.

[0135] [ka]

[0136] In the above formula (b4), R 8b represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R 9b represents an acid dissociable, dissolution inhibiting group.

[0137] 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.

[0138] Above R 9b Examples of acid dissociable, dissolution inhibiting groups represented by the formula (b-12) and (b-13) above include acid dissociable, dissolution inhibiting groups similar to those exemplified in the formulas (b-12) and (b-13) above, as well as tert-butyl groups, cyclohexylethyl groups, cyclopentylethyl groups, cyclohexylpropyl groups, and cyclopentylpropyl groups.

[0139] Furthermore, the polyhydroxystyrene resin (B2) 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.

[0140] [Acrylic resin (B3)] The acrylic resin (B3) is not particularly limited as long as it is an acrylic resin whose solubility in alkali increases under the action of an acid and which has been conventionally incorporated into various photosensitive compositions. In the specification and claims of the present application, a resin containing a structural unit derived from a (meth)acrylate having an acid-dissociable group is defined as the acrylic resin (B3). In addition, in this specification, "(meth)acrylic" means both "acrylic" and "methacrylic." "(meth)acrylate" means both "acrylate" and "methacrylate."

[0141] The acrylic resin (B3) as the resin (B) whose solubility in alkali increases under the action of an acid preferably has a structural unit (B-1) derived from a monomer having one or more phenolic hydroxyl groups and one ethylenically unsaturated double bond.

[0142] In the structural unit (B-1), the phenolic hydroxyl group refers to a hydroxyl group (OH) directly bonded to a carbon atom constituting a six-membered aromatic ring. It should be noted that not only a single six-membered aromatic ring but also a six-membered aromatic ring constituting a fused polycyclic aromatic ring falls under the category of a six-membered aromatic ring. A benzene ring is preferred as the six-membered aromatic ring. In the structural unit (B-1), the structure having an ethylenically unsaturated double 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.

[0143] An example of the structural unit (B-1) is a structural unit represented by the following formula (B-1-1). [ka]

[0144] In the above formula (B-1-1), R b01 represents a hydrogen atom or a methyl group, and R b02 represents a single bond or a divalent organic group. R b02Examples of the divalent organic group as include -COO-, a divalent aliphatic group, a divalent aromatic group, and a divalent group formed by combining these groups.

[0145] The structural unit represented by formula (B-1-1) is preferably a structural unit represented by the following formula (B-1-1a) or a structural unit derived from hydroxystyrene. [ka]

[0146] In the above formula (B1-1-1a), R b01 represents a hydrogen atom or a methyl group, and R b03 represents a single bond or an alkylene group. R b03 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 b03 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.

[0147] When the acrylic resin (B3) contains the structural unit (B-1), the content of the structural unit (B-1) in the acrylic resin (B3) is not particularly limited, but is preferably from 1 mol % to 80 mol %, and more preferably from 5 mol % to 60 mol %.

[0148] The acrylic resin (B3) preferably contains a structural unit (b-3) derived from an acrylic acid ester containing an -SO- containing cyclic group or a lactone-containing cyclic group, which makes it easier to form a patterned resist film having a desirable cross-sectional shape.

[0149] (-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.

[0150] 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.

[0151] 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.

[0152] 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.

[0153] 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-.

[0154] 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.

[0155] 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.

[0156] 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.

[0157] 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—).

[0158] 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.

[0159] 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.

[0160] 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.

[0161] 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.

[0162] 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.

[0163] 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.

[0164] 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.

[0165] More specific examples of the -SO2- containing cyclic group include groups represented by the following formulas (3-1) to (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 10b 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.

[0166] In the above formulas (3-1) to (3-4), A' is an alkylene group having 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 1 to 5 carbon atoms in A' is preferably a linear or branched alkylene group, and examples thereof include a methylene group, an ethylene group, an n-propylene group, and an isopropylene group.

[0167] 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.

[0168] z may be any of 0, 1, and 2, and is most preferably 0. When z is 2, a plurality of R 10b may be the same or different.

[0169] R 10bExamples 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.

[0170] Specific examples of cyclic groups represented by the above formulas (3-1) to (3-4) are shown below, in which "Ac" represents an acetyl group.

[0171] [ka]

[0172] [ka]

[0173] Of the above, the -SO2- containing cyclic group is preferably a group represented by the aforementioned formula (3-1), more preferably at least one selected from the group consisting of groups represented by any of the aforementioned chemical formulas (3-1-1), (3-1-18), (3-3-1), and (3-4-1), and most preferably a group represented by the aforementioned chemical formula (3-1-1).

[0174] (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.

[0175] The lactone-containing cyclic group in the structural unit (b-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.

[0176] As for the structural unit (b-3), there are no particular limitations on the structure of the other portions as 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 (b-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 (b-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.

[0177] [Structural unit (b-3-S)] More specific examples of the structural unit (b-3-S) include structural units represented by the following formula (b-S1).

[0178] [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 11b is a -SO2- containing cyclic group, and R 12b is a single bond or a divalent linking group.

[0179] In formula (b-S1), R is the same as defined above. R 11b is the same as the -SO2- containing cyclic group listed above. R12b may be either a single bond or a divalent linking group.

[0180] R 12b The divalent linking group in is not particularly limited, but suitable examples include a divalent hydrocarbon group which may have a substituent, and a divalent linking group containing a hetero atom.

[0181] Optionally substituted divalent hydrocarbon group The hydrocarbon group as a divalent linking group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. An aliphatic hydrocarbon group refers to a hydrocarbon group that does not have aromaticity. The aliphatic hydrocarbon group may be saturated or unsaturated. Saturated hydrocarbon groups are usually preferred. More specific examples of the aliphatic hydrocarbon group include linear or branched aliphatic hydrocarbon groups and aliphatic hydrocarbon groups containing a ring in their structure.

[0182] 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.

[0183] The linear aliphatic hydrocarbon group is preferably a linear alkylene group, such as a methylene group [-CH-], an ethylene group [-(CH)-], a trimethylene group [-(CH)-], a tetramethylene group [-(CH)-], or a pentamethylene group [-(CH)-].

[0184] The branched aliphatic hydrocarbon group is preferably a branched alkylene group. Specific examples 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.

[0185] The linear or branched aliphatic hydrocarbon group may or may not have a substituent (a group or atom other than a hydrogen atom) substituting a hydrogen atom. Examples of the substituent include a fluorine atom, a fluorinated alkyl group having from 1 to 5 carbon atoms and substituted with a fluorine atom, and an oxo group (═O).

[0186] Examples of the aliphatic hydrocarbon group containing a ring in the above structure include cyclic aliphatic hydrocarbon groups (groups in which two hydrogen atoms have been removed from an aliphatic hydrocarbon ring) which may contain a substituent containing a heteroatom in the ring structure, groups in which the cyclic aliphatic hydrocarbon group is bonded to the end of a linear or branched aliphatic hydrocarbon group, and groups in which the cyclic aliphatic hydrocarbon group is interposed in the middle of a linear or branched aliphatic hydrocarbon group. Examples of the linear or branched aliphatic hydrocarbon group include the same as those described above.

[0187] 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.

[0188] The cyclic aliphatic hydrocarbon group may be polycyclic or monocyclic. 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 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 include adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane, etc.

[0189] The cyclic aliphatic hydrocarbon group may or may not have a substituent (a group or atom other than a hydrogen atom) substituting a hydrogen atom. Examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, and an oxo group (═O).

[0190] The alkyl group as the above-mentioned 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.

[0191] The alkoxy group as the above-mentioned substituent is preferably an alkoxy group having 1 to 5 carbon atoms, more preferably a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, or a tert-butoxy group, and particularly preferably a methoxy group or an ethoxy group.

[0192] 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.

[0193] Examples of the halogenated alkyl group as the substituent include the above alkyl groups in which some or all of the hydrogen atoms have been substituted with the above halogen atoms.

[0194] In the cyclic aliphatic hydrocarbon group, some of the carbon atoms constituting the ring structure may be substituted with -O- or -S-. Preferred examples of the substituent containing a hetero atom include -O-, -C(=O)-O-, -S-, -S(=O)2-, and -S(=O)2-O-.

[0195] The aromatic hydrocarbon group as a divalent hydrocarbon group is a divalent hydrocarbon group having at least one aromatic ring, which may have a substituent. The aromatic ring is not particularly limited as long as it is a cyclic conjugated system having 4n+2 π electrons, and may be monocyclic or polycyclic. The number of carbon atoms in the aromatic ring is preferably 5 to 30, more preferably 5 to 20, even more preferably 6 to 15, and particularly preferably 6 to 12. However, this number of carbon atoms does not include the number of carbon atoms of the substituent.

[0196] Specific examples of aromatic rings include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; and aromatic heterocycles in which some of the carbon atoms constituting the aromatic hydrocarbon rings are substituted with heteroatoms. Examples of heteroatoms in aromatic heterocycles include oxygen atoms, sulfur atoms, and nitrogen atoms. Specific examples of aromatic heterocycles include pyridine rings and thiophene rings.

[0197] 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 or aromatic heterocycles (arylene groups or heteroarylene groups); groups in which two hydrogen atoms have been removed from aromatic compounds containing two or more aromatic rings (e.g., biphenyl, fluorene, etc.); and groups in which one hydrogen atom of a group in which one hydrogen atom has been removed from the above-mentioned aromatic hydrocarbon rings or aromatic heterocycles (aryl groups or heteroaryl groups) has been substituted with an alkylene group (e.g., groups in which one further hydrogen atom has been removed from the aryl group in an arylalkyl group such as a benzyl group, phenethyl group, 1-naphthylmethyl group, 2-naphthylmethyl group, 1-naphthylethyl group, or 2-naphthylethyl group).

[0198] The alkylene group bonded to the aryl group or heteroaryl 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.

[0199] The aromatic hydrocarbon group may have a hydrogen atom substituted with a substituent. For example, a hydrogen atom bonded to an aromatic ring in the aromatic hydrocarbon group may be substituted with a substituent. Examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, and an oxo group (═O).

[0200] The alkyl group as the above-mentioned 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.

[0201] The alkoxy group as the above-mentioned substituent is preferably an alkoxy group having 1 to 5 carbon atoms, more preferably a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, or a tert-butoxy group, and more preferably a methoxy group or an ethoxy group.

[0202] 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.

[0203] Examples of the halogenated alkyl group as the substituent include the above alkyl groups in which some or all of the hydrogen atoms have been substituted with the above halogen atoms.

[0204] Divalent linking groups containing heteroatoms The heteroatom in the divalent linking group containing a heteroatom is an atom other than a carbon atom or a hydrogen atom, and examples thereof include an oxygen atom, a nitrogen atom, a sulfur atom, and a halogen atom.

[0205] Specific examples of divalent linking groups containing a heteroatom 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-, as well as combinations of at least one of these non-hydrocarbon linking groups with a divalent hydrocarbon group. Examples of the divalent hydrocarbon group include the same as the divalent hydrocarbon group described above which may have a substituent, and linear or branched aliphatic hydrocarbon groups are preferred.

[0206] 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.

[0207] R 12b As the divalent linking group in the above, a linear or branched alkylene group, a cyclic aliphatic hydrocarbon group, or a divalent linking group containing a hetero atom is particularly preferred.

[0208] R 12b When the divalent linking group in the formula (I) is a linear or branched alkylene group, the number of carbon atoms in the alkylene group is preferably from 1 to 10, more preferably from 1 to 6, particularly preferably from 1 to 4, and most preferably from 1 to 3. Specific examples include the same linear alkylene groups and branched alkylene groups as those exemplified as the linear or branched aliphatic hydrocarbon groups in the description of the "divalent hydrocarbon group which may have a substituent" above as the divalent linking group.

[0209] R 12b When the divalent linking group in is a cyclic aliphatic hydrocarbon group, examples of the cyclic aliphatic hydrocarbon group include the same cyclic aliphatic hydrocarbon groups as the "aliphatic hydrocarbon group containing a ring in its structure" in the description of the "divalent hydrocarbon group which may have a substituent" as the above-mentioned divalent linking group.

[0210] As the cyclic aliphatic hydrocarbon group, a group in which two or more hydrogen atoms have been removed from cyclopentane, cyclohexane, norbornane, isobornane, adamantane, tricyclodecane, or tetracyclododecane is particularly preferred.

[0211] R 12b When the divalent linking group in the formula (I) is a divalent linking group containing a hetero atom, preferred examples of the linking group include -O-, -C(=O)-O-, -C(=O)-, -OC(=O)-O-, -C(=O)-NH-, -NH- (H may be substituted with a substituent such as an alkyl group or an acyl group), -S-, -S(=O)2-, -S(=O)2-O-, and groups represented by the general formula -Y 1b -OY 2b -, -[Y 1b -C(=O)-O] m’ -Y 2b - or -Y 1b -OC(=O)-Y 2b -, wherein Y 1b , and Y 2b are each independently a divalent hydrocarbon group which may have a substituent, O is an oxygen atom, and m' is an integer of 0 or more and 3 or less.

[0212] R 12b When the divalent linking group in the formula (I) is -NH-, the hydrogen atom in -NH- may be substituted with a substituent such as an alkyl group, acyl, etc. The number of carbon atoms in the substituent (alkyl group, acyl group, etc.) 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.

[0213] Formula-Y 1b -OY 2b -, -[Y 1b -C(=O)-O] m’ -Y 2b - or -Y 1b -OC(=O)-Y 2b -Medium, Y 1b , and Y 2bare each independently a divalent hydrocarbon group which may have a substituent. Examples of the divalent hydrocarbon group include the same as the "divalent hydrocarbon group which may have a substituent" listed above in the description of the divalent linking group.

[0214] Y 1b As the alkyl group, a straight-chain aliphatic hydrocarbon group is preferable, a straight-chain alkylene group is more preferable, a straight-chain alkylene group having 1 to 5 carbon atoms is even more preferable, and a methylene group and an ethylene group are particularly preferable.

[0215] Y 2b 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. The alkyl group in the alkylmethylene group is preferably a linear alkyl group having 1 to 5 carbon atoms, more preferably a linear alkyl group having 1 to 3 carbon atoms, and particularly preferably a methyl group.

[0216] Formula − [Y 1b -C(=O)-O] m’ -Y 2b In the group represented by -, 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, in the group represented by the formula -[Y 1b -C(=O)-O] m’ -Y 2b The group represented by - is a group represented by the formula -Y 1b -C(=O)-OY 2b Particularly preferred is a group represented by the formula -(CH2) a’ -C(=O)-O-(CH2) b’ In the formula, a' is an integer of 1 to 10, preferably an integer of 1 to 8, more preferably an integer of 1 to 5, even more preferably 1 or 2, and most preferably 1. b' is an integer of 1 to 10, preferably an integer of 1 to 8, more preferably an integer of 1 to 5, even more preferably 1 or 2, and most preferably 1.

[0217] R 12bAs for the divalent linking group in the formula (I), the divalent linking group containing a hetero atom is preferably an organic group consisting of a combination of at least one non-hydrocarbon group and a divalent hydrocarbon group. Among them, a linear group having an oxygen atom as a hetero atom, for example, a group containing an ether bond or an ester bond, is preferred, and the divalent linking group in the formula (I) is preferably an organic group consisting of at least one non-hydrocarbon group and a divalent hydrocarbon group. 1b -OY 2b -, -[Y 1b -C(=O)-O] m’ -Y 2b - or -Y 1b -OC(=O)-Y 2b - is more preferred, and is a group represented by the above formula -[Y 1b -C(=O)-O] m’ -Y 2b - or -Y 1b -OC(=O)-Y 2b A group represented by - is particularly preferred.

[0218] R 12b The divalent linking group in is preferably an alkylene group or one containing an ester bond (-C(=O)-O-).

[0219] The alkylene group is preferably a linear or branched alkylene group. Suitable examples of the linear aliphatic hydrocarbon 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-.

[0220] The divalent linking group containing an ester bond is particularly a group represented by the formula: -R 13b -C(=O)-O-[wherein, R 13b is a divalent linking group.] is preferred. That is, the structural unit (b-3-S) is preferably a structural unit represented by the following formula (b-S1-1).

[0221] [ka] (Wherein, R and R 11b are the same as above, and R 13b is a divalent linking group.

[0222] R 13b is not particularly limited, and examples thereof include the above-mentioned R 12b Examples of the divalent linking group include the same as the divalent linking group in the above. R 13bThe divalent linking group 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 is preferably a linear or branched alkylene group or a divalent linking group containing an oxygen atom as a heteroatom.

[0223] 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-.

[0224] 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 1b -OY 2b -, -[Y 1b -C(=O)-O] m’ -Y 2b - or -Y 1b -OC(=O)-Y 2b - is more preferable. Y 1b , and Y 2b are each independently a divalent hydrocarbon group which may have a substituent, and m' is an integer of 0 to 3. 1b -OC(=O)-Y 2b - 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.

[0225] As the structural unit (b-3-S), a structural unit represented by the following formula (b-S1-11) or (b-S1-12) is particularly preferred, and a structural unit represented by formula (b-S1-12) is more preferred.

[0226] [ka] (In the formula, R, A', R 10b, z, and R 13b are the same as above.)

[0227] In formula (b-S1-11), A' is preferably a methylene group, an oxygen atom (-O-), or a sulfur atom (-S-).

[0228] R 13b R is preferably a linear or branched alkylene group or a divalent linking group containing an oxygen atom. 13b Examples of the linear or branched alkylene group and the divalent linking group containing an oxygen atom in the formula (I) include the same linear or branched alkylene group and the divalent linking group containing an oxygen atom as those described above, respectively.

[0229] As the constitutional unit represented by formula (b-S1-12), constitutional units represented by the following formula (b-S1-12a) or (b-S1-12b) are particularly preferred.

[0230] [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.)

[0231] [Structural unit (b-3-L)] Examples of the structural unit (b-3-L) include R 11b with a lactone-containing cyclic group, and more specific examples include structural units represented by the following formulas (b-L1) to (b-L5).

[0232] [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 12b 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 is 0 or 1.

[0233] R in the formulae (b-L1) to (b-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.

[0234] 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.

[0235] R 12b is R in the above formula (b-S1). 12b is the same as: In formula (b-L1), s″ is preferably 1 or 2. Specific examples of the structural units represented by the above formulas (b-L1) to (b-L3) are shown below. In each of the following formulas, R α represents a hydrogen atom, a methyl group, or a trifluoromethyl group.

[0236] [ka]

[0237] [ka]

[0238] [ka]

[0239] The structural unit (b-3-L) is preferably at least one selected from the group consisting of structural units represented by the aforementioned formulas (b-L1) to (b-L5), more preferably at least one selected from the group consisting of structural units represented by the aforementioned formulas (b-L1) to (b-L3), and particularly preferably at least one selected from the group consisting of structural units represented by the aforementioned formula (b-L1) or (b-L3). Among these, at least one selected from the group consisting of structural units represented by the aforementioned formulas (b-L1-1), (b-L1-2), (b-L2-1), (b-L2-7), (b-L2-12), (b-L2-14), (b-L3-1), and (b-L3-5) is preferred.

[0240] Furthermore, as the structural unit (b-3-L), structural units represented by the following formulas (b-L6) to (b-L7) are also preferred. [ka] In formulas (b-L6) and (b-L7), R and R 12b is the same as above.

[0241] The acrylic resin (B3) preferably contains structural units represented by the following formulas (b5) to (b7) having an acid-dissociable group as structural units that increase the alkali solubility of the acrylic resin (B3) by the action of an acid. The structural units represented by the following formulas (b5) to (b7) are structural units derived from a (meth)acrylate having an acid-dissociable group.

[0242] [ka]

[0243] In the above formulas (b5) to (b7), R 14b , and R 18b ~R 23beach 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 15b ~R 17b 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 16b and R 17b 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 b 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.

[0244] 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).

[0245] Above R 16b and R 17b When R 15b , R 16b , and R 17bIn 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. 19b , R 20b , R 22b , R 23b is preferably a hydrogen atom or a methyl group.

[0246] Above R 16b and R 17b 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).

[0247] Furthermore, the above R 16b and R 17b 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.

[0248] Above Y bis 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).

[0249] Furthermore, the above Y b 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.

[0250] Also, Y b 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.

[0251] Preferred specific examples of the structural unit represented by the above formula (b5) include those represented by the following formulae (b5-1) to (b5-33).

[0252] [ka]

[0253] In the above formulas (b5-1) to (b5-33), R 24b represents a hydrogen atom or a methyl group.

[0254] Preferred specific examples of the structural unit represented by the above formula (b6) include those represented by the following formulas (b6-1) to (b6-26).

[0255] [ka]

[0256] In the above formulas (b6-1) to (b6-26), R 24b represents a hydrogen atom or a methyl group.

[0257] Preferred specific examples of the structural unit represented by the above formula (b7) include those represented by the following formulas (b7-1) to (b7-15).

[0258] [ka]

[0259] In the above formulas (b7-1) to (b7-15), R 24b represents a hydrogen atom or a methyl group.

[0260] Among the structural units represented by the formulas (b5) to (b7) explained above, the structural unit represented by the formula (b6) is preferred because it is easy to synthesize and relatively easy to achieve high sensitivity. b is an alkyl group, and R 19b and R 20b A structural unit in which one or both of the above are alkyl groups is preferred.

[0261] Furthermore, the acrylic resin (B3) is preferably a resin made of a copolymer containing structural units derived from a polymerizable compound having an ether bond, in addition to the structural units represented by the above formulas (b5) to (b7).

[0262] Examples of the polymerizable compound having an ether bond include radically polymerizable compounds such as (meth)acrylic acid derivatives having an ether bond and an ester bond. Specific examples 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 polymerizable compound having an ether bond is preferably 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, or methoxytriethylene glycol (meth)acrylate. These polymerizable compounds may be used alone or in combination of two or more.

[0263] Furthermore, the acrylic resin (B3) may contain other polymerizable compounds as structural units in order to appropriately control the physical and chemical properties of the resin. Examples of such polymerizable compounds include known radical polymerizable compounds and anion polymerizable compounds.

[0264] 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, butyl (meth)acrylate, and cyclohexyl (meth)acrylate; and (meth)acrylic acid hydroxyalkyl esters such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate. esters; (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.

[0265] As described above, the acrylic resin (B3) 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 (B3) is preferably 20 mol % or less, more preferably 15 mol % or less, and particularly preferably 5 mol % or less. In the acrylic resin (B3), 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.

[0266] Examples of the polymerizable compound include (meth)acrylic acid esters having an acid-non-dissociable aliphatic polycyclic group, vinyl group-containing aromatic compounds, etc. As the acid-non-dissociable aliphatic polycyclic group, tricyclodecanyl, adamantyl, tetracyclododecanyl, isobornyl, norbornyl, etc. 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.

[0267] Specific examples of the (meth)acrylic acid esters having an acid-non-dissociable aliphatic polycyclic group include those having structures of the following formulae (b8-1) to (b8-5).

[0268] [ka]

[0269] In the above formulas (b8-1) to (b8-5), R 25b represents a hydrogen atom or a methyl group.

[0270] The acrylic resin (B3) may contain a structural unit derived from a (meth)acrylic acid derivative having a cyclic carbonate group and an ester bond. An example of the cyclic carbonate group is a group in which one hydrogen atom has been removed from ethylene carbonate. Specific examples of the structural unit derived from a (meth)acrylic acid derivative having a cyclic carbonate group and an ester bond include the following formulae (b9-1) to (b9-4).

[0271] [ka]

[0272] In the above formulas (b9-1) to (b9-4), R b26 represents a hydrogen atom or a methyl group.

[0273] When the acrylic resin (B3) contains a structural unit (b-3) containing an -SO2- containing cyclic group or a lactone-containing cyclic group, the content of the structural unit (b-3) in the acrylic resin (B3) 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 (b-3) in an amount within the above range, it is easy to achieve both good developability and good pattern shape.

[0274] The acrylic resin (B3) 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 (b5) to (b7).

[0275] The acrylic resin (B3) preferably contains a structural unit derived from the polymerizable compound having an ether bond. The content of the structural unit derived from the polymerizable compound having an ether bond in the acrylic resin (B3) is preferably 0 mol % or more and 50 mol % or less, and more preferably 5 mol % or more and 30 mol % or less.

[0276] The acrylic resin (B3) 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 (B3) is preferably 0 mol % or more and 50 mol % or less, and more preferably 5 mol % or more and 30 mol % or less.

[0277] 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 (B3) is preferably from 0 mol % to 50 mol %, more preferably from 5 mol % to 40 mol %.

[0278] As long as the photosensitive composition contains a predetermined amount of acrylic resin (B3), acrylic resins other than the acrylic resin (B3) described above can also be used as resin (B). Such acrylic resins other than acrylic resin (B3) are not particularly limited as long as they contain structural units represented by the above formulas (b5) to (b7).

[0279] The polystyrene-equivalent weight average molecular weight of the resin (B) 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.

[0280] The polydispersity of the resin (B) 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.

[0281] The content of the resin (B) is preferably 5 mol % or more and 99 mol % or less based on the total solid content of the photosensitive composition.

[0282] <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 immersed in a 2.38% by weight aqueous solution of TMAH (tetramethylammonium hydroxide) for 1 minute. This does not fall under the category of resin (B) (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).

[0283] [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.

[0284] 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.

[0285] 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.

[0286] 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.

[0287] [Polyhydroxystyrene resin (D2)] Examples of the hydroxystyrene-based 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.

[0288] 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.

[0289] [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.

[0290] 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.

[0291] 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.

[0292] 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.

[0293] 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.

[0294] <Sulfur-containing compounds (E)> The photosensitive composition contains a sulfur-containing compound (E). The sulfur-containing compound (E) is, for example, a compound containing a sulfur atom capable of coordinating to a metal. The sulfur-containing compound (E) includes a compound represented by the following formula (E1). X e -(-R 1e -SH) ne (E1) (In formula (E1), X e is an aromatic group-containing group with a valence of ne, and R 1e is an alkylene group, and X e and n e is an integer of 2 or more and 4 or less.

[0295] X e The aromatic group contained in the ne-valent aromatic group-containing group as mentioned above may be either an aromatic hydrocarbon group or an aromatic heterocyclic group, but is preferably an aromatic hydrocarbon group. When the aromatic group-containing group contains an aromatic hydrocarbon group, the aromatic hydrocarbon group may be a monocyclic group, a group formed by condensing two or more aromatic hydrocarbon groups, or a group formed by bonding two or more aromatic hydrocarbon groups via a single bond. Examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, a biphenylyl group, and groups obtained by removing one or more hydrogen atoms from these groups. When the aromatic group-containing group contains an aromatic heterocyclic group, the aromatic heterocyclic group may be a monocyclic group or a polycyclic group. Examples of the aromatic heterocyclic group include a pyridyl group, a furyl group, a thienyl group, an imidazolyl group, a pyrazolyl group, an oxazolyl group, a thiazolyl group, an isoxazolyl group, an isothiazolyl group, a benzoxazolyl group, a benzothiazolyl group, and a benzimidazolyl group, as well as groups obtained by removing one or more hydrogen atoms from these groups.

[0296] X e The aromatic group contained in the ne-valent aromatic group-containing group as defined above may have a substituent, such as an alkyl group or a halogen atom. The number of carbon atoms in the alkyl group as a substituent is preferably 1 or more and 10 or less. The alkyl group may be linear or branched. Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an isobutyl group, and a tert-butyl group. Examples of the halogen atom as a substituent include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0297] X e The ne-valent aromatic group-containing group as (I) may be the aromatic group itself which may have the above-mentioned substituent, or may be a group in which two or more aromatic groups which may have the above-mentioned substituent are linked by a linking group. Examples of the linking group include an alkylene group, -O-, -S-, and an ester bond.

[0298] X e The ne-valent aromatic group-containing group as X is preferably an ne-valent aromatic hydrocarbon group which may have a substituent. The substituent and the aromatic hydrocarbon group are the same as those in the case where the aromatic group-containing group contains an aromatic hydrocarbon group, and X e The substituents are the same as the substituents that the aromatic group contained in the ne-valent aromatic group-containing group may have. Examples of the ne-valent aromatic hydrocarbon group as Xe, which may have a substituent, include a phenylene group, a benzenetriyl group, and a benzenetetrayl group, which may have a substituent.

[0299] R e1 Examples of the alkylene group as the alkylene group include alkylene groups having 1 to 4 carbon atoms, and specific examples 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. R e1 The alkylene group as is preferably a methylene group.

[0300] Specific examples of the compound represented by formula (E1) include the following compounds and compounds in which the methylene groups in the following compounds are changed to ethane-1,2-diyl groups, ethane-1,1-diyl groups, propane-1,3-diyl groups, propane-1,2-diyl groups, butane-1,4-diyl groups, butane-1,3-diyl groups, butane-2,3-diyl groups, or butane-1,2-diyl groups. [ka]

[0301] 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 (B) and the alkali-soluble resin (D).

[0302] <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.

[0303] [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.

[0304] 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).

[0305] The nitrogen-containing compound (F1) 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 (B) and the alkali-soluble resin (D).

[0306] [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.

[0307] 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.

[0308] 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 (B) and the alkali-soluble resin (D) described below.

[0309] 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).

[0310] <Organic solvent (S)> The photosensitive composition may or may not contain an organic solvent (S). As the organic solvent (S), various organic solvents that have conventionally been added to various photosensitive compositions can be used.

[0311] 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.

[0312] 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 for thick film applications such that the thickness of the photosensitive layer obtained by a spin coating method or the like is 5 μm or more, it is preferable to use the organic solvent (S) in such a range that the solid content concentration of the photosensitive composition is 20 mass % or more and 70 mass % or less.

[0313] <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.

[0314] 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.

[0315] 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).

[0316] The photosensitive composition may further contain an acid or an acid anhydride in order to finely adjust the solubility in the developer.

[0317] 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.

[0318] The photosensitive composition may further contain a sensitizer to improve sensitivity. The photosensitive composition may further contain a dye or a pigment. The photosensitive composition may further contain a polymerization inhibitor.

[0319] <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.

[0320] <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.

[0321] 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.

[0322] 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.

[0323] 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.

[0324] <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.

[0325] 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.

[0326] 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.

[0327] 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.

[0328] 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.

[0329] 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 (A) to generate an acid.

[0330] 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.

[0331] 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.

[0332] 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.

[0333] 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.

[0334] 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.

[0335] 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.

[0336] <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. Finally, the remaining mold is removed using a stripping solution or the like according to conventional methods.

[0337] 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.

[0338] 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.

[0339] 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. [Example]

[0340] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[0341] In the examples and comparative examples, the following P1 to P4 and RP1 to RP7 were used as the acid generator (A). [ka]

[0342] [ka]

[0343] In the examples and comparative examples, the following resins A1 to A25 (acrylic resin (B3)) and PHS-1 (polyhydroxystyrene resin (B2)) were used as resins (resin (B)) whose solubility in alkali increases under the action of acid. The numbers in the brackets 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 A25 and PHS-1 are as follows. Furthermore, resins A1 to A24 all have a dispersity (Mw / Mn) of 2.8. Resin A25 has a dispersity (Mw / Mn) of 2.0. PHS-1 has a dispersity (Mw / Mn) of 1.0. (Weight average molecular weight (Mw) of resin (B)) Resin A1: 40000 Resin A2:7000 Resin A3: 120,000 Resin A4~A15:40000 Resin A16:7000 Resin A17: 40000 Resin A18: 120000 Resin A19~A24: 40,000 Resin A25:10000 Resin PHS-1:10000

[0344] [ka]

[0345] [ka]

[0346] [ka]

[0347] [ka]

[0348] [ka]

[0349] In the examples and comparative examples, the following resins PHS-2 and N-1 were used as the alkali-soluble resin (D). PHS-2 (polyhydroxystyrene resin (D2)) has a weight-average molecular weight Mw of 2500 and a dispersity (Mw / Mn) of 2.4. N-1 (novolac resin (D1)) has a weight-average molecular weight Mw of 6500 and a dispersity (Mw / Mn) of 5.0. [ka] [ka]

[0350] In the examples and comparative examples, the following T1 to T5 and RT1 to RT6 were used as the sulfur-containing compound (E). [ka] [ka]

[0351] In the examples and comparative examples, the following Q1 to Q4 were 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. Q2: Triamylamine Q3: 2,6-diphenylpyridine Q4: N,N-dibenzylaniline

[0352] [Examples 1 to 50 and Comparative Examples 1 to 13] The resin (B) and alkali-soluble resin (D) of the types and parts by mass shown in Tables 1 to 3, the acid generator (A), the sulfur-containing compound (E), the acid diffusion controller (F), and 0.05 parts by mass of a surfactant (BYK310, manufactured by BYK-Chemie) 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 50 and Comparative Examples 1 to 13.

[0353] The photosensitive compositions obtained in each of the Examples and Comparative Examples were evaluated for rectangularity and footing by the following methods. The results are shown in Tables 1 to 3.

[0354] [Footing 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 prebaked at 140°C for 300 seconds. After prebaking, 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 under a scanning electron microscope, and the footing amount (the amount of overhang of the resist pattern onto the non-resist portion on the substrate surface) was measured for each example and comparative example. Specifically, the footing amount was measured as follows. A schematic diagram of a cross section perpendicular to the surface direction of the resist pattern of the resist and non-resist portions when measuring the footing amount is shown in FIG. 1. In FIG. 1, a resist pattern including a resist portion 12 and a non-resist portion 13 is formed on a substrate 11. First, an inflection point 15 was determined on a sidewall 14, which is the interface between the resist portion 12 and the non-resist portion 13, as the point where footing on the sidewall 14 begins. A perpendicular line 16 was drawn from the inflection point 15 toward the surface of the substrate 11, and the intersection of the perpendicular line 16 and the surface of the substrate 11 was determined as the footing start point 17. The intersection of the curve of the sidewall 14 and the surface of the substrate 11 was determined as the footing end point 18. The width Wf between the footing start point 17 and the footing end point 18 thus determined was defined as the footing amount. The footing amount was a value measured for any one sidewall 14 of any one non-resist portion in the resist pattern. The degree of footing was evaluated based on the obtained footing amount value according to the following criteria. <Fitting evaluation criteria> A: 0μm or more and 0.1μm or less B: Over 0.1 μm and less than 0.5 μm C: 0.5μm or more

[0355] [Rectangularity evaluation] The cross section (cross section perpendicular to the surface direction of the resist pattern) of the resist pattern obtained in the above [Footing Evaluation] was observed using a scanning electron microscope, and the maximum hole width (width of the non-resist portion) CD 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 of is to 0, the better the cross-sectional shape of the hole is rectangular. <Evaluation criteria for rectangularity> A: 0μm or more and 1μm or less B: Over 1 μm and less than 3 μm C: 3μm or more

[0356] [Table 1]

[0357] [Table 2]

[0358] [Table 3]

[0359] Tables 1 to 3 show that a chemically amplified positive-tone photosensitive composition comprising an acid generator (A), a resin (B), and a sulfur-containing compound (E), wherein the acid generator (A) comprises a sulfonium salt composed of a sulfonium cation and an anion represented by formula (A1), and the sulfur-containing compound (E) comprises a compound represented by formula (E1), can form a patterned resist film having a rectangular cross-sectional shape and suppressed footing.

Claims

1. The composition comprises an acid generator (A) that generates an acid when irradiated with actinic rays or radiation, a resin (B) whose solubility in alkali increases under the action of an acid, and a sulfur-containing compound (E), The acid generator (A) is a compound represented by the following formula (A1): Cf-SO ２ -N － -SO ２ -Cf・・・(A1) (In formula (A1), 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.) and an anion represented by the formula: The sulfur-containing compound (E) is represented by the following formula (E1): X ｅ -(-R １ｅ -SH) ｎｅ ・・・(E1) (In formula (E1), X ｅ is an aromatic group-containing group with a valence of ne, and R １ｅ is an alkylene group, and X ｅ and ne is an integer of 2 or more and 4 or less. A chemically amplified positive photosensitive composition comprising a compound represented by the formula:

2. R in the formula (E1) １ｅ 2. The chemically amplified positive photosensitive composition according to claim 1, wherein the alkylene group as represented by the formula (I) is a methylene group.

3. X in the formula (E1) ｅ 2. The chemically amplified positive-working photosensitive composition according to claim 1, wherein the aromatic group-containing group having a valence of ne is an aromatic hydrocarbon group having a valence of ne, which may have a substituent.

4. 4. The chemically amplified positive-working photosensitive composition according to claim 3, wherein the aromatic hydrocarbon group having a valence of ne as Xe in formula (E1) is a phenylene group, a benzenetriyl group, or a benzenetetrayl group, each of which may have a substituent.

5. A photosensitive dry film having a base film and a photosensitive layer formed on the surface of the base film, wherein the photosensitive layer is made of the chemically amplified positive photosensitive composition according to any one of claims 1 to 4.

6. A method for producing a photosensitive dry film, comprising applying the chemically amplified positive photosensitive composition according to any one of claims 1 to 4 onto a substrate film to form a photosensitive layer.

7. a lamination step of laminating a photosensitive layer made of the chemically amplified positive photosensitive composition according to any one of claims 1 to 4 on a substrate; an exposure step of position-selectively irradiating the photosensitive layer with actinic rays or radiation; a developing step of developing the photosensitive layer after exposure.

8. a lamination step of laminating a photosensitive layer made of the chemically amplified positive photosensitive composition according to any one of claims 1 to 4 on a substrate; an exposure step of position-selectively irradiating the photosensitive layer with actinic rays or radiation; and a development step of developing the photosensitive layer after exposure to produce a mold for forming a plated object.

9. A method for producing a plated shaped object, comprising the step of plating the mold-equipped substrate produced by the method for producing a mold-equipped substrate according to claim 8 to form a plated shaped object in the mold.

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