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 having good post-exposure aging stability after exposure, 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: A chemically amplified positive-type photosensitive composition comprising 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, a sulfur-containing compound (E), and an acid diffusion inhibitor (F), wherein the resin (B) comprises an acrylic resin (B3), and the acid generator (A) comprises an acid generator (A1) that generates an acid having a pKa of - 3. 5 or more and less than 0.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 structures such as bumps, metal posts, and Cu rewiring through 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 through a predetermined mask pattern and developed to form a photoresist pattern used as a mold from which portions from which plated structures are to be formed are selectively removed (peeled off). A conductor such as copper is then embedded in these removed portions (non-resist portions) by plating, and the surrounding photoresist pattern is then removed to form plated structures such as bumps, metal posts, and Cu rewiring. For example, a chemically amplified photoresist composition containing an acid generator (A), a resin (B) whose alkali solubility increases under the action of acid, and a specific acid diffusion inhibitor has been disclosed (see Patent Document 1). [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Japanese Patent Publication No. 2022-104198 Summary of the Invention [Problem to be solved by the invention]

[0007] 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. Furthermore, it is also desirable that a photoresist layer formed using a chemically amplified photoresist composition exhibits minimal changes in the dimensions of the resulting resist pattern even when left for a certain period of time after exposure, i.e., excellent post-exposure delay (PED).

[0008] The present invention has been made in view of the above-mentioned problems, and aims to provide a chemically amplified positive-working photosensitive composition that can form a patterned resist film having a rectangular cross-sectional shape and has good stability over time after exposure to light; 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 substrate with a mold 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]

[0009] As a result of extensive research to achieve the above object, the present inventors have found that the above problem 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 the acid, a sulfur-containing compound (E), and an acid diffusion inhibitor (F), wherein the resin (B) comprises an acrylic resin (B3), and the acid generator (A) comprises an acid generator (A1) that generates an acid having a pKa of −3.5 or more and less than 0, and have thereby completed the present invention. Specifically, the present invention provides the following.

[0010] [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 acid, a sulfur-containing compound (E), and an acid diffusion inhibitor (F), the resin (B) contains an acrylic resin (B3), The chemically amplified positive photosensitive composition, wherein the acid generator (A) comprises an acid generator (A1) that generates an acid having a pKa of −3.5 or more and less than 0.

[0011] [2] The acid generator (A1) has a van der Waals volume of 90 Å 3 More than 200Å 3 The chemically amplified positive photosensitive composition according to the above [1], which generates less than 1000 ppm of acid.

[0012] [3] The acid generator (A1) is represented by the following formula (ai): [ka] (In formula (ai), R a01 is a halogen atom, R a02 is an organic group, -OH, -SH or -NH2, n01 is an integer between 1 and 5, n02 is an integer between 0 and 4, If n01 is an integer between 2 and 5, multiple R a01 may be the same or different, If n02 is an integer between 2 and 4, multiple R a02 may be the same or different.) The chemically amplified positive photosensitive composition according to the above [1] or [2], which generates an acid containing an anion represented by the following formula:

[0013] [4] The chemically amplified positive photosensitive composition according to any one of the above [1] to [3], wherein the acid generator (A1) includes a nonionic acid generator having a naphthalimide structure.

[0014] [5] The acrylic resin (B3) is represented by the following formula (b5'): [ka] (In formula (b5'), R 14b’ each independently represents a hydrogen atom or a linear or branched alkyl group having 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, 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. The chemically amplified positive photosensitive composition according to any one of the above [1] to [4], which has a structural unit represented by the following formula:

[0015] [6] The acid generator (A) includes an acid generator (A2) that does not fall under the category of the acid generator (A1), The acid generator (A2) has the following formula (aiii) as an anion moiety: [ka] (In formula (aiii), R a07 , R a08 , R a09 , and R a010 are each independently a hydrocarbon group which may have a substituent or a heterocyclic group which may have a substituent, and R a07 , R a08 , R a09 , and R a010 At least one of the groups is an aromatic hydrocarbon group which may have a substituent. or an anion represented by the following formula (aiv): Cf-SO2-N - -SO2-Cf···(aiv) (In formula (aiv), 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.) The chemically amplified positive photosensitive composition according to any one of the above [1] to [5], wherein the compound is an onium salt containing an anion represented by the following formula:

[0016] [7] The chemically amplified positive photosensitive composition according to any one of the above [1] to [6], further comprising an alkali-soluble resin (D).

[0017] [8] The chemically amplified positive photosensitive composition according to the above [7], wherein the alkali-soluble resin (D) comprises at least one resin selected from the group consisting of a novolak resin (D1), a polyhydroxystyrene resin (D2), and an acrylic resin (D3).

[0018] [9] 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 described in any one of [1] to [8] above.

[0019] A method for producing a photosensitive dry film, comprising applying the chemically amplified positive photosensitive composition according to any one of [1] to [8] above onto a substrate film to form a photosensitive layer.

[0020]

[11] A lamination step of laminating a photosensitive layer made of the chemically amplified positive photosensitive composition described in any one of [1] to [8] above on a substrate; an exposure step of exposing the photosensitive layer to actinic rays or radiation in a position-selective manner; a developing step of developing the photosensitive layer after exposure.

[0021]

[12] A lamination step of laminating a photosensitive layer made of the chemically amplified positive photosensitive composition according to any one of [1] to [8] above on a substrate having a metal surface; an exposure step of exposing the photosensitive layer to actinic rays or radiation in a position-selective manner; and a development step of developing the photosensitive layer after exposure to produce a mold for forming a plated object.

[0022]

[13] A method for producing a plated object, comprising a plating step of plating the mold-equipped substrate produced by the mold-equipped substrate production method described in

[12] above, to form a plated object within the mold. [Effects of the Invention]

[0023] According to the present invention, it is possible to provide a chemically amplified positive-working photosensitive composition that can form a patterned resist film having a rectangular cross-sectional shape and that has good stability over time when left in a storage state after exposure; a photosensitive dry film that has 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 substrate with a mold using the chemically amplified positive-working photosensitive composition; and a method for manufacturing a plated object using the chemically amplified positive-working photosensitive composition. DETAILED DESCRIPTION OF THE INVENTION

[0024] <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 an acid, a sulfur-containing compound (E), and an acid diffusion inhibitor (F). The resin (B) includes an acrylic resin (B3). The acid generator (A) includes an acid generator (A1) that generates an acid having a pKa of −3.5 or more and less than 0. The photosensitive composition may contain components such as an alkali-soluble resin (D) as needed.

[0025] Essential and optional components contained in the photosensitive composition and a method for producing the photosensitive composition will be described below.

[0026] <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) contained in the photosensitive composition includes an acid generator (A1) that generates an acid having a pKa of −3.5 or more and less than 0.

[0027] The photosensitive composition contains, together with the acrylic resin (B3), the acid generator (A1) that generates an acid having a pKa of −3.5 or more and less than 0. As shown in the examples described later, this allows the formation of a patterned resist film having a rectangular cross-sectional shape, and the photosensitive composition has good stability over time after exposure.

[0028] Furthermore, the photosensitive composition can also have good post-coating delay (PCD) by containing, together with the acrylic resin (B3), the acid generator (A1) that generates an acid having a pKa of −3.5 or more and less than 0. Good PCD can reduce changes in the dimensions of the resulting resist pattern even if the photosensitive composition is left for a certain period of time after coating before exposure.

[0029] The pKa of the acid generated by the acid generator (A1) may be from −3.5 to less than 0, preferably from −3.0 to −0.1, and more preferably from −2.5 to −2.0. Here, pKa (acid dissociation constant) is a commonly used index that indicates the acid strength of a substance of interest. Note that pKa in this specification is a value at a temperature condition of 25°C.

[0030] The van der Waals volume of the acid generated by the acid generator (A1) is 90 Å 3 More than 200Å 3 (i.e., the acid generator (A1) has a van der Waals volume of 90 Å or less) 3 More than 200Å3 (generating less than 100 Å of acid) 3 More than 170Å 3 More preferably, it is 110 Å or less. 3 More than 138Å 3 It is even more preferable that:

[0031] The van der Waals volume (VDW volume) is the volume of the region occupied by a van der Waals sphere based on the van der Waals radius. The van der Waals volume (VDW volume) can be calculated using CAChe Worksystem Pro. Version 6.1.12.33 (manufactured by Fujitsu Ltd.). In CAChe Worksystem Pro. Version 6.1.12.33, a structural optimization calculation is performed, and the van der Waals volume is calculated for the obtained stable structure.

[0032] The acid generator (A1) is preferably an acid generator that generates an acid containing an anion represented by the following formula (ai) or the following formula (aii), and particularly preferably an acid generator that generates an acid containing an anion represented by the following formula (ai): [ka] (In formula (ai), R a01 is a halogen atom, R a02 is an organic group, -OH, -SH or -NH2, n01 is an integer between 1 and 5, n02 is an integer between 0 and 4, If n01 is an integer between 2 and 5, multiple R a01 may be the same or different, If n02 is an integer between 2 and 4, multiple R a02 may be the same or different.)

[0033] [ka] (In formula (aii), R a03 is an alkyl group or a fluorinated alkyl group, R a04 is -OH, -SH or -NH2, n03 is an integer between 1 and 5, n04 is an integer between 0 and 4, If n03 is an integer between 2 and 5, multiple R a03 may be the same or different, If n04 is an integer between 2 and 4, multiple R a04 may be the same or different.)

[0034] In the above formula (ai), R a01 Examples of halogen atoms as R include chlorine atoms, bromine atoms, iodine atoms, and fluorine atoms. a01 As the halogen atom for , a fluorine atom is preferred. R a02 The organic group as R has at least one carbon atom. a02Suitable examples of the organic group as the aryl group include an alkoxy group, an alkyl group, and a fluorinated alkyl group. The number of carbon atoms in the alkoxy group is preferably 1 to 18, more preferably 1 to 12, and even more preferably 1 to 8. Specific examples of 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-hexyloxy group, an n-octyloxy group, a 2-ethylhexyloxy group, an n-decyloxy group, an n-dodecyloxy group, and an n-octadecyloxy group. The number of carbon atoms in the alkyl group is preferably 1 to 18, more preferably 1 to 12, and even more preferably 1 to 8. Specific examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, isohexyl, n-octyl, 2-ethylhexyl, n-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl, n-octadecyl, and isooctadecyl. The number of carbon atoms in the fluorinated alkyl group is preferably 1 or more and 18 or less, more preferably 1 or more and 12 or less, and even more preferably 1 or more and 8 or less. Specific examples of the fluorinated alkyl group include the above alkyl groups in which some or all of the hydrogen atoms have been substituted with fluorine atoms. In the above formula (ai), R a01 is a fluorine atom, and n01 is 5 and n02 is 0.

[0035] In the above formula (aii), R a03 The alkyl group and fluorinated alkyl group as R a02 Examples include the same alkyl groups and fluorinated alkyl groups as those mentioned above.

[0036] The acid generator (A1) may be a nonionic acid generator or an onium salt acid generator, and is preferably a nonionic acid generator. Nonionic acid generators suitable as the acid generator (A1) include imide sulfonate-based acid generators and amido sulfonate-based acid generators having a structure represented by >NO-SO2-; oxime sulfonate-based acid generators having a structure represented by >C=NO-SO2-; and diazomethane-based acid generators having a structure represented by -SO2-C(=N2)-SO2-. As the imide sulfonate acid generator, an acid generator having a naphthalimide skeleton (naphthalic acid imide structure) or an acid generator having a phthalimide skeleton is preferred. As the amidosulfonate acid generator, an amidosulfonate compound composed of an N-alkylnaphthalenecarboxylic acid amide or an N-alkylcoumarincarboxylic acid amide and an organic sulfonic acid is preferred. As the oxime sulfonate acid generator, an oxime sulfonate compound in which the following group is bonded to an organic sulfonyloxy group is preferred. [ka] (In the above structure, * represents a bond.) When these acid generators (A1) have a ring in their structure, the ring may be substituted with a substituent such as an alkyl group or an alkoxy group. Among the nonionic acid generators as the acid generator (A1), imide sulfonate acid generators are preferred, and acid generators having a naphthalimide skeleton are more preferred. The nonionic acid generator as the acid generator (A1) having a naphthalimide skeleton has a particularly good PCD.

[0037] Examples of onium salts that can serve as the acid generator (A1) include onium salts containing an anion represented by the above formula (ai) or formula (aii) as the anion moiety. An onium salt containing an anion represented by formula (ai) as the anion moiety generates an acid consisting of an anion represented by formula (ai) and a proton upon irradiation with actinic rays or radiation. An onium salt containing an anion represented by formula (aii) as the anion moiety generates an acid consisting of an anion represented by formula (aii) and a proton upon irradiation with actinic rays or radiation. In the onium salt containing the anion represented by formula (ai) or formula (aii) as the anion moiety, the cation is not particularly limited. Suitable cations include, for example, sulfonium cations and iodonium cations, and sulfonium cations are more preferred. The cation is preferably a sulfonium cation having a structure represented by the following formula (a1): [ka]

[0038] 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. R1a , R 2a , R 3a When is a phenyl group which may have a substituent, preferred substituents include a hydroxyl group, a linear or branched alkoxy group having from 1 to 6 carbon atoms, and a linear or branched alkyl group having from 1 to 6 carbon atoms.

[0039] [ka]

[0040] 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.

[0041] 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.

[0042] 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.

[0043] 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.

[0044] Suitable examples of the sulfonium cation represented by formula (a1) include sulfonium cations represented by the following formulas: [ka]

[0045] In the onium salt containing the anion represented by formula (ai) or formula (aii) as the anion moiety, the cation is preferably a sulfonium cation having a structure represented by the following formula (a4). [ka]

[0046] 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]

[0047] 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.

[0048] 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.

[0049] Suitable examples of the sulfonium cation represented by formula (a4) include sulfonium cations represented by the following formulas: [ka]

[0050] In onium salts containing an anion represented by formula (ai) or formula (aii) as the anion moiety, the cation is preferably an iodonium cation having a structure represented by the following formula (a6). [ka]

[0051] In the above formula (a6), R 8a 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.

[0052] Specific examples of the acid generator (A1) that generates an acid having a pKa of −3.5 or more and less than 0 include the following compounds. [ka] (In the formula, Bu represents an n-butyl group.) [ka] (In the formula, Bu represents an n-butyl group.)

[0053] The acid generator (A1) may be one type or two or more types. When the acid generator (A1) is composed of an anion and a cation, it can be produced by ion exchange using compounds having the constituent anions and cations as raw materials.

[0054] The acid generator (A) may contain only an acid generator (A1) that generates an acid having a pKa of −3.5 or more and less than 0, or may contain, together with the acid generator (A1), an acid generator (A2) that does not fall under the category of the acid generator (A1). When the acid generator (A) contains an acid generator (A2), the ratio of the mass of the acid generator (A1) to the mass of the acid generator (A) is preferably 10% by mass or more and 90% by mass or less, more preferably 20% by mass or more and 80% by mass or less, and even more preferably 30% by mass or more and 70% by mass or less.

[0055] The acid generator (A2) satisfies at least one of the following conditions (a) and (b): (a) The pKa of the acid to be generated is 0 or higher. (b) The pKa of the acid to be generated is less than -3.5. As the acid generator (A2), any photoacid generator that has conventionally been incorporated into various photosensitive compositions can be used without any particular limitation.

[0056] Examples of the acid generator (A2) include onium salts containing, as the anion moiety, an anion represented by the following formula (aiii) or an anion represented by the following formula (aiv). [ka] (In formula (aiii), R a07 , R a08 , R a09 , and Ra010 are each independently a hydrocarbon group which may have a substituent or a heterocyclic group which may have a substituent, and R a07 , R a08 , R a09 , and R a010 At least one of the groups is an aromatic hydrocarbon group which may have a substituent. Cf-SO2-N - -SO2-Cf···(aiv) (In formula (aiv), 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.)

[0057] R in formula (aiii) a07 ~R a010 The number of carbon atoms in the hydrocarbon group or heterocyclic group is not particularly limited, but is preferably 1 or more and 50 or less, more preferably 1 or more and 30 or less, and particularly preferably 1 or more and 20 or less. R a07 ~R a010 Specific examples of the hydrocarbon group as the alkyl group include a linear or branched alkyl group, a linear or branched alkenyl group, a linear or branched alkynyl group, an aromatic hydrocarbon group, an alicyclic hydrocarbon group, and an aralkyl group. As mentioned above, R a07 ~R a010 At least one of R is an aromatic hydrocarbon group which may have a substituent; a07 ~R a010 More preferably, three or more of R are aromatic hydrocarbon groups which may have a substituent, a07 ~R a010 It is particularly preferred that all of the groups are aromatic hydrocarbon groups which may have a substituent.

[0058] R a07 ~R a010Examples of the substituent that the hydrocarbon group or heterocyclic group may have include a halogenated alkyl group having from 1 to 18 carbon atoms, a halogenated aliphatic cyclic group having from 3 to 18 carbon atoms, a nitro group, a hydroxyl group, a cyano group, an alkoxy group having from 1 to 18 carbon atoms, an aryloxy group having from 6 to 14 carbon atoms, an aliphatic acyl group having from 2 to 19 carbon atoms, an aromatic acyl group having from 7 to 15 carbon atoms, an aliphatic acyloxy group having from 2 to 19 carbon atoms, an aromatic acyloxy group having from 7 to 15 carbon atoms, an alkylthio group having from 1 to 18 carbon atoms, an arylthio group having from 6 to 14 carbon atoms, an amino group in which one or two hydrogen atoms bonded to the nitrogen atom may be substituted with a hydrocarbon group having from 1 to 18 carbon atoms, and a halogen atom. R a07 ~R a010 When the hydrocarbon group as the aromatic hydrocarbon group is an aromatic hydrocarbon group, the aromatic hydrocarbon group may be substituted with one or more substituents selected from the group consisting of alkyl groups having from 1 to 18 carbon atoms, alkenyl groups having from 2 to 18 carbon atoms, and alkynyl groups having from 2 to 18 carbon atoms.

[0059] R a07 ~R a010 When the hydrocarbon group has a substituent, the number of the substituents is not particularly limited and may be 1 or more than 2. When the number of the substituents is more than one, the more than one substituents may be the same or different.

[0060] R a07 ~R a010When is an alkyl group, preferred specific examples include straight-chain alkyl groups such as a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an n-octyl 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, an n-octadecyl group, an n-nonadecyl group, and an n-icosyl group; and branched-chain alkyl groups such as an isopropyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an isopentyl group, a neopentyl group, a tert-pentyl group, an isohexyl group, a 2-ethylhexyl group, and a 1,1,3,3-tetramethylbutyl group.

[0061] R a07 ~R a010 When is an alkenyl group or an alkynyl group, preferred examples include alkenyl groups and alkynyl groups corresponding to the above-mentioned groups preferred as the alkyl group.

[0062] R a07 ~R a010 When is an aromatic hydrocarbon group, preferred examples include a phenyl group, an α-naphthyl group, a β-naphthyl group, a biphenyl-4-yl group, a biphenyl-3-yl group, a biphenyl-2-yl group, an anthryl group, and a phenanthryl group.

[0063] R a07 ~R a010 When is an alicyclic hydrocarbon group, preferred examples include cycloalkyl groups such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclopentyl group, a cyclooctyl group, a cyclononyl group, and a cyclodecyl group; and bridged alicyclic hydrocarbon groups such as a norbornyl group, an adamantyl group, a tricyclodecyl group, and a pinanyl group.

[0064] R a07 ~R a010When is an aralkyl group, preferred examples include a benzyl group, a phenethyl group, an α-naphthylmethyl group, a β-naphthylmethyl group, an α-naphthylethyl group, and a β-naphthylethyl group.

[0065] R a07 ~R a010 When is a heterocyclic group, preferred examples thereof include a thienyl group, a furanyl group, a selenophenyl group, a pyranyl group, a pyrrolyl group, an oxazolyl group, a thiazolyl group, a pyridyl group, a pyrimidyl group, a pyrazinyl group, an indolyl group, a benzofuranyl group, a benzothienyl group, a quinolyl group, an isoquinolyl group, a quinoxalinyl group, a quinazolinyl group, a carbazolyl group, an acridinyl group, a phenothiazinyl group, a phenazinyl group, a xanthenyl group, a thianthrenyl group, a phenoxazinyl group, a phenoxathiinyl group, a chromanyl group, an isochromanyl group, a dibenzothienyl group, a xanthonyl group, a thioxanthonyl group, and a dibenzofuranyl group.

[0066] Preferable specific examples of the anion moiety represented by formula (aiii) include: tetrakis(4-nonafluorobiphenyl)boron anion, tetrakis(1-heptafluoronaphthyl)boron anion, tetrakis(pentafluorophenyl)boron anion, tetrakis(3,4,5-trifluorophenyl)boron anion, tetrakis(2-nonaphenylbiphenyl)boron anion, tetrakis(2-heptafluoronaphthyl)boron anion, tetrakis(7-nonafluoroanthryl)boron anion, tetrakis(4'-(methoxy)octafluorobiphenyl)boron anion, tetrakis(2,4,6-tris(trifluoromethyl)phenyl)boron anion, tetrakis(3,5-bis(trifluoromethyl)phenyl)boron anion, tetrakis(2,3-bis(pentafluoroethyl)naphthyl)boron anion, tetrakis(2-isopropoxy-hexafluoronaphthyl)boron anion, tetrakis(9,10-bis(heptafluoropropyl)heptafluoroanthryl)boron anion, tetrakis(9-nonafluorophenanthryl)boron anion, tetrakis(4-[tri(isopropyl)silyl]-tetrafluorophenyl)boron anion, tetrakis(9,10-bis(p-tolyl)-heptafluorophenanthryl)boron anion, tetrakis(4-[dimethyl(t-butyl)silyl]-tetrafluorophenyl)boron anion, monophenyltris(pentafluorophenyl)boron anion, and Examples thereof include monoperfluorobutyltris(pentafluorophenyl)boron anion, and more preferably, the following anions are listed. [ka]

[0067] In formula (aiv), 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 Cfs in formula (aiv) may be the same or different, and are preferably the same.

[0068] Specific examples of the anion represented by formula (aiv) include the following anions. [ka]

[0069] Examples of cations in onium salts containing an anion represented by formula (aiii) or an anion represented by formula (aiv) as the anion moiety include the same cations as the cations in the above-mentioned onium salts containing an anion represented by formula (ai) or formula (aii).

[0070] Specific examples of the acid generator (A2) include the following compounds. [ka] (In the formula, Bu represents an n-butyl group.)

[0071] 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.

[0072] <Resin (B)> Resins (B) whose solubility in alkali increases under the action of an acid include various resins such as novolac resins (B1), styrene-based resins (B2), acrylic resins (B3), etc. The photosensitive composition essentially contains acrylic resin (B3) as the resin (B) whose solubility in alkali increases under the action of an acid. The photosensitive composition may contain a novolak resin (B1) or a styrene-based resin (B2) as the resin (B) whose solubility in alkali increases under the action of an acid. In the novolak resin (B1), at least some of the phenolic hydroxyl groups are protected with acid-dissociable, dissolution-inhibiting groups. The styrene-based resin (B2) contains structural units derived from at least one selected from styrene, hydroxystyrene, and hydroxystyrene in which the phenolic hydroxyl groups are protected with acid-dissociable, dissolution-inhibiting groups. For example, in the styrene-based resin (B2), at least some of the phenolic hydroxyl groups may be protected with acid-dissociable, dissolution-inhibiting groups. The styrene-based resin (B2) may also contain structural units derived from a (meth)acrylate having an acid-dissociable group. The acrylic resin (B3) contains a structural unit derived from a (meth)acrylate having an acid-dissociable group. In this specification, a resin that falls under the category of the styrene-based resin (B2) does not fall under the category of the acrylic resin (B3).

[0073] [Novolac resin (B1)] As the novolac resin (B1), a resin containing a structural unit represented by the following formula (b-11) can be used.

[0074] [ka]

[0075] 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.

[0076] 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.

[0077] [ka]

[0078] 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 7b represents a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms; o represents 0 or 1.

[0079] 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.

[0080] 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.

[0081] [Styrene-based resin (B2)] As the styrene-based resin (B2), a resin containing a structural unit represented by the following formula (b4) can be used: The resin containing a structural unit represented by the following formula (b4) is a resin in which at least some of the phenolic hydroxyl groups are protected with acid-dissociable, dissolution-inhibiting groups.

[0082] [ka]

[0083] 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.

[0084] 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.

[0085] 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.

[0086] Examples of the styrene-based resin (B2) include a resin containing a structural unit derived from at least one selected from styrene, hydroxystyrene, and hydroxystyrene in which the phenolic hydroxyl group is protected with an acid-dissociable, dissolution-inhibiting group, and a structural unit derived from a (meth)acrylate having an acid-dissociable group. The styrene-based resin (B2) may contain a structural unit represented by formula (b4) and a structural unit derived from a (meth)acrylate having an acid-dissociable group. The structural unit derived from a (meth)acrylate having an acid-dissociable group is, for example, a structural unit represented by formulas (b5) to (b7) or formula (b5') described below.

[0087] Furthermore, the styrene-based 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.

[0088] [Acrylic resin (B3)] The acrylic resin (B3) is not particularly limited as long as it contains a structural unit derived from a (meth)acrylate having an acid-dissociable group, and its solubility in alkali increases under the action of an acid, and it is an acrylic resin that has conventionally been incorporated into various photosensitive compositions. In addition, in this specification, "(meth)acrylic" means both "acrylic" and "methacrylic." "(meth)acrylate" means both "acrylate" and "methacrylate."

[0089] The acrylic resin (B3) serving as the resin (B) whose solubility in alkali increases under the action of an acid may have a structural unit derived from a (meth)acrylate having a cyclic ether structure. Examples of the cyclic ether structure include a structure having a tetrahydrofuran ring and a structure having a dioxolane ring.

[0090] Examples of structural units derived from (meth)acrylates having a cyclic ether structure include structural units derived from tetrahydrofurfuryl (meth)acrylate and structural units derived from (2-methyl-2-ethyl-1,3-dioxolan-4-yl)methyl (meth)acrylate.

[0091] When the acrylic resin (B3) has a structural unit derived from a (meth)acrylate having a cyclic ether structure, the content of the structural unit derived from a (meth)acrylate having a cyclic ether structure in the acrylic resin (B3) is not particularly limited, but is preferably from 1% by mass to 30% by mass, and more preferably from 5% by mass to 20% by mass.

[0092] The acrylic resin (B3) serving as the resin (B) whose solubility in alkali increases under the action of an acid may have a structural unit represented by the following formula (b3-1). [ka] (In formula (b3-1), R b01 represents a hydrogen atom or a methyl group, and R b02 represents a single bond or an alkylene group.

[0093] R b02 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 b02 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.

[0094] When the acrylic resin (B3) has a structural unit represented by formula (b3-1), the content of the structural unit represented by formula (b3-1) in the acrylic resin (B3) is not particularly limited, but is preferably from 1% by mass to 50% by mass, and more preferably from 5% by mass to 35% by mass.

[0095] 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.

[0096] (-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.

[0097] 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.

[0098] 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.

[0099] 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.

[0100] 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-.

[0101] 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.

[0102] 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.

[0103] 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.

[0104] 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—).

[0105] 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.

[0106] 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.

[0107] 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.

[0108] 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.

[0109] 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.

[0110] 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.

[0111] 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.

[0112] 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.

[0113] 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.

[0114] 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.

[0115] 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.

[0116] R 10b Examples 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.

[0117] 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.

[0118] [ka]

[0119] [ka]

[0120] 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).

[0121] (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.

[0122] 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.

[0123] 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.

[0124] [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).

[0125] [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.

[0126] In formula (b-S1), R is the same as defined above. R 11b is the same as the -SO2- containing cyclic group listed above. R 12b may be either a single bond or a divalent linking group.

[0127] 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.

[0128] 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.

[0129] 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.

[0130] 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)-].

[0131] 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.

[0132] 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).

[0133] 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.

[0134] 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.

[0135] 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.

[0136] 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).

[0137] 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.

[0138] 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.

[0139] 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.

[0140] 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.

[0141] 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-.

[0142] 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.

[0143] 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.

[0144] 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).

[0145] 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.

[0146] 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).

[0147] 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.

[0148] 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.

[0149] 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.

[0150] 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.

[0151] 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.

[0152] 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.

[0153] 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.

[0154] R 12bAs 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.

[0155] 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.

[0156] 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.

[0157] 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.

[0158] 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.

[0159] 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.

[0160] 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 2b are 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.

[0161] Y 1b As the alkyl group, a linear aliphatic hydrocarbon group is preferable, a linear alkylene group is more preferable, a linear alkylene group having 1 to 5 carbon atoms is more preferable, and a methylene group and an ethylene group are particularly preferable.

[0162] 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.

[0163] 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.

[0164] R 12b As 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.

[0165] R 12b The divalent linking group in is preferably an alkylene group or one containing an ester bond (-C(=O)-O-).

[0166] 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-.

[0167] 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).

[0168] [ka] (Wherein R and R 11b are the same as above, and R 13b is a divalent linking group.

[0169] 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.

[0170] 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-.

[0171] 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.

[0172] 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.

[0173] [ka] (In the formula, R, A', R 10b, z, and R 13b are the same as above.)

[0174] In formula (b-S1-11), A' is preferably a methylene group, an oxygen atom (-O-), or a sulfur atom (-S-).

[0175] 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.

[0176] 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.

[0177] [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.)

[0178] [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).

[0179] [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 represents 0 or 1.

[0180] 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.

[0181] 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.

[0182] 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.

[0183] [ka]

[0184] [ka]

[0185] [ka]

[0186] 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.

[0187] 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.

[0188] The acrylic resin (B3) may also contain 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.

[0189] [ka]

[0190] 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.

[0191] 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).

[0192] 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.

[0193] 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).

[0194] 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.

[0195] 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).

[0196] 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.

[0197] 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.

[0198] The above formula (b5) is preferably a structure represented by the following formula (b5'). [ka] (In formula (b5'), R 14b’ is R in formula (b5). 14b Similar to R 15b’ ~R 17b’are each independently R in formula (b5). 15b ~R 17b represents a linear or branched alkyl group having 1 to 6 carbon atoms, an aliphatic cyclic group having 5 to 20 carbon atoms, or an aromatic hydrocarbon group having 6 to 15 carbon atoms, and 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.

[0199] The above formula (b5 ’ ) in R 16b’ and R 17b’ form an aliphatic cyclic group having 5 to 20 carbon atoms together with the carbon atom to which they are bonded, or R 15b’ ~R 17b’ are each independently a linear or branched alkyl group having 1 to 6 carbon atoms (i.e., the formula (b5 ’ ) is a structural unit derived from a tertiary alkyl ester, and R 16b’ and R 17b’ More preferably, R forms an aliphatic cyclic group having 5 to 20 carbon atoms together with the carbon atom to which they are bonded. 16b’ and R 17b’ The PED is particularly good because the compound has a structural unit represented by formula (b5') in which the two groups form an aliphatic cyclic group having 5 to 20 carbon atoms together with the carbon atom to which they are bonded.

[0200] 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).

[0201] [ka]

[0202] In the above formulas (b5-1) to (b5-33), R 24b represents a hydrogen atom or a methyl group.

[0203] 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).

[0204] [ka]

[0205] In the above formulas (b6-1) to (b6-26), R 24b represents a hydrogen atom or a methyl group.

[0206] 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).

[0207] [ka]

[0208] In the above formulas (b7-1) to (b7-15), R 24b represents a hydrogen atom or a methyl group.

[0209] Of the constitutional units represented by formulas (b5) to (b7) explained above, the constitutional unit represented by formula (b5) is preferred.

[0210] 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 that is not a cyclic ether structure.

[0211] Examples of the polymerizable compound having an ether bond that is not a cyclic ether structure include radically polymerizable compounds such as (meth)acrylic acid derivatives having an ether bond and an ester bond that are not a cyclic ether structure. 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, and methoxypolypropylene glycol (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.

[0212] 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.

[0213] 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.

[0214] 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% by mass or less, and more preferably 15% by mass 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.

[0215] 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.

[0216] 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).

[0217] [ka]

[0218] In the above formulas (b8-1) to (b8-5), R 25b represents a hydrogen atom or a methyl group.

[0219] 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).

[0220] [ka]

[0221] In the above formulas (b9-1) to (b9-4), R b26 represents a hydrogen atom or a methyl group.

[0222] 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% by mass or more, more preferably 10% by mass or more, particularly preferably 10% by mass or more to 50% by mass or less, and most preferably 10% by mass or more to 30% by mass or less. 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.

[0223] Furthermore, when the acrylic resin (B3) contains structural units represented by the aforementioned formulas (b5) to (b7), the acrylic resin (B3) preferably contains 5% by mass or more of the structural units represented by the aforementioned formulas (b5) to (b7), more preferably 10% by mass or more, and particularly preferably 10% by mass or more to 60% by mass or less.

[0224] When the acrylic resin (B3) contains the above-mentioned structural units derived from a polymerizable compound having an ether bond that does not have a cyclic ether structure, the content of the structural units derived from a polymerizable compound having an ether bond that does not have a cyclic ether structure in the acrylic resin (B3) is preferably from 1% by mass to 50% by mass, and more preferably from 5% by mass to 40% by mass.

[0225] When the acrylic resin (B3) contains the structural units derived from a (meth)acrylic acid ester having the above-mentioned acid-non-dissociable aliphatic polycyclic group, the content of the structural units derived from a (meth)acrylic acid ester having an acid-non-dissociable aliphatic polycyclic group in the acrylic resin (B3) is preferably from 1% by mass to 60% by mass, more preferably from 5% by mass to 50% by mass.

[0226] 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 1 to 50% by mass, more preferably from 5 to 40% by mass.

[0227] 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.

[0228] 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.

[0229] The content of the resin (B) is preferably 5% by mass or more and 99% by mass or less based on the total solid content of the photosensitive composition.

[0230] <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).

[0231] [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.

[0232] 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.

[0233] 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.

[0234] 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.

[0235] [Polyhydroxystyrene resin (D2)] Examples of the hydroxystyrene compound constituting the polyhydroxystyrene resin (D2) include p-hydroxystyrene, α-methylhydroxystyrene, and α-ethylhydroxystyrene. Furthermore, the polyhydroxystyrene resin (D2) is preferably a copolymer with a styrene resin. Examples of styrene-based compounds constituting such styrene resins include styrene, chlorostyrene, chloromethylstyrene, vinyltoluene, and α-methylstyrene.

[0236] 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.

[0237] [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.

[0238] 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.

[0239] 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.

[0240] 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.

[0241] 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.

[0242] <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 that can be coordinated to a metal. Regarding a compound that can produce two or more tautomers, if at least one tautomer contains a sulfur atom that can be coordinated to a metal that constitutes the surface of a metal substrate, the compound falls under the category of a sulfur-containing compound.

[0243] As the sulfur-containing compound, for example, compounds containing a mercapto group (-SH), a thiocarboxy group (-CO-SH), a dithiocarboxy group (-CS-SH), a thiocarbonyl group (-CS-), and the like are preferable. The sulfur-containing compound preferably has a mercapto group, since this facilitates coordination with metals and provides an excellent effect of suppressing footing.

[0244] A preferred example of the sulfur-containing compound having a mercapto group is a compound represented by the following formula (e1). [ka] (In the formula, R e1 and R e2 each independently represents a hydrogen atom or an alkyl group, and R e3 represents a single bond or an alkylene group, and R e4 represents a u-valent aliphatic group which may contain atoms other than carbon, and u represents an integer of 2 or more and 4 or less.

[0245] R e1 and R e2 When R is an alkyl group, the alkyl group may be linear or branched, and is preferably linear. e1 and R e2 When R is an alkyl group, the number of carbon atoms in the alkyl group is not particularly limited as long as it does not impair the object of the present invention. The number of carbon atoms in the alkyl group is preferably 1 or more and 4 or less, more preferably 1 or 2, and most preferably 1. e1 and R e2 As a combination of the above, one is preferably a hydrogen atom and the other is an alkyl group, and particularly preferably one is a hydrogen atom and the other is a methyl group.

[0246] R e3 When R is an alkylene group, the alkylene group may be linear or branched, and is preferably linear. e3 When is an alkylene group, the number of carbon atoms of the alkylene group is not particularly limited as long as it does not impair the object of the present invention. The number of carbon atoms of the alkylene group is preferably 1 to 10, more preferably 1 to 5, particularly preferably 1 or 2, and most preferably 1.

[0247] R e4 R is a divalent to tetravalent aliphatic group which may contain atoms other than carbon. e4Examples of atoms other than carbon that may be contained in R include a nitrogen atom, an oxygen atom, a sulfur atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. e4 The structure of the aliphatic group may be linear, branched, or cyclic, or may be a combination of these structures.

[0248] Among the compounds represented by formula (e1), the compound represented by the following formula (e2) is more preferred. [ka] (In formula (e2), R e4 and u are the same as in formula (e1).

[0249] Among the compounds represented by the above formula (e2), the following compounds are preferred. [ka]

[0250] Compounds represented by the following formulae (e3-L1) to (e3-L7) are also preferred examples of the sulfur-containing compound having a mercapto group. [ka] (In formulas (e3-L1) to (e3-L7), R', s", A", and r are the same as those in formulas (b-L1) to (b-L7) described above for the acrylic resin (B3).)

[0251] Specific preferred examples of the mercapto compounds represented by the above formulae (e3-L1) to (e3-L7) include the following compounds. [ka]

[0252] Compounds represented by the following formulae (e3-1) to (e3-4) are also preferred examples of the sulfur-containing compound having a mercapto group. [ka] (The definitions of the abbreviations in formulas (e3-1) to (e3-4) are as described above for the acrylic resin (B3) and for formulas (3-1) to (3-4).)

[0253] Specific preferred examples of the mercapto compounds represented by the above formulae (e3-1) to (e3-4) include the following compounds.

[0254] [ka]

[0255] Furthermore, a suitable example of the compound having a mercapto group is a compound represented by the following formula (e4). [ka] (In formula (e4), R e5 is a group selected from the group consisting of a hydroxyl group, an alkyl group having from 1 to 4 carbon atoms, an alkoxy group having from 1 to 4 carbon atoms, an alkylthio group having from 1 to 4 carbon atoms, a hydroxyalkyl group having from 1 to 4 carbon atoms, a mercaptoalkyl group having from 1 to 4 carbon atoms, a halogenated alkyl group having from 1 to 4 carbon atoms, and a halogen atom; n1 is an integer of from 0 to 3, and n0 is an integer of from 0 to 3; when n1 is 2 or 3, R e5 may be the same or different.)

[0256] R e5 Specific examples of when is an alkyl group having from 1 to 4 carbon atoms which may have a hydroxyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group. Among these alkyl groups, a methyl group, a hydroxymethyl group, and an ethyl group are preferred.

[0257] R e5Specific examples of when is an alkoxy group having from 1 to 4 carbon atoms include a methoxy group, an ethoxy group, an n-propyloxy group, an isopropyloxy group, an n-butyloxy group, an isobutyloxy group, a sec-butyloxy group, and a tert-butyloxy group. Among these alkoxy groups, a methoxy group and an ethoxy group are preferred, and a methoxy group is more preferred.

[0258] R e5 Specific examples of when is an alkylthio group having from 1 to 4 carbon atoms include a methylthio group, an ethylthio group, an n-propylthio group, an isopropylthio group, an n-butylthio group, an isobutylthio group, a sec-butylthio group, and a tert-butylthio group. Among these alkylthio groups, a methylthio group and an ethylthio group are preferred, and a methylthio group is more preferred.

[0259] R e5 Specific examples of when is a hydroxyalkyl group having from 1 to 4 carbon atoms include a hydroxymethyl group, a 2-hydroxyethyl group, a 1-hydroxyethyl group, a 3-hydroxy-n-propyl group, and a 4-hydroxy-n-butyl group. Among these hydroxyalkyl groups, a hydroxymethyl group, a 2-hydroxyethyl group, and a 1-hydroxyethyl group are preferred, and a hydroxymethyl group is more preferred.

[0260] R e5 Specific examples of when is a mercaptoalkyl group having from 1 to 4 carbon atoms include a mercaptomethyl group, a 2-mercaptoethyl group, a 1-mercaptoethyl group, a 3-mercapto-n-propyl group, and a 4-mercapto-n-butyl group. Among these mercaptoalkyl groups, a mercaptomethyl group, a 2-mercaptoethyl group, and a 1-mercaptoethyl group are preferred, and a mercaptomethyl group is more preferred.

[0261] R e5 When R is a halogenated alkyl group having 1 to 4 carbon atoms, examples of the halogen atom contained in the halogenated alkyl group include fluorine, chlorine, bromine, and iodine.e5 Specific examples of when is a halogenated alkyl group having 1 to 4 carbon atoms include a chloromethyl group, a bromomethyl group, an iodomethyl group, a fluoromethyl group, a dichloromethyl group, a dibromomethyl group, a difluoromethyl group, a trichloromethyl group, a tribromomethyl group, a trifluoromethyl group, a 2-chloroethyl group, a 2-bromoethyl group, a 2-fluoroethyl group, a 1,2-dichloroethyl group, a 2,2-difluoroethyl group, a 1-chloro-2-fluoroethyl group, a 3-chloro-n-propyl group, a 3-bromo-n-propyl group, a 3-fluoro-n-propyl group, and a 4-chloro-n-butyl group. Among these halogenated alkyl groups, a chloromethyl group, a bromomethyl group, an iodomethyl group, a fluoromethyl group, a dichloromethyl group, a dibromomethyl group, a difluoromethyl group, a trichloromethyl group, a tribromomethyl group, and a trifluoromethyl group are preferred, and a chloromethyl group, a dichloromethyl group, a trichloromethyl group, and a trifluoromethyl group are more preferred.

[0262] R e5 When is a halogen atom, specific examples include fluorine, chlorine, bromine, and iodine.

[0263] In formula (e4), n1 is an integer of 0 to 3, and more preferably 1. When n1 is 2 or 3, a plurality of R e5 may be the same or different.

[0264] In the compound represented by formula (e4), R on the benzene ring e5 The substitution position of R on the benzene ring is not particularly limited. e5 The substitution position is -(CH2) n0 It is preferably in the meta or para position relative to the bonding position of --SH.

[0265] The compound represented by formula (e4) includes R e5 As R, a compound having at least one group selected from the group consisting of an alkyl group, a hydroxyalkyl group, and a mercaptoalkyl group is preferred. e5More preferred is a compound having one group selected from the group consisting of an alkyl group, a hydroxyalkyl group, and a mercaptoalkyl group as R e5 When the alkyl group has one group selected from the group consisting of an alkyl group, a hydroxyalkyl group, and a mercaptoalkyl group, the substitution position of the alkyl group, the hydroxyalkyl group, or the mercaptoalkyl group on the benzene ring is -(CH2) n0 The position is preferably meta or para relative to the bonding position of --SH, and more preferably para.

[0266] In formula (e4), n0 is an integer of 0 to 3. In terms of ease of preparation and availability of the compound, n0 is preferably 0 or 1, and more preferably 0.

[0267] Specific examples of the compound represented by formula (e4) include p-mercaptophenol, p-thiocresol, m-thiocresol, 4-(methylthio)benzenethiol, 4-methoxybenzenethiol, 3-methoxybenzenethiol, 4-ethoxybenzenethiol, 4-isopropyloxybenzenethiol, 4-tert-butoxybenzenethiol, 3,4-dimethoxybenzenethiol, 3,4,5-trimethoxybenzenethiol, 4-ethylbenzenethiol, 4-isopropylbenzenethiol, 4-n-butylbenzenethiol, 4 -tert-butylbenzenethiol, 3-ethylbenzenethiol, 3-isopropylbenzenethiol, 3-n-butylbenzenethiol, 3-tert-butylbenzenethiol, 3,5-dimethylbenzenethiol, 3,4-dimethylbenzenethiol, 3-tert-butyl-4-methylbenzenethiol, 3-tert-4-methylbenzenethiol, 3-tert-butyl-5-methylbenzenethiol, 4-tert-butyl-3-methylbenzenethiol, 4-mercaptobenzyl alcohol, 3-mercaptobenzyl alcohol phenol, 4-(mercaptomethyl)phenol, 3-(mercaptomethyl)phenol, 1,4-di(mercaptomethyl)phenol, 1,3-di(mercaptomethyl)phenol, 4-fluorobenzenethiol, 3-fluorobenzenethiol, 4-chlorobenzenethiol, 3-chlorobenzenethiol, 4-bromobenzenethiol, 4-iodobenzenethiol, 3-bromobenzenethiol, 3,4-dichlorobenzenethiol, 3,5-dichlorobenzenethiol, 3,4-difluorobenzenethiol, 3,5-difluorobenzene Examples of the thiol include 4-mercaptocatechol, 2,6-di-tert-butyl-4-mercaptophenol, 3,5-di-tert-butyl-4-methoxybenzenethiol, 4-bromo-3-methylbenzenethiol, 4-(trifluoromethyl)benzenethiol, 3-(trifluoromethyl)benzenethiol, 3,5-bis(trifluoromethyl)benzenethiol, 4-methylthiobenzenethiol, 4-ethylthiobenzenethiol, 4-n-butylthiobenzenethiol, and 4-tert-butylthiobenzenethiol.

[0268] Examples of the sulfur-containing compound having a mercapto group include a compound containing a nitrogen-containing aromatic heterocycle substituted with a mercapto group, and a tautomer of a compound containing a nitrogen-containing aromatic heterocycle substituted with a mercapto group. Specific preferred examples of the nitrogen-containing aromatic heterocycle include imidazole, pyrazole, 1,2,3-triazole, 1,2,4-triazole, oxazole, thiazole, pyridine, pyrimidine, pyridazine, pyrazine, 1,2,3-triazine, 1,2,4-triazine, 1,3,5-triazine, indole, indazole, benzimidazole, benzoxazole, benzothiazole, 1H-benzotriazole, quinoline, isoquinoline, cinnoline, phthalazine, quinazoline, quinoxaline, and 1,8-naphthyridine, with 1,2,4-triazole being particularly preferred.

[0269] Specific examples of nitrogen-containing heterocyclic compounds suitable as sulfur-containing compounds and tautomers of nitrogen-containing heterocyclic compounds include the following compounds. [ka]

[0270] Examples of the sulfur-containing compound having a mercapto group include the compound represented by the following formula (e5). [ka] (In formula (e5), R e6 are each independently a hydrogen atom, a hydrocarbon group, or an acid-dissociable group, R e7 , and R e11 are each independently a hydrogen atom or an alkyl group, or R e7 and R e11 and may be bonded to each other to form a divalent group selected from the group consisting of -O-, -S-, -CH2-, and -C(CH3)2-, R e8 , R e9 , R e10 , R e12are each independently a hydrogen atom or a mercapto group, R e13 is a hydrogen atom, a hydrocarbon group, or an acid-dissociable group, R e6 , and e13 at least one of is a hydrogen atom or an acid-dissociable group, R e8 , R e9 , R e10 , and R e12 At least one of the groups is a mercapto group.

[0271] In equation (e5), R e6 is a hydrocarbon group, R e6 As the alkyl group, a hydrocarbon group having 1 to 20 carbon atoms is preferred, a saturated aliphatic hydrocarbon group having 1 to 20 carbon atoms or an aromatic hydrocarbon group having 6 to 20 carbon atoms is more preferred, a saturated aliphatic hydrocarbon group having 1 to 20 carbon atoms is even more preferred, a saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms is particularly preferred, and a saturated aliphatic hydrocarbon group having 1 to 6 carbon atoms is most preferred. R e6 When is a saturated aliphatic hydrocarbon group, the saturated aliphatic hydrocarbon group may be linear or branched, and is preferably linear.

[0272] R e6 When is an aromatic hydrocarbon group, specific preferred examples of the aromatic hydrocarbon group include a phenyl group, a naphthalene-1-yl group, a naphthalene-2-yl group, a 4-phenylphenyl group, a 3-phenylphenyl group, and a 2-phenylphenyl group. Of these, a phenyl group is preferred.

[0273] R e6 When R is a saturated aliphatic hydrocarbon group, the saturated aliphatic hydrocarbon group is preferably an alkyl group, since the compound represented by formula (e5) can be easily synthesized and obtained. e6Regarding the above, 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, an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, and an n-decyl group. Of these, methyl, ethyl, n-propyl, and isopropyl groups are preferred, and methyl and ethyl groups are more preferred.

[0274] In equation (e5), R e6 When is an acid-dissociable group, the acid-dissociable group may be the same as the acid-dissociable, dissolution-inhibiting group described for resin (B). R e6 Suitable examples of the acid-dissociable group as include groups of the following formulae: [ka]

[0275] In formula (e5), R e13 The hydrocarbon group or acid-dissociable group as R e6 This is similar to the hydrocarbon group and acid-dissociable group in the above.

[0276] Specific preferred examples of the compound represented by the above formula (e5) include the following compounds. [ka]

[0277] [ka]

[0278] Among the sulfur-containing compounds (E), compounds in which a mercapto group is directly bonded to a cyclic group are preferred, compounds in which a mercapto group is directly bonded to an aromatic ring are more preferred, and compounds in which a mercapto group is directly bonded to a nitrogen-containing heterocycle are particularly preferred, in that they can form a patterned resist film having a rectangular cross-sectional shape.

[0279] 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).

[0280] <Acid diffusion controller (F)> The photosensitive composition contains 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.

[0281] [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'-diaminodiphenylether, 4,4'-diaminobenzophenone, 4,4'-diaminodiphenylamine, formamide, N-methylformamide, N,N-dimethylformamide, acetamide, N-methylacetamide, N,N-dimethylacetamide, Examples of suitable amines include 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, pyridine, triamylamine, diphenylpyridine, N,N-dibenzylaniline, 4-hydroxypiperidine, diisopropylaniline, N-Boc-4-hydroxypiperidine, and N-Boc-pyrrolidine. These may be used alone or in combination of two or more.

[0282] 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).

[0283] The nitrogen-containing compound (F1) is preferably used in an amount of 0.001 to 5 parts by mass, particularly preferably 0.01 to 3 parts by mass, per 100 parts by mass of the total mass of the resin (B) and the alkali-soluble resin (D).

[0284] [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.

[0285] 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.

[0286] 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.

[0287] 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).

[0288] <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.

[0289] 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.

[0290] 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.

[0291] <Other ingredients>

[0292] The photosensitive composition may or may not contain a Lewis acid compound. When the photosensitive composition contains a Lewis acid compound, a photosensitive composition with high sensitivity is easily obtained.

[0293] Here, the term "Lewis acidic compound" means "a compound that has an empty orbital that can accept at least one electron pair and acts as an electron pair acceptor." The Lewis acid compound is not particularly limited as long as it meets the above definition and is recognized as a Lewis acid compound by those skilled in the art. As the Lewis acid compound, a compound that does not fall under the category of a Bronsted acid (protonic acid) is preferably used. Specific examples of Lewis acidic compounds include boron fluoride, boron fluoride ether complexes (e.g., BF3·Et2O, BF3·Me2O, BF3·THF, etc., where Et is an ethyl group, Me is a methyl group, and THF is tetrahydrofuran), organic boron compounds (e.g., tri-n-octyl borate, tri-n-butyl borate, triphenyl borate, and triphenylboron, etc.), titanium chloride, aluminum chloride, aluminum bromide, and gallium chloride. Examples of the inorganic fluoride include ammonium chloride, gallium bromide, indium chloride, thallium trifluoroacetate, tin chloride, zinc chloride, zinc bromide, zinc iodide, zinc trifluoromethanesulfonate, zinc acetate, zinc nitrate, zinc tetrafluoroborate, manganese chloride, manganese bromide, nickel chloride, nickel bromide, nickel cyanide, nickel acetylacetonate, cadmium chloride, cadmium bromide, stannous chloride, stannous bromide, stannous sulfate, and stannous tartrate.

[0294] When the photosensitive composition contains a Lewis acid compound, the Lewis acid compound is preferably used in an amount of 0.01 to 5 parts by mass, more preferably 0.01 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.

[0295] 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.

[0296] 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.

[0297] 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).

[0298] The photosensitive composition may further contain an acid or an acid anhydride in order to finely adjust the solubility in the developer.

[0299] 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.

[0300] 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.

[0301] <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.

[0302] <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.

[0303] 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.

[0304] 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.

[0305] 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.

[0306] <Method for producing patterned resist film and method for producing substrate with mold> There is no particular limitation 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 having a rectangular cross-sectional shape, and therefore, by using such a patterned resist film as a mold, a plated object having a rectangular cross-sectional shape can be formed. 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.

[0307] 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.

[0308] 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 thickness. The 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 30 μm.

[0309] 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 (PAB). 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. The photosensitive composition described above has good post-coating shelf stability (PCD), which means that even if a long time (e.g., 24 hours or more) passes between coating, pre-baking (PAB), and exposure, the resulting resist pattern exhibits minimal changes in dimensions, etc.

[0310] 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.

[0311] 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.

[0312] 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. The photosensitive composition described above has good post-exposure shelf stability (PED), and therefore, even if a long time (e.g., 12 hours or more) passes after exposure and before post-exposure bake (PEB), there is little change in the dimensions of the resulting resist pattern.

[0313] 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.

[0314] 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.

[0315] 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.

[0316] 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.

[0317] 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.

[0318] <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.

[0319] 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.

[0320] 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.

[0321] 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]

[0322] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[0323] In the examples and comparative examples, the following P1 to P7 (acid generators (A1)) and RP1 to RP7 were used as the acid generator (A). The van der Waals volumes and pKa of the acids generated by P1 to P7 and RP1 to RP7 are shown in Tables 1 to 10. The van der Waals volumes of the acids generated by P1 to P7 and RP1 to RP7 were calculated using the above-mentioned CAChe Worksystem Pro. Version 6.1.12.33 for the acids generated from each photoacid generator. [ka]

[0324] [ka] (In the formula, Bu represents an n-butyl group.)

[0325] In the examples and comparative examples, the following resins A1 to A41 (acrylic resin (B3)) and H1 to H11 (styrene-based resin (B2)) were used as resins (resin (B)) whose solubility in alkali increases under the action of acid. The numbers in parentheses to the right of each structural unit in the following structural formulas indicate the content (mass%) of the structural unit in the resin. The weight-average molecular weights (Mw) of resins A1 to A41 and H1 to H11 are as follows. Furthermore, resins A1 to A41 all have a dispersity (Mw / Mn) of 2.8. H1, H2, H10, and H11 have a dispersity (Mw / Mn) of 2.0. H3 to H9 have a dispersity (Mw / Mn) of 1.0. (Weight average molecular weight (Mw) of resin (B)) Resin A1~A28, A31~A33, A36~A38, A41:40000 Resin A29, A34, A39:100000 Resin A30, A35, A40: 200,000 Resin H1~H4, H6~H11:10000 Resin H5:20000

[0326] [ka]

[0327] [ka]

[0328] [ka]

[0329] [ka]

[0330] [ka]

[0331] [ka]

[0332] [ka]

[0333] In the examples and comparative examples, the following resins H12 to H14 and N1 to N3 were used as the alkali-soluble resin (D). H12 and H13 (polyhydroxystyrene resin (D2)) had a weight-average molecular weight Mw of 2500, H14 (polyhydroxystyrene resin (D2)) had a weight-average molecular weight Mw of 8000, and H12 to H14 had a dispersity (Mw / Mn) of 1.0. N1 (novolac resin (D1)) had a weight-average molecular weight Mw of 6500, N2 (novolac resin (D1)) had a weight-average molecular weight Mw of 20000, and N3 (novolac resin (D1)) had a weight-average molecular weight Mw of 10000, and N1 to N3 had a dispersity (Mw / Mn) of 5.0. [ka] [ka]

[0334] In the examples and comparative examples, the following T1 to T8 were used as the sulfur-containing compound (E). [ka]

[0335] In the examples and comparative examples, the following Q1 to Q8 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. [ka]

[0336] In the examples and comparative examples, the following S1 and S2 were used as the organic solvent (S). S1: A mixed solvent of 3-methoxybutyl acetate (MA) and propylene glycol monomethyl ether acetate (PGMEA) (MA / PGMEA = 6 / 4 (volume ratio)) S2: Propylene glycol monomethyl ether acetate (PGMEA)

[0337] [Examples 1 to 90 and Comparative Examples 1 to 15] The resin (B) and alkali-soluble resin (D), the acid generator (A), the sulfur-containing compound (E), the acid diffusion controller (F), 0.05 parts by mass of a surfactant (BYK310, manufactured by BYK-Chemie), and 0.05 parts by mass of tri-n-octyl borate, each of the types and parts by mass shown in Tables 1 to 10, were dissolved in the organic solvent (S) of the type shown in Tables 1 to 10 so that the solid content was 35% by mass in Examples where the film thickness shown in the tables was 5 μm, so that the solid content was 38% by mass in Examples and Comparative Examples where the film thickness shown in the tables was 10 μm, and so that the solid content was 48% by mass in Examples where the film thickness shown in the tables was 30 μm, to obtain photosensitive compositions of Examples 1 to 90 and Comparative Examples 1 to 15.

[0338] The photosensitive compositions obtained in each Example and Comparative Example were evaluated for rectangularity, PED (post-exposure storage stability over time), and PCD (post-coating storage stability over time) by the following methods. The results are shown in Tables 1 to 10.

[0339] [Rectangularity evaluation] The photosensitive compositions of the Examples and Comparative Examples were applied to an 8-inch diameter silicon wafer (copper substrate) on the surface of which a copper sputtered film was formed, to form a photosensitive layer with a film thickness (5 μm, 10 μm, or 30 μm) as shown in Tables 1 to 10. The photosensitive layer was then prebaked (PAB) at 135°C for 300 seconds. After prebaking, the layer was subjected to pattern exposure with i-line light using a mask with a line and space pattern having a line width of 5 μm and a space width of 5 μm and an exposure system FPA-5510iV (Canon Inc.) (NA 0.18). The exposure dose was determined by measuring the line width (CD) at the middle of the thickness direction of the substrate at the cross section of the resist pattern (cross section perpendicular to the surface direction of the resist pattern). middle The exposure dose was set to give a thickness of 5 μm. Next, the substrate was placed on a hot plate and subjected to post-exposure baking (PEB) at 95°C for 180 seconds. Thereafter, a 2.38 wt% aqueous solution of tetramethylammonium hydroxide (TMAH) (developer, NMD-3, manufactured by Tokyo Ohka Kogyo Co., Ltd.) was dropped onto the exposed photosensitive layer, followed by leaving the layer at 23°C. This operation was repeatedly carried out. In Examples and Comparative Examples in which the film thickness shown in the table was 5 μm or 10 μm, the leaving time was 30 seconds, and the number of repetitions was three. In Examples in which the film thickness shown in the table was 30 μm, the leaving time was 60 seconds, and the number of repetitions was four. The resist pattern surface was then washed with running water, followed by nitrogen blowing to obtain a resist pattern. The cross-section of the resist pattern (cross-section perpendicular to the surface direction of the resist pattern) was observed using a scanning electron microscope, and the maximum line 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 minThe closer the value of is to 0, the more it means that the cross-sectional shape of the line is a good rectangle. <Evaluation Criteria for Rectangularity> A: 0 μm or more and less than 0.1 μm B: 0.1 μm or more and less than 0.3 μm C: 0.3 μm or more and less than 0.5 μm D: 0.5 μm or more and less than 1.0 μm E: 1.0 μm or more

[0340] [Evaluation of PCD] A resist pattern (line and space pattern) was formed in the same manner as in the above [Evaluation of Rectangularity]. At this time, the time from after pre-baking (PAB) until exposure was set to 0 hours (exposure immediately after PAB), 24 hours, or 48 hours, and resist patterns were formed respectively. The ratio (CD (Critical Dimension) fluctuation rate) of the average value of the top line width (line width) of the resist pattern obtained when exposure was performed immediately after PAB to the average value of the top line width (line width) of the resist pattern obtained when the time from after PAB until exposure was 24 hours or 48 hours was determined, and PCD was evaluated according to the following criteria. <Evaluation Criteria for PCD> A: In both cases where the time until exposure is 48 hours and 24 hours, the CD fluctuation rate is within 10%. B: When the time until exposure is 24 hours, the CD fluctuation rate is within 10%, but when it is 48 hours, the CD fluctuation rate is greater than 10%. E: In both cases where the time until exposure is 48 hours and 24 hours, the CD fluctuation rate is greater than 10%.

[0341] [Evaluation of PED] A resist pattern (line and space pattern) was formed in the same manner as the above [Evaluation of Rectangularity]. At this time, after pattern exposure, the time until post-exposure bake (PEB) was performed was set to 0 hours (PEB immediately after pattern exposure), 12 hours, or 18 hours, and resist patterns were formed respectively. The ratio (CD (Critical Dimension) variation rate) of the average value of the top line width (line width) of the resist pattern obtained when PEB was performed immediately after pattern exposure to the average value of the top line width (line width) of the resist pattern obtained when the time until PEB was performed was 12 hours or 18 hours after pattern exposure was determined, and PED was evaluated according to the following criteria. <Evaluation Criteria for PED> A: In both cases where the time until PEB is performed is 18 hours and 12 hours, the CD variation rate is within 10%. B: When the time until PEB is performed is 12 hours, the CD variation rate is within 10%, but when it is 18 hours, the CD variation rate is greater than 10%. E: In both cases where the time until PEB is performed is 18 hours and 12 hours, the CD variation rate is greater than 10%.

[0342]

Table 1

[0343]

Table 2

[0344]

Table 3

[0345]

Table 4

[0346]

Table 5

[0347] [Table 6]

[0348] [Table 7]

[0349] [Table 8]

[0350] [Table 9]

[0351] [Table 10]

[0352] Tables 1 to 10 show that a chemically amplified positive-tone photosensitive composition comprising an acid generator (A), a resin (B), a sulfur-containing compound (E), and an acid diffusion inhibitor (F), wherein the resin (B) comprises an acrylic resin (B3), and the acid generator (A) comprises an acid generator (A1) that generates an acid having a pKa of −3.5 or more and less than 0, can form a patterned resist film having a rectangular cross-sectional shape and has good PED.

Claims

1. The composition comprises 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, a sulfur-containing compound (E), and an acid diffusion inhibitor (F), The resin (B) contains an acrylic resin (B3), the acid generator (A) contains an acid generator (A1) that generates an acid having a pKa of −3.5 or more and less than 0; Chemically amplified positive photosensitive composition.

2. The acid generator (A1) has a van der Waals volume of 90 Å ３ More than 200 Å ３ 2. The chemically amplified positive-working photosensitive composition according to claim 1, wherein the composition generates less than 1000 ppm of acid.

3. The acid generator (A1) is represented by the following formula (ai): 【Chemistry 1】 (In formula (ai), R ａ０１ is a halogen atom, R ａ０２ represents an organic group, —OH, —SH, or —NH ２ and n01 is an integer of 1 to 5, n02 is an integer of 0 to 4, When n01 is an integer of 2 or more and 5 or less, a plurality of R ａ０１ may be the same or different, When n02 is an integer of 2 or more and 4 or less, a plurality of R ａ０２ may be the same or different.) 3. The chemically amplified positive photosensitive composition according to claim 2, which generates an acid containing an anion represented by the following formula:

4. 2. The chemically amplified positive photosensitive composition according to claim 1, wherein the acid generator (A1) comprises a nonionic acid generator having a naphthalimide structure.

5. The acrylic resin (B3) is represented by the following formula (b5'): 【Chemistry 2】 (In formula (b5'), R １４ｂ’ each independently represents a hydrogen atom or a linear or branched alkyl group having 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, 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.

2. The chemically amplified positive photosensitive composition according to claim 1, which has a structural unit represented by the formula:

6. the acid generator (A) includes an acid generator (A2) that does not fall under the category of the acid generator (A1), The acid generator (A2) has an anion moiety represented by the following formula (aiii): 【Transformation 3】 (In formula (aiii), R ａ０７ , R ａ０８ , R ａ０９ , and R ａ０１０ are each independently a hydrocarbon group which may have a substituent or a heterocyclic group which may have a substituent, and R ａ０７ , R ａ０８ , R ａ０９ , and R ａ０１０ At least one of the groups is an aromatic hydrocarbon group which may have a substituent. or an anion represented by the following formula (aiv): Cf-SO ２ -N － -SO ２ -Cf・・・(aiv) (In formula (aiv), 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.) 2. The chemically amplified positive photosensitive composition according to claim 1, wherein the compound is an onium salt containing an anion represented by the formula:

7. 2. The chemically amplified positive-working photosensitive composition according to claim 1, further comprising an alkali-soluble resin (D).

8. 8. The chemically amplified positive photosensitive composition according to claim 7, wherein the alkali-soluble resin (D) comprises at least one resin selected from the group consisting of a novolak resin (D1), a polyhydroxystyrene resin (D2), and an acrylic resin (D3).

9. 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 8.

10. A method for producing a photosensitive dry film, comprising applying the chemically amplified positive photosensitive composition according to any one of claims 1 to 8 onto a substrate film to form a photosensitive layer.

11. a lamination step of laminating a photosensitive layer made of the chemically amplified positive photosensitive composition according to any one of claims 1 to 8 on a substrate; an exposure step of exposing the photosensitive layer to actinic rays or radiation in a position-selective manner; a developing step of developing the photosensitive layer after exposure.

12. a lamination step of laminating a photosensitive layer made of the chemically amplified positive photosensitive composition according to any one of claims 1 to 8 on a substrate having a metal surface; an exposure step of exposing the photosensitive layer to actinic rays or radiation in a position-selective manner; and a development step of developing the photosensitive layer after exposure to produce a mold for forming a plated object.

13. A method for producing a plated shaped object, comprising a plating step of plating the mold-equipped substrate produced by the method for producing a mold-equipped substrate according to claim 12, to form a plated shaped object in the mold.

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