Chemical amplification photosensitive composition, photosensitive dry film and method for producing the same, method for producing resist film, and acid diffusion inhibitor

Abstract

This invention provides a chemically amplified positive photosensitive composition that easily forms resist patterns with high resolution, dimensional control, and good rectangularity in cross-sectional shape; a photosensitive dry film having a photosensitive layer composed of the chemically amplified positive photosensitive composition; a method for manufacturing the photosensitive dry film; a method for manufacturing a patterned resist film using the chemically amplified positive photosensitive composition; and an acid diffusion inhibitor incorporated into the chemically amplified positive photosensitive composition. The chemically amplified positive photosensitive composition contains an acid-generating agent (A) that generates acid upon irradiation by active light or radiation and a resin (B) whose solubility in alkalis increases due to the action of the acid, and incorporates an acid diffusion inhibitor (C) with a specific structure.

Description

TECHNICAL FIELD

[0001] The present application relates to a chemically amplified positive photosensitive composition, a photosensitive dry film provided with a photosensitive layer composed of the chemically amplified positive photosensitive composition, a method for producing the photosensitive dry film, a method for producing a patterned resist film using the chemically amplified positive photosensitive composition, and an acid diffusion inhibitor. BACKGROUND

[0002] At present, photofabrication has become mainstream of precision microfabrication technology. Photofabrication is a general term for a technology for manufacturing various precision parts such as semiconductor packages by coating a photoresist composition on a surface of an object to be processed to form a photoresist layer, patterning the photoresist layer using a photolithography technique, and performing chemical etching, electrolytic etching, or electroforming mainly using plating as a mask with the patterned photoresist layer (photoresist pattern).

[0003] In addition, in recent years, with the miniaturization of electronic devices, high-density mounting technology of semiconductor packages is being advanced, and improvement in mounting density based on multi-pin thin film mounting of packages, miniaturization of package size, 2-dimensional mounting technology of flip chip type, and 3-dimensional mounting technology are being sought. In such high-density mounting technology, for example, a protruding electrode (mounting terminal) such as a bump protruding from a package, or a metal pillar connecting a redistribution wire extended from a peripheral terminal on a wafer to a mounting terminal is precisely arranged on a substrate as a connection terminal.

[0004] A photoresist composition is used in photofabrication as described above, and as such a photoresist composition, a chemically amplified photosensitive composition containing an acid generator is known (see Patent Documents 1 and 2, etc.). The chemically amplified photosensitive composition is a composition that generates acid from an acid generator by irradiation of a radiation (exposure), and promotes diffusion of the acid by a heating treatment, thereby causing an acid catalytic reaction with respect to a base resin or the like in the composition, and changing the alkali solubility.

[0005] Such a chemically amplified photosensitive composition is used not only for the formation of a patterned insulating film, an etching mask, but also for forming a plating shaped object such as a bump, a metal pillar, and a Cu redistribution line, etc. by a plating process. Specifically, a chemically amplified photosensitive composition is used to form a photoresist layer of a desired film thickness on a support such as a metal substrate, exposure is performed through a prescribed mask pattern and development is performed to form a photoresist pattern used as a mold for selectively removing (stripping) a portion where a plating shaped object is formed. Then, after a conductor such as copper is embedded in the removed portion (non-resist portion) by plating, the photoresist pattern around it is removed, whereby a bump, a metal pillar, and a Cu redistribution line can be formed.

[0006] Prior Art Documents

[0007] Patent Documents

[0008] Patent Document 1: Japanese Patent Application Laid-Open (JP-A) No. 9-176112

[0009] Patent Document 2: Japanese Patent Application Laid-Open (JP-A) No. 11-52562 SUMMARY

[0010] PROBLEMS TO BE SOLVED BY THE INVENTION

[0011] With the higher density of semiconductor packages, further higher density and higher precision of the protruding electrodes and metal pillars are required. In order to achieve further higher density and higher precision of the protruding electrodes and metal pillars, a chemically amplified positive photosensitive composition capable of forming a resist pattern having high resolution and size controllability and good rectangularity of cross-sectional shape is desired.

[0012] However, in the case of using the conventional chemically amplified resist composition disclosed in Patent Documents 1 and 2, the resolution and size controllability are insufficient, and it is often difficult to form a resist pattern having good rectangularity of cross-sectional shape. For example, if a conventional chemically amplified resist composition is used, near the contact surface (interface) between the substrate surface and the resist pattern, a shape of a kickstand (a shape of a folded edge) in which the resist portion extends to the non-resist portion side or a shape of a recess opposite to the kickstand shape is formed, and in addition, the verticality of the cross-sectional shape is poor, and a resist pattern having a rectangular cross-sectional shape cannot be obtained.

[0013] The present application was achieved in view of the above technical problems, and aims to provide a chemically amplified positive photosensitive composition which is easy to form a resist pattern having high resolution and size controllability and good rectangularity of cross-sectional shape, a photosensitive dry film having a photosensitive layer composed of the chemically amplified positive photosensitive composition, a method for producing the photosensitive dry film, a method for producing a patterned resist film using the chemically amplified positive photosensitive composition, and an acid diffusion inhibitor to be blended in the chemically amplified positive photosensitive composition.

[0014] Approach for solving the above technical problems

[0015] The present inventors have made intensive studies in order to achieve the above object, and as a result, have found that the above technical problems can be solved by blending an acid diffusion inhibitor (C) having a specific structure in a chemically amplified positive photosensitive composition containing an acid generator (A) which generates an acid by irradiation with active light or radiation and a resin (B) whose solubility to a base is increased by the action of the acid, and thus have completed the present application. Specifically, the present application provides the following approach.

[0016] The first aspect of the present invention is a chemically amplified positive photosensitive composition comprising: an acid-generating agent (A) that generates acid upon irradiation with active light or radiation; a resin (B) whose solubility in alkali is increased by the action of the acid; and an acid diffusion inhibitor (C).

[0017] The acid diffusion inhibitor (C) comprises a compound represented by the following formula (C1).

[0018] [Chemistry 1]

[0019]

[0020] (In formula (C1),)

[0021] R 1c It is an alkyl or aralkyl group.

[0022] R 2c It is an alkyl or aralkyl group.

[0023] R 3c It is a hydrogen atom or an alkyl group.

[0024] R 4c It is a single bond or an alkylene group.

[0025] n1 is an integer greater than 0 and less than 5.

[0026] n2 is an integer greater than 0 and less than 5.

[0027] n3 is either 0 or 1.

[0028] (Note that when n3 is 1, n1 and n2 are not both 0.)

[0029] The second aspect of the present invention is a photosensitive dry film having a substrate film and a photosensitive layer formed on the surface of the substrate film, the photosensitive layer being composed of the chemically amplified photosensitive composition of the first aspect.

[0030] The third aspect of the present invention is a method for manufacturing a photosensitive dry film, comprising coating a chemically amplified positive-type photosensitive composition of the first aspect onto a substrate film to form a photosensitive layer.

[0031] The fourth aspect of the present invention is a method for manufacturing a patterned resist film, comprising:

[0032] In the lamination process, a photosensitive layer composed of the chemically amplified positive-type photosensitive composition of the first scheme is laminated on the substrate;

[0033] The exposure process involves selectively irradiating the photosensitive layer with active light or radiation.

[0034] The developing process involves developing the exposed photosensitive layer.

[0035] The fifth aspect of the present invention is an acid diffusion inhibitor, incorporated into a chemically amplified positive photosensitive composition comprising an acid-generating agent (A) that generates acid upon irradiation by active light or radiation and a resin (B) whose solubility in alkalis increases due to the action of the acid.

[0036] The acid diffusion inhibitor comprises a compound represented by the following formula (C1).

[0037] [Chemistry 2]

[0038]

[0039] (In formula (C1),)

[0040] R 1c It is an alkyl or aralkyl group.

[0041] R 2c It is an alkyl or aralkyl group.

[0042] R 3c It is a hydrogen atom or an alkyl group.

[0043] R 4c It is a single bond or an alkylene group.

[0044] n1 is an integer greater than 0 and less than 5.

[0045] n2 is an integer greater than 0 and less than 5.

[0046] n3 is either 0 or 1.

[0047] (Note that when n3 is 1, n1 and n2 are not both 0.)

[0048] Invention Effects

[0049] According to the present invention, a chemically amplified positive photosensitive composition that can easily form resist patterns with high resolution and dimensional control and good rectangularity of cross-sectional shape is provided; a photosensitive dry film having a photosensitive layer composed of the chemically amplified positive photosensitive composition; a method for manufacturing the photosensitive dry film; a method for manufacturing a patterned resist film using the chemically amplified positive photosensitive composition; and an acid diffusion inhibitor incorporated into the chemically amplified positive photosensitive composition are provided. Detailed Implementation

[0050] Chemically Amplified Positive Photosensitive Compositions

[0051] The chemically amplified positive-type photosensitive composition (hereinafter also referred to as the photosensitive composition) contains an acid-generating agent (A) that produces acid upon irradiation with active light or radiation (hereinafter also referred to as acid-generating agent (A)), a resin (B) whose solubility in alkali increases due to the action of acid (hereinafter also referred to as resin (B)), and an acid diffusion inhibitor (C). As described below, the acid diffusion inhibitor (C) has a specific structure. The photosensitive composition may also, as needed, contain components such as an alkali-soluble resin (D), a sulfur-containing compound (E), and an organic solvent (S).

[0052] <Acid-producing agent (A)>

[0053] The acid-generating agent (A) is a compound that produces acid through irradiation with active light or radiation. There is no particular limitation as long as the compound produces acid directly or indirectly through light. Preferably, the acid-generating agents of the first to fifth embodiments described below are preferred as acid-generating agents (A). Hereinafter, preferred embodiments of the acid-generating agent (A) preferably used in the photosensitive composition will be described as the first to fifth embodiments.

[0054] As a first option among acid-producing agents (A), a compound represented by the following formula (a1) can be cited.

[0055] [Chemistry 3]

[0056]

[0057] In the above formula (a1), X 1a The valence g represents a sulfur or iodine atom, where g is 1 or 2. h indicates the number of repeating units in the structure within the brackets. R 1a To be with X 1a The bonded organic group represents an aryl group with 6 to 30 carbon atoms, a heterocyclic group with 4 to 30 carbon atoms, an alkyl group with 1 to 30 carbon atoms, an alkenyl group with 2 to 30 carbon atoms, or an alkynyl group with 2 to 30 carbon atoms. R 1a It can be substituted by at least one group selected from alkyl, hydroxy, alkoxy, alkyl carbonyl, aryl carbonyl, alkoxy carbonyl, aryloxy carbonyl, arylthio carbonyl, acyloxy, arylthio, alkylthio, aryl, heterocyclic, aryloxy, alkyl sulfinyl, aryl sulfinyl, alkyl sulfonyl, aryl sulfonyl, alkyleneoxy, amino, cyano, nitro groups, and halogens. 1a The number of elements is g + h(g-1) + 1, R 1a They can be the same as each other or different. Furthermore, two or more R's... 1a They can bond directly to each other or via -O-, -S-, -SO-, -SO2-, -NH-, -NR 2a-, -CO-, -COO-, -CONH-, and alkylene or phenylene groups with 1 to 3 carbon atoms are bonded together to form a group containing X. 1a The ring structure. R 2a It is an alkyl group with 1 to 5 carbon atoms or an aryl group with 6 to 10 carbon atoms.

[0058] X 2a The structure is represented by the following formula (a2).

[0059] [Chemistry 4]

[0060]

[0061] In the above formula (a2), X 4a X represents a divalent group in alkylene compounds with 1 to 8 carbon atoms, arylene compounds with 6 to 20 carbon atoms, or heterocyclic compounds with 8 to 20 carbon atoms. 4a It can be substituted by at least one group selected from the group consisting of alkyl groups having 1 to 8 carbon atoms, alkoxy groups having 1 to 8 carbon atoms, aryl, hydroxyl, cyano, and nitro groups having 6 to 10 carbon atoms, and halogens. 5a This represents -O-, -S-, -SO-, -SO2-, -NH-, -NR 2a -, -CO-, -COO-, -CONH-, and alkylene or phenylene compounds with 1 to 3 carbon atoms. h indicates the number of repeating units in the parentheses. h+1 X 4a And h X 5a They can be the same or different. R 2a Same as the definition above.

[0062] X 3a - As counterions to onyx, examples include fluoroalkyl fluorophosphate anions represented by formula (a17) or borate anions represented by formula (a18).

[0063] [Chemistry 5]

[0064] [(R 3a ) j PF 6-j ] - (a17)

[0065] In the above formula (a17), R 3a This indicates an alkyl group obtained by replacing more than 80% of its hydrogen atoms with fluorine atoms. j represents the number of alkyl groups, an integer between 1 and 5. j alkyl groups 3a They can be the same or different.

[0066] [Chemistry 6]

[0067]

[0068] In the above formula (a18), R 4a ~R 7a Each of the above independently represents a fluorine atom or a phenyl group, wherein some or all of the hydrogen atoms of the phenyl group may be substituted with at least one of the groups consisting of a fluorine atom and a trifluoromethyl group.

[0069] Examples of onium ions in compounds represented by formula (a1) above include triphenylsulfonium, tri-p-tolylsulfonium, 4-(phenylthio)phenyldiphenylsulfonium, bis[4-(diphenylsulfonyl)phenyl]sulfide, bis[4-{bis[4-(2-hydroxyethoxy)phenyl]sulfonyl}phenyl]sulfide, bis{4-[bis(4-fluorophenyl)sulfonyl]phenyl}sulfide, and 4-(4-benzoyl-2-chlorobenzene) 7-Isopropyl-9-oxo-10-thio-9,10-dihydroanthracene-2-yldi-p-tolylsulfonium, 7-Isopropyl-9-oxo-10-thio-9,10-dihydroanthracene-2-yldiphenylsulfonium, 2-[(diphenyl)sulfonyl]thioxanthone, 4-[4-(4-tert-butylbenzoyl)phenylthio]phenyldi-p-tolylsulfonium, 4-(4- Benzoylphenylthio)phenyl diphenylsulfonium, diphenylbenzoylmethylsulfonium, 4-hydroxyphenylmethylbenzylsulfonium, 2-naphthylmethyl(1-ethoxycarbonyl)ethylsulfonium, 4-hydroxyphenylmethylbenzoylmethylsulfonium, phenyl[4-(4-biphenylthio)phenyl]4-biphenylsulfonium, phenyl[4-(4-biphenylthio)phenyl]3-biphenylsulfonium, [4-(4-acetylphenylthio)phenyl]diphenylsulfonium, Octadecylmethylbenzoylmethylsulfonium, diphenyliodonium, di-p-tolyliodonium, bis(4-dodecylphenyl)iodonium, bis(4-methoxyphenyl)iodonium, (4-octoxyphenyl)phenyliodonium, bis(4-decoxyphenyl)phenyliodonium, 4-(2-hydroxytetradecoxy)phenylphenyliodonium, 4-isopropylphenyl(p-tolyl)iodonium, or 4-isobutylphenyl(p-tolyl)iodonium, etc.

[0070] Among the onnnium ions in the compounds represented by the above formula (a1), the preferred onnnium ion is the sulfonium ion represented by the following formula (a19).

[0071] [Chemistry 7]

[0072]

[0073] In the above formula (a19), R 8a Each of these groups independently represents a group selected from the group consisting of hydrogen atom, alkyl, hydroxyl, alkoxy, alkyl carbonyl, alkyl carbonyloxy, alkyloxy carbonyl, halogen atom, aryl group which may have substituents, and aryl carbonyl. 2a This indicates that X in the above formula (a1) is related to...2a Same meaning.

[0074] Specific examples of sulfonium ions represented by the above formula (a19) include 4-(phenylthio)phenyl diphenylsulfonium, 4-(4-benzoyl-2-chlorophenylthio)phenyl bis(4-fluorophenyl)sulfonium, 4-(4-benzoylphenylthio)phenyl diphenylsulfonium, phenyl[4-(4-biphenylthio)phenyl]4-biphenylsulfonium, phenyl[4-(4-biphenylthio)phenyl]3-biphenylsulfonium, [4-(4-acetylphenylthio)phenyl]diphenylsulfonium, and diphenyl[4-(p-triphenylthio)phenyl]diphenylsulfonium.

[0075] In the fluoroalkyl fluorophosphate anion represented by the above formula (a17), R 3a The alkyl group obtained by substitution with fluorine atoms preferably has 1 to 8 carbon atoms, and more preferably 1 to 4 carbon atoms. Specific examples of alkyl groups include straight-chain alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, and octyl; branched-chain alkyl groups such as isopropyl, isobutyl, sec-butyl, and tert-butyl; and cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl. The proportion of hydrogen atoms in the alkyl group substituted by fluorine atoms is usually 80% or more, preferably 90% or more, and more preferably 100%. When the substitution rate of fluorine atoms is less than 80%, the acid strength of the onium fluorinated alkyl fluorophosphate represented by the above formula (a1) decreases.

[0076] Specially selected R 3a It is a straight-chain or branched perfluoroalkyl group with 1 to 4 carbon atoms and a fluorine substitution rate of 100%. Specific examples include CF3, CF3CF2, (CF3)2CF, CF3CF2CF2, CF3CF2CF2CF2, (CF3)2CFCF2, CF3CF2(CF3)CF, and (CF3)3C. 3a The number j is an integer between 1 and 5, preferably between 2 and 4, and especially preferably 2 or 3.

[0077] As a preferred example of a fluoroalkyl fluorophosphate anion, [(CF3CF2)2PF4] can be cited. - [(CF3CF2)3PF3] - [((CF3)2CF)2PF4] - [((CF3)2CF)3PF3] - [(CF3CF2CF2)2PF4] - [(CF3CF2CF2)3PF3] - [((CF3)2CFCF2)2PF4] - [((CF3)2CFCF2)3PF3]- [(CF3CF2CF2CF2)2PF4] - Or [(CF3CF2CF2)3PF3] - Of which, [(CF3CF2)3PF3] is particularly preferred. - [(CF3CF2CF2)3PF3] - [((CF3)2CF)3PF3] - [((CF3)2CF)2PF4] - [((CF3)2CFCF2)3PF3] - Or [((CF3)2CFCF2)2PF4] - .

[0078] As a preferred specific example of the borate anion represented by the above formula (a18), tetratetra(pentafluorophenyl)borate ([B(C6F5)4]) can be cited. - ), tetra[(trifluoromethyl)phenyl]borate ([B(C6H4CF3)4] - ), difluorobis(pentafluorophenyl)borate ([(C6F5)2BF2] - ), trifluoro(pentafluorophenyl)borate ([(C6F5)BF3] - ), tetra(difluorophenyl)borate ([B(C6H3F2)4] - ), etc. Of particular preference is tetra(pentafluorophenyl)borate ([B(C6F5)4]). - ).

[0079] As a second option in acid-producing agent (A), examples include 2,4-bis(trichloromethyl)-6-piperyl-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(2-furanyl)vinyl]triazine, 2,4-bis(trichloromethyl)-6-[2-(5-methyl-2-furanyl)vinyl]triazine, 2,4-bis(trichloromethyl)-6-[2-(5-ethyl-2-furanyl)vinyl]triazine, 2,4-bis(trichloromethyl)-6-[2-(5-propyl-2-furanyl)vinyl]triazine, 2,4-bis(trichloromethyl)-6-[2-(3,5-dimethoxyphenyl)vinyl]triazine, 2,4-bis(trichloromethyl)-6-[2-(3,5-dimethoxyphenyl)vinyl]triazine, 2,4-bis(trichloromethyl)-6-[2-(3,5-dimethoxyphenyl)vinyl]triazine, 2,4-bis(trichloromethyl)-6-[2-(2-(2-furanyl)vinyl]triazine, 2,4-bis(trichloromethyl)-6-[2-(2-(2-furanyl)vinyl]triazine, 2,4-bis(trichloromethyl)-6-[2-(2-(2-furanyl)vinyl]triazine, 2,4-bis(trichloromethyl)-6-[2-(2-(2-(2-furanyl)vinyl) ... 2,4-bis(trichloromethyl)-6-[2-(3,5-diethoxyphenyl)vinyl]triazine, 2,4-bis(trichloromethyl)-6-[2-(3,5-dipropoxyphenyl)vinyl]triazine, 2,4-bis(trichloromethyl)-6-[2-(3-methoxy-5-ethoxyphenyl)vinyl]triazine, 2,4-bis(trichloromethyl)-6-[2-(3-methoxy-5-propoxyphenyl)vinyl]triazine, 2,4-bis(trichloromethyl)-6-[2-(3,4-methylenedioxyphenyl)vinyl]triazine, 2,4-bis(trichloromethyl)-6-(3,4-methylenedioxyphenyl)triazine, 2,4-bis-trichloromethyl-6-(3-bromo-4- 2,4-bis-trichloromethyl-6-(2-bromo-4-methoxy)phenyltriazine, 2,4-bis-trichloromethyl-6-(2-bromo-4-methoxy)styrylphenyltriazine, 2,4-bis-trichloromethyl-6-(3-bromo-4-methoxy)styrylphenyltriazine, 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-[2-(2-furanyl)vinyl]-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-[2-(5-methyl-2-furanyl)vinyl]- Halogenated triazine compounds such as 4,6-bis(trichloromethyl)-1,3,5-triazine, 2-[2-(3,5-dimethoxyphenyl)vinyl]-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-[2-(3,4-dimethoxyphenyl)vinyl]-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(3,4-methylenedioxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, tris(1,3-dibromopropyl)-1,3,5-triazine, tris(2,3-dibromopropyl)-1,3,5-triazine, and trihalomethanes, and halogenated triazine compounds represented by the following formula (a3), such as tris(2,3-dibromopropyl)isocyanurate.

[0080] [Chemistry 8]

[0081]

[0082] In the above formula (a3), R 9a R 10a R 11a Each can be represented independently as a haloalkyl group.

[0083] Furthermore, as a third option among the acid-producing agents (A), examples include α-(p-toluenesulfonyloxyimino)-phenylacetonitrile, α-(benzenesulfonyloxyimino)-2,4-dichlorophenylacetonitrile, α-(benzenesulfonyloxyimino)-2,6-dichlorophenylacetonitrile, α-(2-chlorobenzenesulfonyloxyimino)-4-methoxyphenylacetonitrile, α-(ethylsulfonyloxyimino)-1-cyclopentenylacetonitrile, and compounds containing an oxime sulfonate group represented by the following formula (a4).

[0084] [Chemistry 9]

[0085]

[0086] In the above formula (a4), R 12a R represents an organic group that is monovalent, divalent, or trivalent. 13a This indicates a substituted or unsubstituted saturated hydrocarbon group, an unsaturated hydrocarbon group, or an aromatic group, and n indicates the number of repeating units in the structure within the parentheses.

[0087] In formula (a4) above, aromatic groups can be exemplified by aryl groups such as phenyl and naphthyl, or heteroaryl groups such as furanyl and thiophene. They may have one or more suitable substituents on the ring, such as halogen atoms, alkyl groups, alkoxy groups, nitro groups, etc. Furthermore, R... 13a Alkyl groups having 1 to 6 carbon atoms are particularly preferred; examples include methyl, ethyl, propyl, and butyl. R is particularly preferred. 12a Aromatic groups, R 13a Compounds consisting of alkyl groups having 1 to 4 carbon atoms.

[0088] As an acid-producing agent represented by the above formula (a4), R can be cited as an example when n=1. 12a It is any one of phenyl, methylphenyl, and methoxyphenyl, and R 13a Compounds containing methyl groups, specifically, include α-(methylsulfonyloxyimino)-1-phenylacetonitrile, α-(methylsulfonyloxyimino)-1-(p-methylphenyl)acetonitrile, α-(methylsulfonyloxyimino)-1-(p-methoxyphenyl)acetonitrile, and [2-(propylsulfonyloxyimino)-2,3-dihydroxythiophene-3-ethylene](o-tolyl)acetonitrile. When n = 2, as acid-producing agents represented by the above formula (a4), examples include acid-producing agents represented by the following formula.

[0089] [Chemistry 10]

[0090]

[0091] Furthermore, as a fourth option in the acid-producing agent (A), an onium salt having a naphthalene ring in the cation portion can be cited as an example. "Having a naphthalene ring" means having a structure derived from naphthalene, specifically a structure having at least two rings, and maintaining their aromaticity. This naphthalene ring can have substituents such as straight-chain or branched alkyl groups, hydroxyl groups, or straight-chain or branched alkoxy groups having 1 to 6 carbon atoms. Although the structure derived from the naphthalene ring can be a monovalent group (free valence of 1) or a divalent group (free valence of 2 or more), it is desirable to be a monovalent group (wherein, the portion bonded to the aforementioned substituents is removed to count the free valence). The number of naphthalene rings is preferably 1 to 3 or less.

[0092] As such a cation portion of an onium salt having a naphthalene ring in the cation portion, the structure represented by the following formula (a5) is preferred.

[0093] [Chemistry 11]

[0094]

[0095] In the above formula (a5), R 14a R 15a R 16a At least one of them represents a group represented by formula (a6) below, and the remainder represents a straight-chain or branched alkyl group having 1 to 6 carbon atoms, a phenyl group that may have substituents, a hydroxyl group, or a straight-chain or branched alkoxy group having 1 to 6 carbon atoms. Alternatively, R 14a R 15a R 16a One of them is a group represented by the following formula (a6), and the other two are independently linear or branched alkylene groups with 1 to 6 carbon atoms, and their ends can be bonded together to form a ring.

[0096] [Chemistry 12]

[0097]

[0098] In the above formula (a6), R 17a R 18a Each of the following can be independently represented as a hydroxyl group, a straight-chain or branched alkoxy group having 1 to 6 carbon atoms, or a straight-chain or branched alkyl group having 1 to 6 carbon atoms. 19aThis indicates a straight-chain or branched alkylene group with a single bond or having 1 to 6 carbon atoms that may have substituents. l and m each independently represent an integer from 0 to 2, and l+m is 3 or less. Where multiple R groups are present... 17a In the case of R, they can be the same as each other or different. Furthermore, when there are multiple R... 18a In this case, they can be the same as each other or different.

[0099] From the perspective of compound stability, the above R 14a R 15a R 16a The number of groups represented by the above formula (a6) is preferably one, and the remainder are straight-chain or branched alkylene groups with 1 to 6 carbon atoms, whose ends can be bonded to form a ring. In this case, the above two alkylene groups contain sulfur atoms to form a three- to nine-membered ring. The number of atoms constituting the ring (including sulfur atoms) is preferably 5 to 6.

[0100] Furthermore, examples of substituents that the aforementioned alkylene group may have include oxygen atoms (in which case, together with the carbon atoms constituting the alkylene group, they form a carbonyl group), hydroxyl groups, etc.

[0101] Furthermore, examples of substituents that phenyl groups may have include hydroxyl groups, straight-chain or branched alkoxy groups having 1 to 6 carbon atoms, and straight-chain or branched alkyl groups having 1 to 6 carbon atoms.

[0102] Preferred structures for these cation portions include those represented by formulas (a7) and (a8), with the structure represented by formula (a8) being particularly preferred.

[0103] [Chemistry 13]

[0104]

[0105] The cation could be either an iodonium salt or a matte salt, but from the perspective of acid production efficiency, a matte salt would be preferred.

[0106] Therefore, the preferred anion for the anion portion of an onium salt having a naphthalene ring in the cation portion is preferably an anion capable of forming a sulfonium salt.

[0107] The anionic portion of such an acid-producing agent is a fluoroalkyl sulfonate ion or an aryl sulfonate ion in which some or all of the hydrogen atoms are fluorinated.

[0108] The alkyl group in the fluoroalkyl sulfonate ion can be a straight-chain, branched, or cyclic alkyl group with 1 to 20 carbon atoms. From the perspective of the size of the generated acid and its diffusion distance, a carbon number of 1 to 10 is preferred. In particular, branched or cyclic alkyl groups are preferred because they have shorter diffusion distances. Furthermore, from the viewpoint of being able to synthesize inexpensively, methyl, ethyl, propyl, butyl, octyl, and the like are preferred groups.

[0109] The aryl group in the aryl sulfonate ion is an aryl group with 6 to 20 carbon atoms, and examples include phenyl and naphthyl groups that can be substituted with or not substituted by alkyl or halogen atoms. In particular, from the viewpoint of being able to be synthesized inexpensively, aryl groups with 6 to 10 carbon atoms are preferred. Specific examples of preferred aryl groups include phenyl, toluenesulfonyl, ethylphenyl, naphthyl, and methylnaphthyl.

[0110] In the case where some or all of the hydrogen atoms in the aforementioned fluoroalkyl sulfonate ions or aryl sulfonate ions are fluorinated, the fluorination rate is preferably 10% to 100%, more preferably 50% to 100%, and substances obtained by replacing all hydrogen atoms with fluorine atoms are preferred because the acid strength increases. Examples of such substances include trifluoromethane sulfonates, perfluorobutane sulfonates, perfluorooctane sulfonates, and perfluorobenzene sulfonates.

[0111] Among them, the preferred anion section can be represented by the following formula (a9).

[0112] [Chemistry 14]

[0113] R 20a SO3 - (a9)

[0114] In the above equation (a9), R 20a These are groups represented by the following formulas (a10), (a11), and (a12).

[0115] [Chemistry 15]

[0116]

[0117] In equation (a10) above, x represents an integer greater than 1 and less than 4. Furthermore, in equation (a11) above, R... 21a The term "y" represents a hydrogen atom, a hydroxyl group, a straight-chain or branched alkyl group having 1 to 6 carbon atoms, or a straight-chain or branched alkoxy group having 1 to 6 carbon atoms, where "y" represents an integer of 1 to 3. From a safety perspective, trifluoromethane sulfonate and perfluorobutane sulfonate are preferred.

[0118] In addition, as an anion section, a nitrogen-containing anion section represented by the following formulas (a13) and (a14) can also be used.

[0119] [Chemistry 16]

[0120]

[0121] In the above equations (a13) and (a14), X a This refers to a straight-chain or branched alkylene group obtained by replacing at least one hydrogen atom with a fluorine atom, wherein the alkylene group has 2 to 6 carbon atoms, preferably 3 to 5, and most preferably 3 carbon atoms. Furthermore, Y a Z a Each of the above refers independently to a straight-chain or branched alkyl group obtained by replacing at least one hydrogen atom with a fluorine atom, wherein the alkyl group has 1 to 10 carbon atoms, preferably 1 to 7, and more preferably 1 to 3.

[0122] X a The number of carbon atoms in the alkylene group or Y a Z a The smaller the number of carbon atoms in the alkyl group, the better its solubility in organic solvents, and therefore it is preferred.

[0123] Furthermore, in X a alkylene or Y a Z a In an alkyl group, the more hydrogen atoms replaced by fluorine atoms, the stronger the acid, which is therefore preferred. The proportion of fluorine atoms in the alkylene or alkyl group, i.e., the fluorination rate, is preferably 70% to 100%, more preferably 90% to 100%, and most preferably a perfluoroalkylene or perfluoroalkyl group obtained by replacing all hydrogen atoms with fluorine atoms.

[0124] Compounds that are preferred as onium salts having a naphthalene ring in the cation portion include those represented by the following formulas (a15) and (a16).

[0125] [Chemistry 17]

[0126]

[0127] Furthermore, as a fifth option in acid-producing agent (A), examples include bis(p-toluenesulfonyl)diazomethane, bis(1,1-dimethylethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(2,4-dimethylphenylsulfonyl)diazomethane, and other bissulfonyl diazonium methane derivatives; nitrobenzyl derivatives such as 2-nitrobenzyl p-toluenesulfonic acid, 2,6-dinitrobenzyl p-toluenesulfonic acid, nitrobenzyl toluenesulfonic acid, dinitrobenzyl toluenesulfonic acid, nitrobenzyl sulfonate, nitrobenzyl carbonate, and dinitrobenzyl carbonate; and pyrogallol trimethylsulfonate, pyrogallol tritoluenesulfonate, benzyl toluenesulfonic acid, benzyl sulfonate, N-methylsulfonyloxysuccinimide, N-trichloromethylsulfonyloxysuccinimide, N-phenylsulfonyloxymaleimide, and N-methylsulfonyl... Sulfonates such as oxy-phthalimide; trifluoromethanesulfonates such as N-(trifluoromethanesulfonyloxy)phthalimide, N-(trifluoromethanesulfonyloxy)-1,8-naphthalenediamide, and N-(trifluoromethanesulfonyloxy)-4-butyl-1,8-naphthalenediamide; ononium salts such as diphenyliodonium hexafluorophosphate, (4-methoxyphenyl)phenyliodonium trifluoromethanesulfonate, bis(p-tert-butylphenyl)iodonium trifluoromethanesulfonate, triphenylsulfonium hexafluorophosphate, (4-methoxyphenyl)diphenylsulfonium trifluoromethanesulfonate, and (p-tert-butylphenyl)diphenylsulfonium trifluoromethanesulfonate; benzoin toluene sulfonate and α-methylbenzoin toluene sulfonate; and other diphenyliodonium salts, triphenylsulfonium salts, phenyldiazoonium salts, and benzyl carbonate.

[0128] As an acid-producing agent (A), a naphthalene dicarboxylic acid derivative represented by the following formula (a21) is also preferred.

[0129] [Chemistry 18]

[0130]

[0131] (In formula (a21), R) 22a R is a monovalent organic group. 23a R 24a R 25a and R 26a Each of the following is an organic group that is independently a hydrogen atom or a monovalent organic group: R 23a With R 24a R 24a With R 25a or R 25a With R 26a They can bond together to form rings.

[0132] As R 22aThe organic group is not particularly limited to any extent that it does not impair the purpose of this invention. The organic group may be a hydrocarbon group or may contain heteroatoms such as O, N, S, P, or halogen atoms. Furthermore, the structure of the organic group may be linear, branched, cyclic, or a combination of these structures.

[0133] As R 22a Preferred organic groups may include aliphatic hydrocarbon groups having 1 to 18 carbon atoms that can be replaced by halogen atoms and / or alkylthio groups, aryl groups having 6 to 20 carbon atoms that can have substituents, aralkyl groups having 7 to 20 carbon atoms that can have substituents, alkylaryl groups having 7 to 20 carbon atoms that can have substituents, camphor-10-yl groups, and groups represented by the following formula (a21a).

[0134] -R 27a -(O) a -R 28a -(O) b -Y 1 -R 29a ...(a21a)

[0135] (In formula (a21a), Y) 1 It is a single bond or an alkyldiyl group with 1 to 4 carbon atoms. R 27a and R 28a These are, respectively, alkyldiyl groups with 2 to 6 carbon atoms that can be replaced by halogen atoms, or aryl groups with 6 to 20 carbon atoms that can be replaced by halogen atoms. R 29a The alkyl group has 1 to 18 carbon atoms that can be replaced by a halogen atom; the alicyclic hydrocarbon group has 3 to 12 carbon atoms; the aryl group has 6 to 20 carbon atoms that can be replaced by a halogen atom; and the aralkyl group has 7 to 20 carbon atoms that can be replaced by a halogen atom. (a and b are 0 or 1, and at least one of a and b is 1.)

[0136] As R 22a When an organic group has a halogen atom as a substituent, examples of such halogen atoms include chlorine, bromine, iodine, and fluorine.

[0137] As R 22a When the organic group is an alkyl group that has 1 to 18 carbon atoms obtained by replacing it with an alkylthio group, the alkylthio group preferably has 1 to 18 carbon atoms.

[0138] Examples of alkylthio groups with 1 to 18 carbon atoms include methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, sec-butylthio, tert-butylthio, isobutylthio, n-pentylthio, isopentylthio, tert-pentylthio, n-hexylthio, n-heptylthio, isoheptylthio, tert-heptylthio, n-octylthio, isooctylthio, tert-octylthio, 2-ethylhexylthio, n-nonylthio, n-decylthio, n-undecylthio, n-dodecylthio, n-tridecylthio, n-tetradecylthio, n-pentadecanylthio, n-hexadecylthio, n-heptadecylthio, and n-octadecylthio.

[0139] As R 22a When the organic group is an aliphatic hydrocarbon group with 1 to 18 carbon atoms that can be replaced by a halogen atom and / or an alkylthio group, the aliphatic hydrocarbon group may contain an unsaturated double bond.

[0140] Furthermore, the structure of this aliphatic hydrocarbon group is not particularly limited; it can be linear, branched, cyclic, or a combination of these structures.

[0141] As in R 22a Preferred examples of organic groups that are alkenyl groups include allyl and 2-methyl-2-propenyl.

[0142] As in R 22a Preferred examples of the organic group being alkyl include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, isobutyl, n-pentyl, isopentyl, tert-pentyl, n-hexyl, n-hexane-2-yl, n-hexane-3-yl, n-heptyl, n-heptane-2-yl, n-heptane-3-yl, isoheptyl, tert-heptyl, n-octyl, isooctyl, tert-octyl, 2-ethylhexyl, n-nonyl, isononyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecanyl, n-hexadecyl, n-heptadecyl, and n-octadecyl.

[0143] As R 22a When the organic group is an alicyclic hydrocarbon group, examples of alicyclic hydrocarbons that form the main skeleton of the alicyclic hydrocarbon group include cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclodecane, bicyclo[2.1.1]hexane, bicyclo[2.2.1]heptane, bicyclo[3.2.1]octane, bicyclo[2.2.2]octane, and adamantane. Preferably, the alicyclic hydrocarbon group is obtained by removing one hydrogen atom from these alicyclic hydrocarbons.

[0144] As in R22aPreferred examples of organic groups that are aliphatic hydrocarbon groups obtained by substituting halogen atoms include trifluoromethyl, pentafluoroethyl, 2-chloroethyl, 2-bromoethyl, heptafluoropropyl, 3-bromopropyl, nonafluorobutyl, tridecafluorohexyl, heptadecafluorooctyl, 2,2,2-trifluoroethyl, 1,1-difluoroethyl, 1,1-difluoro-propyl, 1,1,2,2-tetrafluoro-propyl, 3,3,3-trifluoro-propyl, 2,2,3,3,3-pentafluoro-propyl, 2-norbornyl-1,1-difluoroethyl, 2-norbornyltetrafluoroethyl, and 3-adamantyl-1,1,2,2-tetrafluoropropyl.

[0145] As in R 22a Preferred examples of organic groups that are aliphatic hydrocarbon groups obtained by replacing alkylthio groups include 2-methylthioethyl, 4-methylthio-n-butyl, and 2-n-butylthioethyl.

[0146] As in R 22a A preferred example of the organic group being an aliphatic hydrocarbon group obtained by replacing the organic group with a halogen atom and an alkylthio group is 3-methylthio-1,1,2,2-tetrafluoro-n-propyl.

[0147] As in R 22a Preferred examples of organic groups being aryl include phenyl, naphthyl, and biphenyl.

[0148] As in R 22a Preferred examples of the organic group being an aryl group obtained by replacing a halogen atom include pentafluorophenyl, chlorophenyl, dichlorophenyl, and trichlorophenyl.

[0149] As in R 22a Preferred examples of the organic group being an aryl group obtained by substituting an alkylthio group include 4-methylthiophenyl, 4-n-butylthiophenyl, 4-n-octylthiophenyl, and 4-n-dodecylthiophenyl.

[0150] As in R 22a Preferred examples of the organic group being an aryl group obtained by substituting a halogen atom and an alkylthio group include 1,2,5,6-tetrafluoro-4-methylthiophenyl, 1,2,5,6-tetrafluoro-4-n-butylthiophenyl, and 1,2,5,6-tetrafluoro-4-n-dodecylthiophenyl.

[0151] As in R 22a Preferred examples of the organic group being aralkyl include benzyl, phenethyl, 2-phenylpropane-2-yl, diphenylmethyl, and triphenylmethyl.

[0152] As in R 22aPreferred examples of the organic group being an aralkyl group obtained by replacing a halogen atom include pentafluorophenylmethyl, phenyldifluoromethyl, 2-phenyltetrafluoroethyl, and 2-(pentafluorophenyl)ethyl.

[0153] As in R 22a In the case where the organic group is an aralkyl group obtained by replacing the alkylthio group, a preferred example is p-methylthiobenzyl.

[0154] As in R 22a In the case where the organic group is an aralkyl group obtained by replacing a halogen atom and an alkylthio group, a preferred example is 2-(2,3,5,6-tetrafluoro-4-methylthiophenyl)ethyl.

[0155] As in R 22a Preferred examples of organic groups that are alkylaryl groups include 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 3-isopropylphenyl, 4-isopropylphenyl, 4-n-butylphenyl, 4-isobutylphenyl, 4-tert-butylphenyl, 4-n-hexylphenyl, 4-cyclohexylphenyl, 4-n-octylphenyl, 4-(2-ethyl-n-hexyl)phenyl, 2,3-dimethylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl, 2, 6-Dimethylphenyl, 3,4-Dimethylphenyl, 3,5-Dimethylphenyl, 2,4-Di-tert-butylphenyl, 2,5-Di-tert-butylphenyl, 2,6-Di-tert-butylphenyl, 2,4-Di-tert-pentylphenyl, 2,5-Di-tert-pentylphenyl, 2,5-Di-tert-octylphenyl, 2-Cyclohexylphenyl, 3-Cyclohexylphenyl, 4-Cyclohexylphenyl, 2,4,5-Trimethylphenyl, 2,4,6-Trimethylphenyl, 2,4,6-Triisopropylphenyl.

[0156] The group represented by formula (a21a) is a group containing an ether group.

[0157] In equation (a21a), Y is used as the basis for the equation. 1 Alkyl groups representing alkyl groups with 1 to 4 carbon atoms can be exemplified by methylene, ethane-1,2-diyl, ethane-1,1-diyl, propane-1,3-diyl, propane-1,2-diyl, butane-1,4-diyl, butane-1,3-diyl, butane-2,3-diyl, and butane-1,2-diyl.

[0158] In equation (a21a), R is used as the base. 27a or R 28aAlkyl groups representing alkane groups with 2 to 6 carbon atoms include, for example, ethane-1,2-diyl, propane-1,3-diyl, propane-1,2-diyl, butane-1,4-diyl, butane-1,3-diyl, butane-2,3-diyl, butane-1,2-diyl, pentane-1,5-diyl, pentane-1,3-diyl, pentane-1,4-diyl, pentane-2,3-diyl, hexane-1,6-diyl, hexane-1,2-diyl, hexane-1,3-diyl, hexane-1,4-diyl, hexane-2,5-diyl, hexane-2,4-diyl, and hexane-3,4-diyl.

[0159] In equation (a21a), in R 27a or R 28a In the case of alkyl diesters with 2 to 6 carbon atoms obtained by substitution of halogen atoms, examples of halogen atoms include chlorine, bromine, iodine, and fluorine. Examples of alkyl diesters obtained by substitution of halogen atoms include tetrafluoroethane-1,2-diyl, 1,1-difluoroethane-1,2-diyl, 1-fluoroethane-1,2-diyl, 1,2-difluoroethane-1,2-diyl, hexafluoropropane-1,3-diyl, 1,1,2,2,-tetrafluoropropane-1,3-diyl, and 1,1,2,2,-tetrafluoropentane-1,5-diyl.

[0160] In equation (a21a), as in R 27a or R 28a Examples of arylene groups include 1,2-phenylene, 1,3-phenylene, 1,4-phenylene, 2,5-dimethyl-1,4-phenylene, biphenyl-4,4'-diyl, diphenylmethane-4,4'-diyl, 2,2'-diphenylpropane-4,4'-diyl, naphthalene-1,2-diyl, naphthalene-1,3-diyl, naphthalene-1,4-diyl, naphthalene-1,5-diyl, naphthalene-1,6-diyl, naphthalene-1,7-diyl, naphthalene-1,8-diyl, naphthalene-2,3-diyl, naphthalene-2,6-diyl, and naphthalene-2,7-diyl.

[0161] In equation (a21a), in R 27a or R 28a In the case of an arylene obtained by substitution of a halogen atom, examples of halogen atoms include chlorine, bromine, iodine, and fluorine atoms. Examples of arylene obtained by substitution of a halogen atom include 2,3,5,6-tetrafluoro-1,4-phenylene.

[0162] In equation (a21a), R is used as the base. 29aThe alkyl group represented is a branched alkyl group with 1 to 18 carbon atoms, and examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, isobutyl, n-pentyl, isopentyl, tert-pentyl, n-hexyl, n-hexane-2-yl, n-hexane-3-yl, n-heptyl, n-heptane-2-yl, n-heptane-3-yl, isoheptyl, tert-heptyl, n-octyl, isooctyl, tert-octyl, 2-ethylhexyl, n-nonyl, isononyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecanyl, n-hexadecyl, n-heptadecyl, and n-octadecyl.

[0163] In equation (a21a), in R 29a When the alkyl group obtained by substitution of a halogen atom has 1 to 18 carbon atoms, examples of halogen atoms include chlorine, bromine, iodine, and fluorine. Examples of alkyl groups obtained by substitution of a halogen atom include trifluoromethyl, pentafluoroethyl, heptafluoro-n-propyl, nonafluoro-n-butyl, tridecafluoro-n-hexyl, heptafluoro-n-octyl, 2,2,2-trifluoroethyl, 1,1-difluoroethyl, 1,1-difluoro-n-propyl, 1,1,2,2-tetrafluoro-n-propyl, 3,3,3-trifluoro-n-propyl, 2,2,3,3,3-pentafluoro-n-propyl, and 1,1,2,2-tetrafluorotetradecyl.

[0164] In equation (a21a), in R 29a In the case of an alicyclic hydrocarbon group having 3 to 12 carbon atoms, examples of alicyclic hydrocarbons constituting the main skeleton of such alicyclic hydrocarbon group include cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclodecane, bicyclo[2.1.1]hexane, bicyclo[2.2.1]heptane, bicyclo[3.2.1]octane, bicyclo[2.2.2]octane, and adamantane. As an alicyclic hydrocarbon group, it is preferable to have a group obtained by removing one hydrogen atom from these alicyclic hydrocarbons.

[0165] In equation (a21a), in R 29a In the case of aryl, haloaryl, aralkyl, or haloaralkyl groups, preferred examples of these groups are the same as R. 22a The same applies to these groups.

[0166] Among the groups represented by formula (a21a), the preferred groups are those represented by R. 27a The indicated group is a group obtained by replacing the carbon atom bonded to the sulfur atom with a fluorine atom. The preferred groups described above preferably have 2 or more and 18 or less carbon atoms.

[0167] As R 22a Preferred is a perfluoroalkyl group having 1 to 8 carbon atoms. Furthermore, camphor-10-yl is also preferred as R from the perspective of easily forming highly fine resist patterns. 22a.

[0168] In equation (a21), R 23a ~R 26a It can be a hydrogen atom or a monovalent organic group. Furthermore, R... 23a With R 24a R 24a With R 25a or R 25a With R 26a They can be bonded together to form rings. For example, this can be achieved by making R... 25a With R 26a It bonds with the naphthalene ring to form a five-membered ring, thus forming the acenaphthene skeleton.

[0169] As a monovalent organic group, preferably an alkyl or alkoxy group that can be substituted with an alicyclic hydrocarbon group, a heterocyclic group, or a halogen atom and has a branched chain with 4 to 18 carbon atoms; a heterocyclic alkoxy group; an alkylthio group that can be substituted with an alicyclic hydrocarbon group, a heterocyclic group, or a halogen atom and has a branched chain with 4 to 18 carbon atoms; or a heterocyclic thio group.

[0170] Furthermore, it is preferably a group obtained by substituting a methylene group at any position not adjacent to an oxygen atom of the alkoxy group with -CO-.

[0171] Preferably, the alkoxy group is obtained by interrupting the alkoxy group with a -O-CO- bond or a -O-CO-NH- bond. In addition, the left end of the -O-CO- bond and the -O-CO-NH- bond is close to the naphthalene dicarboxylic acid core in the alkoxy group.

[0172] Furthermore, alkylthio groups with 4 to 18 carbon atoms that can be substituted by alicyclic hydrocarbon groups, heterocyclic groups, or halogen atoms and can have branches are also preferred as R. 23a ~R 26a .

[0173] It is also preferably a group obtained by substituting a methylene group at any position not adjacent to a sulfur atom of the alkylthio group with -CO-.

[0174] Preferably, the alkylthio group is obtained by interrupting the -O-CO- or -O-CO-NH- bond. In addition, the left end of the -O-CO- and -O-CO-NH- bonds is close to the naphthalene dicarboxylic acid core in the alkylthio group.

[0175] As R 23a ~R 26a R is preferred 23a Organic groups, R 24a ~R 26a It is a hydrogen atom, or R 24a Organic groups, R23a R 25a and R 26a It is a hydrogen atom. Furthermore, R... 23a ~R 26a It can also consist entirely of hydrogen atoms.

[0176] As R 23a ~R 26a Examples of unsubstituted alkyl groups include n-butyl, sec-butyl, tert-butyl, isobutyl, n-pentyl, isopentyl, tert-pentyl, n-hexyl, n-heptyl, isoheptyl, tert-heptyl, n-octyl, isooctyl, tert-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecanyl, n-hexadecyl, n-heptadecyl, and n-octadecyl.

[0177] As R 23a ~R 26a Examples of unsubstituted alkoxy groups include n-butoxy, sec-butoxy, tert-butoxy, isobutoxy, n-pentoxy, isopentoxy, tert-pentoxy, n-hexoxy, n-heptoxy, isoheptoxy, tert-heptoxy, n-octoxy, isooctoxy, tert-octoxy, 2-ethylhexyl, n-nonoxy, n-decoxy, n-undecyloxy, n-dodecyloxy, n-tridecyloxy, n-tetradecyloxy, n-pentadecanyloxy, n-hexadecyloxy, n-heptadecyloxy, and n-octadecyloxy.

[0178] As R 23a ~R 26a Examples of unsubstituted alkylthio groups include n-butylthio, sec-butylthio, tert-butylthio, isobutylthio, n-pentylthio, isopentylthio, tert-pentylthio, n-hexylthio, n-heptylthio, isoheptylthio, tert-heptylthio, n-octylthio, isooctylthio, tert-octylthio, 2-ethylhexylthio, n-nonylthio, n-decylthio, n-undecylthio, n-dodecylthio, n-tridecylthio, n-tetradecylthio, n-pentadecanylthio, n-hexadecylthio, n-heptadecylthio, and n-octadecylthio.

[0179] In R 23a ~R 26a In the case of alkyl, alkoxy, or alkathioyl groups obtained by substitution with alicyclic hydrocarbon groups, examples of alicyclic hydrocarbons constituting the main skeleton of the alicyclic hydrocarbon group include cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclodecane, bicyclo[2.1.1]hexane, bicyclo[2.2.1]heptane, bicyclo[3.2.1]octane, bicyclo[2.2.2]octane, and adamantane. As an alicyclic hydrocarbon group, it is preferable to have a group obtained by removing one hydrogen atom from these alicyclic hydrocarbons.

[0180] In R 23a ~R 26aIn the case of alkyl, alkoxy, or alkylthio groups obtained by substitution with heterocyclic groups, or in the case of R 23a ~R 26a In the case of a heterocyclic group, examples of heterocycles that form the main skeleton of the heterocyclic group or heterocyclic group include pyrrole, thiophene, furan, pyran, thiopyran, imidazole, pyrazole, thiazole, isothiazole, oxazole, isoxazole, pyridine, pyrazine, pyrimidine, pyridazine, pyrrolidine, pyrazolidine, imidazoleidine, isoxazolidine, isothiazolidine, piperidine, piperazine, morpholine, thiomorpholine, chromium, thiochromium, isochromium, isothiochromium, indole, etc. Dolline, isoindoline, 4-azaindene, meso-azaindene, indole, indazole, purine, quinazine, isoquinoline, quinoline, naphthidine, phthalazine, quinoxaline, quinazoline, cyclophosphine, pteridine, acridine, phenanthroline, carbazole, carbline, phenazine, antilysodium, thiadiazole, oxadiazole, triazine, triazole, tetrazolium, benzimidazole, benzoxazole, benzothiazole, benzothiadiazole, benzofluoroethane, naphthimidazole, benzotriazole, tetraazaindene. Furthermore, saturated heterocycles obtained by hydrogenating the rings containing conjugated bonds in these heterocycles are preferred.

[0181] As a heterocyclic group that substituted for alkyl, alkoxy, or alkylthio groups, or a heterocyclic group contained in a heterocyclic group, it is preferably a group obtained by removing one hydrogen atom from the aforementioned heterocycle.

[0182] As R 23a ~R 26a Examples of alkoxy groups containing alicyclic hydrocarbon groups include cyclopentyloxy, methylcyclopentyloxy, cyclohexyloxy, fluorocyclohexyloxy, chlorocyclohexyloxy, cyclohexylmethyloxy, methylcyclohexyloxy, norbornyloxy, ethylcyclohexyloxy, cyclohexylethyloxy, dimethylcyclohexyloxy, methylcyclohexylmethyloxy, norbornylmethyloxy, trimethylcyclohexyloxy, 1-cyclohexylbutyloxy, adamantyloxy, menthyloxy, n-butylcyclohexyloxy, tert-butylcyclohexyloxy, bornyloxy, isobornyloxy, decahydronaphthyloxy, dicyclopentadienoxy, 1-cyclohexylpentyloxy, methyladamantyloxy, adamantylmethyloxy, 4-pentylcyclohexyloxy, cyclohexylcyclohexyloxy, adamantylethyloxy, and dimethyladamantyloxy.

[0183] As R 23a ~R 26a Examples of heterocyclic oxy groups include tetrahydrofuranyloxy, furfuryloxy, tetrahydrofuranyloxy, tetrahydropyranyloxy, butyrolactoneyloxy, and indolyloxy.

[0184] As R 23a ~R 26a Examples of alkylthio groups that include alicyclic hydrocarbon groups include cyclopentylthio, cyclohexylthio, cyclohexylmethylthio, norbornylthio, and isonorbornylthio.

[0185] As R 23a ~R 26a Examples of heterocyclic thio groups include furfural thio and tetrahydrofuran thio.

[0186] As R 23a ~R 26a Examples of groups obtained by substituting a methylene group at any position not adjacent to an oxygen atom of an alkoxy group with -CO- include 2-ketobutyl-1-oxy, 2-ketopentyl-1-oxy, 2-ketohexyl-1-oxy, 2-ketoheptyl-1-oxy, 2-ketooctyl-1-oxy, 3-ketobutyl-1-oxy, 4-ketopentyl-1-oxy, 5-ketohexyl-1-oxy, 6-ketoheptyl-1-oxy, 7-ketooctyl-1-oxy, 3-methyl-2-ketopentane-4-oxy, 2-ketopentane-4-oxy, 2-methyl-2-ketopentane-4-oxy, 3-ketoheptane-5-oxy, and 2-adamantanone-5-oxy.

[0187] As R 23a ~R 26a Examples of groups obtained by substituting a methylene group at any position not adjacent to a sulfur atom in an alkylthio group with -CO- include 2-ketobutyl-1-thio, 2-ketopentyl-1-thio, 2-ketohexyl-1-thio, 2-ketoheptyl-1-thio, 2-ketooctyl-1-thio, 3-ketobutyl-1-thio, 4-ketopentyl-1-thio, 5-ketohexyl-1-thio, 6-ketoheptyl-1-thio, 7-ketooctyl-1-thio, 3-methyl-2-ketopentane-4-thio, 2-ketopentane-4-thio, 2-methyl-2-ketopentane-4-thio, and 3-ketoheptane-5-thio.

[0188] As specific examples of compounds represented by formula (a21), the following compounds can be cited.

[0189] [Chemistry 19]

[0190]

[0191] [Chemistry 20]

[0192]

[0193] [Chemistry 21]

[0194]

[0195] [Chemistry 22]

[0196]

[0197] [Chemistry 23]

[0198]

[0199] [Chemistry 24]

[0200]

[0201] [Chemistry 25]

[0202]

[0203] [Chemistry 26]

[0204]

[0205] [Chemistry 27]

[0206]

[0207] [Chemistry 28]

[0208]

[0209] As an acid-producing agent (A), a naphthalene dicarboxylic acid derivative represented by the following formula (a22) is also preferred.

[0210] [Chemistry 29]

[0211]

[0212] In equation (a22), R b1 It is a hydrocarbon group with 1 to 30 carbon atoms.

[0213] As R b1 When the hydrocarbon group contains more than one methylene group, at least a portion of the methylene group can be derived from -O-, -S-, -CO-, -CO-O-, -SO-, -SO2-, -CR b4 R b5 -and-NR b6 - The selected groups are substituted within the group.

[0214] As R b1 When the hydrocarbon group contains a hydrocarbon ring, at least one carbon atom constituting the hydrocarbon ring may be replaced by a heteroatom or a group of atoms containing the heteroatom selected from the group consisting of N, O, P, S and Se.

[0215] R b4 and R b5 Each can be independently a hydrogen atom or a halogen atom, R b4 and R b5 At least one of them is a halogen atom.

[0216] Rb6 It consists of a hydrocarbon group with 1 to 6 hydrogen atoms or carbon atoms.

[0217] R a1 and R a2 Each of the following is independently a hydrogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms that may have substituents, an aromatic group having 5 to 20 ring atoms that may have substituents, or an aromatic group with -R a3 -R a4 The group indicated.

[0218] R a1 and R a2 They are not both hydrogen atoms.

[0219] As R a1 or R a2 When an aliphatic hydrocarbon group contains more than one methylene group, at least a portion of the methylene group can be derived from -O-, -S-, -CO-, -CO-O-, -SO-, -SO2-, and -NR. a5 - The selected groups are substituted within the group.

[0220] R a5 It consists of a hydrocarbon group with 1 to 6 hydrogen atoms or carbon atoms.

[0221] R a3 It can be methylene, -O-, -CO-, -CO-O-, -SO-, -SO2- or -NR a6 -

[0222] R a6 It consists of a hydrocarbon group with 1 to 6 hydrogen atoms or carbon atoms.

[0223] R a4 It is an aromatic group having 5 to 20 or fewer ring atoms that may have substituents, a perfluoroalkyl group having 1 to 6 or fewer carbon atoms, an aralkyl group having 7 to 20 or fewer carbon atoms that may have substituents, or a heteroarylalkyl group containing an aromatic heterocyclic group having 5 to 20 or fewer ring atoms that may have substituents.

[0224] Q 1 And Q 2 Each is independently a perfluoroalkyl group having 1 to 6 carbon atoms.

[0225] L represents an ester bond.

[0226] In equation (a22), R is... a1 and R a2 Aliphatic hydrocarbon groups with 1 to 20 carbon atoms can be straight-chain, branched, cyclic, or a combination of these structures.

[0227] As an aliphatic hydrocarbon group, alkyl is preferred. Specific examples of preferred alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, and n-decyl.

[0228] As R a1 and R a2 Aliphatic hydrocarbons with 1 to 20 carbon atoms can have substituents, including hydroxyl, mercapto, amino, halogen, oxygen, nitro, and cyano groups. The number of substituents is arbitrary. As R... a1 and R a2 The substituent is an aliphatic hydrocarbon group having 1 to 20 carbon atoms, such as perfluoroalkyl groups having 1 to 6 carbon atoms. Specific examples include CF3-, CF3CF2-, (CF3)2CF-, CF3CF2CF2-, CF3CF2CF2CF2-, (CF3)2CFCF2-, CF3CF2(CF3)CF-, and (CF3)3C-.

[0229] In equation (a22), R is... a1 and R a2 The ring containing substituents can be an aromatic group with 5 to 20 atoms, which can be an aromatic hydrocarbon group or an aromatic heterocyclic group.

[0230] Examples of aromatic groups include aryl groups such as phenyl and naphthyl, or heteroaryl groups such as furanyl and thiophene.

[0231] Aromatic groups with 5 to 20 atoms constituting a ring may have substituents and as R a1 and R a2 Aliphatic hydrocarbons with 1 to 20 carbon atoms can have the same substituents.

[0232] In equation (a22), R is... a4 The ring containing substituents can be an aromatic group having 5 to 20 atoms, and the R... a1 and R a2 The rings that can have substituents are the same as aromatic groups with 5 to 20 atoms.

[0233] In equation (a22), R is... a4 Perfluoroalkyl groups with 1 to 6 carbon atoms and as R a1 and R a2 The description refers to perfluoroalkyl groups with 1 to 6 carbon atoms.

[0234] In equation (a22), R is... a4 Specific examples of aralkyl groups having a substituent group having 7 to 20 carbon atoms include benzyl, phenethyl, α-naphthylmethyl, β-naphthylmethyl, 2-α-naphthylethyl, and 2-β-naphthylethyl.

[0235] In formula (a22), heteroarylalkyl refers to a group in an arylalkyl group in which a portion of the carbon atom constituting the aromatic hydrocarbon ring is replaced by a heteroatom such as N, O, or S. As R a4 Specific examples of heteroarylalkyl groups containing 5 to 20 aromatic heterocyclic atoms that may have substituents include pyridin-2-ylmethyl, pyridin-3-ylmethyl, pyridin-4-ylmethyl, etc.

[0236] In equation (a22), R is... a5 Hydrocarbon groups with 1 to 6 carbon atoms can be aliphatic, aromatic, or a combination of aliphatic and aromatic hydrocarbon groups. Aliphatic hydrocarbon groups can be linear, branched, cyclic, or combinations of these structures.

[0237] Examples of aliphatic hydrocarbon groups include alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, and n-hexyl.

[0238] As an aromatic hydrocarbon group, phenyl can be cited as an example.

[0239] In equation (a22), R is... a6 Hydrocarbon groups with 1 to 6 carbon atoms and the opposite R a5 The hydrocarbon groups with 1 to 6 carbon atoms are the same.

[0240] In equation (a22), R is... b1 Hydrocarbon groups with 1 to 30 carbon atoms can be aliphatic, aromatic, or a combination of aliphatic and aromatic hydrocarbon groups. Aliphatic hydrocarbon groups can be linear, branched, cyclic, or combinations of these structures.

[0241] Examples of aliphatic hydrocarbon groups include chain-like aliphatic hydrocarbon groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, and n-hexyl, as well as cyclic aliphatic hydrocarbon groups (hydrocarbon rings) such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, and norbornyl.

[0242] Examples of aromatic hydrocarbon groups include phenyl and naphthyl.

[0243] Examples of groups that combine aliphatic and aromatic hydrocarbon groups include benzyl, phenethyl, and furanylmethyl.

[0244] As R b1 When the hydrocarbon group contains a hydrocarbon ring, examples of heteroatoms that substitute for at least one carbon atom constituting the hydrocarbon ring include -CO-, -CO-O-, -SO-, -SO2-, -SO2-O-, and -P(=O)-(OR b7 )3. R b7 It is a hydrocarbon group with 1 to 6 carbon atoms, and is related to R. a5 The hydrocarbon groups with 1 to 6 carbon atoms are the same.

[0245] In equation (a22), R is... b4 and R b5 Specific examples of halogen atoms include chlorine, fluorine, bromine, and iodine atoms.

[0246] In equation (a22), R is... b6 Hydrocarbon groups with 1 to 6 carbon atoms, and R in formula (a22) a5 The hydrocarbon groups with 1 to 6 carbon atoms are the same.

[0247] In equation (a22), Q is... 1 And Q 2 A perfluoroalkyl group having 1 to 6 carbon atoms, and used as R in formula (a22). a1 and R a2 The description refers to perfluoroalkyl groups with 1 to 6 carbon atoms.

[0248] In the compound represented by formula (a22), the direction of the ester bond as L is not particularly limited and can be either -CO-O- or -O-CO-.

[0249] The compound represented by formula (a22) is preferably a compound represented by the following formula (a22-1).

[0250] [Chemistry 30]

[0251]

[0252] (R in equation (a22-1)) b1 R a1 Q 1 And Q 2 These are the same as those in equation (a22).

[0253] In equation (a22-1) R a1 The substituent is an aliphatic hydrocarbon group with 1 to 20 carbon atoms, as R a1When the aliphatic hydrocarbon group contains one or more methylene groups, preferably at least a portion of the methylene groups can be derived from -O-, -S-, -CO-, -CO-O-, -SO-, -SO2-, and -NR. a5 - A compound represented by formula (a22-1) whose selected groups are substituted.

[0254] The compound represented by formula (a22) can be manufactured by the following method for manufacturing N-organosulfonyloxy compounds.

[0255] In a method for manufacturing an N-organosulfonyloxy compound capable of producing a compound represented by formula (a22), the method includes reacting an N-hydroxy compound (a') with a sulfonyl fluoride compound (b') in the presence of a basic compound (d'). The method for manufacturing an N-organosulfonyloxy compound is characterized in that, during the reaction of the N-hydroxy compound (a') with the sulfonyl fluoride compound (b'), a silanizing agent (c') is present in the system. The sulfonyl fluoride compound (b') is represented by the following formula (b1-1). The silanizing agent (c') can convert the hydroxyl group on the nitrogen atom of the N-hydroxy compound (a') into a silanoxy group represented by the following formula (ac1).

[0256] -O-Si(R c1 )3...(ac1)

[0257] (In formula (ac1), R) c1 Each group is an independent hydrocarbon group with 1 to 10 carbon atoms.

[0258] R b1 -L-CQ 1 Q 2 -SO2-F...(b1-1)

[0259] (In equation (b1-1), R) b1 L, Q 1 And Q 2 These are the same as those in equation (a22) above.

[0260] Furthermore, the method for manufacturing an N-organosulfonyloxy compound capable of producing a compound represented by formula (a22) includes: a silanization step, in which an N-hydroxy compound (a') is silanized using a silanizing agent (c'); and a condensation step, in which the silanized N-hydroxy compound (a') generated in the silanization step is condensed with a sulfonyl fluoride compound (b') in the presence of an alkaline compound (d'), the sulfonyl fluoride compound (b') being represented by the above formula (b1-1), wherein the silanizing agent (c') can convert the hydroxyl group on the nitrogen atom of the N-hydroxy compound (a') into a methoxy group represented by the above formula (ac1).

[0261] N-hydroxy compounds (a') are compounds represented by the following formula (a22-2).

[0262] [Chemistry 31]

[0263]

[0264] R in equation (a22-2) a1 and R a2 These are the same as those in equation (a22) above.

[0265] N-hydroxy compounds (a') can be synthesized by conventional methods, such as those disclosed in International Publication No. 2014 / 084269 and Japanese Patent Publication No. 2017-535595. For example, starting with a commercially available bromide, the bromine group on naphthalenecarboxylic anhydride is converted to R by a reaction shown in the following formula. a1 Subsequently, hydroxylamine compounds such as hydroxylamine hydrochloride are reacted with an anhydride group to perform N-hydroxyimideation, thereby synthesizing R represented by formula (a22-1). a2 Compounds containing hydrogen atoms. Furthermore, as an N-hydroxy compound (a'), commercially available products can be used.

[0266] [Chemistry 32]

[0267]

[0268] Sulfonyl fluoride compounds (b') can be synthesized using conventional methods. For example, in (b1-1), Q 1 And Q 2 Compounds containing fluorine atoms can be synthesized via reactions represented by the following formula. Furthermore, commercially available products can be used as sulfonyl fluoride compounds (b').

[0269] [Chemistry 33]

[0270]

[0271] In equation (ac1), R is used as c1 Hydrocarbon groups with 1 to 10 carbon atoms can be aliphatic, aromatic, or a combination of aliphatic and aromatic hydrocarbon groups. Aliphatic hydrocarbon groups can be linear, branched, cyclic, or combinations of these structures.

[0272] Examples of aliphatic hydrocarbon groups include alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, and n-decyl.

[0273] Examples of aromatic hydrocarbon groups include phenyl and naphthyl.

[0274] Examples of compounds represented by the following formula (c1) can be cited as silanizing agents (c').

[0275] X-Si(R c1 )3...(c1)

[0276] (In formula (c1), R) c1 R in equation (ac1) c1 (Similarly, X is a halogen atom.)

[0277] In formula (c1), specific examples of halogen atoms of X include chlorine, fluorine, bromine and iodine atoms.

[0278] Specific examples of silanizing agents (c') include trimethylchlorosilane, trimethylfluorosilane, trimethylbromosilane, tert-butyldimethylchlorosilane, ethyldimethylchlorosilane, and isopropyldimethylchlorosilane.

[0279] Basic compounds (d') can be organic or inorganic bases.

[0280] As organic bases, examples include nitrogen-containing basic compounds, such as amines like methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, trimethylamine, triethylamine, methyl diethylamine, N-ethyl diisopropylamine, tri-n-propylamine, triisopropylamine, monoethanolamine, diethanolamine, and triethanolamine; cyclic basic compounds like pyrrole, piperidine, 1,8-diazabicyclo[5,4,0]-7-undecene, and 1,5-diazabicyclo[4,3,0]-5-nonane; and quaternary ammonium salts like tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide, tetrapropylammonium hydroxide (TPAH), tetrabutylammonium hydroxide, methyl tripropylammonium hydroxide, methyl tributylammonium hydroxide, benzyl trimethylammonium hydroxide, benzyl triethylammonium hydroxide, and trimethyl(2-hydroxyethyl)ammonium hydroxide.

[0281] Examples of inorganic bases include metal hydroxides, metal bicarbonates, and metal bicarbonates. Specific examples of inorganic bases include metal hydroxides such as lithium hydroxide, potassium hydroxide, sodium hydroxide, rubidium hydroxide, cesium hydroxide, magnesium hydroxide, calcium hydroxide, strontium hydroxide, and barium hydroxide; metal carbonates such as lithium carbonate, potassium carbonate, sodium carbonate, rubidium carbonate, cesium carbonate, magnesium carbonate, calcium carbonate, strontium carbonate, and barium carbonate; and metal bicarbonates such as lithium bicarbonate, potassium bicarbonate, sodium bicarbonate, rubidium bicarbonate, and cesium bicarbonate.

[0282] In the method for manufacturing N-organosulfonyloxy compounds, such N-hydroxy compounds (a') are reacted with sulfonyl fluoride compounds (b') in the presence of a silanizing agent (c') and a basic compound (d').

[0283] In this way, when an N-hydroxy compound (a') is reacted with a sulfonyl fluoride compound (b') in the presence of a basic compound (d'), the presence of a silanizing agent (c') enables the efficient production of N-organosulfonyloxy compounds. For example, the N-organosulfonyloxy compound can be obtained at a yield of 65% or more relative to the N-hydroxy compound (a') and the sulfonyl fluoride compound (b') of the starting materials.

[0284] By means of manufacturing N-organosulfonyloxy compounds, it is possible to obtain a group having the hydrogen atom of the hydroxyl group bonded to the nitrogen atom in an N-hydroxy compound (a') removed, and an R group derived from a sulfonyl fluoride compound (b'). b1 N-organosulfonyloxy compounds with a structure obtained by -SO2- bonding.

[0285] In the method for manufacturing N-organosulfonyloxy compounds, when reacting N-hydroxy compound (a') with sulfonyl fluoride compound (b') in the presence of basic compound (d'), the presence of silanizing agent (c') in the system is sufficient. N-hydroxy compound (a'), sulfonyl fluoride compound (b'), silanizing agent (c') and basic compound (d') can be mixed simultaneously. Alternatively, sulfonyl fluoride compound (b') and basic compound (d') can be added after N-hydroxy compound (a') has partially reacted with silanizing agent (c') or after N-hydroxy compound (a') has completely reacted with silanizing agent (c').

[0286] If such an N-hydroxy compound (a') is reacted with a sulfonyl fluoride compound (b') in the presence of a silanizing agent (c') and a basic compound (d'), the N-hydroxy compound (a') is silanized by the silanizing agent (c'), and the hydroxyl group on the nitrogen atom is converted into a silanoxy group represented by the above formula (ac1) (step 1: silanization process).

[0287] Then, the silanized N-hydroxy compound (a') generated in the silanization step is condensed with the sulfonyl fluoride compound (b') formed by the reaction with the basic compound (d') (step 2: condensation step). This yields an N-organosulfonyloxy compound.

[0288] As an example of a method for manufacturing N-organosulfonyloxy compounds, the following shows the use of a compound represented by the above formula (a22-2) as an N-hydroxy compound (a'), and the use of Q in the above formula (b1-1). 1 And Q 2The reaction equations are shown below, with the fluorine atom as the sulfonyl fluoride compound (b'), trimethylchlorosilane as the silanizing agent (c'), and triethylamine as the basic compound (d'). Furthermore, the reaction mechanisms shown below are not analytically confirmed, but rather inferred from the behavior of the reactants in the reaction.

[0289] [Chemistry 34]

[0290] Step 1

[0291]

[0292] [Chemistry 35]

[0293] Step 2

[0294]

[0295] Organic solvents that can be used in the reaction include, for example, esters such as ethyl acetate, butyl acetate, and acetic acid solvents; ketones such as acetone, methyl ethyl ketone, isobutyl ketone, and methyl isobutyl ketone; esters such as ethyl acetate, butyl acetate, and diethyl malonate; amides such as N-methylpyrrolidone and N,N-dimethylformamide; ethers such as diethyl ether, ethylcyclopentyl ether, tetrahydrofuran, and dioxane; aromatic hydrocarbons such as toluene and xylene; aliphatic hydrocarbons such as hexane, heptane, octane, and decahydronaphthalene; halogenated hydrocarbons such as chloroform, dichloromethane, methylene dichloro, and dichloroethane; nitrile solvents such as acetonitrile and propionitrile; and dimethyl sulfoxide and dimethyl sulfonamide. One solvent can be used, or two or more solvents can be used in combination.

[0296] The reaction temperature that can be used is, for example, in the range of -10°C to 200°C, preferably in the range of 0°C to 150°C, and more preferably in the range of 5°C to 120°C.

[0297] The possible reaction times are, for example, 5 minutes to 20 hours, 10 minutes to 15 hours, or 30 minutes to 12 hours.

[0298] Relative to the N-hydroxy compound (a'), it is preferable to use an excess of the sulfonyl fluoride compound (b'), the silanizing agent (c'), and the basic compound (d'). For example, relative to 1.0 mole of the N-hydroxy compound (a'), it is preferable to use the sulfonyl fluoride compound (b') in amounts of 1.1 moles to 2.5 moles, the silanizing agent (c') in amounts of 1.1 moles to 2.5 moles, and the basic compound (d') in amounts of 1.1 moles to 2.5 moles.

[0299] Acid-generating agent (A) can be used alone or in combination with two or more other agents. Furthermore, the content of acid-generating agent (A) relative to the total solid content of the photosensitive composition is preferably 0.1% to 10% by mass, more preferably 0.2% to 6% by mass, and particularly preferably 0.5% to 3% by mass. By keeping the amount of acid-generating agent (A) within the above range, it is easy to prepare a photosensitive composition that exhibits good sensitivity, is a homogeneous solution, and has excellent storage stability.

[0300] <Resin (B)>

[0301] The resin (B) whose solubility in alkali increases due to the action of acid is not particularly limited, and any resin whose solubility in alkali increases due to the action of acid can be used. Among them, it is preferable to contain at least one resin selected from the group consisting of phenolic varnish resin (B1), polyhydroxystyrene resin (B2), and acrylic resin (B3).

[0302] [Phenolic varnish resin (B1)]

[0303] As a phenolic varnish resin (B1), a resin comprising structural units represented by the following formula (b1) can be used.

[0304] [Chemistry 36]

[0305]

[0306] In the above formula (b1), R 1b R represents an acid dissociation and solubility inhibition group. 2b R 3b Each can be used independently to represent an alkyl group having 1 to 6 hydrogen atoms or carbon atoms.

[0307] As for the above R 1b The acid dissociation and dissolution inhibition group represented is preferably a group represented by the following formulas (b2) and (b3), a straight-chain, branched, or cyclic alkyl group, vinyloxyethyl group, tetrahydropyranyl group, tetrahydrofuranyl group, or trialkylsilyl group having 1 to 6 carbon atoms.

[0308] [Chemistry 37]

[0309]

[0310] In equations (b2) and (b3) above, R 4b R 5b Each of the following independently represents a hydrogen atom or a straight-chain or branched alkyl group having 1 to 6 carbon atoms: R 6b R represents a straight-chain, branched, or cyclic alkyl group having 1 to 10 carbon atoms. 7bIt indicates a straight-chain, branched, or cyclic alkyl group with 1 to 6 carbon atoms, and o indicates 0 or 1.

[0311] Examples of linear or branched alkyl groups include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, isopentyl, and neopentyl. Examples of cyclic alkyl groups include cyclopentyl and cyclohexyl.

[0312] Here, examples of acid dissociation-inhibiting groups represented by formula (b2) above include methoxyethyl, ethoxyethyl, n-propoxyethyl, isopropoxyethyl, n-butoxyethyl, isobutoxyethyl, tert-butoxyethyl, cyclohexyloxyethyl, methoxypropyl, ethoxypropyl, 1-methoxy-1-methyl-ethyl, and 1-ethoxy-1-methylethyl. Furthermore, examples of acid dissociation-inhibiting groups represented by formula (b3) above include tert-butoxycarbonyl and tert-butoxycarbonylmethyl. Additionally, examples of trialkylsilyl groups include trimethylsilyl, tri-tert-butyldimethylsilyl, and groups where each alkyl group has 1 to 6 carbon atoms.

[0313] [Polyhydroxystyrene resin (B2)]

[0314] As a polyhydroxystyrene resin (B2), a resin comprising structural units represented by the following formula (b4) can be used.

[0315] [Chemistry 38]

[0316]

[0317] In equation (b4) above, R 8b R indicates an alkyl group having 1 to 6 hydrogen atoms or carbon atoms. 9b This indicates an acid dissociation and dissolution inhibition group.

[0318] The aforementioned alkyl groups having 1 to 6 carbon atoms are, for example, straight-chain, branched, or cyclic alkyl groups having 1 to 6 carbon atoms. Examples of straight-chain or branched alkyl groups include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, isopentyl, and neopentyl, while examples of cyclic alkyl groups include cyclopentyl and cyclohexyl.

[0319] As mentioned above, R 9b The acid dissociation dissolution inhibition group indicated can be the same acid dissociation dissolution inhibition group as those exemplified in formulas (b2) and (b3) above.

[0320] Furthermore, for the purpose of appropriately controlling physical and chemical properties, polyhydroxystyrene resin (B2) can contain other polymerizable compounds as structural units. Examples of such polymerizable compounds include known free radical polymerizable compounds and anionic polymerizable compounds. Other examples 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 with carboxyl and ester bonds such as 2-methacryloyloxyethyl succinic acid, 2-methacryloyloxyethyl maleic acid, 2-methacryloyloxyethyl phthalic acid, and 2-methacryloyloxyethyl hexahydrophthalic acid; alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, and butyl methacrylate; and hydroxyalkyl methacrylates such as 2-hydroxyethyl methacrylate and 2-hydroxypropyl methacrylate. Classes include: phenyl methacrylate, benzyl methacrylate, and other aryl methacrylates; diethyl maleate, dibutyl fumarate, and other dicarboxylic acid diesters; vinyl-containing aromatic compounds such as styrene, α-methylstyrene, chlorostyrene, chloromethylstyrene, vinyltoluene, hydroxystyrene, α-methylhydroxystyrene, and α-ethylhydroxystyrene; vinyl acetate and other vinyl-containing aliphatic compounds; butadiene, isoprene, and other conjugated dienes; acrylonitrile, methacrylonitrile, and other nitrile-containing polymeric compounds; vinyl chloride, vinylidene chloride, and other chlorine-containing polymeric compounds; and acrylamide, methacrylamide, and other polymeric compounds containing amide bonds.

[0321] [Acrylic resin (B3)]

[0322] As for acrylic resin (B3), there are no particular limitations as long as it is an acrylic resin whose solubility in alkali increases due to the action of acid, and which has been mixed in various photosensitive compositions.

[0323] The acrylic resin (B3) preferably contains structural units (b-3) derived from acrylates containing, for example, -SO2- cyclic groups or lactone cyclic groups. In this case, when forming the resist pattern, it is easy to form a resist pattern with a preferred cross-sectional shape.

[0324] (Contains -SO2- cyclic group)

[0325] Here, "-SO2-containing cyclic group" refers to a cyclic group whose ring skeleton contains a ring containing -SO2-. Specifically, it is a cyclic group in which the sulfur atom (S) in -SO2- forms part of the ring skeleton of the cyclic group. In this ring skeleton, the ring containing -SO2- is counted as the first ring. If only this ring is present, it is called a monocyclic group. If other ring structures are present, regardless of their structure, it is called a polycyclic group. -SO2-containing cyclic groups can be monocyclic or polycyclic.

[0326] The cyclic group containing -SO2- is particularly preferred to be a cyclic group that contains -O-SO2- in its ring skeleton, that is, a cyclic group containing -OS- in -O-SO2- forming a sulfonyl lactone ring as part of the ring skeleton.

[0327] The number of carbon atoms containing the -SO2- cyclic group is preferably 3 to 30, more preferably 4 to 20, even more preferably 4 to 15, and particularly preferably 4 to 12. This number of carbon atoms refers to the number of carbon atoms constituting the cyclic skeleton and does not include the number of carbon atoms in the substituents.

[0328] The -SO2- cyclic group can be an aliphatic cyclic group or an aromatic cyclic group containing -SO2-. Preferably, it is an aliphatic cyclic group containing -SO2-.

[0329] As an aliphatic cyclic group containing -SO2-, examples include groups obtained by removing at least one hydrogen atom from an aliphatic hydrocarbon ring in which a portion of the carbon atoms constituting its ring skeleton are replaced by -SO2- or -O-SO2-. More specifically, examples include groups obtained by removing at least one hydrogen atom from an aliphatic hydrocarbon ring in which -CH2- constituting its ring skeleton is replaced by -SO2-, and groups obtained by removing at least one hydrogen atom from an aliphatic hydrocarbon ring in which -CH2-CH2- constituting its ring is replaced by -O-SO2-.

[0330] The alicyclic hydrocarbon ring preferably has 3 to 20 carbon atoms, more preferably 3 to 12 or less. The alicyclic hydrocarbon ring can be polycyclic or monocyclic. As a monocyclic alicyclic hydrocarbon group, it is preferably a group obtained by removing two hydrogen atoms from a monocyclic alkane with 3 to 6 carbon atoms. Examples of such monocyclic alkane include cyclopentane and cyclohexane. As a polycyclic alicyclic hydrocarbon ring, it is preferably a group obtained by removing two hydrogen atoms from a polycyclic alkane with 7 to 12 carbon atoms. Specific examples of such polycyclic alkane include adamantane, norbornane, isoboronane, tricyclodecane, and tetracyclododecane.

[0331] The -SO2- cyclic group can have substituents. Examples of such substituents include alkyl, alkoxy, halogen atom, haloalkyl, hydroxyl, oxygen atom (=O), -COOR", -OC(=O)R", hydroxyalkyl, cyano, etc.

[0332] The alkyl group used as the substituent is preferably an alkyl group having 1 to 6 carbon atoms. This alkyl group is preferably straight-chain or branched. Examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, and n-hexyl. Among these, methyl or ethyl is preferred, and methyl is particularly preferred.

[0333] The alkoxy group used as the substituent is preferably an alkoxy group having 1 to 6 carbon atoms. This alkoxy group is preferably linear or branched. Specifically, examples of alkyl groups used as the substituent are groups formed by bonding an alkyl group to an oxygen atom (-O-).

[0334] Examples of halogen atoms that can be used as substituents include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms, with fluorine atoms being preferred.

[0335] Haloalkyl groups, which are substituents, can be exemplified by groups obtained by replacing some or all of the hydrogen atoms of the alkyl group with the halogen atoms.

[0336] The haloalkyl group that serves as the substituent can be exemplified by groups obtained by replacing some or all of the hydrogen atoms of the alkyl group exemplified as the above-mentioned substituent with the halogen atom. The haloalkyl group is preferably a fluoroalkyl group, and particularly preferably a perfluoroalkyl group.

[0337] In the above-mentioned -COOR” and -OC(=O)R”, R” is a straight-chain, branched or cyclic alkyl group with 1 to 15 carbon atoms.

[0338] When R” is a straight-chain or branched alkyl group, the number of carbon atoms in the alkyl group is preferably 1 to 10, more preferably 1 to 5, and particularly preferably 1 or 2.

[0339] When R” is a cyclic alkyl group, the number of carbon atoms in the cyclic alkyl group is preferably 3 to 15, more preferably 4 to 12, and particularly preferably 5 to 10. Specifically, examples include groups obtained by removing one or more hydrogen atoms from monocyclic alkanes that can be substituted or not substituted by fluorine atoms or fluorinated alkyl groups, or from polycyclic alkanes such as bicyclic alkanes, tricyclic alkanes, and tetracyclic alkanes. More specifically, examples include groups obtained by removing one or more hydrogen atoms from monocyclic alkanes such as cyclopentane and cyclohexane, or from polycyclic alkanes such as adamantane, norbornane, isobornane, tricyclic decane, and tetracyclic dodecane.

[0340] The hydroxyalkyl group used as the substituent is preferably a hydroxyalkyl group having 1 to 6 carbon atoms. Specifically, examples of alkyl groups used as the above-mentioned substituents include groups obtained by substituting at least one hydrogen atom of the alkyl group with a hydroxyl group.

[0341] More specifically, examples of groups represented by the following formulas (3-1) to (3-4) can be cited as -SO2- cyclic groups.

[0342] [Chemistry 39]

[0343]

[0344] (In the formula, A' is an alkylene group, oxygen atom, or sulfur atom with a carbon number of 1 to 5 that may contain oxygen or sulfur atoms, z is an integer of 0 to 2, and R...) 10b (The R group can be alkyl, alkoxy, haloalkyl, hydroxy, -COOR", -OC(=O)R", hydroxyalkyl or cyano, where R is a hydrogen atom or alkyl group.)

[0345] In formulas (3-1) to (3-4) above, A' is an alkylene group, oxygen atom, or sulfur atom containing 1 to 5 carbon atoms, which may include an oxygen atom (-O-) or a sulfur atom (-S-). As the alkylene group containing 1 to 5 carbon atoms in A', it is preferably a straight-chain or branched alkylene group, and examples include methylene, ethylene, n-propylene, isopropylene, etc.

[0346] When the alkylene group contains an oxygen atom or a sulfur atom, examples include groups with -O- or -S- intermediates at the end of the alkylene group or between carbon atoms, such as -O-CH2-, -CH2-O-CH2-, -S-CH2-, -CH2-S-CH2-, etc. As A', an alkylene group or -O- with 1 to 5 carbon atoms is preferred, an alkylene group with 1 to 5 carbon atoms is more preferred, and a methylene group is most preferred.

[0347] z can be any of 0, 1, and 2, with 0 being the optimal value. When z is 2, multiple R... 10b They can be the same or different.

[0348] As R 10b The alkyl, alkoxy, haloalkyl, -COOR", -OC(=O)R", and hydroxyalkyl groups mentioned above can be the same as the alkyl, alkoxy, haloalkyl, -COOR", -OC(=O)R", and hydroxyalkyl groups that can be exemplified as substituents that can be present in the -SO2-cyclic group described above.

[0349] The following examples illustrate specific cyclic groups represented by the above formulas (3-1) to (3-4). Additionally, "Ac" in the formulas represents an acetyl group.

[0350] [Chemistry 40]

[0351]

[0352] [Chemistry 41]

[0353]

[0354] As a -SO2- cyclic group, it is preferably a group represented by the above formula (3-1), more preferably at least one selected from the group consisting of any one of the groups represented by the chemical formulas (3-1-1), (3-1-18), (3-3-1) and (3-4-1), and most preferably a group represented by the chemical formula (3-1-1).

[0355] (Contains lactone cyclic group)

[0356] "Lactone-containing cyclic group" indicates a cyclic group whose ring skeleton contains a ring (lactone ring) including -OC (=O)-. The lactone ring is designated as the first ring. In the case of only a lactone ring, it is called a monocyclic group; in the case of other ring structures, regardless of their structure, it is called a polycyclic group. Lactone-containing cyclic groups can be either monocyclic or polycyclic.

[0357] The lactone-containing cyclic group in structural unit (b-3) is not particularly limited, and any lactone-containing cyclic group can be used. Specifically, examples of lactone-containing monocyclic groups include groups obtained by removing one hydrogen atom from a four- to six-membered ring lactone, such as groups obtained by removing one hydrogen atom from β-propiolactone, groups obtained by removing one hydrogen atom from γ-butyrolactone, and groups obtained by removing one hydrogen atom from δ-pentanolactone. Furthermore, examples of lactone-containing polycyclic groups include groups obtained by removing one hydrogen atom from bicyclic alkanes, tricyclic alkanes, and tetracyclic alkanes having a lactone ring.

[0358] As for the structural unit (b-3), as long as it is a structural unit having a -SO2- cyclic group or a lactone cyclic group, the structure of other parts is not particularly limited. Preferably, at least one structural unit is selected from the group consisting of structural units (b-3-S) that are derived from acrylates in which the hydrogen atom bonded to the carbon atom at the α position can be replaced by a substituent, and structural units (b-3-L) that are derived from acrylates in which the hydrogen atom bonded to the carbon atom at the α position can be replaced by a substituent, and structural units (b-3-L) that are derived from acrylates in which the hydrogen atom bonded to the carbon atom at the α position can be replaced by a substituent.

[0359] [Structural Unit (b-3-S)]

[0360] As an example of the structural unit (b-3-S), more specifically, a structural unit represented by the following formula (b-S1) can be cited.

[0361] [Chemistry 42]

[0362]

[0363] (In the formula, R is a hydrogen atom, an alkyl group with 1 to 5 carbon atoms, or a haloalkyl group with 1 to 5 carbon atoms.) 11b R is a ring-containing group containing -SO2-. 12b (A single bond or a divalent linker.)

[0364] In equation (b-S1), R is the same as above.

[0365] R 11b It is the same as the -SO2- cyclic group listed above.

[0366] R 12b It can be any of the single bond or divalent linker groups.

[0367] As R 12b The divalent linking group in the linking group is not particularly limited. Preferred examples include divalent hydrocarbon groups that may have substituents and divalent linking groups containing heteroatoms.

[0368] • Divalent hydrocarbon groups that may have substituents

[0369] The hydrocarbon group serving as the divalent linking group can be either an aliphatic hydrocarbon group or an aromatic hydrocarbon group. An aliphatic hydrocarbon group refers to a hydrocarbon group that is not aromatic. This aliphatic hydrocarbon group can be saturated or unsaturated. Saturated hydrocarbon groups are generally preferred. More specifically, examples of this aliphatic hydrocarbon group include straight-chain or branched aliphatic hydrocarbon groups, and aliphatic hydrocarbon groups containing rings in their structure.

[0370] The number of carbon atoms in the straight-chain or branched aliphatic hydrocarbon group is preferably 1 to 10, more preferably 1 to 8, and even more preferably 1 to 5.

[0371] As a straight-chain aliphatic hydrocarbon group, a straight-chain alkylene group is preferred. Specifically, examples include methylene [-CH2-], ethylene [-(CH2)2-], propylene [-(CH2)3-], butylene [-(CH2)4-], and pentylene [-(CH2)5-].

[0372] As a branched aliphatic hydrocarbon group, a branched alkylene group is preferred. Specifically, examples 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-; alkylpropylene groups such as -CH(CH3)CH2CH2- and -CH2CH(CH3)CH2-; and alkylalkylene groups such as -CH(CH3)CH2CH2CH2- and -CH2CH(CH3)CH2CH2-. As for the alkyl group in the alkyl alkylene group, a straight-chain alkyl group with 1 to 5 carbon atoms is preferred.

[0373] The aforementioned straight-chain or branched aliphatic hydrocarbon groups may have substituents (groups or atoms other than hydrogen atoms) that replace hydrogen atoms, or they may not have substituents. Examples of such substituents include fluorine atoms, fluoroalkyl groups with 1 to 5 carbon atoms obtained by replacing fluorine atoms, and oxo groups (=O).

[0374] Examples of the aforementioned aliphatic hydrocarbon groups containing rings in their structure include cyclic aliphatic hydrocarbon groups containing heteroatoms in their ring structure (groups obtained by removing two hydrogen atoms from an aliphatic hydrocarbon ring), groups obtained by bonding such cyclic aliphatic hydrocarbon groups to the ends of straight-chain or branched aliphatic hydrocarbon groups, and groups where the cyclic aliphatic hydrocarbon group is intermediate between straight-chain and branched aliphatic hydrocarbon groups. Examples of the aforementioned straight-chain or branched aliphatic hydrocarbon groups are groups identical to those described above.

[0375] The number of carbon atoms in the cyclic aliphatic hydrocarbon group is preferably 3 to 20, more preferably 3 to 12.

[0376] The cyclic aliphatic hydrocarbon group can be polycyclic or monocyclic. As a monocyclic aliphatic hydrocarbon group, it is preferably a group obtained by removing two hydrogen atoms from a monocyclic alkane. The monocyclic alkane preferably has 3 to 6 carbon atoms. Examples include cyclopentane and cyclohexane. As a polycyclic aliphatic hydrocarbon group, it is preferably a group obtained by removing two hydrogen atoms from a polycyclic alkane. The polycyclic alkane preferably has 7 to 12 carbon atoms. Examples include adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane.

[0377] Cyclic aliphatic hydrocarbon groups may have substituents (groups or atoms other than hydrogen atoms) that replace hydrogen atoms, or they may not have substituents. Examples of such substituents include alkyl groups, alkoxy groups, halogen atoms, haloalkyl groups, hydroxyl groups, and oxo groups (=O).

[0378] The alkyl group used as the above-mentioned substituent is preferably an alkyl group having 1 to 5 carbon atoms, and more preferably methyl, ethyl, propyl, n-butyl, and tert-butyl.

[0379] The alkoxy group used as the above-mentioned substituent is preferably an alkoxy group having 1 to 5 carbon atoms, more preferably methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, and tert-butoxy, and particularly preferably methoxy and ethoxy.

[0380] Examples of halogen atoms that can be used as substituents include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms, with fluorine atoms being the most preferred.

[0381] Haloalkyl groups, which are substituents as described above, can be exemplified by groups obtained by replacing some or all of the hydrogen atoms of the alkyl group with the halogen atoms described above.

[0382] In cyclic aliphatic hydrocarbon groups, some carbon atoms constituting the ring structure can be replaced by -O- or -S-. Preferred substituents containing heteroatoms are -O-, -C(=O)-O-, -S-, -S(=O)2-, and -S(=O)2-O-.

[0383] The aromatic hydrocarbon group, being a divalent hydrocarbon group, is a divalent hydrocarbon group having at least one aromatic ring and may have substituents. The aromatic ring is not particularly limited as long as it is a cyclic conjugated system having 4n+2 π electrons; it can be monocyclic or polycyclic. The number of carbon atoms in the aromatic ring is preferably 5 to 30, more preferably 5 to 20, further preferably 6 to 15, and particularly preferably 6 to 12. This number of carbon atoms does not include the number of carbon atoms in the substituents.

[0384] Examples of aromatic rings include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; and aromatic heterocycles formed by replacing some carbon atoms in the aforementioned aromatic hydrocarbon rings with heteroatoms. Examples of heteroatoms in aromatic heterocycles include oxygen atoms, sulfur atoms, and nitrogen atoms. Examples of aromatic heterocycles include pyridine rings and thiophene rings.

[0385] As a divalent hydrocarbon group, aromatic hydrocarbon groups can specifically include groups (aryl or heteroaryl) obtained by removing two hydrogen atoms from the aforementioned aromatic hydrocarbon ring or aromatic heterocycle; groups obtained by removing two hydrogen atoms from an aromatic compound containing two or more aromatic rings (e.g., biphenyl, fluorene, etc.); and groups obtained by substituting one hydrogen atom of an aryl or heteroaryl group obtained by removing one hydrogen atom from the aforementioned aromatic hydrocarbon ring or aromatic heterocycle (e.g., groups obtained by further removing one hydrogen atom from an aryl group in arylalkyl groups such as benzyl, phenethyl, 1-naphthylmethyl, 2-naphthylmethyl, 1-naphthylethyl, 2-naphthylethyl, etc.).

[0386] The alkylene group bonded to the above-mentioned aryl or heteroaryl group preferably has 1 to 4 carbon atoms, more preferably 1 to 2, and particularly preferably 1.

[0387] In the aforementioned aromatic hydrocarbon group, the hydrogen atom of the aromatic hydrocarbon group can be replaced by a substituent. For example, the hydrogen atom bonded to the aromatic ring in the aromatic hydrocarbon group can be replaced by a substituent. Examples of such substituents include alkyl groups, alkoxy groups, halogen atoms, haloalkyl groups, hydroxyl groups, oxo groups (=O), etc.

[0388] The alkyl group used as the above-mentioned substituent is preferably an alkyl group having 1 to 5 carbon atoms, and more preferably methyl, ethyl, n-propyl, n-butyl and tert-butyl.

[0389] The alkoxy group used as the above-mentioned substituent is preferably an alkoxy group having 1 to 5 carbon atoms, and preferably methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, and tert-butoxy, more preferably methoxy and ethoxy.

[0390] Examples of halogen atoms that can be used as substituents include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms, with fluorine atoms being preferred.

[0391] Haloalkyl groups, which are substituents as described above, can be exemplified by groups obtained by replacing some or all of the hydrogen atoms of the alkyl group with the halogen atoms.

[0392] • Divalent linking groups containing heteroatoms

[0393] In a divalent linker containing heteroatoms, heteroatoms refer to atoms other than carbon and hydrogen atoms, such as oxygen, nitrogen, sulfur, and halogen atoms.

[0394] Specifically, examples of non-hydrocarbon linking groups containing heteroatoms include -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 this divalent hydrocarbon group include groups identical to the divalent hydrocarbon groups that may have substituents described above, preferably straight-chain or branched aliphatic hydrocarbon groups.

[0395] In the above, the H atoms in -NH-, -NH-, and -NH-C(=NH)- of -C(=O)-NH- can be replaced by substituents such as alkyl or acyl groups. The number of carbon atoms in the substituent is preferably 1 to 10, more preferably 1 to 8, and particularly preferably 1 to 5.

[0396] As R 12b The divalent linking group in the linking group is particularly preferred to be a straight-chain or branched alkylene group, a cyclic aliphatic hydrocarbon group, or a divalent linking group containing heteroatoms.

[0397] In R 12b When the divalent linking group is a straight-chain or branched alkylene group, the number of carbon atoms in the alkylene group is preferably 1 to 10, more preferably 1 to 6, particularly preferably 1 to 4, and most preferably 1 to 3. Specifically, examples can be given of straight-chain or branched alkylene groups that are exemplified as straight-chain or branched aliphatic hydrocarbon groups in the description of "divalent hydrocarbon groups that may have substituents" as the divalent linking group.

[0398] In R 12b When the divalent linking group is a cyclic aliphatic hydrocarbon group, the same cyclic aliphatic hydrocarbon group as the one exemplified as "aliphatic hydrocarbon group containing a ring in the structure" in the description of "a divalent hydrocarbon group that may have substituents" as the divalent linking group can be cited.

[0399] The cyclic aliphatic hydrocarbon group is particularly preferably a group obtained by removing two or more hydrogen atoms from cyclopentane, cyclohexane, norbornene, isoboronane, adamantane, tricyclodecane or tetracyclododecane.

[0400] In R 12bWhen the divalent linking group is a divalent linking group containing heteroatoms, preferred examples of such linking groups include -O-, -C(=O)-O-, -C(=O)-, -OC(=O)-O-, -C(=O)-NH-, -NH- (H can be substituted by alkyl, acyl, or other substituents), -S-, -S(=O)2-, -S(=O)2-O-, and those with the general formula -Y. 1 -OY 2 -、-[Y 1 -C(=O)-O] m’ -Y 2 -or-Y 1 -OC(=O)-Y2- represents the group [where Y is the group]. 1 and Y 2 Each can be independently a divalent hydrocarbon group that may have substituents, where O is an oxygen atom and m' is an integer between 0 and 3, etc.

[0401] In R 12b When the divalent linking group is -NH-, the hydrogen atom in -NH- can be replaced by a substituent such as an alkyl group or an acyl group. The number of carbon atoms in the substituent (alkyl group, acyl group, etc.) is preferably 1 to 10, more preferably 1 to 8, and particularly preferably 1 to 5.

[0402] Formula-Y 1 -OY 2 -、-[Y 1 -C(=O)-O] m’ -Y 2 -or-Y 1 -OC(=O)-Y 2 -Medium,Y 1 and Y 2 Each is a divalent hydrocarbon group that may have substituents, and each can be independently represented by a substituent. Examples of such divalent hydrocarbon groups are the same groups that are "divalent hydrocarbon groups that may have substituents" as described in the description of the divalent linking groups.

[0403] As Y 1 Preferably, it is a straight-chain aliphatic hydrocarbon group, more preferably a straight-chain alkylene group, even more preferably a straight-chain alkylene group with 1 to 5 carbon atoms, and particularly preferably methylene and ethylene.

[0404] As Y 2 Preferably, the alkyl group is a straight-chain or branched aliphatic hydrocarbon group, more preferably methylene, ethylene, or alkylmethylene. The alkyl group in the alkylmethylene group is preferably a straight-chain alkyl group with 1 to 5 carbon atoms, more preferably a straight-chain alkyl group with 1 to 3 carbon atoms, and particularly preferably methyl.

[0405] In the formula -[Y1 -C(=O)-O] m’ -Y 2 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, as a group represented by the formula -[Y 1 -C(=O)-O] m’ -Y 2 -The group represented by the formula -Y is particularly preferred. 1 -C(=O)-OY 2 - represents a group. Preferably, it is represented by the formula -(CH2). a’ -C(=O)-O-(CH2) b’ - represents a group. In this formula, a' is an integer of 1 to 10, preferably an integer of 1 to 8, more preferably an integer of 1 to 5, further 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, further preferably 1 or 2, and most preferably 1.

[0406] For R 12b The divalent linking group in the formula, as a divalent linking group containing a heteroatom, is preferably an organic group composed of at least one non-hydrocarbon group and a divalent hydrocarbon group. Preferably, it is a straight-chain group having an oxygen atom as a heteroatom, such as a group containing an ether bond or an ester bond, and more preferably a group of the above formula -Y. 1 -OY 2 -、-[Y 1 -C(=O)-O] m’ -Y 2 -or-Y 1 -OC(=O)-Y 2 -The group represented by - is particularly preferred to be in the form of the above formula -[Y 1 -C(=O)-O] m’ -Y 2 -or-Y 1 -OC(=O)-Y 2 - indicates a functional group.

[0407] As R 12b The divalent linking group in the linking group is preferably an alkylene group or a divalent linking group containing an ester bond (-C(=O)-O-).

[0408] The alkylene group is preferably a straight-chain or branched alkylene group. Examples of the straight-chain aliphatic hydrocarbon group include methylene [-CH2-], ethylene [-(CH2)2-], propylene [-(CH2)3-], butylene [-(CH2)4-], and pentylene [-(CH2)5-]. Preferred examples of this 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-; alkylpropylene groups such as -CH(CH3)CH2CH2- and -CH2CH(CH3)CH2-; and alkylalkylene groups such as -CH(CH3)CH2CH2CH2- and -CH2CH(CH3)CH2CH2-.

[0409] As a divalent linking group containing an ester bond, it is particularly preferred to have the formula: -R 13b -C(=O)-O-[where, R 13b The group is represented by a divalent linking group. That is, the structural unit (b-3-S) is preferably a structural unit represented by the following formula (b-S1-1).

[0410] [Chemistry 43]

[0411]

[0412] (where R and R) 11b As described above, R 13b It is a divalent linker.

[0413] As R 13b There are no particular limitations; for example, examples related to R can be cited. 12b The same group with a divalent linker.

[0414] As R 13b The divalent linking group is preferably a straight-chain or branched alkylene group, an aliphatic hydrocarbon group containing a ring in the structure, or a divalent linking group containing a heteroatom, more preferably a straight-chain or branched alkylene group or a divalent linking group containing an oxygen atom as a heteroatom.

[0415] As a straight-chain alkylene group, methylene or ethylene is preferred, and methylene is particularly preferred. As a branched alkylene group, alkylmethylene or alkylethylene is preferred, and -CH(CH3)-, -C(CH3)2- or -C(CH3)2CH2- is particularly preferred.

[0416] As a divalent linking group containing an oxygen atom, a divalent linking group containing an ether bond or an ester bond is preferred, and the aforementioned -Y is more preferred. 1 -OY 2 -、-[Y 1 -C(=O)-O] m’ -Y 2 -or-Y 1 -OC(=O)-Y 2 -. Y 1 and Y 2 Each is independently a divalent hydrocarbon group that may have substituents, and m' is an integer between 0 and 3. Preferably, -Y is preferred. 1 -OC(=O)-Y 2 -, with a particular preference for -(CH2) c -OC(=O)-(CH2) d - indicates a group. c is an integer of 1 to 5, preferably 1 or 2. d is an integer of 1 to 5, preferably 1 or 2.

[0417] As a structural unit (b-3-S), it is particularly preferred to be a structural unit represented by the following formula (b-S1-11) or (b-S1-12), and more preferably a structural unit represented by formula (b-S1-12).

[0418] [Chemistry 44]

[0419]

[0420] (where R, A', R) 10b , z and R 13b (The same applies to the above.)

[0421] In formula (b-S1-11), A' is preferably a methylene group, an oxygen atom (-O-), or a sulfur atom (-S-).

[0422] As R 13b Preferably, it is a linear or branched alkylene group or a divalent linker containing an oxygen atom. As R 13b The linear or branched alkylene groups and divalent linking groups containing oxygen atoms in the above-mentioned linear or branched alkylene groups and divalent linking groups containing oxygen atoms can be examples of groups that are the same as the linear or branched alkylene groups and divalent linking groups containing oxygen atoms.

[0423] As a structural unit represented by formula (b-S1-12), it is particularly preferred to be a structural unit represented by the following formula (b-S1-12a) or (b-S1-12b).

[0424] [Chemistry 45]

[0425]

[0426] (In the formula, R and A' are the same as above, and c to e are independent integers above 1 and below 3.)

[0427] [Structural Unit (b-3-L)]

[0428] As an example of a structural unit (b-3-L), one could exemplify R in the above equation (b-S1). 11b Structural units obtained by substitution with lactone-containing cyclic groups, more specifically, can be exemplified by structural units represented by the following formulas (b-L1) to (b-L5).

[0429] [Chemistry 46]

[0430]

[0431] (In the formula, R is a hydrogen atom, an alkyl group with 1 to 5 carbon atoms, or a haloalkyl group with 1 to 5 carbon atoms; R' is independently a hydrogen atom, alkyl group, alkoxy group, haloalkyl group, hydroxyl group, -COOR", -OC(=O)R", hydroxyalkyl group, or cyano group, and R" is a hydrogen atom or alkyl group; R 12b (This refers to a single bond or a divalent linking group; s” is an integer between 0 and 2; A” is an alkylene group, oxygen atom, or sulfur atom containing 1 to 5 carbon atoms; r is 0 or 1.)

[0432] The R in equations (b-L1) to (b-L5) is the same as above.

[0433] As for alkyl, alkoxy, haloalkyl, -COOR", -OC(=O)R", and hydroxyalkyl in R', examples can be made of the same groups as those previously described as substituents that may be present in the -SO2-cyclic group.

[0434] If industrial availability is taken into consideration, R' is preferably a hydrogen atom.

[0435] The alkyl group in "R" can be any of the following: straight-chain, branched, or cyclic.

[0436] When R” is a straight-chain or branched alkyl group, it is preferable that the number of carbon atoms is 1 to 10, and more preferably that the number of carbon atoms is 1 to 5.

[0437] When R” is a cyclic alkyl group, it is preferable to have 3 to 15 carbon atoms, more preferably 4 to 12 carbon atoms, and most preferably 5 to 10 carbon atoms. Specifically, examples can be given by removing one or more hydrogen atoms from monocyclic alkanes that can be substituted or not substituted by fluorine atoms or fluoroalkyl groups, or from polycyclic alkanes such as bicyclic alkanes, tricyclic alkanes, and tetracyclic alkanes. Specifically, examples can be given by removing one or more hydrogen atoms from monocyclic alkanes such as cyclopentane and cyclohexane, or from polycyclic alkanes such as adamantane, norbornane, isobornane, tricyclic decane, and tetracyclic dodecane.

[0438] As "A", examples can be the same group as A' in the above formula (3-1). "A" is preferably an alkylene group, an oxygen atom (-O-), or a sulfur atom (-S-) with 1 to 5 carbon atoms, more preferably an alkylene group or -O- with 1 to 5 carbon atoms. As an alkylene group with 1 to 5 carbon atoms, it is more preferably methylene or dimethylmethylene, and most preferably methylene.

[0439] R 12b R in the above formula (b-S1) 12b same.

[0440] In formula (b-L1), s” is preferably 1 or 2.

[0441] The following examples illustrate specific structural units represented by the above equations (b-L1) to (b-L3). In the following equations, R... α It represents a hydrogen atom, a methyl group, or a trifluoromethyl group.

[0442] [Chemistry 47]

[0443]

[0444] [Chemistry 48]

[0445]

[0446] [Chemistry 49]

[0447]

[0448] As a structural unit (b-3-L), it is preferable to select at least one from the group consisting of structural units represented by the above formulas (b-L1) to (b-L5), more preferably to select at least one from the group consisting of structural units represented by formulas (b-L1) to (b-L3), and particularly preferably to select at least one from the group consisting of structural units represented by the above formulas (b-L1) or (b-L3).

[0449] Preferably, at least one is selected from the group consisting of structural units represented by the above 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).

[0450] Furthermore, the structural unit (b-3-L) is preferably represented by the following formulas (b-L6) to (b-L7).

[0451] [Transformation 50]

[0452]

[0453] In equations (b-L6) and (b-L7), R and R 12b Same as above.

[0454] Furthermore, in acrylic resin (B3), as a structural unit that improves the solubility of acrylic resin (B3) in alkali due to the action of acid, there are structural units with acid-dissociable groups represented by the following formulas (b5) to (b7).

[0455] [Chemistry 51]

[0456]

[0457] In equations (b5) to (b7) above, R 14b and R 18b ~R 23b Each of the following independently represents a hydrogen atom, a straight-chain or branched alkyl group having 1 to 6 carbon atoms, a fluorine atom, or a straight-chain or branched fluoroalkyl group having 1 to 6 carbon atoms. R 15b ~R 17b Each of the following can be independently represented as a straight-chain or branched alkyl group having 1 to 6 carbon atoms, a straight-chain or branched fluoroalkyl group having 1 to 6 carbon atoms, or an aliphatic cyclic group having 5 to 20 carbon atoms. 16b and R 17b They can bond with each other and together with the carbon atoms bonded to them, form a hydrocarbon ring with 5 to 20 carbon atoms. bIt indicates an aliphatic cyclic group or alkyl group that may have substituents, p represents an integer greater than or equal to 0 and less than or equal to 4, and q represents 0 or 1.

[0458] In addition, examples of linear or branched alkyl groups include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, isopentyl, and neopentyl. Furthermore, fluoroalkyl refers to a group obtained by replacing some or all of the hydrogen atoms of the aforementioned alkyl groups with fluorine atoms.

[0459] Specific examples of aliphatic cyclic groups include groups obtained by removing one or more hydrogen atoms from monocyclic alkanes or polycyclic alkanes such as bicyclic alkanes, tricyclic alkanes, and tetracyclic alkanes. Specifically, examples include groups obtained by removing one hydrogen atom from monocyclic alkanes such as cyclopentane, cyclohexane, cycloheptane, and cyclooctane, or polycyclic alkanes such as adamantane, norbornane, isoboronane, tricyclic decane, and tetracyclic dodecane. Particularly preferred are groups obtained by removing one hydrogen atom from cyclohexane or adamantane (which may further have substituents).

[0460] In the above R 16b and R 17b In the absence of mutual bonding to form hydrocarbon rings, from the perspective of high contrast, resolution, and coke depth width, the aforementioned R... 15b R 16b and R 17b Preferably, it is a straight-chain or branched alkyl group having 1 to 4 carbon atoms, more preferably a straight-chain or branched alkyl group having 2 to 4 carbon atoms. As described above, R... 19b R 20b R 22b R 23b Preferably, it contains hydrogen atoms or methyl groups.

[0461] The above R 16b and R 17b It can also form an aliphatic cyclic group with 5 to 20 carbon atoms together with the carbon atoms bonded to both. Specific examples of such aliphatic cyclic groups include groups obtained by removing one or more hydrogen atoms from monocyclic alkanes or polycyclic alkanes such as bicyclic alkanes, tricyclic alkanes, and tetracyclic alkanes. Specifically, examples include groups obtained by removing one or more hydrogen atoms from monocyclic alkanes such as cyclopentane, cyclohexane, cycloheptane, and cyclooctane, or polycyclic alkanes such as adamantane, norbornane, isoboronane, tricyclic decane, and tetracyclic dodecane. Particularly preferred are groups obtained by removing one or more hydrogen atoms from cyclohexane and adamantane (which may further have substituents).

[0462] Furthermore, in the aforementioned R 16b and R 17bWhen the formed aliphatic cyclic group has substituents on its cyclic skeleton, examples of such substituents include polar groups such as hydroxyl, carboxyl, cyano, and oxygen atom (=O), or straight-chain or branched alkyl groups having 1 to 4 carbon atoms. As polar groups, oxygen atom (=O) is particularly preferred.

[0463] The above Y b The group is an aliphatic cyclic group or alkyl group, and examples include groups obtained by removing one or more hydrogen atoms from monocyclic alkanes or polycyclic alkanes such as bicyclic alkanes, tricyclic alkanes, and tetracyclic alkanes. Specifically, examples include groups obtained by removing one or more hydrogen atoms from monocyclic alkanes such as cyclopentane, cyclohexane, cycloheptane, and cyclooctane, or polycyclic alkanes such as adamantane, norbornane, isoboronane, tricyclic decane, and tetracyclic dodecane. Groups obtained by removing one or more hydrogen atoms from adamantane are particularly preferred (and may further have substituents).

[0464] Furthermore, in the aforementioned Y b When an aliphatic cyclic group has substituents on its cyclic skeleton, examples of such substituents include polar groups such as hydroxyl, carboxyl, cyano, and oxygen atom (=O), or straight-chain or branched alkyl groups having 1 to 4 carbon atoms. As polar groups, oxygen atom (=O) is particularly preferred.

[0465] Furthermore, in Y b When the alkyl group is alkyl, it is preferred to have a straight-chain or branched alkyl group with 1 to 20 carbon atoms, and more preferably 6 to 15 carbon atoms. Such alkyl groups are particularly preferred to be alkoxyalkyl groups, and examples of such alkoxyalkyl groups include 1-methoxyethyl, 1-ethoxyethyl, 1-n-propoxyethyl, 1-isopropoxyethyl, 1-n-butoxyethyl, 1-isobutoxyethyl, 1-tert-butoxyethyl, 1-methoxypropyl, 1-ethoxypropyl, 1-methoxy-1-methyl-ethyl, 1-ethoxy-1-methylethyl, etc.

[0466] As a preferred specific example of the structural unit represented by the above formula (b5), structural units represented by the following formulas (b5-1) to (b5-33) can be cited.

[0467] [Chemistry 52]

[0468]

[0469] In the above equations (b5-1) to (b5-33), R 24b It represents a hydrogen atom or a methyl group.

[0470] As a preferred specific example of the structural unit represented by the above formula (b6), structural units represented by the following formulas (b6-1) to (b6-26) can be cited.

[0471] [Chemistry 53]

[0472]

[0473] In the above equations (b6-1) to (b6-26), R 24b It represents a hydrogen atom or a methyl group.

[0474] As a preferred specific example of the structural unit represented by the above formula (b7), structural units represented by the following formulas (b7-1) to (b7-15) can be cited.

[0475] [Chemistry 54]

[0476]

[0477] In the above equations (b7-1) to (b7-15), R 24b It represents a hydrogen atom or a methyl group.

[0478] Of the structural units represented by formulas (b5) to (b7) described above, from the viewpoint of ease of synthesis and relatively easy high sensitivity, the structural unit represented by formula (b6) is preferred. Furthermore, in the structural unit represented by formula (b6), Y is preferred. b It is an alkyl structural unit, and R is preferred. 19b and R 20b One or both of them are alkyl structural units.

[0479] Furthermore, the acrylic resin (B3) is preferably a resin composed of a copolymer comprising structural units represented by the above formulas (b5) to (b7) and structural units derived from polymerizable compounds having ether bonds.

[0480] Examples of the aforementioned polymerizable compounds containing ether bonds include free radical polymerizable compounds such as (meth)acrylic acid derivatives containing both ether and ester bonds. Specific examples include 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, methoxytriethylene glycol (meth)acrylate, 3-methoxybutyl (meth)acrylate, ethyl carbitol (meth)acrylate, phenoxy polyethylene glycol (meth)acrylate, methoxy polyethylene glycol (meth)acrylate, methoxypolypropylene glycol (meth)acrylate, and tetrahydrofurfuryl (meth)acrylate. Furthermore, the aforementioned polymerizable compounds containing ether bonds are preferably 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, and methoxytriethylene glycol (meth)acrylate. These polymerizable compounds can be used alone or in combination of two or more.

[0481] Furthermore, for the purpose of appropriately controlling physical and chemical properties, other polymeric compounds can be included as structural units in acrylic resin (B3). Examples of such polymeric compounds include well-known free radical polymeric compounds and anionic polymeric compounds.

[0482] Examples of such polymeric 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 containing carboxyl groups and ester bonds, such as 2-methacryloyloxyethyl succinic acid, 2-methacryloyloxyethyl maleic acid, 2-methacryloyloxyethyl phthalic acid, and 2-methacryloyloxyethyl hexahydrophthalic acid; alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, butyl methacrylate, and cyclohexyl methacrylate; and hydroxyl methacrylates such as 2-hydroxyethyl methacrylate and 2-hydroxypropyl methacrylate. Alkyl esters; aryl esters of (meth)acrylate such as phenyl methacrylate and benzyl methacrylate; dicarboxylic acid diesters such as diethyl maleate and dibutyl fumarate; aromatic compounds containing vinyl groups such as styrene, α-methylstyrene, chlorostyrene, chloromethylstyrene, vinyltoluene, hydroxystyrene, α-methylhydroxystyrene, and α-ethylhydroxystyrene; aliphatic compounds containing vinyl groups such as vinyl acetate; conjugated dienes such as butadiene and isoprene; polymeric compounds containing nitrile groups such as acrylonitrile and methacrylonitrile; chlorine-containing polymeric compounds such as vinyl chloride and vinylidene chloride; polymeric compounds containing amide bonds such as acrylamide and methacrylamide.

[0483] As described above, acrylic resin (B3) may also contain structural units derived from polymeric compounds containing carboxyl groups, such as monocarboxylic acids or dicarboxylic acids. However, from the viewpoint of easily forming a resist pattern including a rectangular non-resist portion with a better cross-sectional shape, acrylic resin (B3) preferably does not substantially contain structural units derived from polymeric compounds containing carboxyl groups. Specifically, the proportion of structural units derived from polymeric compounds containing carboxyl groups in acrylic resin (B3) is preferably 20% by mass or less, more preferably 15% by mass or less, and particularly preferably 10% by mass or less.

[0484] In acrylic resin (B3), it is preferable to use an acrylic resin containing a larger amount of structural units derived from polymeric compounds having carboxyl groups in combination with an acrylic resin containing only a small amount or no structural units derived from polymeric compounds having carboxyl groups.

[0485] Furthermore, examples of polymerizable compounds include (meth)acrylates with acid-non-dissociative aliphatic polycyclic groups and vinyl-containing aromatic compounds. From the viewpoint of easy industrial availability, tricyclic decyl, adamantyl, tetracyclic dodecyl, isobornyl, norbornyl, etc., are particularly preferred as acid-non-dissociative aliphatic polycyclic groups. These aliphatic polycyclic groups can have straight-chain or branched alkyl groups with 1 to 5 carbon atoms as substituents.

[0486] As a type of (meth)acrylate with an aliphatic polycyclic group that is acid-non-dissociable, specifically, compounds with structures of the following formulas (b8-1) to (b8-5) can be exemplified.

[0487] [Chemistry 55]

[0488]

[0489] In the above equations (b8-1) to (b8-5), R 25b It represents a hydrogen atom or a methyl group.

[0490] When the acrylic resin (B3) contains structural units (b-3) containing -SO2- cyclic groups or lactone cyclic groups, the content of structural units (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 and 50% by mass or less, and most preferably 10% by mass or more and 30% by mass or less. When the photosensitive composition contains structural units (b-3) in amounts within the above-mentioned ranges, it is easy to achieve both good developability and good pattern shape.

[0491] Furthermore, the acrylic resin (B3) preferably contains 5% or more by mass, more preferably 10% or more by mass, and particularly preferably 10% or more and 50% or less by mass of structural units represented by the above formulas (b5) to (b7).

[0492] The acrylic resin (B3) preferably contains structural units derived from the polymerizable compound having ether bonds described above. The content of structural units derived from the polymerizable compound having ether bonds in the acrylic resin (B3) is preferably 0% by mass or more and 50% by mass or less, more preferably 5% by mass or more and 40% by mass or less, and even more preferably 5% by mass or more and 30% by mass or less.

[0493] The acrylic resin (B3) preferably contains structural units derived from the above-mentioned aliphatic polycyclic groups with acid non-dissociation properties of (meth)acrylates. In the acrylic resin (B3), the content of structural units derived from aliphatic polycyclic groups with acid non-dissociation properties of (meth)acrylates is preferably 0% by mass or more than 60% by mass, more preferably 5% by mass or more than 50% by mass, and even more preferably 5% by mass or more than 30% by mass.

[0494] As long as the photosensitive composition contains a specified amount of acrylic resin (B3), an acrylic resin other than the acrylic resin (B3) described above can also be used as resin (B). As for such acrylic resin other than acrylic resin (B3), there are no particular limitations as long as it contains a resin containing the structural unit represented by the formulas (b5) to (b7) described above.

[0495] The polystyrene equivalent weight-average molecular weight of the resin (B) described above is preferably 10,000 to 600,000, more preferably 20,000 to 400,000, and even more preferably 30,000 to 300,000. By setting such a weight-average molecular weight, sufficient strength of the photosensitive layer composed of the photosensitive composition can be maintained without reducing the peelability of the photosensitive layer from the substrate, thereby further preventing the expansion or cracking of the profile during plating.

[0496] Furthermore, the molecular weight distribution coefficient of resin (B) is preferably 1.05 or higher. Here, the molecular weight distribution coefficient refers to the value obtained by dividing the mass-average molecular weight by the number-average molecular weight. By setting such a molecular weight distribution coefficient, the desired stress resistance relative to the plating can be obtained, or the problem of the metal layer obtained due to the plating process becoming prone to expansion can be avoided.

[0497] The content of resin (B) is preferably 5% by mass or more and 60% by mass or less relative to the total mass of the photosensitive composition.

[0498] Furthermore, the content of resin (B) relative to the total solids content of the photosensitive composition is preferably 5% by mass or more and 98% by mass or less, more preferably 10% by mass or more and 95% by mass or less.

[0499] <Acid Diffusion Inhibitor (C)>

[0500] The acid diffusion inhibitor (C) contained in the photosensitive composition comprises a compound represented by the following formula (C1).

[0501] By including a compound represented by formula (C1) as an acid diffusion inhibitor (C) in the photosensitive composition, a resist pattern with good rectangularity of cross-sectional shape can be easily formed, as shown in the examples described later, and a photosensitive composition with high resolution and dimensional control can be obtained.

[0502] Therefore, by using a photosensitive composition, it is possible to form a highly detailed resist pattern with a desired shape and a rectangular cross-sectional shape. Regarding the cross-sectional shape, for example, cases where the resist portion extends towards the non-resist portion (folded edge shape) or becomes recessed near the contact surface between the substrate surface and the resist pattern are suppressed. The perpendicularity of the resist pattern's cross-sectional shape is also improved.

[0503] [Chemistry 56]

[0504]

[0505] (In formula (C1),)

[0506] R 1c It is an alkyl or aralkyl group.

[0507] R 2c It is an alkyl or aralkyl group.

[0508] R 3c It is a hydrogen atom or an alkyl group.

[0509] R 4c It is a single bond or an alkylene group.

[0510] n1 is an integer greater than 0 and less than 5.

[0511] n2 is an integer greater than 0 and less than 5.

[0512] n3 is either 0 or 1.

[0513] (Note that when n3 is 1, n1 and n2 are not both 0.)

[0514] In equation (C1), R is used as 1c The alkyl group can be straight-chain or branched. The number of carbon atoms in the alkyl group is not particularly limited, but preferably 1 to 10, more preferably 6 to 10. Specific examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, tert-pentyl, n-hexyl, n-heptyl, n-octyl, isooctyl, sec-octyl, tert-octyl, 2-ethylhexyl, n-nonyl, isononyl, and n-decyl.

[0515] Composition as R 1cThe alkylene group (aryl-alkylene-) can be linear or branched. The number of carbon atoms in the aryl group is not particularly limited, but is preferably 6 to 20 or less, more preferably 6 to 10 or less. Specific examples of aryl groups include benzyl, 1-phenylethyl, 2-phenylethyl, naphth-1-ylmethyl, and naphth-2-ylmethyl.

[0516] When n1 is an integer greater than 2 and less than 5, multiple R 1c They can be the same or different.

[0517] When n3 is 0, 2 (R) 1c ) n1 -C6H4-R 4c - They can be the same or different. -C6H4- represents phenylene.

[0518] In equation (C1), R is used as 2c alkyl and aralkyl groups with R in formula (C1) 1c same.

[0519] When n² is an integer greater than 2 and less than 5, multiple R 2c They can be the same or different.

[0520] R 1c and R 2c Preferably, the alkyl group has a larger volume and the carbon number is 6 to 10 or the aralkyl group has 6 to 10 carbon atoms.

[0521] In equation (C1), R is used as 3c The alkyl group can be straight-chain or branched. The number of carbon atoms in the alkyl group is not particularly limited, but preferably 1 to 10, more preferably 6 to 10. Specific examples of alkyl groups, and R... 1c The alkyl groups are the same.

[0522] In equation (C1), R is used as 4c The alkylene group can be linear or branched. The number of carbon atoms in the alkylene group is not particularly limited, but it is preferred to have 1 to 5 carbon atoms, and more preferably 1 to 3 carbon atoms. Specific examples of alkylene groups include methylene, ethylene, n-propylene, and isopropylene.

[0523] In compounds represented by formula (C1), n3 is preferably 1 and R 4c Compounds with single bonds, or where n3 is 0 and R 4c Compounds that are alkylene groups.

[0524] The compound represented by formula (C1) is preferably used in a range of 0.01 to 20 parts by mass relative to 100 parts by mass of resin (B), more preferably in a range of 0.01 to 5 parts by mass, and even more preferably in a range of 0.01 to 3 parts by mass.

[0525] In addition, the acid diffusion inhibitor (C) may contain an acid diffusion inhibitor other than the compound represented by the above formula (C1), but the content of the compound represented by formula (C1) in the acid diffusion inhibitor (C) is preferably 50% by mass or more, more preferably 80% by mass or more, and even more preferably 100% by mass.

[0526] <Acid diffusion inhibitor (C')>

[0527] As an acid diffusion control agent other than the compound represented by formula (C1), it is preferably a nitrogen-containing compound (C'1) other than the compound represented by formula (C1), and may also contain an organic carboxylic acid, or an oxyacid of phosphorus or its derivative (C'2) as needed.

[0528] [Nitrogen-containing compounds (C'1)]

[0529] Examples of nitrogen-containing compounds (C'1) include trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, tri-n-pentylamine, tribenzylamine, diethanolamine, triethanolamine, n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, ethylenediamine, N,N,N',N'-tetramethylethylenediamine, tetramethylenediamine, hexamethylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 4,4'-diaminobenzophenone, 4,4'-diaminodiphenylamine, formamide, N-methylformamide, N,N-dimethylformamide, and acetamide. N-methylacetamide, N,N-dimethylacetamide, propionamide, benzamide, pyrrolidone, N-methylpyrrolidone, methylurea, 1,1-dimethylurea, 1,3-dimethylurea, 1,1,3,3'-tetramethylurea, 1,3-diphenylurea, imidazole, benzimidazole, 4-methylimidazolium, 8-hydroxyquinoline, acridine, purine, pyrrolidine, piperidine, 2,4,6-tris(2-pyridyl)triazine, morpholine, 4-methylmorpholine, piperazine, 1,4-dimethylpiperazine, 1,4-diazabicyclo[2.2.2]octane, pyridine, etc. These can be used alone or in combination of two or more.

[0530] In addition, 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) or pyridines such as 2,6-diphenylpyridine and 2,6-di-tert-butylpyridine, which are substituted with substituents such as hydrocarbon groups at the 2,6-position, can be used as nitrogen-containing compounds (C'1).

[0531] The nitrogen-containing compound (C'1) is typically used in a range of 0 to 5 parts by mass relative to the total mass of the above-mentioned resin (B) and the following alkali-soluble resin (D). It is particularly preferred to use in a range of 0 to 3 parts by mass.

[0532] [Organic carboxylic acids, or oxyacids of phosphorus or their derivatives (C'2)]

[0533] Among organic carboxylic acids, or oxyacids of phosphorus or their derivatives (C'2), the organic carboxylic acid is preferably malonic acid, citric acid, malic acid, succinic acid, benzoic acid, salicylic acid, etc., and particularly preferably salicylic acid.

[0534] Examples of oxyacids of phosphorus or their derivatives include phosphoric acid, di-n-butyl phosphate, diphenyl phosphate, and other phosphoric acids and their ester derivatives; phosphonic acids, dimethyl phosphonate, di-n-butyl phosphonate, phenylphosphonic acid, diphenyl phosphonate, dibenzyl phosphonate, and their ester derivatives; and hypophosphonic acids, phenylhydantoin, and their ester derivatives. Among these, phosphonic acids are particularly preferred. These can be used alone or in combination of two or more.

[0535] Relative to the total mass of the above-mentioned resin (B) and the following alkali-soluble resin (D) of 100 parts by mass, the organic carboxylic acid or the oxyacid of phosphorus or its derivative (C'2) is generally used in the range of 0 to 5 parts by mass, and particularly preferably in the range of 0 to 3 parts by mass.

[0536] In addition, in order to form a salt and stabilize it, the organic carboxylic acid, or the oxyacid of phosphorus or its derivative (C'2) is preferably used in the same amount as the nitrogen-containing compound (C'1) mentioned above.

[0537] <Alkali-soluble resin (D)>

[0538] To improve crack resistance, the photosensitive composition preferably also contains an alkali-soluble resin (D). Here, an alkali-soluble resin refers to a resin film with a thickness of 1 μm formed on a substrate by a 20% by weight resin solution (solvent: propylene glycol monomethyl ether acetate), which dissolves at least 0.01 μm when immersed in a 2.38% by weight TMAH aqueous solution for 1 minute. Preferably, the alkali-soluble resin (D) is at least one resin selected from the group consisting of phenolic varnish resin (D1), polyhydroxystyrene resin (D2), and acrylic resin (D3).

[0539] [Phenolic varnish resin (D1)]

[0540] Phenolic varnish resins are obtained, for example, by adding and condensing aromatic compounds (hereinafter referred to as "phenols") with aldehydes under an acid catalyst.

[0541] Examples of the aforementioned 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, phloroglucinol, phloroglucinol, hydroxybiphenyl, bisphenol A, gallic acid, gallic ester, α-naphthol, β-naphthol, etc.

[0542] Examples of aldehydes mentioned above include formaldehyde, furfural, benzaldehyde, nitrobenzaldehyde, and acetaldehyde.

[0543] There are no particular limitations on the catalyst used in addition condensation reactions; for example, acid catalysts such as hydrochloric acid, nitric acid, sulfuric acid, formic acid, oxalic acid, and acetic acid can be used.

[0544] In addition, the flexibility of phenolic varnish resin can be further improved by using o-cresol, replacing the hydrogen atoms of the hydroxyl groups in the resin with other substituents, or using bulky aldehydes.

[0545] The mass-average molecular weight of the phenolic varnish resin (D1) is not particularly limited within the scope of the present invention without hindering the purpose of the present invention, but is preferably 1,000 or more and 50,000 or less.

[0546] [Polyhydroxystyrene resin (D2)]

[0547] Examples of hydroxystyrene compounds that constitute polyhydroxystyrene resin (D2) include p-hydroxystyrene, α-methylhydroxystyrene, and α-ethylhydroxystyrene.

[0548] Furthermore, the polyhydroxystyrene resin (D2) is preferably a copolymer with styrene resin. Examples of styrene compounds constituting styrene resin include styrene, chlorostyrene, chloromethylstyrene, vinyltoluene, and α-methylstyrene.

[0549] The mass-average molecular weight of the polyhydroxystyrene resin (D2) is not particularly limited within the scope of the present invention without hindering the purpose of the present invention, but is preferably 1,000 or more and 50,000 or less.

[0550] [Acrylic resin (D3)]

[0551] As an acrylic resin (D3), it is preferred to contain structural units derived from polymeric compounds having ether bonds and structural units derived from polymeric compounds having carboxyl groups.

[0552] Examples of polymerizable compounds containing ether bonds include 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, tetrahydrofurfuryl (meth)acrylate, and other (meth)acrylate derivatives containing both ether and ester bonds. 2-methoxyethyl acrylate and methoxytriethylene glycol acrylate are preferred among the aforementioned polymerizable compounds containing ether bonds. These polymerizable compounds can be used alone or in combination of two or more.

[0553] Examples of the aforementioned carboxyl-containing 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; and compounds containing both carboxyl groups and ester bonds, such as 2-methacryloyloxyethyl succinic acid, 2-methacryloyloxyethyl maleic acid, 2-methacryloyloxyethyl phthalic acid, and 2-methacryloyloxyethyl hexahydrophthalic acid. Acrylic acid and methacrylic acid are preferred among these carboxyl-containing polymerizable compounds. These polymerizable compounds can be used alone or in combination of two or more.

[0554] The mass-average molecular weight of the acrylic resin (D3) is not particularly limited within the range that does not impede the purpose of the present invention, but is preferably 50,000 to 800,000.

[0555] When the total amount of the above-mentioned resin (B) and alkali-soluble resin (D) is set to 100 parts by mass, the content of alkali-soluble resin (D) is preferably 0 parts by mass or more than 80 parts by mass, and more preferably 0 parts by mass or more than 60 parts by mass. By setting the content of alkali-soluble resin (D) within the above range, there is a tendency to improve crack resistance and prevent film reduction during development.

[0556] <Sulfur-containing compounds (E)>

[0557] When using a photosensitive composition to form a pattern on a metal substrate, the photosensitive composition preferably contains a sulfur-containing compound (E). The sulfur-containing compound (E) is a compound containing sulfur atoms that can coordinate with a metal. Furthermore, regarding compounds capable of producing two or more tautomers, if at least one tautomer contains sulfur atoms that coordinate with a metal constituting the surface of the metal substrate, the compound is considered a sulfur-containing compound.

[0558] When a resist pattern is formed on a surface made of metal such as Cu as a mold for plating, defects in the cross-sectional shape, such as the base (folded edge), sometimes occur. As described above, when using the above-described photosensitive composition, it is easy to form a resist pattern with good rectangularity in cross-sectional shape. On the other hand, for the purpose of more reliably suppressing defects in cross-sectional shape, it is preferable that the photosensitive composition contains a sulfur-containing compound (E). When the photosensitive composition contains a sulfur-containing compound (E), even when the resist pattern is formed on a surface made of metal in the substrate, it is easier and more reliable to suppress the occurrence of defects in cross-sectional shape, such as the base.

[0559] When using the photosensitive composition to form a pattern on a substrate other than a metal substrate, the photosensitive composition does not need to specifically contain sulfur-containing compounds. From the viewpoints of facilitating the manufacture of the photosensitive composition due to the reduced number of components and reducing the manufacturing cost of the photosensitive composition, the photosensitive composition preferably does not contain sulfur-containing compounds (E).

[0560] In addition, there will be no adverse effects caused by the presence of sulfur-containing compounds (E) in the photosensitive composition used to form patterns on substrates other than metal substrates.

[0561] Sulfur atoms that can coordinate with metals can be included in sulfur-containing compounds, for example as mercapto (-SH), thiocarboxyl (-CO-SH), dithiocarboxyl (-CS-SH), and thiocarbonyl (-CS-).

[0562] From the perspectives of easy coordination with metals and excellent suppression effect on the base, sulfur-containing compounds preferably have thiol groups.

[0563] As a preferred example of a sulfur-containing compound having a thiol group, a compound represented by the following formula (e1) can be cited.

[0564] [Chemistry 57]

[0565]

[0566] (where R is in the formula) e1 and R e2 Each can be independently represented by a hydrogen atom or an alkyl group, R e3 Indicates a single bond or alkylene group, R e4 This indicates an aliphatic group with a valence of u, which can contain atoms other than carbon, where u represents an integer between 2 and 4.

[0567] In R e1 and R e2 When the alkyl group is an alkyl group, it can be linear or branched, preferably linear. In R e1 and R e2 When the alkyl group is an alkyl group, the number of carbon atoms in the alkyl group is not particularly limited to a extent that does not impair the purpose of the present invention. The number of carbon atoms in the alkyl group is preferably 1 to 4, particularly preferably 1 or 2, and most preferably 1. As R e1 With R e2 The combination of the two atoms is preferably one of hydrogen atoms and the other of an alkyl group, and particularly preferably one of hydrogen atoms and the other of a methyl group.

[0568] In R e3 When the alkylene group is alkylene, it can be linear or branched, preferably linear. In R e3 When the alkylene group is alkylene, the number of carbon atoms in the alkylene group is not particularly limited to a extent that does not impair the purpose of the present invention. The number of carbon atoms in the alkylene group is preferably 1 to 10, more preferably 1 to 5, particularly preferably 1 or 2, and most preferably 1.

[0569] R e4 It can be an aliphatic group with a valence of more than 2 or less than 4 that can contain atoms other than carbon. As R e4 It can contain atoms other than carbon, such as nitrogen, oxygen, sulfur, fluorine, chlorine, bromine, and iodine. As R e4 The aliphatic group can have a straight chain, a branched chain, a ring, or a combination of these structures.

[0570] Among the compounds represented by formula (e1), compounds represented by formula (e2) are more preferred.

[0571] [Chem.58]

[0572]

[0573] (In equation (e2), R) e4 And u is synonymous with equation (e1).

[0574] Among the compounds represented by the above formula (e2), the following compounds are preferred.

[0575] [Chemistry 59]

[0576]

[0577] Compounds represented by the following formulas (e3-L1) to (e3-L7) are also cited as preferred examples of sulfur-containing compounds having a thiol group.

[0578] [Transformation 60]

[0579]

[0580] (In formulas (e3-L1) to (e3-L7), R', s”, A”, and r are the same as those in formulas (b-L1) to (b-L7) for acrylic resin (B3).)

[0581] As preferred specific examples of thiol compounds represented by the above formulas (e3-L1) to (e3-L7), the following compounds can be cited.

[0582] [Chemistry 61]

[0583]

[0584] Compounds represented by the following formulas (e3-1) to (e3-4) are also cited as preferred examples of sulfur-containing compounds having a thiol group.

[0585] [Chemistry 62]

[0586]

[0587] (The definitions of the abbreviations in formulas (e3-1) to (e3-4) are the same as those for formulas (3-1) to (3-4) concerning acrylic resin (B3).)

[0588] As preferred specific examples of thiol compounds represented by the above formulas (e3-1) to (e3-4), the following compounds can be cited.

[0589] [Chemistry 63]

[0590]

[0591] Furthermore, as a preferred example of a compound having a thiol group, a compound represented by the following formula (e4) can be cited.

[0592] [Chemistry 64]

[0593]

[0594] (In equation (e4), R) e5 The group is selected from the group consisting of hydroxyl, alkyl with 1 to 4 carbon atoms, alkoxy with 1 to 4 carbon atoms, alkylthio with 1 to 4 carbon atoms, hydroxyalkyl with 1 to 4 carbon atoms, mercaptoalkyl with 1 to 4 carbon atoms, haloalkyl with 1 to 4 carbon atoms, and halogen atoms, where n1 is an integer of 0 to 3, n0 is an integer of 0 to 3, and when n1 is 2 or 3, R e5 They can be the same or different.

[0595] As R e5 Specific examples of alkyl groups having hydroxyl groups and having 1 to 4 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and tert-butyl. Among these alkyl groups, methyl, hydroxymethyl, and ethyl are preferred.

[0596] As R e5 Specific examples of alkoxy groups having 1 to 4 carbon atoms include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, and tert-butoxy. Among these alkoxy groups, methoxy and ethoxy are preferred, and methoxy is more preferred.

[0597] As R e5 Specific examples of alkylthio groups with 1 to 4 carbon atoms include methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, isobutylthio, sec-butylthio, and tert-butylthio. Among these alkylthio groups, methylthio and ethylthio are preferred, and methylthio is more preferred.

[0598] As R e5 Specific examples of hydroxyalkyl groups having 1 to 4 carbon atoms include hydroxymethyl, 2-hydroxyethyl, 1-hydroxyethyl, 3-hydroxy-n-propyl, and 4-hydroxy-n-butyl. Among these hydroxyalkyl groups, hydroxymethyl, 2-hydroxyethyl, and 1-hydroxyethyl are preferred, and hydroxymethyl is more preferred.

[0599] As R e5 Specific examples of thiol alkyl groups having 1 to 4 carbon atoms include mercaptomethyl, 2-mercaptoethyl, 1-mercaptoethyl, 3-mercapto-n-propyl, and 4-mercapto-n-butyl. Among these thiol alkyl groups, mercaptomethyl, 2-mercaptoethyl, and 1-mercaptoethyl are preferred, and mercaptomethyl is more preferred.

[0600] In R e5In the case of a haloalkyl group having 1 to 4 carbon atoms, examples of halogen atoms included in the haloalkyl group include fluorine, chlorine, bromine, and iodine. As R e5 Specific examples of alkyl halogens having 1 to 4 carbon atoms include chloromethyl, bromomethyl, iodomethyl, fluoromethyl, dichloromethyl, dibromomethyl, difluoromethyl, trichloromethyl, tribromomethyl, trifluoromethyl, 2-chloroethyl, 2-bromoethyl, 2-fluoroethyl, 1,2-dichloroethyl, 2,2-difluoroethyl, 1-chloro-2-fluoroethyl, 3-chloro-n-propyl, 3-bromo-n-propyl, 3-fluoro-n-propyl, and 4-chloro-n-butyl. Among these alkyl halogens, chloromethyl, bromomethyl, iodomethyl, fluoromethyl, dichloromethyl, dibromomethyl, difluoromethyl, trichloromethyl, tribromomethyl, and trifluoromethyl are preferred, and chloromethyl, dichloromethyl, trichloromethyl, and trifluoromethyl are more preferred.

[0601] As R e5 Specific examples of halogen atoms include fluorine, chlorine, bromine, or iodine.

[0602] In equation (e4), n1 is an integer greater than or equal to 0 and less than or equal to 3, more preferably 1. When n1 is 2 or 3, multiple R... e5 They can be the same or different.

[0603] In the compound represented by formula (e4), the R on the benzene ring e5 The substitution position is not particularly limited. The R on the benzene ring... e5 The substitution position is preferably relative to -(CH2). n0 The bonding position of -SH is either interposition or parallel.

[0604] As a compound represented by formula (e4), it is preferred to have at least one group selected from the group consisting of alkyl, hydroxyalkyl, and mercaptoalkyl as R. e5 The compound, more preferably, has one group selected from the group consisting of alkyl, hydroxyalkyl, and mercaptoalkyl as R. e5 Compounds. The compound represented by formula (e4) has one group selected from the group consisting of alkyl, hydroxyalkyl, and mercaptoalkyl groups as R. e5 In this case, the substitution position on the benzene ring of the alkyl, hydroxyalkyl, or mercaptoalkyl group is preferably relative to -(CH2). n0 The bonding position of -SH is either meta or para, with para being more preferred.

[0605] In formula (e4), n0 is an integer between 0 and 3. From the perspective of making the preparation and acquisition of the compound easier, n0 is preferably 0 or 1, and more preferably 0.

[0606] Specific examples of compounds represented by formula (e4) include p-mercaptophenol, p-thiocresol, m-thiocresol, 4-(methylthio)benzylthiol, 4-methoxybenzylthiol, 3-methoxybenzylthiol, 4-ethoxybenzylthiol, 4-isopropoxybenzylthiol, 4-tert-butoxybenzylthiol, 3,4-dimethoxybenzylthiol, 3,4,5-trimethoxybenzylthiol, 4-ethylbenzylthiol, and 4-isopropylbenzylthiol. Alcohols, 4-n-Butylbenzylthiol, 4-tert-Butylbenzylthiol, 3-Ethylbenzylthiol, 3-Isopropylbenzylthiol, 3-n-Butylbenzylthiol, 3-tert-Butylbenzylthiol, 3,5-Dimethylbenzylthiol, 3,4-Dimethylbenzylthiol, 3-tert-Butyl-4-methylbenzylthiol, 3-tert-Butyl-5-methylbenzylthiol, 4-tert-Butyl-3-methylbenzylthiol, 4-Mercaptobenzyl alcohol, 3 -Mercaptobenzyl alcohol, 4-(mercaptomethyl)phenol, 3-(mercaptomethyl)phenol, 1,4-di(mercaptomethyl)phenol, 1,3-di(mercaptomethyl)phenol, 4-fluorobenzyl mercaptan, 3-fluorobenzyl mercaptan, 4-chlorobenzyl mercaptan, 3-chlorobenzyl mercaptan, 4-bromobenzyl mercaptan, 4-iodobenzyl mercaptan, 3-bromobenzyl mercaptan, 3,4-dichlorobenzyl mercaptan, 3,5-dichlorobenzyl mercaptan, 3,4-difluorobenzyl mercaptan, 3,5- Difluorobenzylthiol, 4-mercaptocatechol, 2,6-di-tert-butyl-4-mercaptophenol, 3,5-di-tert-butyl-4-methoxybenzylthiol, 4-bromo-3-methylbenzylthiol, 4-(trifluoromethyl)benzylthiol, 3-(trifluoromethyl)benzylthiol, 3,5-bis(trifluoromethyl)benzylthiol, 4-methylthiobenzylthiol, 4-ethylthiobenzylthiol, 4-n-butylthiobenzylthiol, and 4-tert-butylthiobenzylthiol, etc.

[0607] Furthermore, examples of sulfur-containing compounds having a thiol group include compounds containing nitrogen-containing aromatic heterocycles obtained by thiol substitution and tautomers of compounds containing nitrogen-containing aromatic heterocycles obtained by thiol substitution.

[0608] Preferred examples of nitrogen-containing aromatic heterocycles 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, cinnamoline, phthalazine, quinazoline, quinoxaline, and 1,8-naphthyridine.

[0609] The following compounds are examples of preferred nitrogen-containing heterocyclic compounds and tautomers of nitrogen-containing heterocyclic compounds that are suitable for use as sulfur-containing compounds.

[0610] [Chemistry 65]

[0611]

[0612] When the photosensitive composition contains a sulfur-containing compound (E), the amount of it used is preferably 0.01 parts or more and 5 parts or less, more preferably 0.02 parts or more and 3 parts or less, and particularly preferably 0.05 parts or more and 2 parts or less, relative to 100 parts by mass of the total mass of the above-mentioned resin (B) and alkali-soluble resin (D).

[0613] <Organic Solvents (S)>

[0614] The photosensitive composition contains an organic solvent (S). Without hindering the objectives of the present invention, the type of organic solvent (S) is not particularly limited, and can be appropriately selected and used from conventional organic solvents used in photosensitive compositions.

[0615] Specific examples of organic solvents (S) include ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl isopentyl ketone, and 2-heptanone; polyols and their derivatives such as monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether, and monophenyl ether of ethylene glycol, ethylene glycol monoacetate, diethylene glycol, diethylene glycol monoacetate, propylene glycol, propylene glycol monoacetate, dipropylene glycol, and dipropylene glycol monoacetate; cyclic ethers such as dioxane; ethyl formate, methyl lactate, ethyl lactate, etc. Esters such as methyl ester, ethyl acetate, butyl acetate, methyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl pyruvate, ethyl ethoxylate, methyl methoxypropionate, ethyl ethoxypropionate, methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, methyl 2-hydroxy-3-methylbutyrate, methyl 3-methoxybutylacetate, and methyl-3-methoxybutylacetate; aromatic hydrocarbons such as toluene and xylene. These can be used alone or in combination of two or more.

[0616] The content of organic solvent (S) is not particularly limited to the extent that it does not impair the purpose of the present invention. When the photosensitive composition is used for thick film applications, such as to achieve a film thickness of 5 μm or more for a photosensitive layer obtained by spin coating or the like, it is preferable to use organic solvent (S) in a range where the concentration of solid components in the photosensitive composition is between 30% by mass and 55% by mass.

[0617] <Other Ingredients>

[0618] To improve plasticity, the photosensitive composition may also contain a polyethylene resin. Specific examples of polyethylene resins include polyvinyl chloride, polystyrene, polyhydroxystyrene, polyvinyl acetate, polyvinylbenzoic acid, polyethylene methyl ether, polyethylene ethyl ether, polyvinyl alcohol, polyvinylpyrrolidone, polyvinylphenol, and copolymers thereof. From the viewpoint of a lower glass transition point, polyethylene methyl ether is preferred.

[0619] The photosensitive composition preferably also contains a Lewis acid compound. By including a Lewis acid compound in the photosensitive composition, a highly sensitive photosensitive composition is readily obtained, and it is easier to use the photosensitive composition to form resist patterns with a rectangular cross-sectional shape.

[0620] Furthermore, when using photosensitive compositions to form patterns, if the time required for each step in the pattern-forming process or the time required between steps is long, it can sometimes result in the pattern being difficult to form the desired shape or size, or in adverse effects such as deterioration of developability. However, by incorporating Lewis acid compounds into the photosensitive composition, such adverse effects on pattern shape or developability can be mitigated, and the process margin can be widened.

[0621] Here, Lewis acidic compounds are defined as "compounds that have empty orbitals capable of accepting at least one electron pair and that act as electron pair acceptors".

[0622] As a Lewis acid compound, there is no particular limitation as long as the compound falls under the above definition and is recognized by those skilled in the art as a Lewis acid compound. Preferably, the compound used is not a Brønsted acid (protic acid).

[0623] 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 ethyl, Me is methyl, and THF is tetrahydrofuran), organoboron compounds (e.g., tri-n-octyl borate, tri-n-butyl borate, triphenyl borate, and triphenylboron), titanium chloride, aluminum chloride, aluminum bromide, gallium 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, etc.

[0624] In addition, other specific examples of Lewis acidic compounds include chlorides, bromides, sulfates, nitrates, carboxylates, or trifluoromethanesulfonates of rare earth metals; and cobalt chloride, ferrous chloride, and yttrium chloride, etc.

[0625] Here, rare earth metal elements include, for example, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, and lutetium.

[0626] From the perspective of easy availability and the good effects brought about by its addition, Lewis acid compounds are preferably Lewis acid compounds containing elements of Group 13 of the periodic table.

[0627] Here, boron, aluminum, gallium, indium, and thallium are examples of elements in Group 13 of the periodic table.

[0628] Among the elements in Group 13 of the periodic table, boron is preferred from the perspective of ease of obtaining Lewis acid compounds and particularly excellent addition effect. That is, Lewis acid compounds preferably contain boron.

[0629] Examples of boron-containing Lewis acid compounds include boron fluoride, boron fluoride ether complexes, boron chloride, boron bromide, and various organoboron compounds. From the perspective of reducing the halogen atom content in the Lewis acid compound and facilitating the application of the photosensitive composition to applications requiring low halogen content, organoboron compounds are preferred.

[0630] As a preferred example of an organoboron compound, a boron compound represented by the following formula (f1) can be cited.

[0631] B(R f1 ) t1 (OR f2 ) (3-t1) ...(f1)

[0632] (in equation (f1), R) f1 and R f2 Each is independently a hydrocarbon group having 1 to 20 carbon atoms, and the hydrocarbon group may have one or more substituents, where t1 is an integer between 0 and 3, and multiple R groups are present. f1 In the case of multiple R f1 Two of them can bond together to form a ring, and there are multiple ORs. f2 In the case of multiple ORs f2 Two of them can bond with each other to form a ring. The photosensitive composition preferably contains one or more boron compounds represented by the above formula (f1) as Lewis acid compounds.

[0633] In equation (f1), in R f1 and R f2 When the group is a hydrocarbon group, the number of carbon atoms in the hydrocarbon group is 1 to 20. A hydrocarbon group with 1 to 20 carbon atoms can be an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a hydrocarbon group composed of aliphatic and aromatic groups.

[0634] As a hydrocarbon group with 1 to 20 carbon atoms, a saturated aliphatic or aromatic hydrocarbon group is preferred. As R f1 and R f2 The number of carbon atoms in the hydrocarbon group is preferably 1 to 10. When the hydrocarbon group is an aliphatic hydrocarbon group, the number of carbon atoms is more preferably 1 to 6, and particularly preferably 1 to 4.

[0635] As R f1 and R f2 The hydrocarbon group can be a saturated hydrocarbon group or an unsaturated hydrocarbon group, but a saturated hydrocarbon group is preferred.

[0636] As R f1 and R f2 When the hydrocarbon group is an aliphatic hydrocarbon group, the aliphatic hydrocarbon group can be straight-chain, branched, cyclic, or a combination of these structures.

[0637] Preferred examples of aromatic hydrocarbon groups include phenyl, naphth-1-yl, naphth-2-yl, 4-phenylphenyl, 3-phenylphenyl, and 2-phenylphenyl. Among these, phenyl is preferred.

[0638] Alkyl groups are preferred as saturated aliphatic hydrocarbon groups. Specific examples of preferred alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, and n-decyl.

[0639] As R f1 and R f2 The hydrocarbon group can have more than one substituent. Examples of substituents include halogen atoms, hydroxyl groups, alkyl groups, aralkyl groups, alkoxy groups, cycloalkyloxy groups, aryloxy groups, aralkyloxy groups, alkylthio groups, cycloalkylthio groups, arylthio groups, arylalkylthio groups, acyl groups, acyloxy groups, acylthio groups, alkoxycarbonyl groups, cycloalkoxycarbonyl groups, aryloxycarbonyl groups, amino groups, N-monosubstituted amino groups, N,N-disubstituted amino groups, carbamoyl groups (-CO-NH2), N-monosubstituted carbamoyl groups, N,N-disubstituted carbamoyl groups, nitro groups, and cyano groups.

[0640] The number of carbon atoms in the substituents is not particularly limited as long as it does not impede the purpose of the present invention, but is preferably 1 to 10, more preferably 1 to 6.

[0641] As a preferred specific example of an organoboron compound represented by the above formula (f1), the following compounds can be cited. In addition, in the following formulas, Pen represents pentyl, Hex represents hexyl, Hep represents heptyl, Oct represents octyl, Non represents nonyl, and Dec represents decyl.

[0642] [Chemistry 66]

[0643]

[0644] [Chemistry 67]

[0645]

[0646] [Chemistry 68]

[0647]

[0648] [Chemistry 69]

[0649]

[0650] [Chemistry 70]

[0651]

[0652] Relative to the total mass of the above-mentioned resin (B) and the above-mentioned alkali-soluble resin (D) of 100 parts by mass, it is preferable to use the Lewis acid compound in the range of 0.01 parts by mass to 5 parts by mass, more preferably in the range of 0.01 parts by mass to 3 parts by mass, and even more preferably in the range of 0.05 parts by mass to 2 parts by mass.

[0653] Furthermore, when the photosensitive composition is used to form a pattern for a mold used to form a plated model, an adhesive aid may be included to improve the adhesion between the mold formed using the photosensitive composition and the metal substrate.

[0654] In addition, to improve coatability, defoaming properties, leveling properties, etc., the photosensitive composition may also contain a surfactant. As a surfactant, fluorinated surfactants or organosilicon surfactants are preferred, for example.

[0655] Specific examples of fluorinated surfactants include commercially available fluorinated surfactants such as BM-1000, BM-1100 (both manufactured by BM Chemicals), MEGAFAC F142D, MEGAFAC F172, MEGAFAC F173, MEGAFAC F183 (all manufactured by Dai Nippon Ink Chemical Industry Co., Ltd.), Fluorad FC-135, Fluorad FC-170C, Fluorad FC-430, Fluorad FC-431 (all manufactured by Sumitomo 3M), Surflon S-112, Surflon S-113, Surflon S-131, Surflon S-141, 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 Co., Ltd.), but are not limited to these.

[0656] As organosilicon surfactants, unmodified organosilicon surfactants, polyether-modified organosilicon surfactants, polyester-modified organosilicon surfactants, alkyl-modified organosilicon surfactants, aralkyl-modified organosilicon surfactants, and reactive organosilicon surfactants are preferably used.

[0657] As a silicone surfactant, commercially available silicone surfactants can be used. Specific examples of commercially available silicone surfactants include PAINTADD M (manufactured by Toray Industries, Inc.), Tepika K1000, Tepika K2000, Tepika K5000 (all manufactured by Takachiho Industries, Inc.), XL-121 (polyether-modified silicone surfactant, manufactured by Clariant), and BYK-310 (polyester-modified silicone surfactant, manufactured by BYK Chemical Co., Ltd.).

[0658] In addition, the photosensitive composition may also contain acids, anhydrides or high-boiling-point solvents to make fine adjustments to the solubility of the developer.

[0659] Specific examples of acids and anhydrides include monocarboxylic acids such as acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, isovaleric acid, benzoic acid, and cinnamic acid; hydroxy monocarboxylic 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, and 1... Polycarboxylic acids such as 2,4-cyclohexanetricarboxylic acid, butanetetracarboxylic acid, trimellitic acid, pyromellitic acid, cyclopentanetetracarboxylic acid, butanetetracarboxylic acid, and 1,2,5,8-naphthalenetetracarboxylic acid; and anhydrides such as itaconic anhydride, succinic anhydride, citraconic anhydride, dodecenylsuccinic anhydride, tricarboxylic anhydride, maleic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, nadic anhydride, 1,2,3,4-butanetetracarboxylic anhydride, cyclopentanetetracarboxylic dianhydride, phthalic anhydride, pyromellitic anhydride, trimellitic anhydride, benzophenonetetracarboxylic anhydride, ethylene glycol ditriphenyltrihydride, and glycerol trimellitic anhydride.

[0660] In addition, specific examples of high-boiling-point solvents include N-methylformamide, N,N-dimethylformamide, N-methylformaniline, N-methylacetamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, benzyl ethyl ether, dihexyl ether, acetone-acetone, isophorone, hexanoic acid, octanoic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, ethylene glycol phenyl ether acetate, etc.

[0661] In addition, to improve sensitivity, the photosensitizing composition may also contain known sensitizers.

[0662] Preparation method of chemically amplified positive-type photosensitive composition

[0663] The composition is prepared by mixing and stirring the constituent components of the chemically amplified positive photosensitive composition using conventional methods. Examples of apparatuses that can be used to mix and stir the components include dissolvers, homogenizers, and three-roll mills. After uniformly mixing the components, the resulting mixture can be further filtered using a sieve, membrane filter, or the like.

[0664] Photosensitive dry film

[0665] A photosensitive dry film has a substrate film and a photosensitive layer formed on the surface of the substrate film. In the photosensitive dry film, the photosensitive layer is composed of the aforementioned photosensitive composition.

[0666] As a substrate film, a film with light transmittance is preferred. Specifically, examples include polyethylene terephthalate (PET) film, polypropylene (PP) film, and polyethylene (PE) film. From the viewpoint of achieving an excellent balance between light transmittance and tensile strength, polyethylene terephthalate (PET) film is preferred.

[0667] The photosensitive composition is coated onto a substrate film to form a photosensitive layer, thereby producing a photosensitive dry film.

[0668] When forming a photosensitive layer on a substrate film, a photosensitive composition is coated on the substrate film using a coater, bar coater, wire bar coater, roller coater, curtain coater, etc., and then dried so that the film thickness after drying 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.

[0669] Photosensitive dry films may also have a protective film on the photosensitive layer. Examples of such protective films include polyethylene terephthalate (PET) film, polypropylene (PP) film, and polyethylene (PE) film.

[0670] Patterned resist film

[0671] The method for forming a patterned resist film on a substrate using the photosensitive composition described above is not particularly limited. This patterned resist film is preferably used as an insulating film, an etching mask, or a mold for forming plated shapes.

[0672] A preferred method for manufacturing a patterned resist film includes the following steps:

[0673] The lamination process involves laminating a photosensitive layer composed of a photosensitive composition onto a substrate.

[0674] The exposure process involves selectively irradiating the photosensitive layer with active light or radiation.

[0675] The developing process involves developing the exposed photosensitive layer.

[0676] The manufacturing method of a molded substrate with a mold for forming a plated shape is the same as the manufacturing method of 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 using development in a development step to make a mold for forming a plated shape.

[0677] There are no particular limitations on the substrate used for stacking the photosensitive layer; conventionally known substrates can be used, such as substrates for electronic components or substrates on which a predetermined wiring pattern is formed. Silicon substrates or glass substrates can also be used as substrates.

[0678] When manufacturing a molded substrate with a mold for forming a plated shape, a substrate with a metallic surface is used as the substrate. Copper, gold, and aluminum are preferred as the type of metal constituting the metallic surface, with copper being more preferred.

[0679] For example, a photosensitive layer can be laminated on a substrate in the following manner: a liquid photosensitive composition is coated onto the substrate, and the solvent is removed by heating, thereby forming a photosensitive layer of the desired film thickness. The thickness of the photosensitive layer is not particularly limited as long as a resist pattern can be formed with the desired film thickness. The film thickness of the photosensitive layer is not particularly limited, but is preferably 0.5 μm or more, more preferably 0.5 μm 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.

[0680] Various methods can be employed for coating a photosensitive composition onto a substrate, including spin coating, slot coating, roller coating, screen printing, and applicator coating. Pre-baking of the photosensitive layer is preferred. The pre-baking conditions vary depending on the type and mixing ratio of the components in the photosensitive composition, the coating film thickness, etc., but are typically between 70°C and 200°C, preferably between 80°C and 150°C, for approximately 2 minutes to 120 minutes.

[0681] The photosensitive layer formed as described above is selectively irradiated (exposed) with active light or radiation, such as ultraviolet or visible light with wavelengths of 300 nm to 500 nm, through a mask with a prescribed pattern.

[0682] As radiation sources, low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, and argon lasers can be used. In addition, radiation includes 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 thickness of the photosensitive layer; for example, when using an ultra-high-pressure mercury lamp, it is 100 mJ / cm². 2 Above 10000mJ / cm 2 Below. In addition, in order to produce acid, the radiation contains light that activates the acid-producing agent (A).

[0683] After exposure, the photosensitive layer is heated using known methods to promote the diffusion of acid, thereby changing the solubility of the photosensitive layer in the exposed portion of the photosensitive layer to developing solutions such as alkaline developing solutions.

[0684] Next, the exposed photosensitive layer is developed using conventional methods to dissolve and remove unwanted portions, thereby forming a predetermined resist pattern or a mold for creating the plated object. An alkaline aqueous solution can be used as the developer at this stage.

[0685] As a developer, aqueous solutions of bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, pyrrole, piperidine, 1,8-diazabicyclo[5,4,0]-7-undecene, and 1,5-diazabicyclo[4,3,0]-5-nonane can also be used. Furthermore, aqueous solutions containing appropriate amounts of water-soluble organic solvents or surfactants such as methanol or ethanol can also be used as developers.

[0686] Furthermore, depending on the composition of the photosensitive composition, organic solvent-based development can also be applied.

[0687] The development time varies depending on the composition of the photosensitive composition and the thickness of the photosensitive layer, and is usually between 1 minute and 30 minutes. The development method can be any of the following: liquid-based development, immersion development, water-pit development, or spray development.

[0688] After development, the substrate is rinsed with running water for 30 to 90 seconds and then dried using an air gun, oven, or similar method. In this way, a resist film patterned into a desired shape is formed on the surface of the substrate. Furthermore, it is possible to manufacture a molded substrate with a resist pattern serving as a mold on the metal surface of a substrate having a metal surface.

[0689] The aforementioned photosensitive composition exhibits high resolution and dimensional controllability. Furthermore, it readily forms resist patterns with excellent rectangular cross-sectional shape. Therefore, it is possible to form highly detailed resist patterns with the desired shape and rectangular cross-sectional shape.

[0690] In the non-resist portion (the portion removed by the developer) of the mold with a mold substrate formed using the above method, a conductor such as a metal is embedded by plating, thereby forming plated shapes such as bumps and metal pillars as connection terminals, or Cu redistribution. Furthermore, the plating process is not particularly limited, and various conventionally known methods can be used. As the plating solution, solder plating solution, copper plating solution, gold plating solution, and nickel plating solution are particularly preferred. The remaining mold is then removed using a stripping solution or the like using conventional methods.

[0691] When manufacturing coated shapes, it is sometimes preferable to perform ashing treatment on the exposed metal surfaces in the non-patterned parts of the resist pattern of the mold used to form the coated shape.

[0692] Specifically, for example, a pattern formed using a photosensitive composition containing a sulfur compound (E) is used as a mold to form a plated model. In this case, the adhesion of the plated model to the metal surface can sometimes be compromised. This defect is more pronounced when using a sulfur compound (E) represented by formula (e1) or a sulfur compound (E) represented by formula (e4).

[0693] However, if the above-mentioned ashing treatment is performed, even if a pattern formed using a photosensitive composition containing sulfur compounds (E) is used as a mold, it is easy to form a plated shape that adheres well to the metal surface.

[0694] Furthermore, when a compound containing a nitrogen-containing aromatic heterocycle substituted with a thiol group is used as the sulfur-containing compound (E), the aforementioned problems related to the adhesion of the plated model are almost non-occurring or only mild. Therefore, when using a compound containing a nitrogen-containing aromatic heterocycle substituted with a thiol group as the sulfur-containing compound (E), it is easy to form a plated model with good adhesion to the metal surface even without ashing treatment.

[0695] Ashing is not particularly limited as long as it does not damage the resist pattern of the mold used to form the plated object to the extent that it prevents the plated object from forming the desired shape.

[0696] As a preferred ashing method, the use of oxygen plasma can be cited as an example. In order to ashing the metal surface on the substrate using oxygen plasma, it is only necessary to use a known oxygen plasma generating device to generate oxygen plasma and irradiate the metal surface on the substrate with the oxygen plasma.

[0697] In the gas used to generate oxygen plasma, various gases that have been conventionally used with oxygen for plasma processing can be mixed in, to a extent that does not impair the purpose of this invention. Examples of such gases include nitrogen, hydrogen, and CF4.

[0698] The ashing conditions using oxygen plasma are not particularly limited to the extent that they do not impair the purpose of the present invention. 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.

[0699] By setting the processing time using oxygen plasma within the range described above, it is easy to improve the adhesion of the plated object without altering the shape of the resist pattern.

[0700] Because the photosensitive composition described above can form a highly precise resist pattern with a desired shape and a rectangular cross-section, this resist pattern can be used as a mold for forming a plated object, thus enabling further high-density and high-precision processing of protruding electrodes or metal pillars.

[0701] Example

[0702] The present invention will be described in more detail below through embodiments, but the present invention is not limited to these embodiments.

[0703] [Preparation Example 1]

[0704] (Synthesis of thiol compound T2)

[0705] In Preparation Example 1, a thiol compound T2 with the following structure was synthesized as a sulfur-containing compound (E).

[0706] [Chemistry 71]

[0707]

[0708] 15.00 g of 7-heptan-5-ene-2,3-dicarboxylic anhydride and 150.00 g of tetrahydrofuran were added to a flask and stirred. Next, 7.64 g of thioacetic acid (AcSH) was added to the flask, and the mixture was stirred at room temperature for 3.5 hours. The reaction mixture was then concentrated to obtain 22.11 g of 5-acetylthio-7-heptan-7-ene-2,3-dicarboxylic anhydride.

[0709] 22.11 g of 5-acetylthio-7-hexaoxadicyclo(2.2.1)heptane-2,3-dicarboxylic anhydride and 30.11 g of 10% (w / w) sodium hydroxide aqueous solution were added to a flask, and the contents of the flask were stirred for 2 hours at room temperature. Then, 80.00 g of 20% (w / w) hydrochloric acid was added to the flask to make the reaction solution acidic. The mixture was then extracted four times with 100 g of ethyl acetate to obtain an extract containing the thiol compound T2. The residue recovered from the concentrated extract was dissolved in 25.11 g of tetrahydrofuran (THF). Heptane was added dropwise to the resulting THF solution to precipitate the thiol compound T2, which was then recovered by filtration. The thiol compound T2... 1 The H-NMR measurement results are recorded below.

[0710] 1 H-NMR (DMSO-d6): δ12.10 (s, 2H), 4.72 (d, 1H), 4.43 (s, 1H), 3.10 (t, 1H), 3.01 (d, 1H), 2.85 (d, 1H), 2.75 (d, 1H), 2.10 (t, 1H), 1.40 (m, 1H)

[0711] [Chemistry 72]

[0712]

[0713] [Examples 1-5 and Comparative Examples 1-4]

[0714] In Examples 1-5 and Comparative Examples 1-4, PAG1 with the following formula was used as the acid-producing agent (A).

[0715] [Chemistry 73]

[0716]

[0717] In Examples 1-5 and Comparative Examples 1-4, the following Resin A1 was used as a resin (Resin (B)) whose solubility in alkali increased due to the action of acid. The numbers in parentheses to the lower right of each structural unit in the following structural formula indicate the content (mass %) of the structural unit in the resin. The mass-average molecular weight Mw of Resin A1 is 42000.

[0718] [Chemistry 74]

[0719]

[0720] In Examples 1-5 and Comparative Examples 1-4, Resin B1 (polyhydroxystyrene resin) and Resin C (phenolic varnish resin (m-cresol condensate)) were used as the alkali-soluble resin (D). The numbers in parentheses at the bottom right of each structural unit in the following structural formulas indicate the content (mass %) of each structural unit in the resin. Resin B1 has a mass-average molecular weight (Mw) of 2500 and a molecular weight distribution coefficient (Mw / Mn) of 2.4. Resin C has a mass-average molecular weight (Mw) of 8000.

[0721] [Chemistry 75]

[0722]

[0723] [Chemistry 76]

[0724]

[0725] As an acid diffusion inhibitor (C), C1 to C7 are used. Furthermore, in C4, n1 and n2 are both 1. Additionally, C2 is a product of the reaction of aniline, N-phenyl, and 2,4,4-trimethylpentene.

[0726] [Chemistry 77]

[0727]

[0728] C5: Triphenylamine

[0729] C6: Triamylamine

[0730] C7: Aniline

[0731] The following sulfur-containing compounds T1 and T2 were used as sulfur-containing compounds (E).

[0732] [Chemistry 78]

[0733]

[0734] The acid-generating agent (A), resin (B), acid diffusion inhibitor (C), alkali-soluble resin (D), sulfur-containing compound (E), and 0.05 parts by weight of surfactant (BYK310, manufactured by BYK Chemical Company) listed in Table 1 were dissolved in 3-methoxybutylacetic acid (MA) to achieve a solid content concentration of 51% by weight, thereby obtaining the photosensitive compositions of each example and comparative example. Note that the units in Table 1 are parts by weight, and only the amount of acid diffusion inhibitor (C) is listed as parts by weight relative to 100 parts by weight of resin (B).

[0735] Using the obtained photosensitive composition, the resolution, dimensional controllability, perpendicularity of the cross section, and interface shape of the cross section were evaluated according to the following methods. These evaluation results are recorded in Table 1.

[0736] [Resolution Evaluation]

[0737] A substrate with a sputtered copper film of 200 nm thickness was prepared on the surface of a Si substrate. The photosensitive compositions of the examples and comparative examples were coated onto the copper layer of this substrate and dried on a hot plate at 145°C for 5 minutes to form a photosensitive layer (coating of the photosensitive composition) with a thickness of 65 μm. Next, a Prisma GHI5452 (Ultratech, NA = 0.16) projection exposure apparatus with a 10 μm diameter hole pattern was used at 500 mJ / cm². 2 The exposure amount was adjusted, and the pattern was exposed using a ghi line. Next, the substrate was placed on a heated plate and exposed at 100°C for 3 minutes using post-exposure heating (PEB). Then, the following operation was repeated a total of 5 times: a 2.38 wt% aqueous solution of tetramethylammonium hydroxide (TMAH) (developer, NMD-3, manufactured by Tokyo Ohka Kogyo Co., Ltd.) was added dropwise to the exposed photosensitive layer, and the substrate was left to stand at 23°C for 60 seconds (water pit development). Afterward, the resist pattern surface was rinsed with running water for 60 seconds, followed by spin drying to obtain the resist pattern.

[0738] The resist patterns (hole patterns) observed using optical microscopy and scanning electron microscopy (SEM) were evaluated as follows: those with a 10 μm pattern were rated as ○, and those without a 10 μm pattern were rated as ×.

[0739] [Evaluation of dimensional control]

[0740] In addition to using a mask with a 30μm aperture pattern as the mask, the same operation as [resolution evaluation] is performed to obtain the resist pattern.

[0741] For the obtained resist pattern (hole pattern), the diameter (hole size) of the surface (bottom) of the resist pattern in contact with the substrate is measured using a scanning electron microscope. Hole sizes within 30 μm ± 10% are evaluated as ◎, those outside the range of 30 μm ± 10% but within 30 μm ± 30% are evaluated as ○, those outside the range of 30 μm ± 30% but within 30 μm ± 50% are evaluated as △, and those outside the range of 30 μm ± 50% are evaluated as ×.

[0742] [Evaluation of the perpendicularity of the cross-section (evaluation of the rectangularity of the cross-sectional shape)]

[0743] The resist pattern (hole pattern) obtained in the [Dimensional Control Evaluation] was observed using a scanning electron microscope. The width Wb of the resist pattern on the substrate-contacting side (bottom), the width Wm of the middle portion of the resist pattern cross-section in the thickness direction, and the width Wt of the resist pattern on the opposite side (top) of the substrate-contacting side were measured. The standard deviation (σ) of Wb, Wm, and Wt was calculated. A value less than 1 was rated as ◎, a value greater than or equal to 1 but less than 2 was rated as ○, a value greater than or equal to 2 but less than 3 was rated as △, and a value greater than or equal to 3 was rated as ×.

[0744] [Evaluation of the interface shape of the cross section (evaluation of the rectangularity of the substrate interface shape)]

[0745] For the resist pattern obtained in [Evaluation of Dimensional Control], the interface between the substrate and the resist pattern was observed using a scanning electron microscope. Cases where no fold (foot) was observed or where the length of the hem was less than 0.5 μm were evaluated as ◎, cases where the length of the hem was 0.5 μm or more but less than 1 μm were evaluated as ○, cases where the length of the hem was 1 μm or more but less than 2 μm were evaluated as △, cases where the length of the hem was 2 μm or more were evaluated as ×, and cases where the shape was concave were evaluated as ××.

[0746] [Table 1]

[0747]

[0748] As can be seen from Examples 1 to 5, a photosensitive composition obtained by incorporating a compound represented by formula (C1) as an acid diffusion inhibitor (C) into a chemically amplified positive photosensitive composition containing an acid-generating agent (A) that generates acid upon irradiation by active light or radiation and a resin (B) whose solubility in alkali increases due to the action of acid, can form a resist pattern with good verticality of cross section and good interface shape and rectangularity, and has high resolution and dimensional control.

[0749] On the other hand, according to Comparative Examples 1 to 4, when the photosensitive composition contains acid diffusion inhibitors, namely C5 to C7, which are not compounds represented by formula (C1), instead of compounds represented by formula (C1), the resolution, size control, verticality of the cross section, and interface shape are all poor.

Claims

1. A chemically amplified positive photosensitive composition, characterized in that, contain: Acid-producing agent (A), which generates acid through irradiation with active light or radiation; resin (B), whose solubility in alkali increases due to the action of acid; acid diffusion inhibitor (C), The acid diffusion inhibitor (C) comprises a compound represented by the following formula (C1). [Chemistry 1] In formula (C1), R 1c It is an alkyl or aralkyl group. R 2c It is an alkyl or aralkyl group. R 3c It is a hydrogen atom or an alkyl group. R 4c It is an alkylene group. n1 is an integer greater than 0 and less than 5. n2 is an integer greater than 0 and less than 5. n3 is 0 or R 1c It is an alkyl or aralkyl group having 6 to 10 carbon atoms. R 2c It is an alkyl or aralkyl group having 6 to 10 carbon atoms. R 3c It is a hydrogen atom or an alkyl group. R 4c It is a single key. n1 is an integer greater than 0 and less than 5. n2 is an integer greater than 0 and less than 5. n3 is 1. n1 and n2 are not both 0.

2. The chemically amplified positive photosensitive composition as described in claim 1, characterized in that, The acid-producing agent (A) comprises a compound represented by the following formula (a21). In equation (a21), R 22a It can be an aliphatic hydrocarbon group having 1 to 18 carbon atoms that can be substituted by a halogen atom and / or an alkylthio group, an aryl group having 6 to 20 carbon atoms that can have a substituent, an aralkyl group having 7 to 20 carbon atoms that can have a substituent, an alkylaryl group having 7 to 20 carbon atoms that can have a substituent, camphor-10-yl, and a group represented by the following formula (a21a). -R 27a -(Oh) a -R 28a -(Oh) b -Y 1 -R 29a ...(s21a) In formula (a21a), Y 1 For single bonds or alkyldiyl groups with 1 to 4 carbon atoms, R 27a and R 28a These are, respectively, alkyldiyl groups with 2 to 6 carbon atoms that can be replaced by halogen atoms, or aryl groups with 6 to 20 carbon atoms that can be replaced by halogen atoms, R 29a The alkyl group having 1 to 18 carbon atoms that can be substituted by a halogen atom, the alicyclic hydrocarbon group having 3 to 12 carbon atoms, the aryl group having 6 to 20 carbon atoms that can be substituted by a halogen atom, and the aralkyl group having 7 to 20 carbon atoms that can be substituted by a halogen atom, wherein a and b are 0 or 1 respectively, and at least one of a and b is 1. R 23a R 24a R 25a and R 26a Each of the following is an organic group that is independently a hydrogen atom or a monovalent organic group: R 23a With R 24a R 24a With R 25a or R 25a With R 26a They can bond together to form rings.

3. The chemically amplified positive photosensitive composition as described in claim 1, characterized in that, The content of the acid diffusion inhibitor (C) is more than 0.01 parts by mass and less than 20 parts by mass relative to 100 parts by mass of resin (B).

4. The chemically amplified positive photosensitive composition according to any one of claims 1 to 3, characterized in that, It also contains alkali-soluble resin (D).

5. The chemically amplified positive photosensitive composition as described in claim 4, characterized in that, The alkali-soluble resin (D) comprises at least one resin selected from the group consisting of phenolic varnish resin (D1), polyhydroxystyrene resin (D2), and acrylic resin (D3).

6. A photosensitive dry film, characterized in that, The film comprises a substrate film and a photosensitive layer formed on the surface of the substrate film, the photosensitive layer being composed of the chemically amplified positive photosensitive composition according to any one of claims 1 to 5.

7. A method for manufacturing a photosensitive dry film, characterized in that, include: A photosensitive layer is formed by coating a substrate film with the chemically amplified positive photosensitive composition according to any one of claims 1 to 5.

8. A method for manufacturing a patterned resist film, characterized in that, include: The lamination process involves laminating a photosensitive layer on a substrate, which is composed of the chemically amplified positive photosensitive composition according to any one of claims 1 to 5. In the exposure process, active light or radiation is selectively irradiated onto the photosensitive layer; and... The developing process involves developing the exposed photosensitive layer.

9. An acid diffusion inhibitor, incorporated in a chemically amplified positive photosensitive composition comprising an acid-generating agent (A) that produces acid upon irradiation by active light or radiation and a resin (B) whose solubility in alkalis increases due to the action of the acid, characterized in that, The acid diffusion inhibitor comprises a compound represented by the following formula (C1), [Chemistry 2] In formula (C1), R 1c It is an alkyl or aralkyl group. R 2c It is an alkyl or aralkyl group. R 3c It is a hydrogen atom or an alkyl group. R 4c It is an alkylene group. n1 is an integer greater than 0 and less than 5. n2 is an integer greater than 0 and less than 5. n3 is 0 or R 1c It is an alkyl or aralkyl group having 6 to 10 carbon atoms. R 2c It is an alkyl or aralkyl group having 6 to 10 carbon atoms. R 3c It is a hydrogen atom or an alkyl group. R 4c For a single key, n1 is an integer greater than or equal to 0 and less than or equal to 5, n2 is an integer greater than or equal to 0 and less than or equal to 5, and n3 is 1. Neither n1 nor n2 can be 0 at the same time.

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