Chemically amplified positive photosensitive composition, photosensitive dry film and method for manufacturing same, patterned resist film, substrate with mold case, and method for manufacturing plated molded article

Abstract

The invention relates to a chemically amplified positive photosensitive composition, a photosensitive dry film and a method for producing the same, a patterned resist film, a substrate with a casting mold, and a method for producing a plated molded article. The present invention addresses the problem of providing: a chemically amplified positive photosensitive composition which is capable of forming a patterned resist film having high surface smoothness and rectangularity and which is capable of suppressing development residues; a photosensitive dry film provided with a photosensitive layer; a method for producing a photosensitive dry film; a method for producing a patterned resist film; a method for manufacturing a substrate with a mold and a method for manufacturing a plated molded article are provided. The solution of the present invention is a chemically amplified positive photosensitive composition comprising: an acid generator (A) that generates an acid having a Van der Waals volume of at least when irradiated with active light or radiation; a resin (B) that increases in solubility in a base by the action of the acid; a non-polymer compound (C) having a phenolic hydroxyl group; and an acid diffusion control agent (F).

Description

Technical Field

[0001] The present invention relates to a chemically amplified positive photosensitive composition, a photosensitive dry film having a photosensitive layer formed from the chemically amplified positive photosensitive composition, a method for manufacturing the photosensitive dry film, a method for manufacturing a patterned resist film using the aforementioned chemically amplified positive photosensitive composition, a method for manufacturing a substrate with a mold, and a method for manufacturing a plated model. Background Technology

[0002] Currently, optoelectronic processing has become the mainstream of precision micro-machining technology. Optoelectronic processing is a general term for the following technologies: coating a photoresist composition onto the surface of the workpiece to form a photoresist layer; using photolithography to pattern the photoresist layer; and using the patterned photoresist layer (photoresist pattern) as a mask to perform chemical etching, electrolytic etching, or electroforming, mainly electroplating, to manufacture various precision components such as semiconductor packages.

[0003] Furthermore, in recent years, with the miniaturization of electronic devices, high-density mounting technology for semiconductor packaging has been continuously advancing, seeking to increase the mounting density based on multi-pin thin-film mounting, miniaturization of package size, two-dimensional mounting technology using flip-chip methods, and three-dimensional mounting technology. In such high-density mounting technologies, protruding electrodes (mounting terminals) such as bumps on the package, and metal pillars connecting the redistribution lines (RDLs) extending from the peripheral terminals on the wafer to the mounting terminals are precisely positioned on the substrate as connection terminals.

[0004] Photoresist compositions are used in the photoelectric processing described above. Among such photoresist compositions, chemically amplified photoresist compositions containing an acid-generating agent are known. Chemically amplified photoresist compositions refer to compositions in which an acid-generating agent generates acid through radiation irradiation (exposure), and the acid diffusion is promoted through heat treatment, causing an acid-catalyzed reaction against the base resin or the like in the composition, thus changing its alkali solubility.

[0005] Such chemically amplified photoresist compositions are used not only for the formation of patterned insulating films and etching masks, but also for the formation of plated shapes such as bumps, metal pillars, and Cu redistribution wiring through a plating process. Specifically, using a chemically amplified photoresist composition, a photoresist layer of desired thickness is formed on a support such as a metal substrate. Exposure and development are performed through a predetermined mask pattern to form a photoresist pattern that serves as a mold for selectively removing (stripping) the portion from which the plated shape is formed. Then, after burying a conductor such as copper into the removed portion (non-resist portion) through plating, the photoresist pattern around it is removed, thereby forming plated shapes such as bumps, metal pillars, and Cu redistribution wiring. For example, a chemically amplified photoresist composition containing an acid-generating agent (A) and a resin (B) whose solubility in alkali is increased by the action of acid, wherein the resin (B) contains a specific acrylic resin (see Patent Document 1).

[0006] Existing technical documents

[0007] Patent documents

[0008] Patent Document 1: Japanese Patent Application Publication No. 2022-129980 Summary of the Invention

[0009] The problem that the invention aims to solve

[0010] Here, during the formation of the resist pattern (the patterned resist film), developer residue often occurs. Therefore, it is desirable to suppress developer residue.

[0011] In addition, it is desirable for the resulting resist pattern to have a high degree of surface smoothness.

[0012] Furthermore, when forming resist patterns, it is generally desirable for the cross-sectional shape to be rectangular. This is especially true in the formation of connecting terminals such as bumps and metal pillars, and in the formation of Cu rewiring, which are carried out through plating processes. For the non-resist portion of the resist pattern that serves as the mold, a rectangular cross-sectional shape is desirable.

[0013] The present invention was made in view of the above-mentioned problems, and its object is to provide a chemically amplified positive photosensitive composition capable of forming a patterned resist film with high surface smoothness and rectangularity and capable of suppressing development residue; a photosensitive dry film having a photosensitive layer formed by the chemically amplified positive photosensitive composition; a method for manufacturing the photosensitive dry film; a method for manufacturing a patterned resist film using the aforementioned chemically amplified positive photosensitive composition; a method for manufacturing a molded substrate using the aforementioned chemically amplified positive photosensitive composition; and a method for manufacturing a plated model using the aforementioned chemically amplified positive photosensitive composition.

[0014] Methods for solving problems

[0015] The inventors of this application conducted repeated and in-depth research to achieve the above-mentioned objectives, and as a result discovered, the above-mentioned problems can be solved using the following chemically amplified positive photosensitive composition, wherein the chemically amplified positive photosensitive composition comprises a van der Waals volume generated by irradiation with active light or radiation. The present invention comprises the above-mentioned acid-producing agent (A), resin (B) whose solubility in alkali is increased by the action of acid, non-polymer compound (C) having phenolic hydroxyl groups, and acid diffusion control agent (F). Specifically, the present invention provides the invention described below.

[0016] [1] A chemically amplified positive photosensitive composition comprising a van der Waals volume generated by irradiation with active light or radiation. The above are acid-producing agents (A), resins whose solubility in alkali increases through the action of acid (B), non-polymer compounds with phenolic hydroxyl groups (C), and acid diffusion control agents (F).

[0017] [2] The chemically amplified positive photosensitive composition as described in [1] above, wherein the amount of phenolic hydroxyl groups is 1.0 mmol / g or more and 8.0 mmol / g or less relative to the mass of the aforementioned nonpolymer compound (C).

[0018] [3] The chemically amplified positive photosensitive composition as described in [1] or [2] above, wherein the aforementioned nonpolymer compound (C) is 9,9-bis(4-hydroxyphenyl)fluorene or 9,9-bis(4-hydroxy-3-methylphenyl)fluorene.

[0019] [4] The chemically amplified positive photosensitive composition as described in any one of [1] to [3] above, wherein the aforementioned resin (B) is an acrylic resin (B3).

[0020] The aforementioned acrylic resin (B3) has structural units derived from (meth)acrylates having aliphatic rings containing oxygen atoms as ring constituent atoms.

[0021] [5] The chemically amplified positive photosensitive composition as described in any one of [1] to [4] above, wherein the molar absorptivity of the aforementioned acid-producing agent (A) at a wavelength of 365 nm is less than 1000 L / (mol·cm).

[0022] [6] The chemically amplified positive photosensitive composition as described in any one of [1] to [5] above, wherein the aforementioned acid-producing agent (A) is an onium salt containing an anion represented by the following formula (ai) or the following formula (aii) as the anion portion.

[0023] [Chemical Formula 1]

[0024]

[0025] (In formula (ai), R) a01 R a02 R a03 and R a04 Each can be independently a hydrocarbon group that may have substituents, or a heterocyclic group that may have substituents, R a01 R a02 R a03 and R a04 At least one of them is an aromatic hydrocarbon group that may have substituents.

[0026] Cf-SO2-N - -SO2-Cf···(aii)

[0027] (In formula (aii), Cf is a fluoroalkyl group with 2 or more carbon atoms, and two fluoroalkyl groups can bond with each other to form a ring.)

[0028] [7] The chemically amplified positive photosensitive composition as described in any one of [1] to [6] above, comprising a sulfur-containing compound (E).

[0029] [8] The chemically amplified positive photosensitive composition as described in any one of [1] to [7] above further contains an alkali-soluble resin (D).

[0030] [9] The chemically amplified positive photosensitive composition as described in [8] above, wherein the aforementioned alkali-soluble resin (D) comprises at least one resin selected from the group consisting of Novolac resin (D1), polyhydroxystyrene resin (D2), and acrylic resin (D3).

[0031]

[10] A photosensitive dry film having a substrate film and a photosensitive layer formed on the surface of the substrate film, wherein the photosensitive layer is formed from any one of the above [1] to [9].

[0032]

[11] A method for manufacturing a photosensitive dry film, comprising a step of coating a chemically amplified positive photosensitive composition as described in any one of [1] to [9] above onto a substrate film to form a photosensitive layer.

[0033]

[12] A method for manufacturing a patterned resist film, comprising the following steps:

[0034] In the lamination process, a photosensitive layer formed by any one of the chemically amplified positive photosensitive compositions described in any one of [1] to [9] is laminated on the substrate;

[0035] The exposure process involves selectively exposing the aforementioned photosensitive layer to active light or radiation; and

[0036] The developing process involves developing the aforementioned photosensitive layer after exposure.

[0037]

[13] A method for manufacturing a substrate with a mold, comprising the following steps:

[0038] In the lamination process, a photosensitive layer formed by any one of the chemically amplified positive photosensitive compositions described in any one of [1] to [9] is laminated on a substrate having a metal surface;

[0039] The exposure process involves selectively exposing the aforementioned photosensitive layer to active light or radiation; and

[0040] The developing process involves developing the aforementioned photosensitive layer after exposure, thereby creating a mold for forming the plated object.

[0041]

[14] A method for manufacturing a plated shape includes the following plating process: plating the aforementioned substrate with a mold manufactured using the method for manufacturing a substrate with a mold described above

[13] , and forming a plated shape in the aforementioned mold.

[0042] Invention Effects

[0043] According to the present invention, a chemically amplified positive photosensitive composition capable of forming a patterned resist film with high surface smoothness and rectangularity and capable of suppressing development residue can be provided; a photosensitive dry film having a photosensitive layer formed by the chemically amplified positive photosensitive composition; a method for manufacturing the photosensitive dry film; a method for manufacturing a patterned resist film using the aforementioned chemically amplified positive photosensitive composition; a method for manufacturing a molded substrate using the aforementioned chemically amplified positive photosensitive composition; and a method for manufacturing a plated model using the aforementioned chemically amplified positive photosensitive composition. Detailed Implementation

[0044] Chemically amplified positive photosensitive compositions

[0045] Chemically amplified positive photosensitive composition (hereinafter also referred to as photosensitive composition) contains a van der Waals volume generated by irradiation with active light or radiation. The above are acid-producing agents (A) (hereinafter also referred to as acid-producing agents (A)), resins whose solubility in alkali increases by the action of acid (B) (hereinafter also referred to as resins (B)), non-polymer compounds with phenolic hydroxyl groups (C) (hereinafter also referred to as non-polymer compounds (C)), and acid diffusion control agents (F).

[0046] As illustrated in the embodiments described later, the process involves generating a van der Waals volume through irradiation with active light or radiation. The chemically amplified positive photosensitive composition comprising the above-mentioned acid-generating agent (A), resin whose solubility in alkali is increased by the action of acid (B), non-polymer compound having phenolic hydroxyl groups (C), and acid diffusion control agent (F) can form a patterned resist film with high surface smoothness and rectangularity, and can suppress development residue. For example, it is possible to form a patterned resist film with an arithmetic mean surface roughness Ra of 15 nm or less and 6 nm or less. In addition, it is possible to form a patterned resist film with a rectangular cross-sectional shape.

[0047] Additionally, the van der Waals volume generated by irradiation with active light or radiation is... The chemically amplified positive photosensitive composition of the above-mentioned acid-generating agent (A), resin whose solubility in alkali is increased by the action of acid (B), non-polymer compound with phenolic hydroxyl group (C), and acid diffusion control agent (F) can form a patterned photoresist film with a high aspect ratio (e.g., a patterned photoresist film with an aspect ratio of 5 or more).

[0048] It should be noted that, for example, when the patterned resist film has a hole pattern, the aspect ratio is the ratio of the hole's height or depth (h) to its diameter (w) (h / w). Furthermore, when the patterned resist film has a line and spacing pattern, the aspect ratio is the ratio of the line's height (h) to the line's width (w) (h / w).

[0049] The photosensitive composition may include, as needed, components such as alkali-soluble resin (D) and sulfur-containing compounds (E).

[0050] The following describes the essential or optional components contained in the photosensitive composition and the method for manufacturing the photosensitive composition.

[0051] <Acid-producing agent (A)>

[0052] Acid-producing agent (A) is generated by irradiation with active light or radiation, resulting in a van der Waals volume of... The above-mentioned acid compounds, and those produced directly or indirectly using light, have a van der Waals volume of... The above are compounds of acids.

[0053] The van der Waals volume of the acid produced by acid-producing agent (A) is more preferably [missing value]. The above is further optimized. That's all. Furthermore, the van der Waals volume of the acid produced by acid-producing agent (A) is preferably... The following is preferred. the following.

[0054] The van der Waals volume (VDW volume) is the volume of the region occupied by a van der Waals sphere based on the van der Waals radius.

[0055] The van der Waals volume (VDW volume) can be calculated using CAChe Worksystem Pro.Version 6.1.12.33 (manufactured by Fujitsu Corporation). It should be noted that CAChe Worksystem Pro.Version 6.1.12.33 is used for structural optimization calculations, and the van der Waals volume is calculated for the resulting stable structure.

[0056] The molar absorptivity of the acid-producing agent (A) contained in the photosensitive composition at a wavelength of 365 nm is preferably 1000 L / (mol·cm) or less.

[0057] The molar absorptivity of the acid-generating agent (A) at a wavelength of 365 nm is more preferably 800 L / (mol·cm) or less, and even more preferably 300 L / (mol·cm) or less. Furthermore, the molar absorptivity of the acid-generating agent (A) at a wavelength of 365 nm is more preferably 50 L / (mol·cm) or more, and even more preferably 100 L / (mol·cm) or more.

[0058] The molar absorptivity at 365 nm can be determined using known methods. For example, the acid-producing agent to be measured is dissolved in PGMEA (propylene glycol monomethyl ether acetate) at a solid concentration of 0.1% by mass to prepare a test solution. This test solution is placed in a quartz dish, and the absorbance A at a measurement wavelength of 365 nm is measured using a spectrophotometer (e.g., Shimadzu UV-3100PC) at a measurement temperature of 25°C. Based on the absorbance A, the molar absorptivity at 365 nm can be calculated using the following formula. It should be noted that in the examples described later, the molar absorptivity at 365 nm was measured using this method.

[0059] ε365=A / (c×d)

[0060] (In the formula, ε365 represents the molar absorptivity at a wavelength of 365 nm, A represents the absorbance, c represents the molar concentration of the solution being measured (mol / L), and d represents the thickness of the quartz dish (cm).)

[0061] Onium salts can be cited as acid-producing agents (A).

[0062] Regarding the onium salt used as the acid-producing agent (A), it is preferable to use an onium salt containing an anion represented by formula (ai) and an anion represented by formula (aii) as the anion portion. An onium salt containing an anion represented by formula (ai) as the anion portion generates an acid formed by an anion represented by formula (ai) and a proton when irradiated with active light or radiation. An onium salt containing an anion represented by formula (aii) as the anion portion generates an acid formed by an anion represented by formula (aii) and a proton when irradiated with active light or radiation.

[0063] [Chemical Formula 2]

[0064]

[0065] (In formula (ai), R) a01 R a02 R a03 and R a04 Each can be independently a hydrocarbon group that may have substituents, or a heterocyclic group that may have substituents, R a01 R a02 R a03 and R a04 At least one of them is an aromatic hydrocarbon group that may have substituents.

[0066] Cf-SO2-N - -SO2-Cf···(aii)

[0067] (In formula (aii), Cf is a fluoroalkyl group with 2 or more carbon atoms, and two fluoroalkyl groups can bond with each other to form a ring.)

[0068] R in the formula (ai) a01 ~R a04 The number of carbon atoms in the hydrocarbon group or heterocyclic group is not particularly limited, but it is preferably 1 to 50, more preferably 1 to 30, and particularly preferably 1 to 20.

[0069] Regarding R a01 ~R a04 Specific examples of hydrocarbon groups include straight-chain or branched alkyl groups, straight-chain or branched alkenyl groups, straight-chain or branched alkynyl groups, aromatic hydrocarbon groups, alicyclic hydrocarbon groups, and aralkyl groups.

[0070] As mentioned above, Ra01 ~R a04 At least one of them is an aromatic hydrocarbon group that may have substituents, more preferably R a01 ~R a04 Three or more of them are aromatic hydrocarbon groups that can have substituents, with R being particularly preferred. a01 ~R a04 All of them are aromatic hydrocarbon groups that can have substituents.

[0071] Regarding R a01 ~R a04 Substituents that the hydrocarbon group or heterocyclic group may have include haloalkyl groups with 1 to 18 carbon atoms, haloaliphatic cyclic groups with 3 to 18 carbon atoms, nitro, hydroxyl, cyano, alkoxy groups with 1 to 18 carbon atoms, aryloxy groups with 6 to 14 carbon atoms, aliphatic acyl groups with 2 to 19 carbon atoms, aromatic acyl groups with 7 to 15 carbon atoms, aliphatic acyloxy groups with 2 to 19 carbon atoms, aromatic acyloxy groups with 7 to 15 carbon atoms, alkyl thio groups with 1 to 18 carbon atoms, aryl thio groups with 6 to 14 carbon atoms, amino groups in which one or two hydrogen atoms bonded to a nitrogen atom can be replaced by hydrocarbon groups with 1 to 18 carbon atoms, and halogen atoms such as chlorine, bromine, iodine, and fluorine atoms.

[0072] As R a01 ~R a04 When the hydrocarbon group is an aromatic hydrocarbon group, the aromatic hydrocarbon group may be substituted by one or more substituents selected from the group consisting of alkyl groups having 1 to 18 carbon atoms, alkenyl groups having 2 to 18 carbon atoms, and alkynyl groups having 2 to 18 carbon atoms.

[0073] As R a01 ~R a04 When a hydrocarbon group has substituents, the number of substituents is not particularly limited; it can be one or more than two. When there are multiple substituents, each substituent can be the same or different.

[0074] As R a01 ~R a04 Preferred specific examples of alkyl groups include straight-chain alkyl groups such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecanyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecanyl, and n-eicosyl; and branched-chain alkyl groups such as isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl, tert-pentyl, isohexyl, 2-ethylhexyl, and 1,1,3,3-tetramethylbutyl.

[0075] As R a01 ~R a04 Preferred examples of alkenyl or alkynyl groups include alkenyl and alkynyl groups that correspond to the above-mentioned groups preferred as alkyl groups.

[0076] As R a01 ~R a04 Preferred examples of aromatic hydrocarbon groups include phenyl, α-naphthyl, β-naphthyl, biphenyl-4-yl, biphenyl-3-yl, biphenyl-2-yl, anthraceneyl, and phenanthreneyl.

[0077] As R a01 ~R a04 Preferred examples of alicyclic hydrocarbon groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopentyl, cyclooctyl, cyclononyl, and cyclodecyl cycloalkyl groups; and bridged aliphatic cycloalkyl groups such as norbornyl, adamantyl, tricyclodecyl, and pinyl.

[0078] As R a01 ~R a04 Preferred examples of aryl alkyl groups include benzyl, phenethyl, α-naphthylmethyl, β-naphthylmethyl, α-naphthylethyl, and β-naphthylethyl.

[0079] As R a01 ~R a04 Preferred examples of heterocyclic groups include thienyl, furanyl, selenoyl, pyranyl, pyrroleyl, oxazolyl, thiazolyl, pyridyl, pyrimidinyl, pyrazinyl, indolyl, benzofuranyl, benzothiophene, quinolinyl, isoquinolinyl, quinoxolinyl, quinazolinyl, carbazolyl, acridineyl, phenothiazinyl, phenothiazinyl, xanthonyl, thiathazinyl, phenothiazinyl, phenothiazinyl, benzodihydropyranyl, isobenzodihydropyranyl, dibenzothiophene, oxoxanone, thiaxanone, and dibenzofuranyl.

[0080] As a preferred example of the anion section represented by formula (ai), the following can be cited:

[0081] Tetra(4-nonafluorobiphenyl)boron anion,

[0082] Tetra(1-heptafluoronaphthyl)boron anion,

[0083] Tetra(pentafluorophenyl)boron anion,

[0084] Tetra(3,4,5-trifluorophenyl)boron anion,

[0085] Tetra(2-nonaphenylbiphenyl)boron anion,

[0086] Tetra(2-heptafluoronaphthyl)boron anion,

[0087] Tetra(7-nonafluoroanthrayl)boron anion,

[0088] Tetra(4'-(methoxy)octafluorobiphenyl)boron anion,

[0089] Tetra(2,4,6-tris(trifluoromethyl)phenyl)boron anion,

[0090] Tetra(3,5-bis(trifluoromethyl)phenyl)boron anion,

[0091] Tetra(2,3-bis(pentafluoroethyl)naphthyl)boron anion,

[0092] Tetra(2-isopropoxy-hexafluoronaphthyl)boron anion,

[0093] Tetra(9,10-bis(heptafluoropropyl)heptafluoroanthrayl)boron anion,

[0094] Tetra(9-nonafluorophenyl)boron anion,

[0095] Tetra(4-[tris(isopropyl)silyl]tetrafluorophenyl)boron anion,

[0096] Tetra(9,10-bis(p-tolyl)-heptafluorophenanthrene)boron anion,

[0097] Tetra(4-[dimethyl(tert-butyl)silyl]tetrafluorophenyl)boron anion,

[0098] Monophenyltris(pentafluorophenyl)boron anion, and

[0099] Mono-perfluorobutyltris(pentafluorophenyl)boron anion, and more preferably the following anions.

[0100] [Chemical Formula 3]

[0101]

[0102] In formula (aii), the fluoroalkyl group having 2 or more carbon atoms as Cf is a straight-chain or branched alkyl group having 2 or more carbon atoms, obtained by substituting at least one hydrogen atom with a fluorine atom. The carbon number of this alkyl group is preferably 2 or more and 10 or less, more preferably 2 or more and 7 or less, and particularly preferably 2 or more and 4 or less.

[0103] The two Cfs in formula (aii) can be the same or different, but it is preferred that they are the same.

[0104] As specific examples of anions represented by formula (aii), the following anions can be cited.

[0105] [Chemical Formula 4]

[0106]

[0107] The cationic portion of the onium salt used as the acid-producing agent (A) is not specifically defined, but a sulfonium cationic portion is preferred.

[0108] The preferred cation is a sulfonium cation having the structure represented by the following formula (a1).

[0109] [Chemical Formula 5]

[0110]

[0111] In the above formula (a1), R 1a R 2a R 3a At least one of them represents a group represented by formula (a2) 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, or a straight-chain or branched alkoxy group having 1 to 6 carbon atoms. Alternatively, R 1a R 2a R 3a One of them is a group represented by the following formula (a2), and the other two are each independently a straight-chain or branched alkylene group with 1 to 6 carbon atoms, and their ends can be bonded together to form a ring.

[0112] Regarding R 1a R 2a R 3a Specific examples of straight-chain or branched alkyl groups having 1 to 6 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, and n-hexyl.

[0113] Regarding R 1a R 2a R 3a Specific examples of straight-chain or branched alkoxy groups with 1 to 6 carbon atoms include methoxy, ethoxy, n-propyloxy, isopropyloxy, n-butyloxy, isobutyloxy, sec-butyloxy, tert-butyloxy, n-pentyloxy, and n-hexyloxy.

[0114] In R 1a R 2a R 3a When the phenyl group may have substituents, preferred substituents include hydroxyl groups, straight-chain or branched alkoxy groups with 1 to 6 carbon atoms, and straight-chain or branched alkyl groups with 1 to 6 carbon atoms.

[0115] [Chemical Formula 6]

[0116]

[0117] In the above formula (a2), R 4a R 5a Each of the following independently represents 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; R 6a This indicates a straight-chain or branched alkylene group with 1 to 6 carbon atoms, which may have a single bond or substituents. l and m each independently represent an integer from 0 to 2, and l+m is 3 or less. Wherein, R... 4a When multiple instances exist, they can be the same as each other or different. Additionally, R... 5a When multiple instances exist, they can be the same as each other or different from each other.

[0118] Regarding R 4a and R 5a Specific examples of straight-chain or branched alkoxy groups with 1 to 6 carbon atoms include methoxy, ethoxy, n-propyloxy, isopropyloxy, n-butyloxy, isobutyloxy, sec-butyloxy, tert-butyloxy, n-pentyloxy, and n-hexyloxy.

[0119] Regarding R 4a and R 5a Specific examples of straight-chain or branched alkyl groups having 1 to 6 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, and n-hexyl.

[0120] Regarding R 6a Specific examples of straight-chain or branched alkylene groups having 1 to 6 carbon atoms include methylene, ethane-1,2-diyl (ethylene), ethane-1,1-diyl, propane-1,3-diyl, propane-1,2-diyl, propane-2,2-diyl, butane-1,4-diyl, pentane-1,5-diyl, and hexane-1,6-diyl.

[0121] From the perspective of compound stability, the above R 1a R 2a R 3a The number of groups represented by formula (a2) above 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 two alkylene groups form a 3 to 9-membered ring containing sulfur atoms. The number of atoms constituting the ring (including sulfur atoms) is preferably 5 to 6.

[0122] In addition, 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.

[0123] In addition, examples of substituents that phenyl groups may have include hydroxyl groups, straight-chain or branched alkoxy groups with 1 to 6 carbon atoms, and straight-chain or branched alkyl groups with 1 to 6 carbon atoms.

[0124] Regarding ions suitable for representation as sulfonium cations using formula (a1), examples include sulfonium cations represented by the following formulas.

[0125] [Chemical Formula 7]

[0126]

[0127] Regarding the cation of the onium salt used as the acid-producing agent (A), a sulfonium cation with the structure represented by the following formula (a4) is preferred.

[0128] [Chemical Formula 8]

[0129]

[0130] In the above formula (a4), R 7a Each independently represents a group selected from the group consisting of hydrogen atom, alkyl, hydroxyl, alkoxy, alkyl carbonyl, alkyl carbonyloxy, alkyloxy carbonyl, halogen atom, aryl (which may have substituents), and aryl carbonyl. X 1a The structure is represented by the following formula (a5).

[0131] [Chemical Formula 9]

[0132]

[0133] In the above formula (a5), X 2a 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. 2a 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 groups having 6 to 10 carbon atoms, hydroxyl groups, cyano groups, nitro groups, and halogens. X 3a This represents -O-, -S-, -SO-, -SO2-, -NH-, -NR 30a -, -CO-, -COO-, -CONH-, alkylene or phenylene with 1 to 3 carbon atoms. h indicates the number of repeating units in the parentheses, where h is an integer between 0 and 4. h+1 X 2a and h X 3a They can be the same or different. R 30a It is an alkyl group with 1 to 5 carbon atoms or an aryl group with 6 to 10 carbon atoms.

[0134] Specific examples of sulfonium ions represented by the above formula (a4) include 4-(phenylthio)phenyldiphenylsulfonium, 4-(4-benzoyl-2-chlorophenylthio)phenylbis(4-fluorophenyl)sulfonium, 4-(4-benzoylphenylthio)phenyldiphenylsulfonium, phenyl[4-(4-biphenylthio)phenyl]4-biphenylsulfonium, phenyl[4-(4-biphenylthio)phenyl]3-biphenylsulfonium, [4-(4-acetylphenylthio)phenyl]diphenylsulfonium, and diphenyl[4-(p-triphenylthio)phenyl]diphenylsulfonium.

[0135] Regarding ions suitable as sulfonium cations represented by formula (a4), examples include sulfonium cations represented by the following formulas.

[0136] [Chemical Formula 10]

[0137]

[0138] As the acid-generating agent (A), onium salts formed from anions represented by formula (a1) and sulfonium cations with structures represented by formula (a4) are particularly preferred. By using onium salts formed from anions represented by formula (a1) and sulfonium cations with structures represented by formula (a4) as the acid-generating agent (A), it is possible to form resist patterns with particularly excellent rectangularity.

[0139] The following compounds are examples of onium salts formed by anions represented by formula (a1) and sulfonium cations with structures represented by formula (a4).

[0140] [Chemical Formula 11]

[0141]

[0142] When the acid-producing agent (A) is an onium salt, compounds having anions and cations in their composition can be used as raw materials and manufactured by ion exchange.

[0143] In addition, as an acid-producing agent (A), examples of nonionic acid-producing agents include compounds represented by the following formula (a12) that produce van der Waals volumes of... The above-mentioned acid compounds. The compounds represented by the following formula (a12) produce sulfonic acid upon irradiation with active light or radiation.

[0144] [Chemical Formula 12]

[0145]

[0146] (In formula (a12), R) 22a R is a monovalent organic group. 23a ~R 28aEach is independently a hydrogen atom or a monovalent organic group, R 23a With R 24a R 24a With R 25a R 25a With R 26a R 26a With R 27a 、or R 27a With R 28a Each element can bond with the others to form a ring.

[0147] As R 22a The organic group is not particularly limited to any extent that it does not impede the purpose of this invention. The organic group may be a hydrocarbon group, or it 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.

[0148] Regarding suitability as R 22a Organic groups may include aliphatic hydrocarbon groups with 1 to 18 carbon atoms that can be substituted by halogen atoms and / or alkyl thio groups, aryl groups with 6 to 20 carbon atoms that can have substituents, aralkyl groups with 7 to 20 carbon atoms that can have substituents, alkylaryl groups with 7 to 20 carbon atoms that can have substituents, camphor-10-yl groups, and groups represented by the following formula (a12a).

[0149] -R 29a -(O) a -R 30a -(O) b -Y 1 -R 31a ···(a12a)

[0150] (In formula (a12a), Y) 1 It is a single bond or a dimethyl alkane with 1 to 4 carbon atoms. R 29a and R 30a Each is either an alkane dimethyl group with 2 to 6 carbon atoms that can be replaced by halogen atoms, or an aryl group with 6 to 20 carbon atoms that can be replaced by halogen atoms. 31a 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 each 0 or 1, and at least one of a and b is 1.

[0151] As R 22aWhen an organic group has a halogen atom as a substituent, examples of such halogen atoms include chlorine, bromine, iodine, and fluorine.

[0152] As R 22a When the organic group is an alkyl group with 1 to 18 carbon atoms substituted by an alkyl thio group, the number of carbon atoms in the alkyl thio group is preferably 1 to 18 or less.

[0153] Examples of alkyl thio groups with 1 to 18 carbon atoms include methyl thio, ethyl thio, n-propyl thio, isopropyl thio, n-butyl thio, sec-butyl thio, tert-butyl thio, isobutyl thio, n-pentyl thio, isopentyl thio, tert-pentyl thio, n-hexyl thio, n-heptyl thio, isoheptyl thio, tert-heptyl thio, n-octyl thio, isooctyl thio, tert-octyl thio, 2-ethylhexyl thio, n-nonyl thio, n-decyl thio, n-undecyl thio, n-dodecyl thio, n-tridecyl thio, n-tetradecyl thio, n-pentadecanyl thio, n-hexadecyl thio, n-heptadecyl thio, and n-octadecyl thio.

[0154] 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 alkyl thio group, the aliphatic hydrocarbon group may contain an unsaturated double bond.

[0155] Furthermore, the structure of this aliphatic hydrocarbon group is not particularly limited; it can be linear, branched, cyclic, or a combination of these structures.

[0156] Regarding R 22a Preferred examples of organic groups that are alkenyl groups include allyl and 2-methyl-2-propenyl.

[0157] Regarding 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.

[0158] As R 22aWhen 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.

[0159] Regarding R 22a Preferred examples of organic groups that are aliphatic hydrocarbon groups substituted with halogen atoms include trifluoromethyl, pentafluoroethyl, 2-chloroethyl, 2-bromoethyl, heptafluoropropyl, 3-bromopropyl, nonafluorobutyl, tridecafluorohexyl, heptadecafluorooctyl, 2,2,2-trifluoroethyl, 1,1-difluoroethyl, 1,1-difluoropropyl, 1,1,2,2-tetrafluoropropyl, 3,3,3-trifluoropropyl, 2,2,3,3,3-pentafluoropropyl, 2-norbornyl-1,1-difluoroethyl, 2-norbornyltetrafluoroethyl, and 3-adamantyl-1,1,2,2-tetrafluoropropyl.

[0160] Regarding R 22a Preferred examples of organic groups that are aliphatic hydrocarbon groups substituted with alkyl thio groups include 2-methylthioethyl, 4-methylthio-n-butyl, and 2-n-butylthioethyl.

[0161] Regarding R 22a A preferred example of the organic group being an aliphatic hydrocarbon group substituted with a halogen atom and an alkyl thio group is 3-methylthio-1,1,2,2-tetrafluoropropyl.

[0162] Regarding R 22a Preferred examples of organic groups being aryl include phenyl, naphthyl, and biphenyl.

[0163] Regarding R 22a Preferred examples of organic groups that are aryl groups substituted with halogen atoms include pentafluorophenyl, chlorophenyl, dichlorophenyl, and trichlorophenyl.

[0164] Regarding R 22a Preferred examples of the organic group being an aryl group substituted with an alkyl thio group include 4-methylthiophenyl, 4-n-butylthiophenyl, 4-n-octylthiophenyl, and 4-n-dodecylthiophenyl.

[0165] Regarding R 22aPreferred examples of the organic group being an aryl group substituted with a halogen atom and an alkyl thio 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.

[0166] Regarding R 22a Preferred examples of organic groups that are aryl groups include benzyl, phenethyl, 2-phenylpropane-2-yl, diphenylmethyl, and triphenylmethyl.

[0167] Regarding R 22a Preferred examples of the organic group being an aralkyl group substituted with a halogen atom include pentafluorophenylmethyl, phenyldifluoromethyl, 2-phenyltetrafluoroethyl, and 2-(pentafluorophenyl)ethyl.

[0168] Regarding R 22a A preferred example of the organic group being an aralkyl group substituted with an alkylthio group is p-methylthiobenzyl.

[0169] Regarding R 22a A preferred example of the organic group being an aralkyl group substituted with a halogen atom and an alkyl thio group is 2-(2,3,5,6-tetrafluoro-4-methylthiophenyl)ethyl.

[0170] Regarding 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-ethylhexyl)phenyl, 2,3-dimethylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl, 2,6-ethylhexyl ... -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.

[0171] The group represented by formula (a12a) is a group containing an ether group.

[0172] In equation (a12a), Y is used as... 1Examples of alkane dimethyl groups representing alkane atoms with 1 to 4 carbon atoms include 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.

[0173] In equation (a12a), R is used as 29a Or R 30a Examples of alkane diaryles representing 2 to 6 carbon atoms include ethane-1,2-diary, propane-1,3-diary, propane-1,2-diary, butane-1,4-diary, butane-1,3-diary, butane-2,3-diary, butane-1,2-diary, pentane-1,5-diary, pentane-1,3-diary, pentane-1,4-diary, pentane-2,3-diary, hexane-1,6-diary, hexane-1,2-diary, hexane-1,3-diary, hexane-1,4-diary, hexane-2,5-diary, hexane-2,4-diary, and hexane-3,4-diary.

[0174] In equation (a12a), in R 29a Or R 30a In the case of alkane dimethyl groups with 2 to 6 carbon atoms substituted by halogen atoms, examples of halogen atoms include chlorine, bromine, iodine, and fluorine. Examples of alkane dimethyl groups substituted by halogen atoms include tetrafluoroethane-1,2-dimethyl, 1,1-difluoroethane-1,2-dimethyl, 1-fluoroethane-1,2-dimethyl, 1,2-difluoroethane-1,2-dimethyl, hexafluoropropane-1,3-dimethyl, 1,1,2,2,-tetrafluoropropane-1,3-dimethyl, and 1,1,2,2,-tetrafluoropentane-1,5-dimethyl.

[0175] In equation (a12a), R is used as 29a Or R 30a Examples of arylene compounds 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, naphthyl-1,2-diyl, naphthyl-1,3-diyl, naphthyl-1,4-diyl, naphthyl-1,5-diyl, naphthyl-1,6-diyl, naphthyl-1,7-diyl, naphthyl-1,8-diyl, naphthyl-2,3-diyl, naphthyl-2,6-diyl, and naphthyl-2,7-diyl.

[0176] In equation (a12a), in R 29a Or R 30aIn the case of an arylene group substituted with a halogen atom, examples of halogen atoms include chlorine, bromine, iodine, and fluorine atoms. An example of an arylene group substituted with a halogen atom is 2,3,5,6-tetrafluoro-1,4-phenylene.

[0177] In equation (a12a), R is used as 31a The alkyl group represented can have 1 to 18 carbon atoms and may have branches. 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.

[0178] In equation (a12a), in R 31a When the alkyl group having 1 to 18 carbon atoms substituted by a halogen atom is an alkyl group, examples of halogen atoms include chlorine, bromine, iodine, and fluorine. Examples of alkyl groups substituted by halogen atoms include trifluoromethyl, pentafluoroethyl, heptafluoropropyl, nonafluorobutyl, tridecafluorohexyl, heptadecafluorooctyl, 2,2,2-trifluoroethyl, 1,1-difluoroethyl, 1,1-difluoropropyl, 1,1,2,2-tetrafluoropropyl, 3,3,3-trifluoropropyl, 2,2,3,3,3-pentafluoropropyl, and 1,1,2,2-tetrafluorotetradecyl.

[0179] In equation (a12a), in R 31a When the alicyclic hydrocarbon group has 3 to 12 carbon atoms, 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. Preferably, the alicyclic hydrocarbon group is a group obtained by removing one hydrogen atom from these alicyclic hydrocarbons.

[0180] In formula (a12a), R 31a 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.

[0181] Among the groups represented by formula (a12a), the preferred group is R. 29aThe indicated group is a group in which the carbon atom bonded to the sulfur atom is replaced by a fluorine atom. Such a preferred group preferably has 2 or more and 18 or less carbon atoms.

[0182] As R 22a Preferably, it is a perfluoroalkyl group having 1 to 8 carbon atoms. Furthermore, camphor-10-based is also preferred as R, considering its ease of forming highly fine patterned resist films. 22a .

[0183] In equation (a12), R 23a ~R 28a It can be a hydrogen atom or a monovalent organic group. Additionally, R... 23a With R 24a R 24a With R 25a R 25a With R 26a R 26a With R 27a 、or R 27a With R 28a Each element can bond with the others to form a ring. For example, this can be achieved through R... 25a With R 26a The bonds combine with the naphthalene ring to form a 5-membered ring, thus forming the acenaphthene skeleton.

[0184] As a monovalent organic group, the preferred options are: alkyl or alkoxy groups that can be substituted by alicyclic hydrocarbon groups, heterocyclic groups, or halogen atoms and have 4 to 18 carbon atoms with branched chains; heterocyclic oxy groups; alkyl thio groups that can be substituted by alicyclic hydrocarbon groups, heterocyclic groups, or halogen atoms and have 4 to 18 carbon atoms with branched chains; and heterocyclic thio groups.

[0185] In addition, it is also preferred to replace the methylene group at any position not adjacent to the oxygen atom of the alkoxy group with -CO-.

[0186] The group obtained by interrupting the alkoxy group with a -O-CO- or -O-CO-NH- bond is also preferred. It should be noted that the left end of the -O-CO- and -O-CO-NH- bonds is the side of the alkoxy group that is closest to the naphthalene dicarboxylic acid core.

[0187] Furthermore, alkyl thio groups that can be substituted with alicyclic hydrocarbon groups, heterocyclic groups, or halogen atoms and can have branched chains with 4 to 18 carbon atoms are also preferred as R. 23a ~R 28a .

[0188] The alkyl thio group is preferably obtained by replacing the methylene group at any position not adjacent to the sulfur atom with -CO-.

[0189] The group obtained by interrupting the alkyl thio group with a -O-CO- or -O-CO-NH- bond is also preferred. It should be noted that the left end of the -O-CO- and -O-CO-NH- bonds is the side of the alkyl thio group that is closest to the naphthalene dicarboxylic acid core.

[0190] As R 23a ~R 28a R is preferred 24a It is an organic group and R 23a and R 25a ~R 28a It is a hydrogen atom, or R 25a It is an organic group and R 23a R 24a and R 26a ~R 28a It is a hydrogen atom. Additionally, R... 23a ~R 28a It can also consist entirely of hydrogen atoms.

[0191] As R 23a ~R 28a 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.

[0192] As R 23a ~R 28a Examples of unsubstituted alkoxy groups include n-butyloxy, sec-butyloxy, tert-butyloxy, isobutyloxy, n-pentyloxy, isopentyloxy, tert-pentyloxy, n-hexyloxy, n-heptyloxy, isoheptyloxy, tert-heptyloxy, n-octyloxy, isooctyloxy, tert-octyloxy, 2-ethylhexyl, n-nonyloxy, n-decyloxy, n-undecyloxy, n-dodecyloxy, n-tridecyloxy, n-tetradecyloxy, n-pentadecanyloxy, n-hexadecyloxy, n-heptadecyloxy, and n-octadecyloxy.

[0193] As R 23a ~R 28aExamples of unsubstituted alkyl thio 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.

[0194] In R 23a ~R 28a When the alkyl, alkoxy, or alkylthio group is replaced by 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. The alicyclic hydrocarbon group is preferably a group obtained by removing one hydrogen atom from these alicyclic hydrocarbons.

[0195] In R 23a ~R 28a In the case of alkyl, alkoxy, or alkylthio groups substituted with heterocyclic groups, or R 23a ~R 28a In the case of a heterocyclic hydroxyl group, examples of heterocycles that form the main skeleton of the heterocyclic group or heterocyclic hydroxyl group include pyrrole, thiophene, furan, pyran, thiaran, imidazole, pyrazole, thiazole, isothiazole, oxazole, isoxazole, pyridine, pyrazine, pyrimidine, pyridazine, pyrrolidine, pyrazolidine, imidazoleidine, isoxazolidine, isothiazolidine, piperidine, piperazine, morpholine, thiomorpholine, chromium, thiochromium, isochromium, isothiochromium, and isothiochromium. Indoline, isoindoline, 4-azaindene, indoleazine, indole, indazole, purine, quinazine, isoquinoline, quinoline, naphthidine, phthalazine, quinoxaline, quinazoline, cyclophosphine, pteridine, acridine, phenanthroline, carbazole, carbline, phenazine, triazine, thiadiazole, oxadiazole, triazine, triazole, tetrazolium, benzimidazole, benzoxazole, benzothiazole, benzothiadiazole, benzofuran, naphthimazole, benzotriazole, tetraazaindene. Additionally, saturated heterocycles obtained by hydrogenating the rings with conjugated bonds in these heterocycles are also preferred.

[0196] The heterocyclic group that substitutes for an alkyl, alkoxy, or alkyl thio group, or the heterocyclic group contained in a heterocyclic oxy group, is preferably a group obtained by removing one hydrogen atom from the aforementioned heterocycle.

[0197] As R 23a ~R 28aExamples 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, dicyclopentadienyloxy, 1-cyclohexylpentyloxy, methyladamantyloxy, adamantylmethyloxy, 4-pentylcyclohexyloxy, cyclohexylcyclohexyloxy, adamantylethyloxy, and dimethyladamantyloxy.

[0198] As R 23a ~R 28a Examples of heterocyclic oxy groups include tetrahydrofuranyloxy, furfuryloxy, tetrahydrofurfuryloxy, tetrahydropyranyloxy, butyrolactoneoxy, and indolyloxy.

[0199] As R 23a ~R 28a Examples of alkyl thio groups that include alicyclic hydrocarbon groups include cyclopentyl thio, cyclohexyl thio, cyclohexylmethyl thio, norbornyl thio, and isonorbornyl thio.

[0200] As R 23a ~R 28a Examples of heterocyclic thio groups include furfural thio and tetrahydrofuran thio.

[0201] As R 23a ~R 28a Examples of groups obtained by replacing the methylene group at any position not adjacent to the oxygen atom of an alkoxy group with -CO- include 2-oxobutyl-1-oxy, 2-oxopentyl-1-oxy, 2-oxohexyl-1-oxy, 2-oxoheptyl-1-oxy, 2-oxooctyl-1-oxy, 3-oxobutyl-1-oxy, 4-oxopentyl-1-oxy, 5-oxohexyl-1-oxy, 6-oxoheptyl-1-oxy, 7-oxooctyl-1-oxy, 3-methyl-2-oxopentane-4-oxy, 2-oxopentane-4-oxy, 2-methyl-2-oxopentane-4-oxy, 3-oxopentane-5-oxy, and 2-adamantanone-5-oxy.

[0202] As R 23a ~R 28aExamples of groups obtained by replacing the methylene group at any position not adjacent to the sulfur atom in an alkyl thio group with -CO- include 2-oxobutyl-1-thio, 2-oxopentyl-1-thio, 2-oxohexyl-1-thio, 2-oxohepyl-1-thio, 2-oxooctyl-1-thio, 3-oxobutyl-1-thio, 4-oxopentyl-1-thio, 5-oxohexyl-1-thio, 6-oxohepyl-1-thio, 7-oxooctyl-1-thio, 3-methyl-2-oxopentane-4-thio, 2-oxopentane-4-thio, 2-methyl-2-oxopentane-4-thio, and 3-oxohepane-5-thio.

[0203] The following compounds can be cited as specific examples of compounds represented by formula (a12).

[0204] [Chemical Formula 13]

[0205]

[0206] [Chemical Formula 14]

[0207]

[0208] [Chemical Formula 15]

[0209]

[0210] [Chemical Formula 16]

[0211]

[0212] [Chemical Formula 17]

[0213]

[0214] [Chemical Formula 18]

[0215]

[0216] [Chemical Formula 19]

[0217]

[0218] [Chemical Formula 20]

[0219]

[0220] [Chemical Formula 21]

[0221]

[0222] [Chemical Formula 22]

[0223]

[0224] The acid-producing agent (A) can be one type or two or more types.

[0225] The content of the acid-generating agent (A) is preferably 0.01% by mass or more and 20% by mass or less, more preferably 0.03% by mass or more and 10% by mass or less, and particularly preferably 0.05% by mass or more and 8% by mass or less, relative to the total amount of solid components in the photosensitive composition. In this specification, the term "solid components" refers to components other than the organic solvent (S) and water.

[0226] <Resin (B)>

[0227] The resin (B) whose solubility in alkali increases with the action of acid is not particularly limited, and any resin whose solubility in alkali increases with the action of acid can be used. Preferably, it contains at least one resin selected from the group consisting of Novolac resin (B1), styrene-based resin (B2), and acrylic resin (B3), and more preferably, it contains acrylic resin (B3).

[0228] At least a portion of the phenolic hydroxyl groups in Novolac resin (B1) are protected by acid dissociation-inhibiting groups.

[0229] Styrene-based resin (B2) comprises structural units derived from at least one of styrene, hydroxystyrene, and hydroxystyrene in which phenolic hydroxyl groups are protected by acid-dissociative solubility-inhibiting groups. For example, in styrene-based resin (B2), at least a portion of the phenolic hydroxyl groups may be protected by acid-dissociative solubility-inhibiting groups. Additionally, styrene-based resin (B2) may also comprise structural units derived from (meth)acrylates having acid-dissociative groups.

[0230] Furthermore, acrylic resin (B3) contains structural units derived from (meth)acrylates having acid-dissociable groups. It should be noted that, in this specification, resins belonging to the styrene-based resin group (B2) are not acrylic resins (B3).

[0231] [Novolac resin (B1)]

[0232] As the Novolac resin (B1), a resin containing structural units represented by the following formula (b-11) can be used.

[0233] [Chemical Formula 23]

[0234]

[0235] In the above equation (b-11), R 1b This indicates an acid dissociation and dissolution inhibition group. Preferably, it is a so-called acetal-type protecting group. R2b R 3b Each can be independently represented as an alkyl group having 1 to 6 hydrogen atoms or carbon atoms.

[0236] As mentioned above, R 1b The acid dissociation and dissolution inhibition group represented is preferably a group represented by the following formulas (b-12) and (b-13), a straight-chain, branched, or cyclic alkyl group having 1 to 6 carbon atoms, a vinyloxyethyl group, a tetrahydropyranyl group, a tetrahydrofuranyl group, or a trialkylsilyl group.

[0237] [Chemical Formula 24]

[0238]

[0239] In equations (b-12) and (b-13) above, R 4b R 5b Each 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. 7b It indicates a straight-chain, branched, or cyclic alkyl group with 1 to 6 carbon atoms, and o indicates 0 or 1.

[0240] 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.

[0241] Here, examples of acid dissociation-inhibiting groups represented by formula (b-12) include 1-methoxyethyl, 1-ethoxyethyl, 1-n-propoxyethyl, 1-isopropoxyethyl, 1-n-butoxyethyl, 1-isobutoxyethyl, 1-tert-butoxyethyl, 1-cyclohexyloxyethyl, 1-methoxypropyl, 1-ethoxypropyl, 1-methoxy-1-methylethyl, and 1-ethoxy-1-methylethyl. Furthermore, examples of acid dissociation-inhibiting groups represented by formula (b-13) 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.

[0242] [Styrene-based resin (B2)]

[0243] As a styrene-based resin (B2), a resin comprising a structural unit represented by the following formula (b4) can be used. The resin comprising the structural unit represented by the following formula (b4) is a resin in which at least a portion of the phenolic hydroxyl groups are protected by an acid-dissociation-inhibiting group.

[0244] [Chemical Formula 25]

[0245]

[0246] 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.

[0247] 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.

[0248] As mentioned above, R 9b The acid dissociation dissolution inhibition group can be the same acid dissociation dissolution inhibition group as those exemplified in formulas (b-12) and (b-13) above, such as tert-butyl, cyclohexylethyl, cyclopentylethyl, cyclohexylpropyl, cyclopentylpropyl, etc.

[0249] As a styrene-based resin (B2), examples include resins comprising at least one structural unit selected from styrene, hydroxystyrene, and hydroxystyrene with phenolic hydroxyl groups protected by acid dissociation-inhibiting groups, and structural units from (meth)acrylates having acid dissociation groups.

[0250] Styrene-based resins (B2) may also contain structural units represented by formula (b4) and structural units derived from (meth)acrylates having acid-dissociable groups. Structural units derived from (meth)acrylates having acid-dissociable groups are, for example, structural units represented by formulas (b5) to (b7) described later.

[0251] Furthermore, styrene-based resins (B2) may contain other polymeric compounds as structural units for the purpose of moderately controlling physical and chemical properties. Examples of such polymeric compounds include known free radical polymers and anionic polymers. Other examples of such polymeric compounds include, for instance, 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 n-butyl methacrylate; and hydroxyalkyl methacrylates such as 2-hydroxyethyl methacrylate and 2-hydroxypropyl methacrylate. Aryl esters of methacrylates 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; polymeric compounds containing chlorine groups such as vinyl chloride and vinylidene chloride; polymeric compounds containing amide bonds such as acrylamide and methacrylamide; and so on. These polymeric compounds preferably do not possess acid-dissociable properties.

[0252] [Acrylic resin (B3)]

[0253] As for the acrylic resin (B3), there is no particular limitation as long as it is an acrylic resin that has been conventionally incorporated into various photosensitive compositions, which contains structural units derived from (meth)acrylates having acid-dissociable groups and whose solubility in alkali is increased by the action of acid.

[0254] In addition, in this specification, the term "(meth)propylene-" refers to both "propylene-" and "methpropylene-". The term "(meth)acrylate" refers to both "acrylate" and "methacrylate".

[0255] Acrylic resin (B3), which is a resin whose solubility in alkali increases by the action of acid, preferably has structural units derived from (meth)acrylates having aliphatic rings containing oxygen atoms as ring constituent atoms.

[0256] As a structural unit derived from (meth)acrylates having an aliphatic ring containing oxygen atoms as ring constituent atoms, the structural unit represented by the following formula (b3-1) can be cited.

[0257] [Chemical Formula 26]

[0258]

[0259] (In formula (b3-1), ring A is an aliphatic ring containing oxygen atoms as ring constituent atoms, R) b01 R is a straight-chain or branched alkyl group having 1 to 6 carbon atoms or hydrogen atoms. b02 R is a hydrogen atom or a methyl group. b03 It is a single bond or an alkylene group.

[0260] Examples of aliphatic rings A that contain oxygen atoms as ring constituent atoms include lactone rings such as γ-butyrolactone rings (rings containing -OC(=O)-), rings formed by cyclic carbonates such as ethylene carbonate, and rings formed by cyclic ethers such as tetrahydrofuran rings, tetrahydropyran rings, and dioxane rings.

[0261] Regarding R b01 Alkyl groups with 1 to 6 carbon atoms that are either straight-chain or branched, such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl, tert-pentyl, isohexyl, etc.

[0262] Regarding R b03 Examples of alkylene compounds include methylene, ethane-1,2-diyl, ethane-1,1,-diyl, propane-1,3-diyl, propane-2,2-diyl, and butane-1,4-diyl.

[0263] As a specific example of the structural unit represented by equation (b3-1), the structural units represented by the following equations (b3-1-1) to (b3-1-14) can be given.

[0264] [Chemical Formula 27]

[0265]

[0266] In the above equations (b3-1-1) to (b3-1-14), R b02 R in equation (b3-1) b02 same.

[0267] When the acrylic resin (B3) has structural units derived from (meth)acrylates having aliphatic rings containing oxygen atoms as ring constituent atoms, the content of structural units derived from (meth)acrylates having aliphatic rings containing oxygen atoms as ring constituent atoms in the acrylic resin (B3) is not particularly limited, but is preferably 1% by mass or more and 30% by mass or less, more preferably 5% by mass or more and 25% by mass or less.

[0268] Acrylic resin (B3), which is a resin (B) whose solubility in alkali increases by the action of acid, can also have structural units represented by the following formula (b3-2).

[0269] [Chemical Formula 28]

[0270]

[0271] (In formula (b3-2), R b04 R represents a hydrogen atom or a methyl group. b05 Indicates a single bond or an alkylene group.

[0272] As R b05 The number of carbon atoms in the alkylene group is not particularly limited, but it is preferably 1 to 6, more preferably 1 to 4.

[0273] Regarding R b05 Specific examples of alkylene groups include methylene, ethane-1,2-diyl, ethane-1,1,-diyl, propane-1,3-diyl, and butane-1,4-diyl.

[0274] When the acrylic resin (B3) has the structural unit represented by formula (b3-2), the content of the structural unit represented by formula (b3-2) in the acrylic resin (B3) is not particularly limited, but is preferably 1% by mass or more and 50% by mass or less, more preferably 5% by mass or more and 20% by mass or less.

[0275] Furthermore, the acrylic resin (B3) preferably contains structural units (b-3) derived from acrylates, for example, cyclic groups containing -SO2- or cyclic groups containing lactones. In such cases, when forming a patterned resist film, it is easy to form a patterned resist film with an ideal cross-sectional shape.

[0276] (A cyclic group containing -SO2-)

[0277] Here, "cyclic groups containing -SO2-" refers to cyclic groups containing a ring with -SO2- in its ring skeleton. Specifically, it refers to cyclic groups in which the sulfur atom (S) in -SO2- forms part of the ring skeleton of the cyclic group. The ring containing -SO2- in its ring skeleton is counted as the first ring. In the case of only this ring, it is called a monocyclic group. In the case of having other ring structures, regardless of their structure, it is called a polycyclic group. Cyclic groups containing -SO2- can be monocyclic or polycyclic.

[0278] Cyclic groups containing -SO2- are particularly preferred to be cyclic groups that contain -O-SO2- in their ring skeleton, that is, cyclic groups containing -OS- in -O-SO2- forming part of the sultone ring in the ring skeleton.

[0279] The number of carbon atoms in the cyclic group containing -SO2- 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.

[0280] The cyclic group containing -SO2- can be an aliphatic cyclic group or an aromatic cyclic group containing -SO2-. Preferably, it is an aliphatic cyclic group containing -SO2-.

[0281] Examples of aliphatic cyclic groups containing -SO2- include groups obtained by removing at least one hydrogen atom from an aliphatic hydrocarbon ring after a portion of the carbon atoms constituting its ring skeleton has been replaced with -SO2- or -O-SO2-. More specifically, examples include groups obtained by removing at least one hydrogen atom from an aliphatic hydrocarbon ring after replacing -CH2- with -SO2- in its ring skeleton, and groups obtained by removing at least one hydrogen atom from an aliphatic hydrocarbon ring after replacing -CH2-CH2- with -O-SO2- in its ring.

[0282] 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.

[0283] Cyclic groups containing -SO2- may have substituents. Examples of such substituents include alkyl groups, alkoxy groups, halogen atoms, haloalkyl groups, hydroxyl groups, oxygen atoms (=O), -COOR", -OC(=O)R", hydroxyalkyl groups, cyano groups, etc.

[0284] Regarding the alkyl group used as the substituent, it is preferably an alkyl group having 1 to 6 carbon atoms. The alkyl group is preferably straight-chain or branched. Specifically, 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.

[0285] Regarding the alkoxy group used as the substituent, it is preferably an alkoxy group having 1 to 6 carbon atoms. This alkoxy group is preferably linear or branched. Specifically, examples of alkyl groups listed above as substituents, formed by the bonding of an alkyl group with an oxygen atom (-O-), can be cited.

[0286] Regarding the halogen atom that can be used as the substituent, examples include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms, with fluorine atoms being the preferred option.

[0287] The haloalkyl group that serves as the substituent can be a group obtained by replacing some or all of the hydrogen atoms of the aforementioned alkyl group with the aforementioned halogen atoms.

[0288] Regarding the alkyl halogroup as the substituent, examples include groups obtained by substituting some or all of the hydrogen atoms of the alkyl groups listed above as substituents with the aforementioned halogen atoms. The alkyl halogroup is preferably a fluoroalkyl group, and particularly preferably a perfluoroalkyl group.

[0289] In the aforementioned -COOR” and -OC(=O)R”, R” are either hydrogen atoms or straight-chain, branched, or cyclic alkyl groups with 1 to 15 carbon atoms.

[0290] 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.

[0291] 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 polycyclic alkanes such as monocyclic alkanes, bicyclic alkanes, tricyclic alkanes, and tetracyclic alkanes that can be substituted or not substituted by fluorine atoms or fluorinated alkyl groups. More specifically, examples include groups obtained by removing one or more hydrogen atoms from monocyclic alkanes such as cyclopentane and cyclohexane, adamantane, norbornane, isobornane, tricyclic decane, and tetracyclic dodecane.

[0292] Regarding the hydroxyalkyl group used as the substituent, it is preferably a hydroxyalkyl group having 1 to 6 carbon atoms. Specifically, examples of alkyl groups listed above as substituents are groups obtained by substituting at least one hydrogen atom of the alkyl group with a hydroxyl group.

[0293] More specifically, examples of cyclic groups containing -SO2- can be found in the following formulas (3-1) to (3-4).

[0294] [Chemical Formula 29]

[0295]

[0296] (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.)

[0297] In formulas (3-1) to (3-4) above, A' is an alkylene group with 1 to 5 carbon atoms, an oxygen atom, or a sulfur atom that may contain an oxygen atom (-O-) or a sulfur atom (-S-). As the alkylene group with 1 to 5 carbon atoms in A', it is preferably a straight-chain or branched alkylene group, and examples include methylene, ethylene, n-propylene, and isopropylene.

[0298] When the alkylene group contains an oxygen atom or a sulfur atom, specific examples include groups with -O- or -S- at the end of the aforementioned alkylene group or between carbon atoms, such as -O-CH2-, -CH2-O-CH2-, -S-CH2-, -CH2-S-CH2-, etc. As A', it is preferably an alkylene group having 1 to 5 carbon atoms or -O-, more preferably an alkylene group having 1 to 5 carbon atoms, and most preferably a methylene group.

[0299] 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.

[0300] As R 10b The alkyl, alkoxy, haloalkyl, -COOR", -OC(=O)R", and hydroxyalkyl groups mentioned above are the same groups that were described above as substituents that can be present in alkyl, alkoxy, haloalkyl, -COOR", -OC(=O)R", and hydroxyalkyl groups containing -SO2-.

[0301] The following examples illustrate the specific cyclic groups represented by the aforementioned formulas (3-1) to (3-4). It should be noted that "Ac" in the formula represents an acetyl group.

[0302] [Chemical Formula 30]

[0303] [Chemical Formula 31]

[0304]

[0305] As a cyclic group containing -SO2-, the group represented by the aforementioned formula (3-1) is preferred, more preferably at least one group selected from the group represented by any one of the aforementioned chemical formulas (3-1-1), (3-1-18), (3-3-1), and (3-4-1), and most preferably the group represented by the aforementioned chemical formula (3-1-1).

[0306] (Contains a cyclic group containing a lactone)

[0307] The term "cyclic group containing lactone" refers to a cyclic group containing a ring (lactone ring) with -OC (=O)- in its ring skeleton. The lactone ring is considered 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 specific structure, it is called a polycyclic group. Cyclic groups containing lactones can be either monocyclic or polycyclic.

[0308] The cyclic group containing lactone in structural unit (b-3) is not particularly limited, and any cyclic group containing lactone can be used. Specifically, examples of monocyclic groups containing lactone include groups obtained by removing one hydrogen atom from a 4- to 6-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 polycyclic groups containing lactone include groups obtained by removing one hydrogen atom from bicyclic alkanes, tricyclic alkanes, and tetracyclic alkanes having a lactone ring.

[0309] As for the structural unit (b-3), as long as it is a structural unit having a cyclic group containing -SO2- or a cyclic group containing lactone, the structure of other parts is not particularly limited. Preferably, it is selected from at least one structural unit selected from the group consisting of a structural unit derived from an acrylate in which the hydrogen atom bonded to the carbon atom at the α position can be substituted by a substituent, a structural unit containing a cyclic group containing -SO2- (b-3-S), and a structural unit derived from an acrylate in which the hydrogen atom bonded to the carbon atom at the α position can be substituted by a substituent, a structural unit containing a cyclic group containing lactone (b-3-L).

[0310] [Structural Unit (b-3-S)]

[0311] As an example of the structural unit (b-3-S), more specifically, the structural unit represented by the following formula (b-S1) can be cited.

[0312] [Chemical Formula 32]

[0313]

[0314] (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 cyclic group containing -SO2-. 12b (It can be a single bond or a divalent linker.)

[0315] In equation (b-S1), R is the same as before.

[0316] R 11b Similar to the cyclic groups containing -SO2- listed above.

[0317] R 12b It can be either a single bond or a divalent linker.

[0318] As R 12b The divalent linking group in the formula is not particularly limited, but preferred groups include divalent hydrocarbon groups that may have substituents and divalent linking groups that contain heteroatoms.

[0319] • Divalent hydrocarbon groups that may have substituents

[0320] The hydrocarbon group serving as the divalent linker 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.

[0321] The number of carbon atoms in the aforementioned straight-chain or branched aliphatic hydrocarbon groups is preferably 1 to 10, more preferably 1 to 8, and even more preferably 1 to 5.

[0322] As a straight-chain aliphatic hydrocarbon group, a straight-chain alkylene group is preferred. Specifically, examples include methylene [-CH2-], ethylene [-(CH2)2-], 1,3-propylene [-(CH2)3-], 1,4-butylene [-(CH2)4-], and 1,5-pentylene [-(CH2)5-].

[0323] 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-; alkyl-1,3-propylene groups such as -CH(CH3)CH2CH2CH2- and -CH2CH(CH3)CH2CH2-; and alkyl-1,4-butylene groups such as -CH(CH3)CH2CH2CH2- and -CH2CH(CH3)CH2CH2-. The alkyl group in the alkyl alkylene group is preferably a straight-chain alkyl group with 1 to 5 carbon atoms.

[0324] The aforementioned straight-chain or branched aliphatic hydrocarbon groups may or may not have substituents (groups or atoms other than hydrogen atoms) that replace hydrogen atoms. Examples of such substituents include fluorine atoms, fluoroalkyl groups with 1 to 5 carbon atoms obtained by replacing fluorine atoms, and oxo groups (=O).

[0325] Examples of aliphatic hydrocarbon groups containing rings in their structure include cyclic aliphatic hydrocarbon groups (groups obtained by removing two hydrogen atoms from an aliphatic hydrocarbon ring) that may contain substituents containing heteroatoms in their ring structure, groups obtained by bonding such cyclic aliphatic hydrocarbon groups to the ends of straight-chain or branched aliphatic hydrocarbon groups, and groups where such cyclic aliphatic hydrocarbon groups are located in the middle of straight-chain or branched aliphatic hydrocarbon groups. Examples of straight-chain or branched aliphatic hydrocarbon groups mentioned above include the same aliphatic hydrocarbon groups as described above.

[0326] The number of carbon atoms in the cyclic aliphatic hydrocarbon group is preferably 3 to 20, more preferably 3 to 12.

[0327] 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. Specifically, 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. Specifically, examples include adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane.

[0328] Cyclic aliphatic hydrocarbon groups may or may not have substituents (groups or atoms other than hydrogen atoms) that replace hydrogen atoms. Examples of such substituents include alkyl groups, alkoxy groups, halogen atoms, haloalkyl groups, hydroxyl groups, and oxo groups (=O).

[0329] Regarding the alkyl group used as the above-mentioned substituent, it is preferably an alkyl group having 1 to 5 carbon atoms, and more preferably methyl, ethyl, propyl, n-butyl, and tert-butyl.

[0330] Regarding the alkoxy group used as the above-mentioned substituent, it is preferred to be an alkoxy group with 1 to 5 carbon atoms, more preferably methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, and tert-butoxy, and particularly preferably methoxy and ethoxy.

[0331] Regarding the halogen atom that can be used as a substituent, examples include fluorine, chlorine, bromine, and iodine atoms, with fluorine being the preferred option.

[0332] Regarding the haloalkyl group that serves as the substituent mentioned above, examples include groups obtained by replacing some or all of the hydrogen atoms of the aforementioned alkyl group with the aforementioned halogen atoms.

[0333] For cyclic aliphatic hydrocarbon groups, a portion of the carbon atoms constituting its ring structure can be replaced with -O- or -S-. Preferred substituents containing heteroatoms are -O-, -C(=O)-O-, -S-, -S(=O)2-, and -S(=O)2-O-.

[0334] The aromatic hydrocarbon group that is a divalent hydrocarbon group is a divalent hydrocarbon group having at least one aromatic ring, and may have substituents. The aromatic ring is only required to be a cyclic conjugated system having 4n+2 π electrons; there is no particular limitation, and 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.

[0335] Examples of aromatic rings include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; aromatic heterocycles formed by replacing some carbon atoms in the aforementioned aromatic hydrocarbon rings with heteroatoms; and so on. Examples of heteroatoms in aromatic heterocycles include oxygen atoms, sulfur atoms, and nitrogen atoms. Examples of aromatic heterocycles include pyridine rings and thiophene rings.

[0336] Regarding aromatic hydrocarbon groups as divalent hydrocarbon groups, examples 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.); groups obtained by substituting one hydrogen atom of a group (aryl or heteroaryl) obtained by removing one hydrogen atom from the aforementioned aromatic hydrocarbon ring or aromatic heterocycle with an alkylene group (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.); and so on.

[0337] The alkylene group bonded to the aryl or heteroaryl group described above preferably has 1 to 4 carbon atoms, more preferably 1 to 2, and particularly preferably 1.

[0338] For the aforementioned aromatic hydrocarbon group, the hydrogen atoms present in the aromatic hydrocarbon group can be replaced by substituents. For example, the hydrogen atoms bonded to the aromatic ring in the aromatic hydrocarbon group can be replaced by substituents. Examples of such substituents include alkyl groups, alkoxy groups, halogen atoms, haloalkyl groups, hydroxyl groups, oxo groups (=O), etc.

[0339] Regarding the alkyl group used as the above-mentioned substituent, it is preferably an alkyl group having 1 to 5 carbon atoms, and more preferably methyl, ethyl, n-propyl, n-butyl, and tert-butyl.

[0340] Regarding the alkoxy group used as the above-mentioned substituent, it is preferred to be an alkoxy group having 1 to 5 carbon atoms, preferably methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, and tert-butoxy, and more preferably methoxy and ethoxy.

[0341] Regarding the halogen atom that serves as the substituent mentioned above, examples include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms, with fluorine atoms being the preferred option.

[0342] Regarding the haloalkyl group that serves as the substituent mentioned above, examples include groups obtained by replacing some or all of the hydrogen atoms of the aforementioned alkyl group with the aforementioned halogen atoms.

[0343] • Divalent linking groups containing heteroatoms

[0344] The heteroatoms in a divalent linker containing heteroatoms are atoms other than carbon and hydrogen atoms, such as oxygen, nitrogen, sulfur, and halogen atoms.

[0345] Specifically, examples of divalent linking groups containing heteroatoms include non-hydrocarbon linking groups such as -O-, -C(=O)-, -C(=O)-O-, -OC(=O)-O-, -S-, -S(=O)2-, -S(=O)2-O-, -NH-, -NH-C(=O)-, -NH-C(=NH)-, and =N-, as well as combinations of at least one of these non-hydrocarbon linking groups with a divalent hydrocarbon group. Examples of this divalent hydrocarbon group include divalent hydrocarbon groups that may have substituents as described above, preferably linear or branched aliphatic hydrocarbon groups.

[0346] In the above, the H atoms in -NH-, -NH-, and -NH-C(=NH)- can each 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.

[0347] As R 12b The divalent linking group in the form is particularly preferred to be a straight-chain or branched alkylene group, a cyclic aliphatic hydrocarbon group, or a divalent linking group containing heteroatoms.

[0348] 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, the same groups as the straight-chain or branched alkylene groups listed as straight-chain or branched aliphatic hydrocarbon groups in the foregoing description of "divalent hydrocarbon groups that may have substituents" as divalent linking groups can be cited.

[0349] In R 12b When the divalent linking group is a cyclic aliphatic hydrocarbon group, the same cyclic aliphatic hydrocarbon group that was listed as "aliphatic hydrocarbon group containing a ring in the structure" in the above description of "divalent hydrocarbon group that may have substituents" as a divalent linking group can be cited as such.

[0350] The cyclic aliphatic hydrocarbon group is particularly preferred as a group obtained by removing two or more hydrogen atoms from cyclopentane, cyclohexane, norbornene, isobornene, adamantane, tricyclodecane, or tetracyclododecane.

[0351] In R 12bWhen the divalent linking group is a divalent linking group containing a heteroatom, the preferred linking group includes -O-, -C(=O)-O-, -C(=O)-, -OC(=O)-O-, -C(=O)-NH-, -NH- (H can be replaced by alkyl, acyl, or other substituents), -S-, -S(=O)2-, -S(=O)2-O-, and the general formula -Y. 1b -OY 2b -、-[Y 1b -C(=O)-O] m’ -Y 2b - or -Y 1b -OC(=O)-Y 2b - represents a group [where Y is a group that represents ... 1b and Y 2b Each is an independent divalent hydrocarbon group that can have substituents, where O is an oxygen atom and m' is an integer between 0 and 3.

[0352] 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.

[0353] Formula-Y 1b -OY 2b -、-[Y 1b -C(=O)-O] m’ -Y 2b - or -Y 1b -OC(=O)-Y 2b -Medium, Y 1b and Y 2b Each is an independent divalent hydrocarbon group that may have substituents. Examples of such divalent hydrocarbon groups include the same groups listed as "divalent hydrocarbon groups that may have substituents" in the description of the aforementioned divalent linking groups.

[0354] As Y 1b 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.

[0355] As Y 2b 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.

[0356] Formula-[Y 1b -C(=O)-O] m’ -Y 2b In the group represented by -, m' is an integer of 0 to 3, preferably an integer of 0 to 2, more preferably 0 or 1, and particularly preferably 1. That is, as in formula -[Y 1b -C(=O)-O] m’ -Y 2b - represents a group, particularly preferably of the formula -Y 1b -C(=O)-OY 2b - represents a group. Preferably, it is of 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.

[0357] Regarding R 12b The divalent linking group, as a divalent linking group containing a heteroatom, is preferably an organic group formed by a combination 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 aforementioned formula -Y. 1b -OY 2b -、-[Y 1b -C(=O)-O] m’ -Y 2b - or -Y 1b -OC(=O)-Y 2b - represents a group, particularly preferably the aforementioned formula -[Y] 1b -C(=O)-O] m’ -Y 2b - or -Y 1b -OC(=O)-Y 2b - indicates a functional group.

[0358] As R 12b The divalent linking group in the form is preferably an alkylene group or a divalent linking group containing an ester bond (-C(=O)-O-).

[0359] The alkylene group is preferably a straight-chain or branched alkylene group. Preferred examples of such straight-chain aliphatic hydrocarbon groups include methylene [-CH2-], ethylene [-(CH2)2-], 1,3-propylene [-(CH2)3-], 1,4-butylene [-(CH2)4-], and 1,5-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-; alkyl-1,3-propylene groups such as -CH(CH3)CH2CH2CH2- and -CH2CH(CH3)CH2-; and alkyl-1,4-butylene groups such as -CH(CH3)CH2CH2CH2- and -CH2CH(CH3)CH2CH2-.

[0360] As a divalent linking group containing an ester bond, the formula -R is particularly preferred. 13b -C(=O)-O-[where, R 13b It is a divalent linking group. The group represented by ] is preferred. That is, the structural unit (b-3-S) is preferably the structural unit represented by the following formula (b-S1-1).

[0361] [Chemical Formula 33]

[0362]

[0363] (where R and R) 11b As before, R 13b (It is a divalent linker.)

[0364] As R 13b Without specific limitations, for example, examples related to R mentioned above can be cited. 12b The same group as the divalent linker in it.

[0365] 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, preferably a straight-chain or branched alkylene group, or a divalent linking group containing an oxygen atom as a heteroatom.

[0366] 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.

[0367] The divalent linking group containing an oxygen atom is preferably a divalent linking group containing an ether bond or an ester bond, and more preferably the aforementioned -Y linking group. 1b -OY 2b -、-[Y 1b -C(=O)-O] m’ -Y 2b - or -Y 1b -OC(=O)-Y 2b -. Y 1b and Y 2b Each is an independent divalent hydrocarbon group that may have substituents, and m' is an integer between 0 and 3. Preferably, it is -Y. 1b -OC(=O)-Y 2b -, particularly preferred is -(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.

[0368] 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).

[0369] [Chemical Formula 34]

[0370]

[0371] (where R, A', R) 10b , z and R 13b (Same as above.)

[0372] In formula (b-S1-11), A' is preferably a methylene group, an oxygen atom (-O-), or a sulfur atom (-S-).

[0373] 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 mentioned above can be categorized as the same groups as the aforementioned linear or branched alkylene groups and divalent linking groups containing oxygen atoms.

[0374] 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).

[0375] [Chemical Formula 35]

[0376]

[0377] (In the formula, R and A' are the same as before, and c to e are each an independent integer between 1 and 3.)

[0378] [Structural Unit (b-3-L)]

[0379] As an example of a structural unit (b-3-L), one could cite R in the aforementioned equation (b-S1) as an example. 11b Structural units obtained by substitution with cyclic groups containing lactones, more specifically, can be represented by the structural units represented by the following formulas (b-L1) to (b-L5).

[0380] [Chemical Formula 36]

[0381]

[0382] (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 linker; s” is an integer between 0 and 2; A” is an alkylene group, oxygen atom, or sulfur atom with 1 to 5 carbon atoms that may contain oxygen or sulfur atoms; r is 0 or 1.)

[0383] The R in equations (b-L1) to (b-L5) is the same as in the previous text.

[0384] As for alkyl, alkoxy, haloalkyl, -COOR", -OC(=O)R", and hydroxyalkyl in R', the same groups as those listed above for substituents that can be present in alkyl, alkoxy, haloalkyl, -COOR", -OC(=O)R", and hydroxyalkyl containing -SO2- can be described.

[0385] Considering the ease of obtaining isochrones in industry, R' is preferably a hydrogen atom.

[0386] The alkyl group in "R" can be any of the following: straight-chain, branched, or cyclic.

[0387] 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.

[0388] 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 include groups obtained by removing one or more hydrogen atoms from polycyclic alkanes such as monocyclic alkanes, bicyclic alkanes, tricyclic alkanes, and tetracyclic alkanes that can be substituted or not substituted by fluorine atoms or fluorinated alkyl groups. Specifically, examples include groups obtained by removing one or more hydrogen atoms from monocyclic alkanes such as cyclopentane and cyclohexane, and polycyclic alkanes such as adamantane, norbornane, isoboronane, tricyclic decane, and tetracyclic dodecane.

[0389] As "A", the same group as A' in the aforementioned formula (3-1) can be cited. "A" is preferably an alkylene group having 1 to 5 carbon atoms, an oxygen atom (-O-), or a sulfur atom (-S-), more preferably an alkylene group having 1 to 5 carbon atoms, or -O-. As an alkylene group having 1 to 5 carbon atoms, it is more preferably methylene or dimethylmethylene, and most preferably methylene.

[0390] R 12b R in the aforementioned equation (b-S1) 12b same.

[0391] In formula (b-L1), s” is preferably 1 or 2.

[0392] The following examples illustrate specific instances of the structural units represented by the aforementioned equations (b-L1) to (b-L3). In the following equations, R... α It represents a hydrogen atom, a methyl group, or a trifluoromethyl group.

[0393] [Chemical Formula 37]

[0394]

[0395] [Chemical Formula 38]

[0396]

[0397] [Chemical Formula 39]

[0398]

[0399] As a structural unit (b-3-L), it is preferable to select at least one of the groups of structural units represented by the aforementioned formulas (b-L1) to (b-L5), more preferably at least one of the groups of structural units represented by formulas (b-L1) to (b-L3), and particularly preferably at least one of the groups of structural units represented by the aforementioned formulas (b-L1) or (b-L3).

[0400] Preferably, it is selected from at least one of the groups of structural units represented by the aforementioned formulas (b-L1-1), (b-L1-2), (b-L2-1), (b-L2-7), (b-L2-12), (b-L2-14), (b-L3-1), and (b-L3-5).

[0401] In addition, the structural unit (b-3-L) is preferably represented by the following formulas (b-L6) to (b-L7).

[0402] [Chemical Formula 40]

[0403]

[0404] In equations (b-L6) and (b-L7), R and R 12b Same as above.

[0405] Furthermore, the acrylic resin (B3) preferably contains structural units represented by the following formulas (b5) to (b7) having acid-dissociable groups as structural units that improve the solubility of the acrylic resin (B3) in alkali by the action of acid. The structural units represented by the following formulas (b5) to (b7) are structural units derived from (meth)acrylates having acid-dissociable groups.

[0406] [Chemical Formula 41]

[0407]

[0408] 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 independently represent 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, an aliphatic cyclic group having 5 to 20 carbon atoms, or an aromatic hydrocarbon group having 6 to 15 carbon atoms. R 16b and R 17bThey can bond with each other and together with the carbon atoms bonded to them, form a hydrocarbon ring with 5 to 20 carbon atoms. b It indicates an aliphatic cyclic group or alkyl group that may have substituents, p indicates an integer between 0 and 4, and q indicates 0 or 1.

[0409] It should be noted that examples of linear or branched alkyl groups include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, isopentyl, and neopentyl. Furthermore, fluoroalkyl groups are groups obtained by replacing some or all of the hydrogen atoms of the aforementioned alkyl groups with fluorine atoms.

[0410] Specific examples of aliphatic cyclic groups include groups obtained by removing one or more hydrogen atoms from polycyclic alkanes such as monocyclic alkanes, 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, as well as polycyclic alkanes such as adamantane, norbornane, isoboronane, tricyclic decane, and tetracyclic dodecane. Groups obtained by removing one hydrogen atom from cyclohexane and adamantane are particularly preferred (and may further have substituents).

[0411] In the above R 16b and R 17b In the case where they do not bond with each other to form a hydrocarbon ring, as mentioned above, R 15b R 16b and R 17b From the perspectives of high contrast, resolution, and depth of focus, linear or branched alkyl groups with 2 to 4 carbon atoms are preferred. As described above, R... 19b R 20b R 22b R 23b Preferably, it contains hydrogen atoms or methyl groups.

[0412] The above R 16b and R 17b It can 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 polycyclic alkanes such as monocyclic alkanes, 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, as well as polycyclic alkanes such as adamantane, norbornane, isoboronane, tricyclic decane, and tetracyclic dodecane. Groups obtained by removing one or more hydrogen atoms from cyclohexane and adamantane are particularly preferred (and may further have substituents).

[0413] 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), and straight-chain or branched alkyl groups with 1 to 4 carbon atoms. As polar groups, oxygen atom (=O) is particularly preferred.

[0414] The above Y b The group is an aliphatic cyclic group or an alkyl group, and examples include groups obtained by removing one or more hydrogen atoms from polycyclic alkanes such as monocyclic alkanes, 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, as well as 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).

[0415] 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), and straight-chain or branched alkyl groups having 1 to 4 carbon atoms. As polar groups, oxygen atom (=O) is particularly preferred.

[0416] Additionally, in Y b When the alkyl group is an alkyl group, it is preferred to be a straight-chain or branched alkyl group with 1 to 20 carbon atoms, preferably 6 to 15. 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-methylethyl, and 1-ethoxy-1-methylethyl.

[0417] As a preferred specific example of the structural unit represented by the above formula (b5), the structural units represented by the following formulas (b5-1) to (b5-33) can be cited.

[0418] [Chemical Formula 42]

[0419]

[0420] In the above equations (b5-1) to (b5-33), R 24b It represents a hydrogen atom or a methyl group.

[0421] As a preferred specific example of the structural unit represented by the above formula (b6), the structural units represented by the following formulas (b6-1) to (b6-26) can be cited.

[0422] [Chemical Formula 43]

[0423]

[0424] In the above equations (b6-1) to (b6-26), R 24b It represents a hydrogen atom or a methyl group.

[0425] As a preferred specific example of the structural unit represented by the above formula (b7), the structural units represented by the following formulas (b7-1) to (b7-15) can be cited.

[0426] [Chemical Formula 44]

[0427]

[0428] In the above equations (b7-1) to (b7-15), R 24b It represents a hydrogen atom or a methyl group.

[0429] Of the structural units represented by equations (b5) to (b7) described above, the structural unit represented by equation (b6) is preferred from the perspective of ease of synthesis and relatively easy realization of high sensitivity. Furthermore, among the structural units represented by equation (b6), Y is preferred. b The structural unit is alkyl, preferably R. 19b and R 20b One or both of them are alkyl structural units.

[0430] Furthermore, the acrylic resin (B3) is preferably a resin formed from a copolymer containing structural units derived from polymeric compounds having ether bonds that are not cyclic ether structures.

[0431] Examples of polymerizable compounds having ether bonds that are not cyclic ether structures include free radical polymerizable compounds such as (meth)acrylic acid derivatives having ether bonds and ester bonds that are not cyclic ether structures. 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, and methoxypolypropylene glycol (meth)acrylate. Furthermore, the polymerizable compounds having 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.

[0432] Furthermore, in acrylic resin (B3), other polymeric compounds may be included as structural units for the purpose of moderately controlling physical and chemical properties. Examples of such polymeric compounds include known free radical polymers and anionic polymers.

[0433] Examples of such polymeric compounds include, for instance, 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, butyl methacrylate, and cyclohexyl methacrylate; and hydroxyalkyl methacrylates such as 2-hydroxyethyl methacrylate and 2-hydroxypropyl methacrylate. 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; polymeric compounds containing chlorine groups such as vinyl chloride and vinylidene chloride; polymeric compounds containing amide bonds such as acrylamide and methacrylamide; and so on.

[0434] As described above, acrylic resin (B3) may contain structural units derived from polymeric compounds containing carboxyl groups, such as monocarboxylic acids and dicarboxylic acids. 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 5% by mass or less.

[0435] In acrylic resin (B3), acrylic resin containing a relatively large amount of structural units from polymeric compounds having carboxyl groups is preferably used in combination with acrylic resin containing only a small amount of structural units from polymeric compounds having carboxyl groups or acrylic resin not containing structural units from polymeric compounds having carboxyl groups.

[0436] In addition, examples of polymerizable compounds include (meth)acrylates with acid-non-dissociable aliphatic polycyclic groups and aromatic compounds containing vinyl groups. For the acid-non-dissociable aliphatic polycyclic groups, tricyclodecyl, adamantyl, tetracyclododecyl, isobornyl, and norbornyl are particularly preferred from the perspective of industrial availability. These aliphatic polycyclic groups can have straight-chain or branched alkyl groups with 1 to 5 carbon atoms as substituents.

[0437] As a type of (meth)acrylate with an aliphatic polycyclic group that is acid-non-dissociable, specifically, substances with the structures of the following formulas (b8-1) to (b8-5) can be exemplified.

[0438] [Chemical Formula 45]

[0439]

[0440] In the above equations (b8-1) to (b8-5), R 25b It represents a hydrogen atom or a methyl group.

[0441] When the acrylic resin (B3) contains structural units (b-3) comprising cyclic groups containing -SO2- or cyclic groups containing lactones, 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 range, it is easy to simultaneously achieve good developability and good pattern shape.

[0442] Furthermore, when the acrylic resin (B3) contains the structural units represented by the aforementioned formulas (b5) to (b7), the acrylic resin (B3) preferably contains 5% by mass or more of the structural units represented by the aforementioned formulas (b5) to (b7), more preferably contains 10% by mass or more of the structural units represented by the aforementioned formulas (b5) to (b7), and particularly preferably contains 10% by mass or more and 60% by mass or less of the structural units represented by the aforementioned formulas (b5) to (b7).

[0443] When the acrylic resin (B3) contains the above-mentioned structural units from polymeric compounds having ether bonds that are not cyclic ether structures, the content of the structural units from polymeric compounds having ether bonds in the acrylic resin (B3) is preferably 1% by mass or more and 55% by mass or less, more preferably 5% by mass or more and 45% by mass or less.

[0444] When the acrylic resin (B3) contains the above-mentioned structural units of (meth)acrylates derived from aliphatic polycyclic groups having acid non-dissociable properties, the content of the structural units of (meth)acrylates derived from aliphatic polycyclic groups having acid non-dissociable properties in the acrylic resin (B3) is preferably 1% by mass or more than 60% by mass, and more preferably 5% by mass or more than 50% by mass.

[0445] The content of structural units derived from (meth)acrylic acid derivatives having cyclic carbonate groups and ester bonds in the acrylic resin (B3) is preferably 1% by mass or more and 50% by mass or less, more preferably 5% by mass or more and 40% by mass or less.

[0446] The weight-average molecular weight of the resin (B) described above, converted to polystyrene, is preferably 5,000 to 600,000, more preferably 7,000 to 400,000, and even more preferably 10,000 to 300,000. By setting such a weight-average molecular weight, sufficient strength of the photosensitive layer can be maintained without reducing its peelability from the substrate, thereby preventing expansion and cracking of the coating during deposition.

[0447] Furthermore, the dispersion of resin (B) is preferably 1.05 or higher. Here, dispersion is the value obtained by dividing the mass-average molecular weight by the number-average molecular weight. By setting such a dispersion, the desired stress resistance to plating can be achieved, or problems such as the metal layer obtained by plating process becoming prone to expansion can be avoided.

[0448] The content of resin (B) is preferably set to 5% by mass or more and 99% by mass or less relative to the total amount of solid components in the photosensitive composition.

[0449] <Non-polymer compounds with phenolic hydroxyl groups (C)>

[0450] The photosensitive composition contains a nonpolymer compound (C) having a phenolic hydroxyl group.

[0451] In non-polymer compounds (C), the so-called phenolic hydroxyl group refers to a hydroxyl group (OH) directly bonded to the carbon atom constituting a 6-membered aromatic ring. It should be noted that not only are monocyclic aromatic rings 6-membered aromatic rings 6-membered aromatic rings, but also 6-membered aromatic rings constituting fused polycyclic aromatic rings are 6-membered aromatic rings. A benzene ring is preferred as a 6-membered aromatic ring.

[0452] Non-polymer compounds (C) are compounds that are not polymers, such as compounds with a molecular weight of less than 800.

[0453] The nonpolymer compound (C) is preferably nonionic.

[0454] The ratio of the amount of phenolic hydroxyl groups to the mass of the nonpolymer compound (C) is preferably 1.0 mmol / g or more and 8.0 mmol / g or less, more preferably 3.0 mmol / g or more and 7.0 mmol / g or less, and particularly preferably 5.0 mmol / g or more and 6.5 mmol / g or less.

[0455] In addition, in the non-polymer compound (C), the number of hydroxyl groups is, for example, more than 1 and less than 4, and the number of hydroxyl groups is preferably 2.

[0456] It should be noted that the ratio (mmol / g) of the amount of phenolic hydroxyl groups to the mass of the non-polymer compound (C) can be calculated as "the number of hydroxyl groups in one molecule of non-polymer compound with phenolic hydroxyl groups / the molecular weight of the non-polymer compound with phenolic hydroxyl groups × 1000".

[0457] Specific examples of nonpolymer compounds (C) having phenolic hydroxyl groups include 2,3,4-trihydroxybenzophenone, 2,4,4'-trihydroxybenzophenone, 2,4,6-trihydroxybenzophenone, 2,3,6-trihydroxybenzophenone, 2,3,4-trihydroxy-2'-methylbenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2,3',4,4',6-pentahydroxybenzophenone, 2,2',3,4,4'-pentahydroxybenzophenone, and 2,2',3,4,5-pentahydroxybenzophenone. Benzyl ketone, 2,3',4,4',5',6-hexahydroxybenzophenone, and polyhydroxybenzophenones such as 2,3,3',4,4',5'-hexahydroxybenzophenone; bis(2,4-dihydroxyphenyl)methane, bis(2,3,4-trihydroxyphenyl)methane, 2-(4-hydroxyphenyl)-2-(4'-hydroxyphenyl)propane, 2-(2,4-dihydroxyphenyl)-2-(2',4'-dihydroxyphenyl)propane, 2-(2,3,4-trihydroxyphenyl)-2-(2',3',4'-trihydroxyphenyl)propane, 4,4'-{1-[ 4-[2-(4-hydroxyphenyl)-2-propyl]phenyl]ethoxyyl}bisphenol, 3,3'-dimethyl-{1-[4-[2-(3-methyl-4-hydroxyphenyl)-2-propyl]phenyl]ethoxyyl}bisphenol, 1-[[1-(4-hydroxyphenyl)-1-methyl]ethyl]-4-[1,1-di(4-hydroxyphenyl)ethylbenzene, 1,1-bis[4,4-di(4-hydroxyphenyl)cyclohexyl]methane, 1,1,1-tris(4-hydroxyphenyl)ethane, 4,4'-cyclohexylbisphenol and other bis[(poly)hydroxyphenyl]alkanes; tri(4- Tris(hydroxyphenyl)methane, bis(4-hydroxy-3,5-dimethylphenyl)-4-hydroxyphenylmethane, bis(4-hydroxy-2,5-dimethylphenyl)-4-hydroxyphenylmethane, bis(4-hydroxy-3,5-dimethylphenyl)-2-hydroxyphenylmethane, bis(4-hydroxy-2,5-dimethylphenyl)-2-hydroxyphenylmethane, bis(4-hydroxy-2,5-dimethylphenyl)-3,4-dihydroxyphenylmethane, and bis(4-hydroxy-3,5-dimethylphenyl)-3,4-dihydroxyphenylmethane, etc., or their methyl-substituted derivatives;bis(3-cyclohexyl-4-hydroxyphenyl)-3-hydroxyphenylmethane, bis(3-cyclohexyl-4-hydroxyphenyl)-2-hydroxyphenylmethane, bis(3-cyclohexyl-4-hydroxyphenyl)-4-hydroxyphenylmethane, bis(5-cyclohexyl-4-hydroxy-2-methylphenyl)-2-hydroxyphenylmethane, bis(5-cyclohexyl-4-hydroxy-2-methylphenyl)-3-hydroxyphenylmethane, bis(5-cyclohexyl-4-hydroxy-2-methylphenyl)-4-hydroxyphenylmethane, bis(3-cyclohexyl-4-hydroxy-2-methylphenyl)-4-hydroxyphenylmethane, bis(3-cyclohexyl-4-hydroxy-2-methylphenyl)-4-hydroxyphenylmethane, bis(3-cyclohexyl-4-hydroxy-2-methylphenyl)-3-hydroxyphenylmethane, bis(5-cyclohexyl-4-hydroxy-2-methylphenyl)-4-hydroxyphenylmethane, bis(3-cyclohexyl-4-hydroxy-2-methylphenyl)-4-hydroxyphenylmethane, bis(3-cyclohexyl-4-hydroxy-2-methylphenyl)-3 ... bis(5-cyclohexyl-2-hydroxyphenyl)-3-hydroxyphenylmethane, bis(5-cyclohexyl-4-hydroxy-3-methylphenyl)-4-hydroxyphenylmethane, bis(5-cyclohexyl-4-hydroxy-3-methylphenyl)-3-hydroxyphenylmethane, bis(5-cyclohexyl-4-hydroxy-3-methylphenyl)-2-hydroxyphenylmethane, bis(3-cyclohexyl-2-hydroxyphenyl)-4-hydroxyphenylmethane, bis(3-cyclohexyl-2-hydroxyphenyl)-2-hydroxyphenylmethane, bis(5-cyclohexyl-2-hydroxyphenyl)-3-hydroxyphenylmethane Bis(cyclohexyl-4-methylphenyl)-2-hydroxyphenylmethane and bis(5-cyclohexyl-2-hydroxy-4-methylphenyl)-4-hydroxyphenylmethane, etc., are bis(cyclohexylhydroxyphenyl)(hydroxyphenyl)methanes or their methyl-substituted derivatives; phenols or substituted phenols such as phenol, o-methoxyphenol, m-methoxyphenol, p-methoxyphenol, o-cresol, m-cresol, p-cresol, dimethylphenol, hydroquinone, resorcinol, etc.; 1-naphthol, 2-naphthol, 1,4-dihydroxynaphthol, 1,5-dihydroxynaphthol, 1,8-dihydroxynaphthol, etc. Naphthols or dihydroxynaphthols such as 2,6-dihydroxynaphthol and 2,7-dihydroxynaphthol; 9,9-dihydroxyaryl substituted fluorenes such as 9,9-bis(4-hydroxyphenyl)fluorene, 9,9-bis(6-hydroxynaphth-2-yl)fluorene, and 9,9-bis(4-hydroxy-3-methylphenyl)fluorene; 4-methyl-2,6-bis[(2-hydroxy-3,5-dimethylphenyl)methyl]benzene, catechol, pyrogallol, pyrogallol monomethyl ether, pyrogallol-1,3-dimethyl ether, salicylic acid, and other compounds.

[0458] Among these compounds, the following compounds are preferred, particularly 9,9-bis(4-hydroxyphenyl)fluorene or 9,9-bis(4-hydroxy-3-methylphenyl)fluorene.

[0459] [Chemical Formula 46]

[0460]

[0461] The content of the non-polymer compound (C) is preferably set to 0.01% by mass or more and 20% by mass or less relative to the total amount of solid components in the photosensitive composition, more preferably 1% by mass or more and 20% by mass or less, and even more preferably 5% by mass or more and 15% by mass or less.

[0462] <Alkali-soluble resin (D)>

[0463] The photosensitive composition may also contain an alkali-soluble resin (D) to improve alkali solubility. Here, the alkali-soluble resin refers to a resin that dissolves at least 0.01 μm when a 1 μm thick resin film is formed on a substrate using a 20% by weight resin solution (solvent: propylene glycol monomethyl ether acetate) and immersed in a 2.38% by weight TMAH (tetramethylammonium hydroxide) aqueous solution for 1 minute. It refers to a resin that does not belong to the aforementioned resin (B) (typically, a resin whose alkali solubility remains substantially unchanged even under acid treatment). Preferably, the alkali-soluble resin (D) is at least one resin selected from the group consisting of Novolac resin (D1), polyhydroxystyrene resin (D2), and acrylic resin (D3).

[0464] [Novolac resin (D1)]

[0465] Novolac resins can be obtained, for example, by adding and condensing aromatic compounds (hereinafter referred to as "phenols") with aldehydes under an acid catalyst.

[0466] Examples of the aforementioned phenols include, for example, 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, salicylic acid, gallic acid, gallic acid ester, α-naphthol, β-naphthol, etc.

[0467] Examples of aldehydes mentioned above include formaldehyde, furfural, benzaldehyde, nitrobenzaldehyde, and acetaldehyde.

[0468] There are no particular limitations on the catalyst used in addition condensation reactions. For example, hydrochloric acid, nitric acid, sulfuric acid, formic acid, oxalic acid, acetic acid, etc., can be used as acid catalysts.

[0469] It should be noted that the flexibility of Novolac 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 large-volume aldehydes.

[0470] The mass-average molecular weight of the Novolac resin (D1) is not particularly limited to a range that does not impede the purpose of the present invention, but is preferably 1,000 to 50,000.

[0471] [Polyhydroxystyrene resin (D2)]

[0472] Examples of hydroxystyrene compounds that constitute polyhydroxystyrene resin (D2) include p-hydroxystyrene, α-methylhydroxystyrene, and α-ethylhydroxystyrene.

[0473] Furthermore, polyhydroxystyrene resin (D2) is preferably a copolymer with styrene resin. Examples of styrene-based compounds constituting styrene resin include styrene, chlorostyrene, chloromethylstyrene, vinyltoluene, and α-methylstyrene.

[0474] The mass-average molecular weight of the polyhydroxystyrene resin (D2) is not particularly limited within the range that does not hinder the purpose of the present invention, but is preferably 1,000 to 50,000.

[0475] [Acrylic resin (D3)]

[0476] As an acrylic resin (D3), it preferably comprises structural units derived from polymeric compounds having ether bonds and structural units derived from polymeric compounds having carboxyl groups.

[0477] Examples of polymerizable compounds containing ether bonds include 2-methoxyethyl acrylate, methoxytriethylene glycol (meth)acrylate, 3-methoxybutyl acrylate, ethyl carbitol (meth)acrylate, phenoxy polyethylene glycol (meth)acrylate, methoxypolypropylene glycol (meth)acrylate, tetrahydrofurfuryl acrylate, and other (meth)acrylate derivatives containing both ether and ester bonds. 2-methoxyethyl acrylate and methoxytriethylene glycol acrylate are preferred among these polymerizable compounds. These polymerizable compounds can be used alone or in combination of two or more.

[0478] 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; compounds containing both carboxyl and ester bonds, such as 2-methacryloyloxyethyl succinic acid, 2-methacryloyloxyethyl maleic acid, 2-methacryloyloxyethyl phthalic acid, and 2-methacryloyloxyethyl hexahydrophthalic acid; and so on. Acrylic acid and methacrylic acid are preferred among the aforementioned carboxyl-containing polymerizable compounds. These polymerizable compounds can be used alone or in combination of two or more.

[0479] The mass-average molecular weight of the acrylic resin (D3) is not particularly limited within a range that does not hinder the purpose of the present invention, but is preferably 50,000 to 800,000.

[0480] When all solid components of the photosensitive composition are 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 5 parts by mass or more than 70 parts by mass.

[0481] <Sulfur-containing compounds (E)>

[0482] The photosensitive composition may contain a sulfur-containing compound (E). The sulfur-containing compound (E) is, for example, a compound containing sulfur atoms capable of coordinating with a metal. It should be noted that, regarding compounds capable of producing two or more tautomers, if at least one tautomer contains sulfur atoms coordinated with a metal constituting the surface of the metal substrate, the compound is considered a sulfur-containing compound.

[0483] As a sulfur-containing compound (E), it is preferred to be a compound containing, for example, a mercapto group (-SH), a thiocarboxyl group (-CO-SH), a dithiocarboxyl group (-CS-SH), and a thiocarbonyl group (-CS-).

[0484] Considering the ease of coordination with metals and the excellent effect of suppressing foot rot, sulfur-containing compounds preferably have thiol groups.

[0485] As a preferred example of a sulfur-containing compound having a thiol group, a compound represented by the following formula (e1) can be cited.

[0486] [Chemical Formula 47]

[0487]

[0488] (where R is in the formula) e1 and R e2 Each independently represents a hydrogen atom or an alkyl group, R e3 Indicates a single bond or alkylene group, R e4 This represents an aliphatic group with a valence of u, which can contain atoms other than carbon, where u is an integer between 2 and 4.

[0489] 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 impede 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 is preferably one of hydrogen atoms and the other of alkyl, and particularly preferably one of hydrogen atoms and the other of methyl.

[0490] In R e3When 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 impede 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.

[0491] 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 include 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.

[0492] Among the compounds represented by formula (e1), compounds represented by formula (e2) are more preferred.

[0493] [Chemical Formula 48]

[0494]

[0495] (In equation (e2), R) e4 And u has the same meaning as equation (e1).

[0496] Among the compounds represented by the above formula (e2), the following compounds are preferred.

[0497] [Chemical Formula 49]

[0498]

[0499] Compounds represented by the following formulas (e3-L1) to (e3-L7) are also preferred examples of sulfur-containing compounds having a thiol group.

[0500] [Chemical Formula 50]

[0501]

[0502] (In formulas (e3-L1) to (e3-L7), R', s”, A”, and r are the same as those in formulas (b-L1) to (b-L7) described above for acrylic resin (B3).)

[0503] The following compounds are preferred examples of thiol compounds represented by the formulas (e3-L1) to (e3-L7) above.

[0504] [Chemical Formula 51]

[0505]

[0506] Compounds represented by the following formulas (e3-1) to (e3-4) are also preferred examples of sulfur-containing compounds having a thiol group.

[0507] [Chemical Formula 52]

[0508]

[0509] (The abbreviations in formulas (e3-1) to (e3-4) are defined as described above for formulas (3-1) to (3-4) concerning acrylic resin (B3).)

[0510] The following compounds are preferred examples of the mercapto compounds represented by the formulas (e3-1) to (e3-4) above.

[0511] [Chemical Formula 53]

[0512]

[0513] Furthermore, as a preferred example of a compound having a thiol group, a compound represented by the following formula (e4) can be cited.

[0514] [Chemical Formula 54]

[0515]

[0516] (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 from 0 to 3, n0 is an integer from 0 to 3, and when n1 is 2 or 3, R e5 They can be the same or different.

[0517] As R e5 Specific examples of alkyl groups having 1 to 4 carbon atoms and possessing hydroxyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and tert-butyl. Among these alkyl groups, methyl, hydroxymethyl, and ethyl are preferred.

[0518] As R e5Specific examples of alkoxy groups having 1 to 4 carbon atoms include methoxy, ethoxy, n-propyloxy, isopropyloxy, n-butyloxy, isobutyloxy, sec-butyloxy, and tert-butyloxy. Among these alkoxy groups, methoxy and ethoxy are preferred, and methoxy is more preferred.

[0519] As R e5 Specific examples of alkyl thio groups having 1 to 4 carbon atoms include methyl thio, ethyl thio, n-propyl thio, isopropyl thio, n-butyl thio, isobutyl thio, sec-butyl thio, and tert-butyl thio. Among these alkyl thio groups, methyl thio and ethyl thio are preferred, and methyl thio is more preferred.

[0520] As R e5 Specific examples of hydroxyalkyl groups having 1 to 4 carbon atoms include hydroxymethyl, 2-hydroxyethyl, 1-hydroxyethyl, 3-hydroxypropyl, and 4-hydroxybutyl. Among these hydroxyalkyl groups, hydroxymethyl, 2-hydroxyethyl, and 1-hydroxyethyl are preferred, and hydroxymethyl is more preferred.

[0521] As R e5 Specific examples of thiol alkyl groups having 1 to 4 carbon atoms include mercaptomethyl, 2-mercaptoethyl, 1-mercaptoethyl, 3-mercaptopropyl, and 4-mercaptobutyl. Among these thiol alkyl groups, mercaptomethyl, 2-mercaptoethyl, and 1-mercaptoethyl are preferred, and mercaptomethyl is more preferred.

[0522] In R e5 In 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-chloropropyl, 3-bromopropyl, 3-fluoropropyl, and 4-chlorobutyl. 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.

[0523] As R e5 Specific examples of halogen atoms include fluorine, chlorine, bromine, or iodine.

[0524] 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.

[0525] In the compound represented by formula (e4), the R on the benzene ring e5 The substitution position of R on the benzene ring is not particularly limited. e5 The substitution position is preferably relative to -(CH2). n0 -SH can be a meta or para position in terms of its bonding location.

[0526] As a compound represented by formula (e4), it is preferably R having at least one group selected from the group consisting of alkyl, hydroxyalkyl, and mercaptoalkyl. e5 The compound, more preferably, has one group selected from the group consisting of alkyl, hydroxyalkyl, and mercaptoalkyl as R. e5 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 of the alkyl, hydroxyalkyl, or mercaptoalkyl group on the benzene ring is preferably relative to -(CH2). n0 Regarding the bonding position of -SH, it is either meta or para, with para being more preferred.

[0527] In formula (e4), n0 is an integer between 0 and 3. From the perspective of ease of preparation and acquisition of the compound, n0 is preferably 0 or 1, and more preferably 0.

[0528] Specific examples of compounds represented by formula (e4) include p-mercaptophenol, p-thiocresol, m-thiocresol, 4-(methylthio)thiophenol, 4-methoxythiophenol, 3-methoxythiophenol, 4-ethoxythiophenol, 4-isopropyloxythiophenol, 4-tert-butoxythiophenol, 3,4-dimethoxythiophenol, 3,4,5-trimethoxythiophenol, 4-ethylthiophenol, and 4-isopropylthiophenol. 4-n-Butylthiophenol, 4-tert-Butylthiophenol, 3-Ethylthiophenol, 3-Isopropylthiophenol, 3-n-Butylthiophenol, 3-tert-Butylthiophenol, 3,5-Dimethylthiophenol, 3,4-Dimethylthiophenol, 3-tert-Butyl-4-Methylthiophenol, 3-tert-Butyl-4-Methylthiophenol, 3-tert-Butyl-5-Methylthiophenol, 4-tert-Butyl-3-Methylthiophenol, 4-Mercaptobenzyl alcohol, 3- Mercaptobenzyl alcohol, 4-(mercaptomethyl)phenol, 3-(mercaptomethyl)phenol, 1,4-di(mercaptomethyl)phenol, 1,3-di(mercaptomethyl)phenol, 4-fluorobenzylthiophenol, 3-fluorobenzylthiophenol, 4-chlorobenzylthiophenol, 3-chlorobenzylthiophenol, 4-bromobenzylthiophenol, 4-iodobenzylthiophenol, 3-bromobenzylthiophenol, 3,4-dichlorobenzylthiophenol, 3,5-dichlorobenzylthiophenol, 3,4-difluorobenzylthiophenol, 3,5-difluorobenzylthiophenol Thiophenol, 4-mercaptocatechol, 2,6-di-tert-butyl-4-mercaptophenol, 3,5-di-tert-butyl-4-methoxythiophenol, 4-bromo-3-methylthiophenol, 4-(trifluoromethyl)thiophenol, 3-(trifluoromethyl)thiophenol, 3,5-bis(trifluoromethyl)thiophenol, 4-methylthiothiophenol, 4-ethylthiothiophenol, 4-n-butylthiothiophenol, and 4-tert-butylthiothiophenol, etc.

[0529] Examples of sulfur-containing compounds with thiol groups include compounds containing nitrogen-containing aromatic heterocycles substituted with thiol groups, and tautomers of compounds containing nitrogen-containing aromatic heterocycles substituted with thiol groups.

[0530] 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, cyclophosphine, phthalazine, quinazoline, quinoxaline, and 1,8-naphthidine, with 1,2,4-triazole being particularly preferred.

[0531] Specific examples of preferred nitrogen-containing heterocyclic compounds and tautomers of nitrogen-containing heterocyclic compounds as sulfur-containing compounds can be cited as follows.

[0532] [Chemical Formula 55]

[0533]

[0534] Examples of sulfur-containing compounds with thiol groups include compounds represented by the following formula (e5).

[0535] [Chemical Formula 56]

[0536]

[0537] (In equation (e5), R) e6 Each can be independently a hydrogen atom, a hydrocarbon group, or an acid-dissociable group.

[0538] R e7 and R e11 Each is independently a hydrogen atom or an alkyl group, or R e7 With R e11 They can bond with each other to form divalent groups selected from the group consisting of -O-, -S-, -CH2-, and -C(CH3)2-.

[0539] R e8 R e9 R e10 R e12 Each can be independently a hydrogen atom or a thiol group.

[0540] R e13 It can be a hydrogen atom, a hydrocarbon group, or an acid-dissociable group.

[0541] R e6 and e13 At least one of them is a hydrogen atom or an acid-dissociable group.

[0542] R e8 R e9 R e10 and R e12 At least one of them is a thiol group.

[0543] In equation (e5), in R e6 In the case of a hydrocarbon group, as R e6 Preferably, it is a hydrocarbon group with 1 to 20 carbon atoms, more preferably a saturated aliphatic hydrocarbon group with 1 to 20 carbon atoms, or an aromatic hydrocarbon group with 6 to 20 carbon atoms, even more preferably a saturated aliphatic hydrocarbon group with 1 to 20 carbon atoms, particularly preferably a saturated aliphatic hydrocarbon group with 1 to 10 carbon atoms, and most preferably a saturated aliphatic hydrocarbon group with 1 to 6 carbon atoms.

[0544] In R e6 When the saturated aliphatic hydrocarbon group is used, the saturated aliphatic hydrocarbon group can be linear or branched, preferably linear.

[0545] In R e6When the aromatic hydrocarbon group is used, 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.

[0546] In R e6 In the case of a saturated aliphatic hydrocarbon group, considering the ease of synthesis and acquisition of the compound represented by formula (e5), an alkyl group is preferred as the saturated aliphatic hydrocarbon group. Regarding R... e6 Preferred examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, and n-decyl.

[0547] Among them, methyl, ethyl, n-propyl, and isopropyl are preferred, and methyl and ethyl are more preferred.

[0548] In equation (e5), in R e6 In the case of an acid-dissociative group, the acid-dissociative group can be the same group as the acid-dissociative dissolution-inhibiting group described for resin (B).

[0549] Regarding R e6 Preferred examples of acid-dissociable groups include groups with the following formula.

[0550] [Chemical Formula 57]

[0551]

[0552] In equation (e5), R is used as e13 hydrocarbon groups, acid-dissociable groups and R e6 The same applies to hydrocarbon groups and acid-dissociable groups in it.

[0553] As a preferred specific example of the compound represented by the above formula (e5), the following compound can be cited.

[0554] [Chemical Formula 58]

[0555]

[0556] [Chemical Formula 59]

[0557]

[0558] Among sulfur-containing compounds (E), from the viewpoint of being able to form a patterned resist film with a rectangular cross-sectional shape, compounds with thiol groups directly bonded to cyclic groups are preferred, compounds with thiol groups directly bonded to aromatic rings are more preferred, and compounds with thiol groups directly bonded to nitrogen-containing heterocycles are particularly preferred.

[0559] Relative to the total mass of the above-mentioned resin (B) and alkali-soluble resin (D) of 100 parts by mass, the content of sulfur-containing compound (E) is preferably 0.001 parts by mass or more than 5 parts by mass, more preferably 0.005 parts by mass or more than 3 parts by mass, and particularly preferably 0.01 parts by mass or more than 1 part by mass.

[0560] <Acid Diffusion Control Agent (F)>

[0561] The photosensitive composition contains an acid diffusion control agent (F). Examples of acid diffusion control agents (F) include nitrogen-containing compounds (F1), and may also contain organic carboxylic acids, or oxyacids of phosphorus or their derivatives (F2), as needed.

[0562] [Nitrogen-containing compounds (F1)]

[0563] Examples of nitrogen-containing compounds (F1) include trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, tri-n-pentylamine, tribenzylamine, diethanolamine, triethanolamine, n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, ethylenediamine, N,N,N',N'-tetramethylethylenediamine, tetramethylenediamine, hexamethylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 4,4'-diaminobenzophenone, 4,4'-diaminodiphenylamine, formamide, N-methylformamide, N,N-dimethylformamide, acetamide, N-methylacetamide, N,N-dimethylacetamide, and 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, tripentylamine, diphenylpyridine, N,N-dibenzylaniline, 4-hydroxypiperidine, diisopropylaniline, N-Boc-4-hydroxypiperidine, N-Boc-pyrrolidine, etc. These can be used alone or in combination of two or more.

[0564] Alternatively, commercially available hindered amine compounds such as ADK STAB LA-52, ADK STAB LA-57, ADK STAB LA-63P, ADK STAB LA-68, ADK STAB LA-72, ADK STAB LA-77Y, ADK STAB LA-77G, ADK STAB LA-81, ADK STAB LA-82, and ADK STAB LA-87 (all manufactured by ADEKA), 4-hydroxy-1,2,2,6,6-pentamethylpiperidine derivatives, pyridines obtained by substituting the 2,6-position with hydrocarbon groups or other substituents such as 2,6-diphenylpyridine and 2,6-di-tert-butylpyridine, can be used as nitrogen-containing compounds (F1).

[0565] With respect to the total mass of the above-mentioned resin (B) and the alkali-soluble resin (D) below, 100 parts by mass, the nitrogen-containing compound (F1) is preferably used in the range of 0.001 parts by mass to 5 parts by mass, and particularly preferably in the range of 0.01 parts by mass to 3 parts by mass.

[0566] [Organic carboxylic acids, or oxyacids of phosphorus or their derivatives (F2)]

[0567] Among organic carboxylic acids, or oxyacids of phosphorus or their derivatives (F2), the organic carboxylic acid is preferably malonic acid, citric acid, malic acid, succinic acid, benzoic acid, salicylic acid, etc., and particularly preferably salicylic acid.

[0568] 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; hypophosphonic acids, phenylhydantoin, and their ester derivatives; and so on. Among these, phosphonic acids are particularly preferred. They can be used alone or in combination of two or more.

[0569] With respect 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 (F2) is generally used in the range of 0 parts by mass to 5 parts by mass, and is particularly preferred in the range of 0 parts by mass to 3 parts by mass.

[0570] In addition, in order to form a stable salt, the organic carboxylic acid, or the oxyacid of phosphorus or its derivative (F2) is preferably used in the same amount as the nitrogen-containing compound (F1) mentioned above.

[0571] <Organic Solvents (S)>

[0572] The photosensitive composition may or may not contain organic solvents (S).

[0573] As the organic solvent (S), various organic solvents that have been previously added to various photosensitive compositions can be used.

[0574] Specific examples of organic solvents (S) include ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl isopentyl ketone, and 2-heptanone; diols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,3-butanediol, and hexanediol; polyols such as glycerol; polyacetic esters of polyols such as glyceryl triacetate (triacetic acid ester); monools such as benzyl alcohol and terpineol; and ethylene glycol monoacetate, diethylene glycol monoacetate, etc. Monoacetates of glycols such as triethylene glycol monoacetate, propylene glycol monoacetate, dipropylene glycol monoacetate, tripropylene glycol monoacetate, and 1,3-butanediol monoacetate; diacetates of glycols such as ethylene glycol diacetate, diethylene glycol diacetate, triethylene glycol diacetate, propylene glycol diacetate, dipropylene glycol diacetate, tripropylene glycol diacetate, and 1,3-butanediol diacetate; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl Ethers, ethylene glycol monobutyl ether, ethylene glycol monophenyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monophenyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monopropyl ether, triethylene glycol monobutyl ether, triethylene glycol monophenyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monoethyl ether Monoethers of diols, including methyl ethers, dipropylene glycol monoethyl ethers, dipropylene glycol monopropyl ethers, dipropylene glycol monobutyl ethers, dipropylene glycol monophenyl ethers, tripropylene glycol monomethyl ethers, tripropylene glycol monoethyl ethers, tripropylene glycol monopropyl ethers, tripropylene glycol monobutyl ethers, tripropylene glycol monophenyl ethers, 1,3-butanediol monomethyl ethers, 1,3-butanediol monoethyl ethers, 1,3-butanediol monopropyl ethers, 1,3-butanediol monobutyl ethers, and 1,3-butanediol monophenyl ethers;Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monophenyl ether acetate, triethylene glycol monomethyl ether acetate, triethylene glycol monoethyl ether acetate, triethylene glycol monopropyl ether acetate, triethylene glycol monobutyl ether acetate, triethylene glycol monophenyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, propylene glycol monophenyl ether acetate Acetic acid ester, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol monopropyl ether acetate, dipropylene glycol monobutyl ether acetate, dipropylene glycol monophenyl ether acetate, tripropylene glycol monomethyl ether acetate, tripropylene glycol monoethyl ether acetate, tripropylene glycol monopropyl ether acetate, tripropylene glycol monobutyl ether acetate, tripropylene glycol monophenyl ether acetate, 1,3-butanediol monomethyl ether acetate (3-methoxybutyl acetate), 1,3-butanediol monoethyl ether acetate, 1,3-butanediol monopropyl ether acetate, 1,3-butanediol monobutyl ether acetate, 1,3-butanediol monophenyl ether acetate, 3-methyl-3-methoxybutyl acetate, 3- Ethyl-3-methoxybutyl ester, 2-methoxypentyl acetate, 3-methoxypentyl acetate, 4-methoxypentyl acetate, 2-methyl-3-methoxypentyl acetate, 3-methyl-3-methoxypentyl acetate, 3-methyl-4-methoxypentyl acetate, and 4-methyl-4-methoxypentyl acetate are monoether acetates of diols; ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether, ethylene glycol dibutyl ether, ethylene glycol diphenyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, diethylene glycol diphenyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, triethylene glycol dipropyl ether, triethylene glycol dipropyl ether, triethylene glycol Dibutyl ether, triethylene glycol diphenyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether, propylene glycol dibutyl ether, propylene glycol diphenyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol dipropyl ether, dipropylene glycol dibutyl ether, dipropylene glycol diphenyl ether, tripropylene glycol dimethyl ether, tripropylene glycol diethyl ether, tripropylene glycol dipropyl ether, tripropylene glycol dibutyl ether, tripropylene glycol diphenyl ether, 1,3-butanediol dimethyl ether, 1,3-butanediol diethyl ether, 1,3-butanediol dipropyl ether, 1,3-butanediol dibutyl ether, and 1,3-butanediol diphenyl ether, etc., diol diethers; dioxane, dihexyl ether, etc., ethers;Esters such as ethyl formate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, benzyl acetate, ethyl benzoate, methyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl pyruvate, ethyl ethoxylate, methyl methoxypropionate, ethyl ethoxypropionate, methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, methyl 2-hydroxy-3-methylbutyrate, diethyl maleate, cyclohexyl acetate, and γ-butyrolactone; aromatic hydrocarbons such as toluene and xylene; etc. They can be used alone or in combination of two or more.

[0575] When the photosensitive composition contains an organic solvent (S), the content of the organic solvent (S) is not particularly limited to a range that does not impede the purpose of the present invention. When the photosensitive composition is used for applications where the thickness of the photosensitive layer obtained by spin coating or the like is 5 μm or more, it is preferable to use the organic solvent (S) in a range of 20% by mass or more and 70% by mass or less.

[0576] <Other Ingredients>

[0577] The photosensitive composition may or may not contain a Lewis acid compound. By including a Lewis acid compound in the photosensitive composition, a photosensitive composition with high sensitivity can be easily obtained.

[0578] Here, Lewis acidic compounds are defined as "compounds that have empty orbitals capable of accepting at least one electron pair and function as electron pair acceptors".

[0579] As a Lewis acid compound, any compound that falls under the above definition and is recognized by those skilled in the art as a Lewis acid compound is acceptable; there are no particular limitations. Preferably, the compound used is one that is not a Brønsted acid (protic acid).

[0580] 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 acetylacetone, cadmium chloride, cadmium bromide, stannous chloride, stannous bromide, stannous sulfate, and stannous tartrate, etc.

[0581] When the photosensitive composition contains a Lewis acid compound, the Lewis acid compound is preferably used in a range of 0.01 to 5 parts by mass relative to 100 parts by mass of the total mass of the above-described resin (B) and the alkali-soluble resin (D) described later, more preferably in a range of 0.01 to 3 parts by mass, and even more preferably in a range of 0.05 to 2 parts by mass.

[0582] Furthermore, the photosensitive composition may also contain a polyethylene resin to improve plasticity. Specific examples of polyethylene resins include polyvinyl chloride, polystyrene, polyhydroxystyrene, polyvinyl acetate, polyvinylbenzoic acid, polyvinyl methyl ether, polyvinyl ethyl ether, polyvinyl alcohol, polyvinylpyrrolidone, polyvinylphenol, and copolymers thereof. From the perspective of a lower glass transition temperature, polyvinyl methyl ether is preferred.

[0583] In addition, in order to improve the adhesion between the patterned resist film, such as the mold formed using the photosensitive composition, and the substrate, the photosensitive composition may also contain an adhesive aid.

[0584] In addition, to improve coatability, defoaming properties, leveling properties, etc., the photosensitive composition may also contain a surfactant. As a surfactant, for example, fluorinated surfactants and organosilicon surfactants are preferred.

[0585] Specific examples of fluorinated surfactants include BM-1000, BM-1100 (both manufactured by BM CHEMI), MEGAFACE F142D, MEGAFACE F172, MEGAFACE F173, MEGAFACE 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 Ltd.), 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). Commercially available fluorinated surfactants such as those manufactured by SiliconeCo.,Ltd., but not limited to these.

[0586] 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 preferred.

[0587] Commercially available silicone surfactants can be used as surfactants. Specific examples of commercially available silicone surfactants include PAINTAD M (manufactured by Dow Corning Toray Co., Ltd.), Topeka K1000, Topeka K2000, Topeka K5000 (all manufactured by Takachiho Sangyo Co., Ltd.), XL-121 (polyether-modified silicone surfactant, manufactured by Clariant), and BYK-310 (polyester-modified silicone surfactant, manufactured by BYK-Chemie).

[0588] In addition, the photosensitive composition may also contain an acid or anhydride in order to fine-tune its solubility in the developer.

[0589] 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 1,2,4-cyclohexanedicarboxylic acid. - Polycarboxylic acids such as cyclohexanetricarboxylic acid, butanetetracarboxylic acid, trimellitic acid, pyromellitic acid, cyclopentanetetracarboxylic acid, butanetetracarboxylic acid, 1,2,5,8-naphthalenetetracarboxylic acid; anhydrides such as itaconic anhydride, succinic anhydride, citraconic anhydride, dodecenylsuccinic anhydride, triglyceride, maleic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, nadic anhydride, 1,2,3,4-butanetetracarboxylic anhydride, cyclopentanetetracarboxylic dianhydride, phthalic anhydride, pyromellitic anhydride, trimellitic anhydride, benzophenone tetracarboxylic anhydride, ethylene glycol ditriphenyltrihydride, glycerol trimellitic anhydride, etc.; etc.

[0590] In addition, photosensitizing compositions may also contain sensitizers to improve sensitivity.

[0591] In addition, the photosensitive composition may also contain dyes and pigments.

[0592] In addition, the photosensitive composition may also contain a polymerization inhibitor.

[0593] <Preparation Method of Chemically Amplified Positive Photosensitive Composition>

[0594] The chemically amplified positive photosensitive composition can be prepared by mixing and stirring the above-mentioned components using conventional methods. Examples of apparatus that can be used for mixing and stirring the components include a dissolver, a homogenizer, and a three-roll mill. After the components are mixed evenly, the resulting mixture can be further filtered using a sieve, membrane filter, or the like.

[0595] Photosensitive dry film

[0596] The photosensitive dry film has a substrate film and a photosensitive layer formed on the surface of the substrate film, the photosensitive layer being formed from the aforementioned photosensitive composition.

[0597] As a substrate film, a film with light transmittance is preferred. Specifically, polyethylene terephthalate (PET) film, polypropylene (PP) film, and polyethylene (PE) film are examples. Considering the excellent balance between light transmittance and tensile strength, polyethylene terephthalate (PET) film is preferred.

[0598] A photosensitive dry film is manufactured by forming a photosensitive layer by coating the aforementioned photosensitive composition onto a substrate film.

[0599] When forming a photosensitive layer on a substrate film, a coating applicator, bar coater, wire bar coater, roller coater, curtain coating applicator, etc. are used to coat the photosensitive composition on the substrate film in a manner that the thickness of the photosensitive layer is preferably 0.5 μm to 300 μm or less, more preferably 1 μm to 300 μm or less, and particularly preferably 3 μm to 100 μm or less, and then the film is dried as needed.

[0600] Photosensitive dry films may also have a protective film on the photosensitive layer. Examples of such protective films include polyethylene terephthalate (PET) films, polypropylene (PP) films, and polyethylene (PE) films.

[0601] Method for manufacturing patterned resist film and method for manufacturing substrate with mold

[0602] The method for forming a patterned resist film on a substrate using the photosensitive composition described above is not particularly limited. The patterned resist film is suitable for use as a mold for forming a plated model. The photosensitive composition described above can form a patterned resist film with a rectangular cross-sectional shape; therefore, by using the patterned resist film as a mold, a plated model with a rectangular cross-sectional shape can be formed.

[0603] As a preferred method, one can cite the following method for manufacturing a patterned resist film, which includes the following steps:

[0604] The lamination process involves laminating a photosensitive layer formed from a photosensitive composition onto a substrate.

[0605] The exposure process involves selectively exposing the photosensitive layer to active light or radiation in a position-selective manner; and

[0606] The developing process involves developing the exposed photosensitive layer.

[0607] The method for manufacturing a substrate with a mold for forming a plated shape includes a step of laminating a photosensitive layer on the metal surface of a substrate having a metal surface, and a step of producing a mold for forming a plated shape by developing in a developing step. Apart from this, it is the same as the method for manufacturing a patterned resist film.

[0608] 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, glass substrates, etc., can also be used as substrates.

[0609] When manufacturing a substrate with a mold for forming a plated object, a substrate with a metallic surface can be used as the substrate. Copper, gold, and aluminum are preferred as the type of metal constituting the metallic surface, with copper being more preferred.

[0610] The photosensitive layer is laminated onto the substrate, for example, by coating a liquid photosensitive composition onto the substrate and removing the solvent by heating as needed, thereby forming a photosensitive layer of the desired film thickness. Alternatively, the aforementioned photosensitive dry film can also be used to laminate the photosensitive layer onto the substrate.

[0611] The thickness of the photosensitive layer is not particularly limited, as long as it can form a patterned resist film for molding with the desired film thickness. The film thickness of the photosensitive layer is not particularly limited, but it is preferably 0.5 μm or more, more preferably 0.5 μm or more and 300 μm or less, particularly preferably 1 μm or more and 150 μm or less, and most preferably 10 μm or more and 100 μm or less.

[0612] Methods for coating a photosensitive composition onto a substrate include spin coating, slot coating, roller coating, screen printing, and applicator coating. Pre-baking of the photosensitive layer is preferred. Pre-baking conditions vary depending on the type, proportion, and coating thickness of the components in the photosensitive composition, but are typically between 70°C and 200°C, preferably between 80°C and 150°C, for approximately 2 minutes to 120 minutes.

[0613] For the photosensitive layer formed as described above, active light or radiation, such as ultraviolet light or visible light with wavelengths of 300 nm to 500 nm, such as g-line (wavelength 436 nm), h-line (wavelength 405 nm), and i-line (wavelength 365 nm), are selectively irradiated (exposed) through a mask with a specified pattern.

[0614] As sources of radiation, 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 radiation, visible light, ultraviolet radiation, X-rays, gamma rays, electron beams, proton beams, neutron beams, and ion beams. The radiation dose also varies depending on the composition of the photosensitive material and the thickness of the photosensitive layer, for example, 100 J / m². 2 Above 10000J / m 2 Below. In addition, in order to produce acid, the radiation contains light that activates the acid-producing agent (A).

[0615] After exposure, the photosensitive layer is heated using known methods, thereby promoting the diffusion of acid and changing the alkali solubility of the photosensitive layer in the exposed portion of the layer.

[0616] Next, the exposed photosensitive layer is developed using conventional methods to dissolve and remove unwanted portions, thereby forming a patterned resist film or a mold for forming a plated object. An alkaline aqueous solution can be used as the developer at this stage.

[0617] For example, 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, methyl diethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide (tetramethylammonium hydroxide), tetraethylammonium hydroxide, pyrrole, piperidine, 1,8-diazabicyclo[5,4,0]-7-undecene, and 1,5-diazabicyclo[4,3,0]-5-nonane can be used as the developer. Alternatively, an aqueous solution obtained by adding appropriate amounts of water-soluble organic solvents such as methanol and ethanol, or surfactants, to the above-mentioned aqueous solutions of bases can also be used as the developer.

[0618] 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 accumulation method, immersion method, spin-on immersion method, spray development method, etc.

[0619] The above-described photosensitive composition can suppress developing residue. Therefore, a resist pattern with less developing residue can be obtained.

[0620] After development, the substrate is washed with running water for 30 to 90 seconds and then dried using an air gun, oven, or similar equipment. This forms a resist film patterned into a desired shape on the surface of the substrate. Furthermore, this allows the manufacture of a molded substrate with a patterned resist film serving as a mold on the metal surface of a substrate having a metal surface.

[0621] Because of the use of the above-mentioned photosensitive composition, it is possible to form a patterned resist film with high surface smoothness.

[0622] The thickness of the patterned resist film formed using the photosensitive composition is not particularly limited and is applicable to both thick and thin films. The photosensitive composition is preferably used for forming thick patterned resist films. Specifically, the thickness of the patterned resist film formed using the photosensitive composition is preferably 0.5 μm or more, more preferably 0.5 μm or more and 300 μm or less, further preferably 0.5 μm or more and 200 μm or less, and particularly preferably 0.5 μm or more and 150 μm or less.

[0623] The upper limit of the film thickness can be, for example, below 100 μm. The lower limit of the film thickness can be, for example, above 1 μm or above 3 μm.

[0624] Because of the use of the above-mentioned photosensitive composition, it is possible to form a patterned resist film with a high aspect ratio.

[0625] Manufacturing Method of Plated Shaped Objects

[0626] In the non-resist portion (the portion removed by the developer) of the mold of the substrate formed using the above method, a conductor such as a metal is embedded by plating, thereby forming a plated model such as a connecting terminal such as a bump and a metal pillar, or a Cu redistribution circuit. Because the above-described photosensitive composition is used, a plated model with a high aspect ratio can be formed.

[0627] It should be noted that there are no particular restrictions on the plating method; any known method can be used. For the plating solution, soldering solutions, copper plating solutions, gold plating solutions, and nickel plating solutions are particularly preferred. The remaining mold is removed at the end using conventional methods such as stripping solutions.

[0628] When manufacturing coated shapes, it is preferable to perform ashing treatment on the metal surface exposed in the non-patterned portion of the patterned resist film in the mold used to form the coated shape. This is because if a pattern formed using a photosensitive composition containing a sulfur compound (E) is used as a mold to form the coated shape, the adhesion between the coated shape and the metal surface can sometimes be compromised.

[0629] Ashing is not particularly limited as long as it does not damage the patterned resist film of the mold used to form the plated shape to the extent that it prevents the plated shape from forming the desired shape.

[0630] As a preferred ashing method, the use of oxygen plasma can be cited. In order to ashing the metal surface on the substrate using oxygen plasma, an oxygen plasma generating device known can be used to generate oxygen plasma, which is then irradiated onto the metal surface on the substrate.

[0631] In the gas used to generate oxygen plasma, various gases that have been conventionally used together with oxygen for plasma processing can be mixed in, to a extent that does not impede the objectives of the present invention. Examples of such gases include nitrogen, hydrogen, and CF4.

[0632] The ashing conditions using oxygen plasma are not particularly limited to the extent that they do not impede 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.

[0633] By setting the oxygen plasma-based processing time within the aforementioned range, the shape of the patterned resist film is not altered, thus easily achieving an improved adhesion of the plated object.

[0634] Example

[0635] The present invention will be described in more detail below with reference to the embodiments, but the present invention is not limited to these embodiments.

[0636] In the examples and comparative examples, P1 to P3 were used as acid-producing agents (A). The van der Waals volumes of the acids produced by P1 to P3 and the molar absorptivity (ε365nm) of P1 to P3 at a wavelength of 365nm are recorded in Tables 1 to 11.

[0637] It should be noted that the van der Waals volume of the acids produced by P1 to P3 is calculated using CAChe Worksystem Pro.Version 6.1.12.33 as described above, for the acids produced by each photoacid-producing agent.

[0638] [Chemical Formula 60]

[0639]

[0640] In the examples and comparative examples, C1 to C11 were used as nonpolymer compounds (C) having phenolic hydroxyl groups. The proportion of the amount of phenolic hydroxyl groups relative to the mass of nonpolymer compound (C) for C1 to C11 is as follows.

[0641] C1: 4.44 mmol / g

[0642] C2: 5.71 mmol / g

[0643] C3: 5.28 mmol / g

[0644] C4: 6.94 mmol / g

[0645] C5: 7.45 mmol / g

[0646] C6: 7.97 mmol / g

[0647] C7: 8.61 mmol / g

[0648] C8: 9.25 mmol / g

[0649] C9: 7.07 mmol / g

[0650] C10: 9.79 mmol / g

[0651] C11: 12.49 mmol / g

[0652] [Chemical Formula 61]

[0653]

[0654] In the examples and comparative examples, resins A1 to A31 (acrylic resin (B3)) and H1 to H7 (styrene-based resin (B2)) were used as resins whose solubility in alkali increases with the action of acid (resin (B)). The numbers in parentheses below each structural unit in the following structural formulas indicate the content (mass %) of the structural unit in the resin. The weight-average molecular weight (Mw) of resins A1 to A31 and H1 to H7 are as follows. Furthermore, the dispersion (Mw / Mn) of resins A1 to A31 is 2.8. The dispersion (Mw / Mn) of resins H1 to H3 is 1.0. The dispersion (Mw / Mn) of resins H4 to H7 is 2.0. (Weight-average molecular weight (Mw) of resin (B)) Resin A1 to A24: 40000

[0655] Resin A25~A29, A31: 100000; Resin A30: 200000

[0656] Resin H1~H7: 10000

[0657] [Chemical Formula 62]

[0658]

[0659] [Chemical Formula 63]

[0660]

[0661] [Chemical Formula 64]

[0662]

[0663] [Chemical Formula 65]

[0664]

[0665] [Chemical Formula 66]

[0666]

[0667] [Chemical Formula 67]

[0668]

[0669] In the examples and comparative examples, the following resins H8 to H10 and N1 to N3 were used as alkali-soluble resins (D). H8 and H9 (polyhydroxystyrene resin (D2)) had a weight-average molecular weight (Mw) of 2500, H10 (polyhydroxystyrene resin (D2)) had a weight-average molecular weight (Mw) of 8000, and the dispersibility (Mw / Mn) of H8 to H10 was 1.0. N1 (Novolac resin (D1)) had a weight-average molecular weight (Mw) of 6500, N2 (Novolac resin (D1)) had a weight-average molecular weight (Mw) of 20000, N3 (Novolac resin (D1)) had a weight-average molecular weight (Mw) of 10000, and the dispersibility (Mw / Mn) of N1 to N3 was 5.0.

[0670] [Chemical Formula 68]

[0671]

[0672] [Chemical Formula 69]

[0673]

[0674] In the examples and comparative examples, T1 to T8 were used as sulfur-containing compounds (E).

[0675] [Chemical Formula 70]

[0676]

[0677] In the examples and comparative examples, Q1 to Q8 were used as acid diffusion control agents (F).

[0678] Q1: Tetramethyl 1,2,3,4-butanetetracarboxylate, and the transesterification product of 1,2,2,6,6-pentamethyl-4-piperidinol and β,β,β',β'-tetramethyl-2,4,8,10-tetraoxaspiro[5.5]undecane-3,9-diethanol.

[0679] [Chemical Formula 71]

[0680]

[0681] In the examples and comparative examples, S1 and S2 were used as organic solvents (S).

[0682] S1: A mixed solvent of 3-methoxybutyl acetate (MA) and propylene glycol monomethyl ether acetate (PGMEA) (MA / PGMEA = 6 / 4 (volume ratio))

[0683] S2: Propylene glycol monomethyl ether acetate (PGMEA)

[0684] [Examples 1-100 and Comparative Examples 1-4]

[0685] The resin (B) of the types and parts by mass listed in Tables 1 to 11, the alkali-soluble resin (D), the acid-generating agent (A), the non-polymer compound having phenolic hydroxyl groups (C), the sulfur-containing compound (E), the acid diffusion control agent (F), 0.05 parts by mass of the surfactant (BYK310, manufactured by BYK-Chemie), and 0.05 parts by mass of tri-n-octyl borate were dissolved in organic solvents (S) of the types listed in Tables 1 to 11 at a solid component concentration of 48% by mass to obtain the photosensitive compositions of Examples 1 to 100 and Comparative Examples 1 to 4.

[0686] Using the photosensitive compositions obtained in each example and comparative example, the rectangularity, development residue, and surface smoothness were evaluated using the following methods. The results are recorded in Tables 1 to 11.

[0687] [Evaluation of rectangularity]

[0688] The photosensitive compositions of the examples and comparative examples were coated onto an 8-inch diameter silicon wafer (copper substrate) on which a copper sputtered film was formed, forming a photosensitive layer with a film thickness (30 μm) as described in Tables 1-11. Next, the photosensitive layer was pre-baked at 135°C for 300 seconds. After pre-baking, a mask with a 5 μm diameter hole pattern (pitch (center-to-center distance): 10 μm) and an exposure apparatus FPA-5510iV (manufactured by Canon Corporation) (NA0.18) were used for pattern exposure using i-lines. The exposure amount was set to the hole width (width of the non-resist portion) at the middle of the substrate thickness direction in the cross-section of the resist pattern (the cross-section perpendicular to the surface direction of the resist pattern): CD middle This results in an exposure level of 5μm.

[0689] Next, the substrate was placed on a heated plate and subjected to exposure-after-heat (PEB) at 95°C for 180 seconds. Then, the following operation was repeated four 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 mixture was left to stand at 23°C for 60 seconds. Then, the resist pattern surface was washed with running water and purged with nitrogen to obtain the resist pattern.

[0690] The cross-sectional shape (the section perpendicular to the plane of the resist pattern) of the obtained resist pattern was observed using a scanning electron microscope, and the maximum value CD of the aperture width (the width of the non-resist portion) was measured. max and minimum value CD min According to CD max -CD min The value of is used to evaluate the rectangularity according to the following criteria. CD max -CD min The closer the value is to 0, the better the cross-sectional shape of the hole is, which is a rectangle.

[0691] <Evaluation Criteria for Rectangularity>

[0692] A: Above 0μm and below 0.3μm

[0693] B: Above 0.3μm and below 0.5μm

[0694] C: ≥0.5μm and <1.0μm

[0695] D: Above 1.0μm

[0696] [Evaluation of developer residue]

[0697] Using the same method as described above for [evaluation of rectangularity], a resist pattern (hole pattern) is formed. At this time, as masks, a mask with a hole pattern of 5 μm diameter (spacing (center-to-center distance): 10 μm), a mask with a hole pattern of 10 μm diameter (spacing (center-to-center distance): 20 μm), or a mask with a hole pattern of 15 μm diameter (spacing (center-to-center distance): 30 μm) is used to form the resist pattern.

[0698] The substrate (bottom of the hole) after nitrogen blowing was observed using a scanning electron microscope, and the development residue was evaluated according to the following criteria.

[0699] <Evaluation Criteria for Developing Residue>

[0700] A: No residue was observed in any of the following cases: masks with hole patterns of 5 μm, 10 μm, and 15 μm.

[0701] B: No residue was observed with a mask with a hole pattern of 10 μm diameter and a mask with a hole pattern of 15 μm diameter, but residue was observed with a mask with a hole pattern of 5 μm diameter.

[0702] C: No residue was observed with a mask showing a hole pattern with a diameter of 15 μm, but residue was observed with masks showing a hole pattern with a diameter of 5 μm and a hole pattern with a diameter of 10 μm.

[0703] D: Residues were observed in any of the following cases: masks with hole patterns of 5 μm, 10 μm, and 15 μm.

[0704] Evaluation of surface smoothness (arithmetic mean roughness Ra)

[0705] The photosensitive compositions of the examples and comparative examples were coated onto an 8-inch diameter silicon wafer (copper substrate) on which a copper sputtered film was formed, forming a photosensitive layer with a film thickness of 30 μm. Next, the photosensitive layer was pre-baked at 135°C for 300 seconds. After pre-baking, without exposure, the following operation was repeated four 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 layer was left to stand at 23°C for 60 seconds. Then, the surface was washed with running water and purged with nitrogen to obtain a sample for surface roughness evaluation.

[0706] It should be noted that the surface roughness evaluation sample was developed without exposure. Therefore, the surface roughness evaluation sample is equivalent to the resist portion (unexposed portion) in the resist pattern obtained by pattern exposure using a mask followed by development.

[0707] For the obtained surface roughness evaluation samples, the arithmetic mean roughness Ra was measured using an AFM (device name: WIDE-RANGE AFM AS-7B-μX, manufacturer: TAKANO) in accordance with JIS B 0601 (1994), and the surface smoothness was evaluated according to the following criteria.

[0708] <Evaluation Criteria for Surface Smoothness>

[0709] A: The arithmetic mean roughness Ra is below 6 nm.

[0710] B: Arithmetic mean roughness Ra is greater than 6 nm and less than 15 nm

[0711] E: Arithmetic mean roughness Ra is greater than 15 nm [Table 1]

[0712]

[0713] [Table 2]

[0714]

[0715] [Table 3]

[0716]

[0717] [Table 4]

[0718]

[0719] [Table 5]

[0720]

[0721] [Table 6]

[0722]

[0723] [Table 7]

[0724]

[0725] [Table 8]

[0726]

[0727] [Table 9]

[0728]

[0729] [Table 10]

[0730]

[0731] [Table 11]

[0732]

[0733] As shown in Tables 1-11, the chemically amplified positive photosensitive composition of the embodiments containing an acid-generating agent (A), a resin (B), a non-polymer compound having phenolic hydroxyl groups (C), and an acid diffusion control agent (F) can form a patterned resist film with a high aspect ratio (aspect ratio: 30 / 5) and high surface smoothness and rectangularity, and can suppress development residue.

Claims

1. A chemically amplified positive photosensitive composition comprising a van der Waals volume generated by irradiation with active light or radiation. The above are acid-producing agents (A), resins whose solubility in alkali increases through the action of acid (B), non-polymer compounds with phenolic hydroxyl groups (C), and acid diffusion control agents (F).

2. The chemically amplified positive photosensitive composition as described in claim 1, wherein, The amount of phenolic hydroxyl groups relative to the mass of the nonpolymer compound (C) is more than 1.0 mmol / g and less than 8.0 mmol / g.

3. The chemically amplified positive photosensitive composition as described in claim 1, wherein, The nonpolymer compound (C) is 9,9-bis(4-hydroxyphenyl)fluorene or 9,9-bis(4-hydroxy-3-methylphenyl)fluorene.

4. The chemically amplified positive photosensitive composition as described in claim 1, wherein, The resin (B) is an acrylic resin (B3). The acrylic resin (B3) has structural units derived from (meth)acrylates having aliphatic rings containing oxygen atoms as ring-forming atoms.

5. The chemically amplified positive photosensitive composition as described in claim 1, wherein, The molar absorptivity of the acid-producing agent (A) at a wavelength of 365 nm is less than 1000 L / (mol·cm).

6. The chemically amplified positive photosensitive composition as described in claim 1, wherein, The acid-producing agent (A) is an onium salt containing an anion represented by the following formula (ai) or the following formula (aii) as the anionic part. [Chemical Formula 1] In formula (ai), R a01 R a02 R a03 and R a04 Each can be independently a hydrocarbon group that may have substituents, or a heterocyclic group that may have substituents, R a01 R a02 R a03 and R a04 At least one of them is an aromatic hydrocarbon group that may have substituents; Cf-SO2-N - -SO2-Cf···(aii) In formula (aii), Cf is a fluoroalkyl group with 2 or more carbon atoms, and two fluoroalkyl groups can bond with each other to form a ring.

7. The chemically amplified positive photosensitive composition of claim 1, comprising a sulfur-containing compound (E).

8. The chemically amplified positive photosensitive composition as described in claim 1, further comprising an alkali-soluble resin (D).

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

10. A photosensitive dry film having a substrate film and a photosensitive layer formed on the surface of the substrate film, the photosensitive layer being formed from the chemically amplified positive photosensitive composition according to any one of claims 1 to 9.

11. A method for manufacturing a photosensitive dry film, comprising the step of coating a substrate film with the chemically amplified positive photosensitive composition according to any one of claims 1 to 9 to form a photosensitive layer.

12. A method for manufacturing a patterned resist film, comprising the following steps: The lamination process involves laminating a photosensitive layer formed from any one of the chemically amplified positive photosensitive compositions according to claims 1 to 9 onto a substrate; The exposure process involves irradiating the photosensitive layer with active light or radiation in a position-selective manner to perform exposure; and The developing process involves developing the exposed photosensitive layer.

13. A method for manufacturing a substrate with a mold, comprising the following steps: The lamination process involves laminating a photosensitive layer formed from any one of the chemically amplified positive photosensitive compositions according to claims 1 to 9 onto a substrate having a metal surface. The exposure process involves irradiating the photosensitive layer with active light or radiation in a position-selective manner to perform exposure; and The developing process involves developing the exposed photosensitive layer to create a mold for forming the plated object.

14. A method for manufacturing a plated shape, comprising the following plating steps: plating a substrate with a mold manufactured using the method for manufacturing a substrate with a mold as described in claim 13, and forming a plated shape within the mold.

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