Manufacturing method for metal wiring boards

Abstract

To provide a method for manufacturing a metal wiring substrate in which metal wiring formed on a substrate using a chemically amplified photosensitive composition is covered with an insulating film, and other components can be further provided on the insulating film, wherein oxidation of the metal wiring between the substrate and the insulating film can be suppressed. [Solution] A method for manufacturing a metal wiring substrate, comprising the steps of: laminating a photosensitive layer made of a chemically amplified photosensitive composition on a substrate having a metal surface; exposing the photosensitive layer by regioselectively irradiating it with active light or radiation; developing the exposed photosensitive layer to form a mold for forming metal wiring by plating; forming metal wiring by plating the substrate on which the mold has been formed; and covering the metal wiring with an insulating film, wherein the chemically amplified photosensitive composition contains an acid generator (A) that generates acid upon irradiation with active light or radiation, and the acid generator (A) contains an acid generator that generates an acid containing an anion of a specific structure.

Description

[Technical Field]

[0001] This invention relates to a method for manufacturing a metal wiring substrate. [Background technology]

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

[0003] Furthermore, in recent years, with the downsizing of electronic devices, high-density packaging technology for semiconductor packages has advanced, leading to the implementation of multi-pin thin-film packaging, miniaturization of package sizes, and improvements in packaging density based on two-dimensional and three-dimensional packaging technologies using the flip-chip method. In such high-density packaging technologies, connection terminals such as protruding electrodes (mounting terminals) like bumps that protrude from the package, and metal posts that connect rewiring (RDL) extending from peripheral terminals on the wafer to the mounting terminals are arranged on the substrate with high precision.

[0004] Photoresist compositions are used in the photofabrication described above. Among such photoresist compositions, chemically amplified photoresist compositions containing an acid generator are known. In chemically amplified photoresist compositions, acid is generated from the acid generator upon irradiation (exposure), and the diffusion of the acid is promoted by heat treatment, causing an acid-catalyzed reaction with the base resin etc. in the composition, which changes its alkali solubility (see Patent Document 1, etc.).

[0005] Such positive-type photoresist compositions are used, for example, in the formation of plated objects such as bumps, metal posts, and Cu redistributions by the plating process. Specifically, a photoresist layer of a desired thickness is formed on a support such as a metal substrate using a positive-type photoresist composition, exposed through a predetermined mask pattern, and developed to form a photoresist pattern that is used as a mold in which the portion for forming the plated object is selectively removed (exfoliated). Then, after embedding a conductor such as copper in the removed portion (non-resist portion) by plating, the photoresist pattern around it is removed to form bumps, metal posts, and Cu redistributions. [Prior art documents] [Patent Documents]

[0006] [Patent Document 1] Japanese Patent Publication No. 2009-69284 [Overview of the project] [Problems that the invention aims to solve]

[0007] Here, for example, in the manufacturing of semiconductor devices, a chemically amplified photoresist composition is used to form metal wiring as a plated object on a substrate, and then the metal wiring is covered with an insulating film such as a polyimide film, and further metal components such as metal wiring are provided on the insulating film (Semi-Additive Process). Thus, when metal wiring formed on a substrate is covered with an insulating film such as a polyimide film, and other components such as further metal wiring are provided on the insulating film, there is a problem that the metal wiring between the substrate and the insulating film oxidizes when exposed to high temperature and high humidity environments for a long period of time, leading to a decrease in long-term reliability.

[0008] The present invention has been made in view of the above problems, and aims to provide a method for manufacturing a metal wiring substrate in which metal wiring formed on a substrate using a chemically amplified photosensitive composition is covered with an insulating film, and other members can be further provided on the insulating film, and which can suppress oxidation of the metal wiring between the substrate and the insulating film. [Means for solving the problem]

[0009] As a result of diligent research to achieve the above objective, the present inventors have developed a method for manufacturing a metal wiring substrate, comprising: a lamination step of laminating a photosensitive layer made of a chemically amplified photosensitive composition on a substrate having a metal surface; an exposure step of exposing the photosensitive layer by regioselectively irradiating it with active light or radiation; a developing step of developing the photosensitive layer after the exposure step to form a mold for forming metal wiring by plating; a plating step of plating the substrate on which the mold has been formed to form metal wiring; and an insulating film coating step of covering the metal wiring with an insulating film, wherein the chemically amplified photosensitive composition contains an acid generator (A) that generates acid upon irradiation with active light or radiation, and the acid generator (A) is F-SO2-N - -SO2-F, PF6 - We have found that the above problems can be solved by including an acid generator that generates an acid containing at least one anion selected from the group consisting of an anion represented by the following formula (ai) and an anion represented by the following formula (aii), and have completed the present invention. Specifically, the present invention provides the following.

[0010] A first aspect of the present invention is a lamination step of laminating a photosensitive layer made of a chemically amplified photosensitive composition onto a substrate having a metal surface, The photosensitive layer is exposed by positionally irradiating it with active light or radiation, A developing step involves developing the photosensitive layer after the exposure step to form a mold for forming metal wiring by plating, A plating step is performed on the substrate on which the mold is formed to form metal wiring. An insulating film coating step of coating the metal wiring with an insulating film, and a method for manufacturing a metal wiring substrate, including: The chemically amplified photosensitive composition contains an acid generator (A) that generates an acid upon irradiation with actinic rays or radiation. The acid generator (A) is F-SO2-N - -SO2-F, PF6 - An acid generator that generates an acid containing at least one anion selected from the group consisting of an anion represented by the following formula (ai) and an anion represented by the following formula (aii). A method for manufacturing a metal wiring substrate.

Chemical formula

Chemical formula

Advantages of the Invention

[0011] According to the present invention, there is provided a method for manufacturing a metal wiring substrate in which a metal wiring formed on a substrate using a chemically amplified photosensitive composition is coated with an insulating film, and another member can be further provided on the insulating film, and oxidation of the metal wiring between the substrate and the insulating film can be suppressed.

Brief Description of the Drawings

[0012] [Figure 1] Figure 1 is a schematic cross-sectional view showing an example of a method for manufacturing a metal wiring substrate. [Figure 2] Figure 2 is a schematic cross-sectional view showing an example of a method for manufacturing a metal wiring board. [Modes for carrying out the invention]

[0013] ≪Method of manufacturing a metal wiring board≫ The method for manufacturing a metal wiring board is: A lamination process in which a photosensitive layer made of a chemically amplified photosensitive composition is laminated on a substrate having a metal surface, An exposure step in which a photosensitive layer is exposed by positionally irradiating it with active light or radiation, A developing step in which the photosensitive layer after the exposure step is developed to form a mold for forming metal wiring by plating, A plating process in which a mold is formed on a substrate is plated to form metal wiring, The process includes an insulating film coating step of covering metal wiring with an insulating film. The chemically amplified photosensitive composition contains an acid generator (A) that generates acid upon irradiation with active light or radiation. Acid generator (A) is F-SO2-N - -SO2-F, PF6 - The present invention includes an acid generator that generates an acid containing at least one anion selected from the group consisting of an anion represented by the following formula (ai) and an anion represented by the following formula (aii). The method for manufacturing the metal wiring substrate preferably includes a step of forming a further component on the insulating film after the insulating film coating step. Specifically, for example, the method for manufacturing the metal wiring substrate preferably includes a step of forming metal wiring on the insulating film, in which metal wiring is further formed on the insulating film after the insulating film coating step.

[0014] The above-described manufacturing method produces a metal wiring substrate in which metal wiring formed on a substrate is covered with an insulating film. The metal wiring substrate can be further equipped with other components, such as additional metal wiring, on top of the insulating film. The metal wiring substrate manufactured by the above-described manufacturing method can suppress oxidation of the metal wiring between the substrate and the insulating film. Therefore, even when the metal wiring substrate is exposed to high temperature and high humidity environments for a long period of time, oxidation of the metal wiring between the substrate and the insulating film is suppressed, resulting in excellent long-term reliability.

[0015] Thus, the reason why oxidation of the metal wiring between the substrate and the insulating film is suppressed is presumed to be due to the following mechanism. When a mold for metal wiring (plated objects) is formed using a chemically amplified photosensitive composition, the acid generator contained in the chemically amplified photosensitive composition comes into contact with the metal wiring during manufacturing, and even after the mold is removed, a small amount of the acid generator tends to remain on the metal wiring. If the acid generator remains on the metal wiring, oxidation of the metal wiring will progress due to the action of the acid generator, even if the metal wiring is coated with an insulating film such as polyimide. For example, oxidation is particularly likely to progress if the metal wiring is exposed to high temperature and high humidity environments for a long period of time. However, as an acid generator (A) included in the chemically amplified photosensitive composition, F-SO2-N - -SO2-F, PF6 - It is hypothesized that by using an acid generator that produces an anion represented by formula (ai) or an acid containing an anion represented by formula (aii), oxidation of the metal wiring can be suppressed even if the acid generator remains on the metal wiring.

[0016] On the other hand, the acid generator (A) is F-SO2-N - -SO2-F, PF6 - If the acid generator does not produce an anion represented by formula (ai) or an acid containing an anion represented by formula (aii), oxidation of the metal wiring becomes significant, as shown in the comparative example described later.

[0017] Each step in the metal wiring substrate manufacturing process described above will be explained below with reference to Figures 1 and 2. Figures 1 and 2 are schematic cross-sectional views showing an example of a metal wiring substrate manufacturing method.

[0018] [Lamination process] In the lamination process, a photosensitive layer made of a chemically amplified photosensitive composition is laminated onto a substrate having a metal surface. For example, a substrate 11 having a metal layer 10 on its surface is prepared (Figure 1(a)), and a photosensitive layer 12a made of a chemically amplified photosensitive composition is laminated on the metal layer 10 (Figure 1(b)).

[0019] (Substrate with a metal surface) The substrate 11 is not particularly limited and can be any conventionally known substrate, such as a substrate for electronic components. Silicon substrates, glass substrates, etc., can also be used as substrates. The metal species constituting the metal surface of the metal layer 10 is preferably copper, gold, or aluminum, with copper being more preferred. The metal species constituting the metal surface of the metal layer 10 may be different from the metal species constituting the metal wiring 13 formed in the plating process, but it is preferable that they be the same metal. By sputtering or otherwise applying a metal to the surface of the substrate 11, a substrate 11 can be manufactured in which a metal layer 10 is provided on the surface.

[0020] (Chemically amplified photosensitive composition) A chemically amplified photosensitive composition (hereinafter also referred to as the photosensitive composition) contains an acid generator (A) (hereinafter also referred to as acid generator (A)) that generates acid upon irradiation with active light or radiation. Acid generator (A) is F-SO2-N - -SO2-F, PF6 - The acid generator contains an acid that generates an acid comprising at least one anion selected from the group consisting of an anion represented by formula (ai) and an anion represented by formula (aii). The acid generator (A) is F-SO2-N - -SO2-F, PF6 - Preferably, the chemically amplified photosensitive composition consists only of an acid generator that generates an acid containing at least one anion selected from the group consisting of an anion represented by formula (ai) and an anion represented by formula (aii). That is, the chemically amplified photosensitive composition contains F-SO2-N as the acid generator. - -SO2-F, PF6 -Preferably, the acid generator contains only an acid that generates an acid comprising at least one anion selected from the group consisting of an anion represented by formula (ai) and an anion represented by formula (aii).

[0021] The chemically amplified photosensitive composition contains an acid generator (A) that is F-SO2-N - -SO2-F, PF6 - The composition can be the same as conventionally known chemically amplified photosensitive compositions, except that it contains an acid generator that generates an acid containing at least one anion selected from the group consisting of an anion represented by formula (ai) and an anion represented by formula (aii). The chemically amplified photosensitive composition may be a positive-type photosensitive composition whose solubility in the developer increases due to the action of acid generated by exposure, or a negative-type photosensitive composition whose solubility in the developer decreases due to the action of acid generated by exposure.

[0022] Positive-type chemically amplified photosensitive compositions include a photosensitive composition containing an acid generator (A) and a resin (B) which has alkali-soluble groups protected by the action of an acid, such as tert-butyl groups, tert-butoxycarbonyl groups, tetrahydropyranyl groups, acetal groups, and trimethylsilyl groups, and whose solubility in alkali increases with the action of an acid. Examples of negative-type chemically amplified photosensitive compositions include a photosensitive composition comprising an acid generator (A), a condensing agent such as methylolmelamine, and a resin that can be crosslinked by a condensing agent such as a novolac resin. When such a photosensitive composition is exposed to light, the photosensitive composition hardens due to a crosslinking reaction caused by the acid generated by the exposure. Furthermore, as a negative-type chemically amplified photosensitive composition, a photosensitive composition containing an epoxy compound along with an acid generator (A) is also preferred. When such a photosensitive composition is exposed to light, cationic polymerization of the epoxy compound proceeds due to the acid generated by the exposure, and as a result, the photosensitive composition hardens.

[0023] Among these chemically amplified photosensitive compositions, a chemically amplified positive photosensitive composition containing an acid generator (A) and a resin (B) whose solubility in alkali increases due to the action of an acid is preferred because it is particularly easy to achieve the desired level of high sensitivity, and it is easy to impart the desired properties to a patterned resist film by adjusting the type and ratio of constituent units of the resin (B) whose solubility in alkali increases due to the action of an acid.

[0024] The chemically amplified photosensitive composition may optionally contain components such as an alkali-soluble resin (D), a sulfur-containing compound (E), and an acid diffusion control agent (F).

[0025] The following describes a typical example of a chemically amplified positive-type photosensitive composition, which contains an acid generator (A) and a resin (B) whose solubility in alkali increases due to the action of the acid (hereinafter also referred to as resin (B)). The essential or optional components and the manufacturing method will be explained. Furthermore, the acid generator (A), alkali-soluble resin (D), sulfur-containing compound (E), and acid diffusion control agent (F) described below can also be applied to photosensitive compositions other than positive-type photosensitive compositions.

[0026] <Acid Generator (A)> Acid generator (A) is a compound that generates acid upon irradiation with active light or radiation, and is a compound that generates acid directly or indirectly upon exposure to light. Acid generator (A) is F-SO2-N - -SO2-F, PF6 - The present invention includes an acid generator that generates an acid containing at least one anion selected from the group consisting of an anion represented by the following formula (ai) and an anion represented by the following formula (aii).

[0027] [ka] (In formula (ai), R a01 is a halogen atom or alkyl group, n01 is an integer between 0 and 5, If n01 is an integer between 2 and 5, multiple R a01 These may be the same or different.

[0028] [ka] (In formula (aii), R a02 , R a03 , R a04 , and R a05 These are, independently, aromatic hydrocarbon groups that may have substituents.

[0029] In formula (ai), R a01 Examples of halogen atoms include chlorine, bromine, iodine, and fluorine atoms. a01 As the halogen atom, a fluorine atom is preferred. R a01 The number of carbon atoms in the alkyl group is preferably 1 to 18, more preferably 1 to 12, and even more preferably 1 to 8. Specific examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, isohexyl, n-octyl, 2-ethylhexyl, n-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl, n-octadecyl, and isooctadecyl.

[0030] In formula (ai), n01 is preferably an integer between 1 and 5.

[0031] In equation (ai), R a01 is a fluorine atom and n01 is 5, or R a01 Preferably, is an alkyl group having 1 to 8 carbon atoms and n01 is 1.

[0032] The following are specific examples of anions represented by formula (ai): [ka]

[0033] In formula (aii), R a02 , R a03 , R a04 , and R a05 The number of carbon atoms in the aromatic hydrocarbon group is preferably 6 to 20. Specific examples of aromatic hydrocarbon groups include phenyl group, α-naphthyl group, β-naphthyl group, biphenyl-4-yl group, biphenyl-3-yl group, biphenyl-2-yl group, anthryl group, and phenanthryl group.

[0034] R a02 , R a03 , R a04 , and R a05 When an aromatic hydrocarbon group has substituents, the number of substituents is not particularly limited and may be one or more than one. If there are multiple substituents, they may be the same or different. R a02 , R a03 , R a04 , and R a05 Examples of substituents that the aromatic hydrocarbon group may have include halogen atoms such as chlorine, bromine, iodine, and fluorine atoms, 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.

[0035] In equation (aii), R a02 , R a03 , R a04 , and R a05 However, it is preferable that the substituent is a phenyl group having a fluorine atom.

[0036] A concrete example of an anion represented by formula (aii) is: Tetrakis(4-nonafluorobiphenyl)boron anion, Tetrakis(1-heptafluoronaphthyl)boron anion, Tetrakis(pentafluorophenyl)boron anion, Tetrakis(3,4,5-trifluorophenyl)boron anion, Tetrakis(2-heptafluoronaphthyl)boron anion, Tetrakis(7-nonafluoroanthryl)boron anion, Tetrakis(9-nonafluorophenanthryl)boron anion, Examples include monophenyltris(pentafluorophenyl)boron anions, and more preferably the following anions. [ka]

[0037] Acid generator (A) contains F-SO2-N - -SO2-F, PF6 - An example of an acid generator that produces an acid containing at least one anion selected from the group consisting of an anion represented by formula (ai) and an anion represented by formula (aii) is an onium salt containing the anion as the anionic part. The cation portion in these onium salts is not particularly limited. Suitable cation portions include, for example, sulfonium cations and iodonium cations, with sulfonium cations being more preferred. It is preferable that the cation portion does not contain a fluorinated alkyl group.

[0038] As the sulfonium cation, a sulfonium cation having the structure represented by the following formula (a1) is preferred. [ka]

[0039] In the above formula (a1), R 1a , R 2a , R 3aAt least one of these represents a group represented by the following formula (a2), and the remainder represents a linear or branched alkyl group having 1 to 6 carbon atoms, a phenyl group which may have substituents, or a linear or branched alkoxy group having 1 to 6 carbon atoms. Alternatively, R 1a , R 2a , R 3a One of these is a group represented by the following formula (a2), and the remaining two are each independently linear or branched alkylene groups having 1 to 6 carbon atoms, and their ends may be bonded together to form a ring. R 1a , R 2a , R 3a Specific examples of linear 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 groups. R 1a , R 2a , R 3a Specific examples of linear or branched alkoxy groups having 1 to 6 carbon atoms include methoxy, ethoxy, n-propyloxy, isopropyloxy, n-butyloxy, isobutyloxy, sec-butyloxy, tert-butyloxy, n-pentyloxy, and n-hexyloxy groups. R 1a , R 2a , R 3a When is a phenyl group which may have substituents, preferred substituents include hydroxyl groups, linear or branched alkoxy groups having 1 to 6 carbon atoms, linear or branched alkyl groups having 1 to 6 carbon atoms, and the like.

[0040] [ka]

[0041] In the above formula (a2), R 4a , R 5aEach of these independently represents a hydroxyl group, a linear or branched alkoxy group having 1 to 6 carbon atoms, or a linear or branched alkyl group having 1 to 6 carbon atoms, and R 6a represents a linear or branched alkylene group having 1 to 6 carbon atoms, which may have single bonds or substituents. l and m each independently represent integers between 0 and 2, and l+m is 3 or less. However, R 4a If multiple instances exist, they may be the same or different from one another. Also, R 5a If multiple instances exist, they may be the same or different from one another. R 4a , and R 5a Specific examples of linear or branched alkoxy groups having 1 to 6 carbon atoms include methoxy, ethoxy, n-propyloxy, isopropyloxy, n-butyloxy, isobutyloxy, sec-butyloxy, tert-butyloxy, n-pentyloxy, and n-hexyloxy groups. R 4a , and R 5a Specific examples of linear 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 groups. R 6a Specific examples of linear or branched alkylene groups having 1 to 6 carbon atoms include the methylene group, ethane-1,2-diyl group (ethylene group), ethane-1,1-diyl group, propane-1,3-diyl group, propane-1,2-diyl group, propane-2,2-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, and hexane-1,6-diyl group.

[0042] The above R 1a , R 2a , R 3aOf the groups represented by formula (a2) above, the number is preferably one from the viewpoint of the stability of the compound, and the remainder are linear or branched alkylene groups having 1 to 6 carbon atoms, and their ends may be bonded to form a ring. In this case, the two alkylene groups, including the sulfur atom, constitute a 3 to 9-membered ring. The number of atoms (including the sulfur atom) constituting the ring is preferably 5 to 6.

[0043] Furthermore, examples of substituents that the alkylene group may have include an oxygen atom (in this case, forming a carbonyl group together with the carbon atoms constituting the alkylene group), a hydroxyl group, and the like.

[0044] Furthermore, examples of substituents that the phenyl group may have include hydroxyl groups, linear or branched alkoxy groups having 1 to 6 carbon atoms, and linear or branched alkyl groups having 1 to 6 carbon atoms.

[0045] Suitable sulfonium cations represented by formula (a1) include the sulfonium cation represented by the following formula. [ka]

[0046] As a sulfonium cation, a sulfonium cation having the structure represented by the following formula (a4) is also preferred. [ka]

[0047] In the above formula (a4), R 7a Each of these independently represents a group selected from the group consisting of a hydrogen atom, an alkyl group, a hydroxyl group, an alkoxy group, an alkylcarbonyl group, an alkylcarbonyloxy group, an alkyloxycarbonyl group, a halogen atom, an optionally substituted aryl group, and an arylcarbonyl group. In the above formula (a4), the three R 7aAmong them, at least one is an alkylcarbonyl group, and the rest are preferably hydrogen atoms. Examples of the alkylcarbonyl group include an acetyl group, a propionyl group, and a butyryl group. X 1a has a structure represented by the following formula (a5).

Chemical formula

[0048] In the above formula (a5), X 2a represents an alkylene group having 1 to 8 carbon atoms, an arylene group having 6 to 20 carbon atoms, or a divalent group of a heterocyclic compound having 8 to 20 carbon atoms, and X 2a may be substituted with at least one selected from the group consisting of an alkyl having 1 to 8 carbon atoms, an alkoxy having 1 to 8 carbon atoms, an aryl having 6 to 10 carbon atoms, hydroxy, cyano, and nitro groups. X 3a represents -O-, -S-, -SO-, -SO2-, -NH-, -NR 30a -, -CO-, -COO-, -CONH-, an alkylene group having 1 to 3 carbon atoms, or a phenylene group. h represents the number of repeating units of the structure in parentheses, and h represents an integer of 0 or more and 4 or less. h + 1 X 2a and h X 3a may be the same or different from each other. R 30a is an alkyl group having 1 to 5 carbon atoms or an aryl group having 6 to 10 carbon atoms.

[0049] 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-acetophenylthio)phenyl]diphenylsulfonium, and diphenyl[4-(p-terphenylthio)phenyl]diphenylsulfonium.

[0050] Suitable sulfonium cations represented by formula (a4) include the sulfonium cation represented by the following formula. [ka]

[0051] Examples of iodonium cations include iodonium cations with the structure represented by the following formula (a6). [ka]

[0052] In the above formula (a6), R 8a Each of these independently represents a group selected from the group consisting of a hydrogen atom, an alkyl group, a hydroxyl group, an alkoxy group, an alkylcarbonyl group, an alkylcarbonyloxy group, an alkyloxycarbonyl group, a halogen atom, an aryl group which may have a substituent, and an arylcarbonyl group.

[0053] As the Anion Club, F-SO2-N - -SO2-F, PF6 - Specific examples of onium salts containing at least one anion selected from the group consisting of the anion represented by formula (ai) and the anion represented by formula (aii) include the following compounds. [Chemistry]

[0054] [Chemistry]

[0055] [Chemistry]

[0056] An acid generator (A) containing an acid that generates at least one anion selected from the group consisting of F-SO2-N - -SO2-F, PF6 - , the anion represented by formula (ai), and the anion represented by formula (aii) may be a nonionic acid generator. The nonionic acid generator preferably does not contain a fluorinated alkyl group. Examples of the nonionic acid generator include imide sulfonate-based acid generators having a structure represented by >N-O-SO2- and oxime sulfonate-based acid generators having a structure represented by >C=N-O-SO2-. Examples of the imide sulfonate-based acid generator include acid generators having a naphthalimide skeleton (naphthalic acid imide structure) and acid generators having a phthalimide skeleton, and acid generators having a naphthalimide skeleton are preferred.

[0057] Examples of the acid generator having a naphthalimide skeleton include the compound represented by the following formula (a7). The compound represented by the following formula (a7) generates sulfonic acid containing the anion represented by formula (ai) upon irradiation with actinic rays or radiation. [Chemistry] (In formula (a7), R a01 and n01 are the same as R a01 and n01 in formula (ai), respectively, and R 23a ~R 28a are each independently a hydrogen atom or a monovalent organic group, and R23a and R 24a And, R 24a and R 25a And, R 25a and R 26a And, R 26a and R 27a or R 27a and R 28a These elements may be joined to each other to form a ring.

[0058] In equation (a7), R 23a ~R 28a R is a hydrogen atom or a monovalent organic group. 23a and R 24a And, R 24a and R 25a And, R 25a and R 26a And, R 26a and R 27a or R 27a and R 28a These elements may be joined to each other to form a ring. For example, R 25a and R 26a The acenaphthene skeleton may be formed by the bonding of these elements to form a five-membered ring together with the naphthalene ring.

[0059] Preferred monovalent organic groups include alicyclic hydrocarbon groups, heterocyclic groups (heterocyclyl groups), or alkyl or alkoxy groups having 4 to 18 carbon atoms, which may be branched; heterocyclyloxy groups; alicyclic hydrocarbon groups, heterocyclic groups (heterocyclyl groups), or alkylthio groups having 4 to 18 carbon atoms, which may be branched; and heterocyclylthio groups. Furthermore, groups in which a methylene group at any position not adjacent to the oxygen atom of the alkoxy group is substituted with -CO- are also preferred. Groups in which the alkoxy group is interrupted by an -O-CO- bond or an -O-CO-NH- bond are also preferred. Note that the left end of the -O-CO- bond and the -O-CO-NH- bond is closer to the naphthalic acid core in the alkoxy group. Furthermore, alicyclic hydrocarbon groups, heterocyclic groups, or alkylthio groups having 4 to 18 carbon atoms, which may have branches, are also included in R. 23a ~R 28aThis is preferable. A group in which a methylene group at any position not adjacent to the sulfur atom of the alkylthio group is substituted with -CO- is also preferred. Groups in which the alkylthio group is interrupted by an -O-CO- bond or an -O-CO-NH- bond are also preferred. Note that the left end of the -O-CO- bond and the -O-CO-NH- bond is closer to the naphthalic acid core in the alkylthio group.

[0060] R 23a ~R 28a For example, R 24a is an organic group, R 23a and R 25a ~R 28a Is R a hydrogen atom? 25a is an organic group, R 23a , R 24a and R 26a ~R 28a It is preferable that R is a hydrogen atom. 23a ~R 28a It is also possible that all of them are hydrogen atoms.

[0061] R 23a ~R 28a Examples of alkyl groups include n-butyl group, sec-butyl group, tert-butyl group, isobutyl group, n-pentyl group, isopentyl group, tert-pentyl group, n-hexyl group, n-heptyl group, isoheptyl group, tert-heptyl group, n-octyl group, isooctyl group, tert-octyl group, 2-ethylhexyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, and n-octadecyl group.

[0062] R 23a ~R 28aHowever, examples of alkoxy groups include n-butyloxy group, sec-butyloxy group, tert-butyloxy group, isobutyloxy group, n-pentyloxy group, isopentyloxy group, tert-pentyloxy group, n-hexyloxy group, n-heptyloxy group, isoheptyloxy group, tert-heptyloxy group, n-octyloxy group, isooctyloxy group, tert-octyloxy group, 2-ethylhexyl group, n-nonyloxy group, n-decyloxy group, n-undecyloxy group, n-dodecyloxy group, n-tridecyloxy group, n-tetradecyloxy group, n-pentadecyloxy group, n-hexadecyloxy group, n-heptadecyloxy group, and n-octadecyloxy group.

[0063] R 23a ~R 28a However, examples of alkylthio groups include n-butylthio group, sec-butylthio group, tert-butylthio group, isobutylthio group, n-pentylthio group, isopentylthio group, tert-pentylthio group, n-hexylthio group, n-heptylthio group, isoheptylthio group, tert-heptylthio group, n-octylthio group, isooctylthio group, tert-octylthio group, 2-ethylhexylthio group, n-nonylthio group, n-decylthio group, n-undecylthio group, n-dodecylthio group, n-tridecylthio group, n-tetradecylthio group, n-pentadecylthio group, n-hexadecylthio group, n-heptadecylthio group, and n-octadecylthio group.

[0064] R 23a ~R 28aWhen is an alkyl group, alkoxy group, or alkylthio group substituted with an alicyclic hydrocarbon group, examples of alicyclic hydrocarbons constituting the main skeleton of the alicyclic hydrocarbon group include cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclodecane, bicyclo[2.1.1]hexane, bicyclo[2.2.1]heptane, bicyclo[3.2.1]octane, bicyclo[2.2.2]octane, and adamantane. As the alicyclic hydrocarbon group, a group obtained by removing one hydrogen atom from these alicyclic hydrocarbons is preferred.

[0065] R 23a ~R 28a If is an alkyl group, alkoxy group, or alkylthio group substituted with a heterocyclic group, or R 23a ~R 28a When the group is a heterocyclyloxy group, examples of heterocyclic groups or heterocyclic rings that constitute the main skeleton of a heterocyclyloxy group include pyrrole, thiophene, furan, pyran, thiopyran, imidazole, pyrazole, thiazole, isothiazole, oxazole, isoxazole, pyridine, pyrazine, pyrimidine, pyridazine, pyrrolidine, pyrazolidine, imidazolidine, isoxazolidine, isothiazolidine, piperidine, piperazine, morpholine, thiomorpholine, chroman, thiochroman, isochroman, isothiochroman, indoline, isoindoline, and py Examples include lindin, indoridine, indole, indazole, purine, quinoridine, isoquinoline, quinoline, naphthyridine, phthalazine, quinoxaline, quinazoline, cinnoline, pteridine, acridine, perimidine, phenanthroline, carbazole, carborin, phenazine, antilysine, thiadiazole, oxadiazole, triazine, triazole, tetrazole, benzimidazole, benzoxazole, benzothiazole, benzothiadiazole, benzofloxane, naphthoimidazole, benzotriazole, and tetraazaidene. Furthermore, saturated heterocycles obtained by hydrogenating the ring having a conjugated bond among these heterocycles are also preferred. As heterocyclic groups substituted with alkyl groups, alkoxy groups, or alkylthio groups, or heterocyclic groups included in heterocyclyloxy groups, a group obtained by removing one hydrogen atom from the above-mentioned heterocyclic group is preferred.

[0066] R 23a ~R 28a However, examples of alkoxy groups containing alicyclic hydrocarbon groups include cyclopentyloxy group, methylcyclopentyloxy group, cyclohexyloxy group, fluorocyclohexyloxy group, chlorocyclohexyloxy group, cyclohexylmethyloxy group, methylcyclohexyloxy group, norbornyloxy group, ethylcyclohexyloxy group, cyclohexylethyloxy group, dimethylcyclohexyloxy group, methylcyclohexylmethyloxy group, norbornylmethyloxy group, trimethylcyclohexyloxy group, 1 Examples include -cyclohexylbutyloxy group, adamantyloxy group, menthyloxy group, n-butylcyclohexyloxy group, tert-butylcyclohexyloxy group, bornyloxy group, isobornyloxy group, decahydronaphthyloxy group, dicyclopentadienoxy group, 1-cyclohexylpentyloxy group, methyladamantyloxy group, adamantylmethyloxy group, 4-pentylcyclohexyloxy group, cyclohexylcyclohexyloxy group, adamantylethyloxy group, and dimethyladamantyloxy group.

[0067] R 23a ~R 28a However, examples of heterocyclyloxy groups include tetrahydrofuranyloxy, furfuryloxy, tetrahydrofurfuryloxy, tetrahydropyranyloxy, butyrolactonyloxy, and indolyloxy groups.

[0068] R 23a ~R 28a However, examples of alkylthio groups containing alicyclic hydrocarbon groups include cyclopentylthio, cyclohexylthio, cyclohexylmethylthio, norbornylthio, and isonorbornylthio.

[0069] R 23a ~R 28a However, examples of heterocyclylthio groups include the furfurylthio group and the tetrahydrofuranylthio group.

[0070] R 23a ~R 28a However, examples of groups in which a methylene group at any position not adjacent to the oxygen atom of the alkoxy group is substituted with -CO- include 2-ketobutyl-1-oxy group, 2-ketopentyl-1-oxy group, 2-ketohexyl-1-oxy group, 2-ketoheptyl-1-oxy group, 2-ketooctyl-1-oxy group, 3-ketobutyl-1-oxy group, 4-ketopentyl-1-oxy group, 5-ketohexyl-1-oxy group, 6-ketoheptyl-1-oxy group, 7-ketooctyl-1-oxy group, 3-methyl-2-ketopentane-4-oxy group, 2-ketopentane-4-oxy group, 2-methyl-2-ketopentane-4-oxy group, 3-ketoheptane-5-oxy group, and 2-adamantanone-5-oxy group.

[0071] R 23a ~R 28a However, examples of groups in which a methylene group at any position not adjacent to the sulfur atom of the alkylthio group is substituted with -CO- include 2-ketobutyl-1-thio group, 2-ketopentyl-1-thio group, 2-ketohexyl-1-thio group, 2-ketoheptyl-1-thio group, 2-ketooctyl-1-thio group, 3-ketobutyl-1-thio group, 4-ketopentyl-1-thio group, 5-ketohexyl-1-thio group, 6-ketoheptyl-1-thio group, 7-ketooctyl-1-thio group, 3-methyl-2-ketopentan-4-thio group, 2-ketopentan-4-thio group, 2-methyl-2-ketopentan-4-thio group, and 3-ketoheptan-5-thio group.

[0072] Specific examples of compounds represented by formula (a7) include the following: [ka]

[0073] Examples of oximesulfonate-based acid generators include compounds represented by the following formula (a8) and compounds represented by the following formula (a9). [ka] (In equations (a8) and (a9), R a01 n01 and n01 are R in equation (ai), respectively. a01 (And it is the same as n01.)

[0074] Specific examples of compounds represented by formula (a8) and formula (a9) include the following compounds. [ka]

[0075] The total content of the acid generator (A) is preferably 0.01% to 20% by mass, more preferably 0.03% to 10% by mass, and particularly preferably 0.05% to 8% by mass, based on the total solid content of the photosensitive composition. In this specification, solid content refers to components other than the organic solvent (S) and water.

[0076] <Resin (B)> The resin (B) whose solubility in alkali increases due to the action of an acid is not particularly limited, and any resin whose solubility in alkali increases due to the action of an acid can be used. Among these, it is preferable to contain at least one resin selected from the group consisting of novolac resin (B1), styrene resin (B2), and acrylic resin (B3). In novolac resin (B1), at least some of the phenolic hydroxyl groups are protected by acid-dissociation inhibitory groups. The styrene-based resin (B2) contains structural units derived from at least one selected from styrene, hydroxystyrene, and hydroxystyrene in which phenolic hydroxyl groups are protected by acid-dissociation inhibitory groups. For example, in the styrene-based resin (B2), at least some of the phenolic hydroxyl groups may be protected by acid-dissociation inhibitory groups. The styrene-based resin (B2) may also contain structural units derived from (meth)acrylate having acid-dissociable groups. Furthermore, the acrylic resin (B3) contains constituent units derived from (meth)acrylate having acid-dissociable groups. In this specification, resins corresponding to styrene-based resin (B2) do not correspond to acrylic resin (B3).

[0077] [Novolac resin (B1)] As the novolac resin (B1), a resin containing the constituent unit represented by the following formula (b-11) can be used.

[0078] [ka]

[0079] In the above formula (b-11), R 1b This exhibits an acid-dissociation-inhibiting group. A so-called acetal-type protecting group is preferred as the acid-dissociation-inhibiting group. 2b , R 3b Each of these independently represents either a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

[0080] The above R 1b The acid-dissociative dissolution inhibitory group represented by the formulas (b-12) and (b-13) below is preferably a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms, a vinyloxyethyl group, a tetrahydropyranyl group, a tetrahydrofuranyl group, or a trialkylsilyl group.

[0081] [ka]

[0082] In the above equations (b-12) and (b-13), R 4b , R 5b Each of these independently represents a hydrogen atom or a linear or branched alkyl group having 1 to 6 carbon atoms, and R 6b R represents a linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms. 7b represents a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms, and o represents 0 or 1.

[0083] Examples of the linear or branched alkyl groups mentioned above include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, isopentyl, and neopentyl groups. Examples of the cyclic alkyl groups mentioned above include cyclopentyl and cyclohexyl groups.

[0084] Here, examples of acid-dissociative dissolution inhibitory groups represented by formula (b-12) include 1-methoxyethyl group, 1-ethoxyethyl group, 1-n-propoxyethyl group, 1-isopropoxyethyl group, 1-n-butoxyethyl group, 1-isobutoxyethyl group, 1-tert-butoxyethyl group, 1-cyclohexyloxyethyl group, 1-methoxypropyl group, 1-ethoxypropyl group, 1-methoxy-1-methylethyl group, and 1-ethoxy-1-methylethyl group. Furthermore, examples of acid-dissociative dissolution inhibitory groups represented by formula (b-13) include tert-butoxycarbonyl group and tert-butoxycarbonylmethyl group. Additionally, examples of the trialkylsilyl group include trimethylsilyl group and tri-tert-butyldimethylsilyl group, where each alkyl group has 1 to 6 carbon atoms.

[0085] [Styrene resin (B2)] As the styrene-based resin (B2), a resin containing the constituent unit represented by the following formula (b4) can be used. The resin containing the constituent unit represented by the following formula (b4) is a resin in which at least some of the phenolic hydroxyl groups are protected by acid-dissociation-inhibiting groups.

[0086] [ka]

[0087] In the above formula (b4), R 8b R represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. 9b This represents an acid-dissociation-inhibiting group.

[0088] The alkyl groups having 1 to 6 carbon atoms mentioned above are, for example, linear, branched, or cyclic alkyl groups having 1 to 6 carbon atoms. Examples of linear or branched alkyl groups include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, isopentyl, and neopentyl groups, while examples of cyclic alkyl groups include cyclopentyl and cyclohexyl groups.

[0089] The above R 9b As the acid-dissociative dissolution inhibitory group represented by (b-12) and (b-13) above, the same acid-dissociative dissolution inhibitory group as exemplified above, or the tert-butyl group, cyclohexylethyl group, cyclopentylethyl group, cyclohexylpropyl group, cyclopentylpropyl group, etc. can be used.

[0090] Examples of styrene-based resins (B2) include resins containing structural units derived from at least one selected from styrene, hydroxystyrene, and hydroxystyrene in which a phenolic hydroxyl group is protected by an acid-dissociation-inhibiting group, and structural units derived from (meth)acrylate having an acid-dissociation group. The styrene-based resin (B2) may contain a structural unit represented by formula (b4) and a structural unit derived from (meth)acrylate having an acid-dissociable group. Constituent units derived from (meth)acrylates having acid-dissociable groups are, for example, the constituent units represented by formulas (b5) to (b7) described later.

[0091] Furthermore, styrene resins (B2) may contain other polymerizable compounds as constituent units for the purpose of appropriately controlling their physical and chemical properties. Examples of such polymerizable compounds include known radical polymerizable compounds and anionic polymerizable compounds. Other examples of such polymerizable compounds include monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid; dicarboxylic acids such as maleic acid, fumaric acid, and itaconic acid; methacrylic acid derivatives having carboxyl groups and ester bonds such as 2-methacryloyloxyethyl succinic acid, 2-methacryloyloxyethyl maleic acid, 2-methacryloyloxyethyl phthalic acid, and 2-methacryloyloxyethyl hexahydrophthalic acid; alkyl (meth)acrylate esters such as methyl (meth)acrylate, ethyl (meth)acrylate, and n-butyl (meth)acrylate; hydroxyalkyl (meth)acrylate esters such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate; Examples include aryl (meth)acrylates such as phenyl(meth)acrylate and benzyl(meth)acrylate; dicarboxylic acid diesters such as diethyl maleate and dibutyl fumarate; vinyl group-containing aromatic compounds such as styrene, α-methylstyrene, chlorostyrene, chloromethylstyrene, vinyltoluene, hydroxystyrene, α-methylhydroxystyrene, and α-ethylhydroxystyrene; vinyl group-containing aliphatic compounds such as vinyl acetate; conjugated diolefins such as butadiene and isoprene; polymerizable compounds containing nitrile groups such as acrylonitrile and methacrylonitrile; chlorine-containing polymerizable compounds such as vinyl chloride and vinylidene chloride; and polymerizable compounds containing amide bonds such as acrylamide and methacrylamide.

[0092] [Acrylic resin (B3)] The acrylic resin (B3) is not particularly limited as long as it contains constituent units derived from (meth)acrylate having acid-dissociable groups, and its solubility in alkali increases with the action of acid, and has been conventionally incorporated into various photosensitive compositions. The acrylic resin (B3) preferably contains, for example, a structural unit (b-3) derived from an acrylic acid ester containing an -SO2--containing cyclic group or a lactone-containing cyclic group. In this case, it is easier to form a patterned resist film having a preferred cross-sectional shape when forming a patterned resist film.

[0093] (-SO2-containing cyclic group) Here, "-SO2-containing cyclic group" refers to a cyclic group that contains a ring with -SO2- in its cyclic skeleton. Specifically, it refers to a cyclic group in which the sulfur atom (S) in -SO2- forms part of the cyclic skeleton. The ring containing -SO2- in its cyclic skeleton is counted as the first ring. If it consists only of this ring, it is called a monocyclic group. If it has other cyclic structures, it is called a polycyclic group regardless of those structures. A -SO2-containing cyclic group may be monocyclic or polycyclic.

[0094] The -SO2--containing cyclic group is preferably a cyclic group that contains -O-SO2- in its cyclic skeleton, that is, a cyclic group that contains a sultone ring in which the -OS- in -O-SO2- forms part of the cyclic skeleton.

[0095] The number of carbon atoms in the -SO2--containing cyclic group is preferably 3 to 30, more preferably 4 to 20, even more preferably 4 to 15, and particularly preferably 4 to 12. This number of carbon atoms refers to the number of carbon atoms constituting the cyclic skeleton and does not include the number of carbon atoms in substituents.

[0096] The -SO2-containing cyclic group may be an -SO2-containing aliphatic cyclic group or an -SO2-containing aromatic cyclic group. Preferably, it is an -SO2-containing aliphatic cyclic group.

[0097] Examples of -SO2--containing aliphatic cyclic groups include groups obtained by removing at least one hydrogen atom from an aliphatic hydrocarbon ring in which some of the carbon atoms constituting the ring skeleton are substituted with -SO2- or -O-SO2-. More specifically, examples include groups obtained by removing at least one hydrogen atom from an aliphatic hydrocarbon ring in which the -CH2- constituting the ring skeleton are substituted with -SO2-, and groups obtained by removing at least one hydrogen atom from an aliphatic hydrocarbon ring in which the -CH2-CH2- constituting the ring are substituted with -O-SO2-.

[0098] The number of carbon atoms in the alicyclic hydrocarbon ring is preferably 3 to 20, and more preferably 3 to 12. The alicyclic hydrocarbon ring may be polycyclic or monocyclic. As a monocyclic alicyclic hydrocarbon group, a group obtained by removing two hydrogen atoms from a monocycloalkane having 3 to 6 carbon atoms is preferred. Examples of such monocycloalkanes include cyclopentane and cyclohexane. As a polycyclic alicyclic hydrocarbon ring, a group obtained by removing two hydrogen atoms from a polycycloalkane having 7 to 12 carbon atoms is preferred. Specific examples of such polycycloalkanes include adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane.

[0099] The -SO2--containing cyclic group may have substituents. Examples of such substituents include alkyl groups, alkoxy groups, halogen atoms, alkyl halides, hydroxyl groups, oxygen atoms (=O), -COOR'', -OC(=O)R'', hydroxyalkyl groups, cyano groups, and the like.

[0100] The alkyl group used as the substituent is preferably an alkyl group having 1 to 6 carbon atoms. The alkyl group is preferably linear or branched. Specifically, examples include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, n-hexyl group, etc. Among these, the methyl group or ethyl group is preferred, and the methyl group is particularly preferred.

[0101] The alkoxy group used as the substituent is preferably an alkoxy group having 1 to 6 carbon atoms. The alkoxy group is preferably linear or branched. Specifically, this includes groups in which the alkyl group mentioned above as the alkyl substituent is bonded to an oxygen atom (-O-).

[0102] Examples of halogen atoms used as substituents include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms, with fluorine atoms being preferred.

[0103] Examples of halogenated alkyl groups of the substituent include groups in which some or all of the hydrogen atoms of the aforementioned alkyl group are substituted with the aforementioned halogen atoms.

[0104] Examples of halogenated alkyl groups as substituents include groups in which some or all of the hydrogen atoms of the alkyl group listed above as a substituent are substituted with the halogen atoms mentioned above. Fluorinated alkyl groups are preferred as halogenated alkyl groups, and perfluoroalkyl groups are particularly preferred.

[0105] In the aforementioned -COOR'' and -OC(=O)R'', R'' is either a hydrogen atom or a linear, branched, or cyclic alkyl group having 1 to 15 carbon atoms.

[0106] When R'' is a linear or branched alkyl group, the number of carbon atoms in the linear alkyl group is preferably 1 to 10, more preferably 1 to 5, and particularly preferably 1 or 2.

[0107] When “R” is a cyclic alkyl group, the number of carbon atoms of the cyclic alkyl group is preferably 3 or more and 15 or less, more preferably 4 or more and 12 or less, and particularly preferably 5 or more and 10 or less. Specifically, examples include a group obtained by removing one or more hydrogen atoms from a monocycloalkane, a bicycloalkane, a tricycloalkane, a tetracycloalkane, etc., which may or may not be substituted with a fluorine atom or a fluorinated alkyl group. More specifically, examples include a group obtained by removing one or more hydrogen atoms from a monocycloalkane such as cyclopentane and cyclohexane, and a polycycloalkane such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane.

[0108] As the hydroxyalkyl group as the substituent, a hydroxyalkyl group having 1 to 6 carbon atoms is preferable. Specifically, examples include a group in which at least one of the hydrogen atoms of the alkyl group mentioned as the alkyl group as the above-mentioned substituent is substituted with a hydroxyl group.

[0109] As the -SO2-containing cyclic group, more specifically, groups represented by the following formulas (3-1) to (3-4) can be mentioned.

Chemical formula

[0110] In the above formulas (3-1) to (3-4), A’ is an alkylene group having 1 to 5 carbon atoms which may contain an oxygen atom (-O-) or a sulfur atom (-S-), an oxygen atom, or a sulfur atom. As the alkylene group having 1 to 5 carbon atoms in A’, a linear or branched alkylene group is preferred, and examples thereof include a methylene group, an ethylene group, an n-propylene group, an isopropylene group, and the like.

[0111] When the alkylene group contains an oxygen atom or a sulfur atom, specific examples thereof include groups in which -O- or -S- is interposed between the terminal or carbon atoms of the aforementioned alkylene group, and examples thereof include -O-CH2-, -CH2-O-CH2-, -S-CH2-, -CH2-S-CH2-, and the like. As A’, an alkylene group having 1 to 5 carbon atoms or -O- is preferred, an alkylene group having 1 to 5 carbon atoms is more preferred, and a methylene group is most preferred.

[0112] z may be any of 0, 1, and 2, and 0 is most preferred. When z is 2, the plurality of Rs 10b may be the same or different from each other.

[0113] R 10b For the alkyl group, alkoxy group, halogenated alkyl group, -COOR”, -OC(=O)R”, and hydroxyalkyl group in R, the same ones as those described above for the alkyl group, alkoxy group, halogenated alkyl group, -COOR”, -OC(=O)R”, and hydroxyalkyl group which may be substituents possessed by the -SO2-containing cyclic group can be mentioned.

[0114] Specific cyclic groups represented by the above formulas (3-1) to (3-4) are exemplified below. In the formula, “Ac” represents an acetyl group.

[0115]

Chemical Formula

[0116] [ka]

[0117] As for the -SO2- containing cyclic group, among the above, the group represented by formula (3-1) is preferred, at least one selected from the group consisting of any of the above chemical formulas (3-1-1), (3-1-18), (3-3-1), and (3-4-1) is more preferred, and the group represented by chemical formula (3-1-1) is the most preferred.

[0118] (Lactone-containing cyclic group) A "lactone-containing cyclic group" refers to a cyclic group that contains a ring (lactone ring) containing -OC(=O)- within its cyclic skeleton. The lactone ring is counted as the first ring. If it consists only of a lactone ring, it is called a monocyclic group. If it also has other ring structures, it is called a polycyclic group regardless of those structures. A lactone-containing cyclic group may be a monocyclic group or a polycyclic group.

[0119] The lactone-containing cyclic group in the constituent unit (b-3) is not particularly limited and any group can be used. Specifically, as lactone-containing monocyclic groups, there are groups obtained by removing one hydrogen atom from a 4- to 6-membered ring lactone, such as a group obtained by removing one hydrogen atom from β-propionolactone, a group obtained by removing one hydrogen atom from γ-butyrolactone, and a group obtained by removing one hydrogen atom from δ-valerolactone. As lactone-containing polycyclic groups, there are groups obtained by removing one hydrogen atom from bicycloalkanes, tricycloalkanes, and tetracycloalkanes that have a lactone ring.

[0120] As for the constituent unit (b-3), the structure of the other parts is not particularly limited as long as it has an -SO2-containing cyclic group or a lactone-containing cyclic group, but it is preferable to select at least one constituent unit from the group consisting of a constituent unit derived from an acrylic acid ester in which the hydrogen atom bonded to the α-carbon may be substituted with a substituent and which contains an -SO2-containing cyclic group (b-3-S), and a constituent unit derived from an acrylic acid ester in which the hydrogen atom bonded to the α-carbon may be substituted with a substituent and which contains a lactone-containing cyclic group (b-3-L).

[0121] [Constituent unit (b-3-S)] More specifically, an example of a constituent unit (b-3-S) is the constituent unit represented by the following formula (b-S1).

[0122] [ka] (In the formula, R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms, R 11b R is a -SO2-containing cyclic group, 12b (This is a single bond or a divalent linking group.)

[0123] In equation (b-S1), R is the same as described above. R 11b This is similar to the -SO2--containing cyclic group mentioned above. R 12b This can be either a single bond or a divalent linking group.

[0124] R 12b The divalent linking group in this is not particularly limited, but suitable examples include divalent hydrocarbon groups which may have substituents, and divalent linking groups which contain heteroatoms.

[0125] • Divalent hydrocarbon group which may have substituents The hydrocarbon group as the divalent linking group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. The aliphatic hydrocarbon group means a hydrocarbon group having no aromaticity. The aliphatic hydrocarbon group may be saturated or unsaturated. Usually, a saturated hydrocarbon group is preferred. More specifically, examples of the aliphatic hydrocarbon group include a linear or branched aliphatic hydrocarbon group, an aliphatic hydrocarbon group containing a ring in its structure, and the like.

[0126] The number of carbon atoms of the linear or branched aliphatic hydrocarbon group is preferably 1 or more and 10 or less, more preferably 1 or more and 8 or less, and even more preferably 1 or more and 5 or less.

[0127] As the linear aliphatic hydrocarbon group, a linear alkylene group is preferred. Specifically, examples include a methylene group [-CH2-], an ethylene group [-(CH2)2-], a trimethylene group [-(CH2)3-], a tetramethylene group [-(CH2)4-], a pentamethylene group [-(CH2)5-], and the like.

[0128] As the 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)-, -C(CH2CH3)2-; alkylethylene groups such as -CH(CH3)CH2-, -CH(CH3)CH(CH3)-, -C(CH3)2CH2-, -CH(CH2CH3)CH2-, -C(CH2CH3)2-CH2-; alkyltrimethylene groups such as -CH(CH3)CH2CH2-, -CH2CH(CH3)CH2-; alkyltetramethylene groups such as -CH(CH3)CH2CH2CH2-, -CH2CH(CH3)CH2CH2-, and the like, i.e., alkylalkylene groups. The alkyl group in the alkylalkylene group is preferably a linear alkyl group having 1 or more and 5 or less carbon atoms.

[0129] The linear or branched aliphatic hydrocarbon groups described above may or may not have substituents (groups or atoms other than hydrogen atoms) that substitute for hydrogen atoms. Examples of such substituents include fluorine atoms, fluorinated alkyl groups having 1 to 5 carbon atoms substituted with fluorine atoms, and oxo groups (=O).

[0130] Examples of aliphatic hydrocarbon groups containing a ring in the above structure include cyclic aliphatic hydrocarbon groups that may contain substituents containing heteroatoms in the ring structure (groups with two hydrogen atoms removed from an aliphatic hydrocarbon ring), groups in which the cyclic aliphatic hydrocarbon group is bonded to the end of a linear or branched aliphatic hydrocarbon group, and groups in which the cyclic aliphatic hydrocarbon group is interposed in the middle of a linear or branched aliphatic hydrocarbon group. Examples of the linear or branched aliphatic hydrocarbon groups are the same as those described above.

[0131] The number of carbon atoms in the cyclic aliphatic hydrocarbon group is preferably 3 to 20, and more preferably 3 to 12.

[0132] The cyclic aliphatic hydrocarbon group may be polycyclic or monocyclic. A preferred monocyclic aliphatic hydrocarbon group is one obtained by removing two hydrogen atoms from a monocycloalkane. The monocycloalkane preferably has 3 to 6 carbon atoms. Examples include cyclopentane and cyclohexane. A preferred polycyclic aliphatic hydrocarbon group is one obtained by removing two hydrogen atoms from a polycycloalkane. The polycycloalkane preferably has 7 to 12 carbon atoms. Examples include adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane.

[0133] A cyclic aliphatic hydrocarbon group may or may not have substituents that substitute for a hydrogen atom (groups or atoms other than a hydrogen atom). Examples of such substituents include alkyl groups, alkoxy groups, halogen atoms, alkyl halides, hydroxyl groups, oxo groups (=O), and the like.

[0134] As the alkyl group used as the substituent, alkyl groups having 1 to 5 carbon atoms are preferred, and methyl, ethyl, propyl, n-butyl, and tert-butyl groups are more preferred.

[0135] As the alkoxy group used as the substituent, an alkoxy group having 1 to 5 carbon atoms is preferred, a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, and a tert-butoxy group are more preferred, and a methoxy group and an ethoxy group are particularly preferred.

[0136] Examples of halogen atoms used as substituents include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms, with fluorine atoms being preferred.

[0137] Examples of halogenated alkyl groups used as substituents include groups in which some or all of the hydrogen atoms of the aforementioned alkyl group are substituted with the halogen atoms mentioned above.

[0138] A cyclic aliphatic hydrocarbon group may have some of the carbon atoms constituting its ring structure substituted with -O- or -S-. Preferred substituents containing the heteroatom are -O-, -C(=O)-O-, -S-, -S(=O)2-, and -S(=O)2-O-.

[0139] The aromatic hydrocarbon group as a divalent hydrocarbon group is a divalent hydrocarbon group having at least one aromatic ring, and may have substituents. The aromatic ring is not particularly limited as long as it is a cyclic conjugated system having 4n+2 π electrons, and may be monocyclic or polycyclic. The number of carbon atoms in the aromatic ring is preferably 5 to 30, more preferably 5 to 20, even more preferably 6 to 15, and particularly preferably 6 to 12. However, this number of carbon atoms does not include the number of carbon atoms of substituents.

[0140] Specific examples of aromatic rings include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; and aromatic heterocycles in which some of the carbon atoms constituting the aromatic hydrocarbon ring are replaced by heteroatoms. Examples of heteroatoms in aromatic heterocycles include oxygen atoms, sulfur atoms, and nitrogen atoms. Specific examples of aromatic heterocycles include pyridine rings and thiophene rings.

[0141] Examples of aromatic hydrocarbon groups as divalent hydrocarbon groups include: a group obtained by removing two hydrogen atoms from the above-mentioned aromatic hydrocarbon ring or aromatic heterocycle (arylene group or heteroarylene group); a group obtained by removing two hydrogen atoms from an aromatic compound containing two or more aromatic rings (e.g., biphenyl, fluorene, etc.); a group obtained by removing one hydrogen atom from the above-mentioned aromatic hydrocarbon ring or aromatic heterocycle (aryl group or heteroaryl group) and having one of those hydrogen atoms replaced by an alkylene group (e.g., a group obtained by removing one more hydrogen atom from the aryl group in an arylalkyl group such as benzyl group, phenethyl group, 1-naphthylmethyl group, 2-naphthylmethyl group, 1-naphthylethyl group, 2-naphthylethyl group, etc.).

[0142] The number of carbon atoms in the alkylene group bonded to the aryl group or heteroaryl group is preferably 1 to 4, more preferably 1 to 2, and particularly preferably 1.

[0143] The above-mentioned aromatic hydrocarbon group may have its hydrogen atoms substituted with substituents. For example, the hydrogen atoms bonded to the aromatic ring in the aromatic hydrocarbon group may be substituted with substituents. Examples of such substituents include alkyl groups, alkoxy groups, halogen atoms, alkyl halides, hydroxyl groups, oxo groups (=O), and the like.

[0144] As the alkyl group used as the substituent, alkyl groups having 1 to 5 carbon atoms are preferred, and methyl, ethyl, n-propyl, n-butyl, and tert-butyl groups are more preferred.

[0145] As the alkoxy group used as the substituent, an alkoxy group having 1 to 5 carbon atoms is preferred, with methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, and tert-butoxy groups being preferred, and methoxy and ethoxy groups being more preferred.

[0146] Examples of halogen atoms used as substituents include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms, with fluorine atoms being preferred.

[0147] Examples of halogenated alkyl groups used as substituents include groups in which some or all of the hydrogen atoms of the aforementioned alkyl group are substituted with halogen atoms.

[0148] • Divalent linking group containing a heteroatom In a divalent linking group containing a heteroatom, the heteroatom is an atom other than carbon and hydrogen atoms, such as oxygen, nitrogen, sulfur, and halogen atoms.

[0149] 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 such divalent hydrocarbon groups include those similar to the divalent hydrocarbon groups that may have substituents as described above, and linear or branched aliphatic hydrocarbon groups are preferred.

[0150] Of the above, the H atoms in -C(=O)-NH-, -NH-, and -NH-C(=NH)- may each be substituted with substituents such as alkyl groups and 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.

[0151] R 12bIn particular, divalent linking groups in the above are linear or branched alkylene groups, cyclic aliphatic hydrocarbon groups, or divalent linking groups containing heteroatoms.

[0152] R 12b When the divalent linking group in is a linear or branched alkylene group, the number of carbon atoms in the alkylene group is preferably 1 to 10, more preferably 1 to 6, particularly preferably 1 to 4, and most preferably 1 to 3. Specifically, examples include the same linear alkylene group and branched alkylene group listed as linear or branched aliphatic hydrocarbon groups in the description of the "divalent hydrocarbon group which may have substituents" as a divalent linking group mentioned above.

[0153] R 12b In the case where the divalent linking group is a cyclic aliphatic hydrocarbon group, the cyclic aliphatic hydrocarbon group can be the same as the cyclic aliphatic hydrocarbon group listed as "an aliphatic hydrocarbon group containing a ring in its structure" in the description of "a divalent hydrocarbon group which may have substituents" as a divalent linking group mentioned above.

[0154] Particularly preferred cyclic aliphatic hydrocarbon groups are those obtained by removing two or more hydrogen atoms from cyclopentane, cyclohexane, norbornane, isobornane, adamantane, tricyclodecane, or tetracyclododecane.

[0155] R 12b If the divalent linking group in is a divalent linking group containing a heteroatom, preferred linking groups include -O-, -C(=O)-O-, -C(=O)-, -OC(=O)-O-, -C(=O)-NH-, -NH- (H may be substituted with substituents such as alkyl groups or acyl groups), -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- is represented by the base [wherein Y 1b , and Y 2b Each of these is a divalent hydrocarbon group which may have substituents independently, O is an oxygen atom, and m' is an integer between 0 and 3. Examples include [...].

[0156] R 12b In the case where the divalent linking group is -NH-, the hydrogen atoms in -NH- may be substituted with substituents such as alkyl groups or acyl groups. 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.

[0157] Formula-Y 1b -OY 2b -,-[Y 1b -C(=O)-O] m’ -Y 2b -, or -Y 1b -OC(=O)-Y 2b - Middle, Y 1b , and Y 2b These are, independently, divalent hydrocarbon groups which may have substituents. Examples of such divalent hydrocarbon groups are the same as the "divalent hydrocarbon groups which may have substituents" mentioned in the description of the divalent linking group above.

[0158] Y 1b Preferably, the group is a linear aliphatic hydrocarbon group, more preferably a linear alkylene group, even more preferably a linear alkylene group having 1 to 5 carbon atoms, and particularly preferably a methylene group or an ethylene group.

[0159] Y 2b Preferably, the group is a linear or branched aliphatic hydrocarbon group, more preferably a methylene group, an ethylene group, or an alkylmethylene group. The alkyl group in the alkylmethylene group is preferably a linear alkyl group having 1 to 5 carbon atoms, more preferably a linear alkyl group having 1 to 3 carbon atoms, and particularly preferably a methyl group.

[0160] Formula - [Y 1b-C(=O)-O] m’ -Y 2b In the base represented by -, m' is an integer between 0 and 3, preferably between 0 and 2, more preferably 0 or 1, and particularly preferably 1. That is, in the formula -[Y 1b -C(=O)-O] m’ -Y 2b As a base represented by -, formula -Y 1b -C(=O)-OY 2b Groups represented by - are particularly preferred. Among them, the group represented by formula -(CH2) a’ -C(=O)-O-(CH2) b’ A base represented by - is preferred. In the formula, a' is an integer between 1 and 10, preferably between 1 and 8, more preferably between 1 and 5, even more preferably 1 or 2, and most preferably 1. b' is an integer between 1 and 10, preferably between 1 and 8, more preferably between 1 and 5, even more preferably 1 or 2, and most preferably 1.

[0161] R 12b Regarding the divalent linking group in the above, as a divalent linking group containing a heteroatom, an organic group consisting of a combination of at least one non-hydrocarbon group and a divalent hydrocarbon group is preferred. In particular, a linear group having an oxygen atom as the heteroatom, such as a group containing an ether bond or an ester bond, is preferred, as described above for formula -Y 1b -OY 2b -,-[Y 1b -C(=O)-O] m’ -Y 2b -, or -Y 1b -OC(=O)-Y 2b A group represented by - is more preferred, and the aforementioned formula -[Y 1b -C(=O)-O] m’ -Y 2b -, or -Y 1b -OC(=O)-Y 2b A group represented by - is particularly preferred.

[0162] R 12b The divalent linking group in this is preferably an alkylene group or one containing an ester bond (-C(=O)-O-).

[0163] The alkylene group is preferably a linear or branched alkylene group. Preferred examples of the linear aliphatic hydrocarbon group include the methylene group [-CH2-], ethylene group [-(CH2)2-], trimethylene group [-(CH2)3-], tetramethylene group [-(CH2)4-], and pentamethylene group [-(CH2)5-]. Suitable examples of the branched alkylene group include alkylmethylene groups such as -CH(CH3)-, -CH(CH2CH3)-, -C(CH3)2-, -C(CH3)(CH2CH3)-, -C(CH3)(CH2CH2CH3)-, and -C(CH2CH3)2-; alkylethylene groups such as -CH(CH3)CH2-, -CH(CH3)CH(CH3)-, -C(CH3)2CH2-, -CH(CH2CH3)CH2-, and -C(CH2CH3)2-CH2-; alkyltrimethylene groups such as -CH(CH3)CH2CH2- and -CH2CH(CH3)CH2-; and alkylalkylene groups such as alkyltetramethylene groups such as -CH(CH3)CH2CH2CH2- and -CH2CH(CH3)CH2CH2-.

[0164] As a divalent linking group containing an ester bond, in particular, formula: -R 13b -C(=O)-O-[wherein, R 13b is a divalent linking group. A group represented by ] is preferred. That is, the constituent unit (b-3-S) is preferably a constituent unit represented by the following formula (b-S1-1).

[0165] [ka] (In the formula, R and R 11b The same applies to each of the above, and R 13b (This is a divalent linking group.)

[0166] R 13b This is not particularly limited; for example, the aforementioned R 12b Examples include divalent linking groups similar to those in [the relevant context]. R 13bThe divalent linking group is preferably a linear or branched alkylene group, an aliphatic hydrocarbon group containing a ring in its structure, or a divalent linking group containing a heteroatom, with linear or branched alkylene groups or divalent linking groups containing an oxygen atom as the heteroatom being particularly preferred.

[0167] As the linear alkylene group, a methylene group or an ethylene group is preferred, with a methylene group being particularly preferred. As the branched alkylene group, an alkylmethylene group or an alkylethylene group is preferred, with -CH(CH3)-, -C(CH3)2-, or -C(CH3)2CH2- being particularly preferred.

[0168] As for the divalent linking group containing an oxygen atom, a divalent linking group containing an ether bond or an ester bond is preferred, as mentioned above, -Y 1b -OY 2b -,-[Y 1b -C(=O)-O] m’ -Y 2b -, or -Y 1b -OC(=O)-Y 2b - is preferable. 1b , and Y 2b Each of these is independently a divalent hydrocarbon group which may have substituents, and m' is an integer between 0 and 3. In particular, -Y 1b -OC(=O)-Y 2b - is preferred, -(CH2) c -OC(=O)-(CH2) d A base represented by - is particularly preferred. c is an integer between 1 and 5, preferably 1 or 2. d is an integer between 1 and 5, preferably 1 or 2.

[0169] As for the constituent unit (b-3-S), the constituent unit represented by the following formula (b-S1-11) or (b-S1-12) is particularly preferred, and the constituent unit represented by formula (b-S1-12) is more preferred.

[0170] [ka] (In the formula, R, A', R 10b, z, and R 13b These are the same as described above.

[0171] In formula (b-S1-11), A' is preferably a methylene group, an oxygen atom (-O-), or a sulfur atom (-S-).

[0172] R 13b Preferably, the group is a linear or branched alkylene group, or a divalent linking group containing an oxygen atom. 13b Examples of linear or branched alkylene groups and divalent linking groups containing oxygen atoms in this context include those similar to the linear or branched alkylene groups and divalent linking groups containing oxygen atoms described above.

[0173] Of the constituent units represented by formula (b-S1-12), those represented by the following formulas (b-S1-12a) or (b-S1-12b) are particularly preferred.

[0174] [ka] (In the formula, R and A' are the same as described above, and c to e are each independent integers between 1 and 3.)

[0175] [Constituent unit (b-3-L)] An example of a constituent unit (b-3-L) is R in the aforementioned equation (b-S1). 11b Examples include those in which a lactone-containing cyclic group is substituted, and more specifically, examples include the constituent units represented by the following formulas (b-L1) to (b-L5).

[0176] [ka] (wherein R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms; R' is independently a hydrogen atom, an alkyl group, an alkoxy group, a halogenated alkyl group, a hydroxyl group, -COOR'', -OC(=O)R'', a hydroxyalkyl group, or a cyano group, and R'' is a hydrogen atom or an alkyl group; R 12b (where is a single bond or a divalent linking group, s'' is an integer between 0 and 2; A'' is an alkylene group with 1 to 5 carbon atoms, which may contain an oxygen atom or a sulfur atom; r is 0 or 1.)

[0177] The value of R in equations (b-L1) to (b-L5) is the same as described above. The alkyl groups, alkoxy groups, halogenated alkyl groups, -COOR'', -OC(=O)R'', and hydroxyalkyl groups in R' are the same as those previously mentioned for alkyl groups, alkoxy groups, halogenated alkyl groups, -COOR'', -OC(=O)R'', and hydroxyalkyl groups that may be present on the -SO2-containing cyclic group.

[0178] R' is preferably a hydrogen atom, considering factors such as its availability in industry. The alkyl group in R'' may be linear, branched, or cyclic. When R'' is a linear or branched alkyl group, it is preferable that it has 1 to 10 carbon atoms, and more preferably 1 to 5 carbon atoms. When R'' is a cyclic alkyl group, it is preferable that it has 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 polycycloalkanes such as monocycloalkanes, bicycloalkanes, tricycloalkanes, and tetracycloalkanes, which may or may not be substituted with a fluorine atom or a fluorinated alkyl group. Specifically, examples include groups obtained by removing one or more hydrogen atoms from monocycloalkanes such as cyclopentane and cyclohexane, and polycycloalkanes such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane. A'' is the same as A' in formula (3-1) described above. A'' is preferably an alkylene group having 1 to 5 carbon atoms, an oxygen atom (-O-), or a sulfur atom (-S-), and more preferably an alkylene group having 1 to 5 carbon atoms, or -O-. Among the alkylene groups having 1 to 5 carbon atoms, a methylene group or a dimethylmethylene group is more preferred, and a methylene group is most preferred.

[0179] R 12b This is R in the aforementioned equation (b-S1). 12b It is similar to that. In formula (b-L1), s'' is preferably 1 or 2. The following are specific examples of the constituent units represented by the aforementioned equations (b-L1) to (b-L3). In each of the following equations, R α This represents a hydrogen atom, a methyl group, or a trifluoromethyl group.

[0180] [ka]

[0181] [ka]

[0182] [ka]

[0183] The constituent unit (b-3-L) is preferably at least one selected from the group consisting of constituent units represented by the aforementioned formulas (b-L1) to (b-L5), more preferably at least one selected from the group consisting of constituent units represented by the aforementioned formulas (b-L1) to (b-L3), and particularly preferably at least one selected from the group consisting of constituent units represented by the aforementioned formulas (b-L1) or (b-L3). In particular, at least one selected from the group consisting of constituent units represented by the aforementioned formulas (b-L1-1), (b-L1-2), (b-L2-1), (b-L2-7), (b-L2-12), (b-L2-14), (b-L3-1), and (b-L3-5) is preferred.

[0184] Furthermore, as a constituent unit (b-3-L), a constituent unit represented by the following formulas (b-L6) to (b-L7) is also preferred. [ka] In formulas (b-L6) and (b-L7), R and R 12b This is the same as described above.

[0185] Furthermore, the acrylic resin (B3) may contain constituent units represented by the following formulas (b5) to (b7) that have acid-dissociable groups, as constituent units that enhance the solubility of the acrylic resin (B3) in alkali through the action of acid. The constituent units represented by the following formulas (b5) to (b7) are constituent units derived from (meth)acrylate that have acid-dissociable groups.

[0186] [ka]

[0187] In the above formulas (b5) to (b7), R 14b , and R 18b ~R 23bEach of these independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, a fluorine atom, or a linear or branched fluorinated alkyl group having 1 to 6 carbon atoms, R 15b ~R 17b Each independently represents a linear or branched alkyl group having 1 to 6 carbon atoms, a linear or branched fluorinated alkyl group having 1 to 6 carbon atoms, an aliphatic cyclic group having 5 to 20 carbon atoms, or an aromatic hydrocarbon group having 6 to 15 carbon atoms, R 16b and R 17b They may bond with each other to form a hydrocarbon ring with 5 to 20 carbon atoms, Y b represents an aliphatic cyclic group or alkyl group which may have substituents, p represents an integer between 0 and 4, and q represents 0 or 1.

[0188] Examples of the linear or branched alkyl groups mentioned above include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, isopentyl, and neopentyl groups. Furthermore, a fluorinated alkyl group is one in which some or all of the hydrogen atoms of the alkyl group mentioned above are substituted with fluorine atoms. Specific examples of aliphatic cyclic groups include groups obtained by removing one or more hydrogen atoms from polycycloalkanes such as monocycloalkanes, bicycloalkanes, tricycloalkanes, and tetracycloalkanes. Specifically, these include groups obtained by removing one hydrogen atom from monocycloalkanes such as cyclopentane, cyclohexane, cycloheptane, and cyclooctane, and polycycloalkanes such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane. In particular, groups obtained by removing one hydrogen atom from cyclohexane and adamantane (which may further have substituents) are preferred.

[0189] The above R 16b and R 17b If the above R does not bond to each other to form a hydrocarbon ring, 15b , R 16b , and R 17bAs such, it is preferable that the alkyl group has 2 to 4 carbon atoms and is linear or branched. 19b , R 20b , R 22b , R 23b Preferably, it is a hydrogen atom or a methyl group.

[0190] The above R 16b and R 17b These two components may form an aliphatic cyclic group with 5 to 20 carbon atoms together with the carbon atom to which they are bonded. Specific examples of such aliphatic cyclic groups include groups obtained by removing one or more hydrogen atoms from polycycloalkanes such as monocycloalkanes, bicycloalkanes, tricycloalkanes, and tetracycloalkanes. Specifically, these include groups obtained by removing one or more hydrogen atoms from monocycloalkanes such as cyclopentane, cyclohexane, cycloheptane, and cyclooctane, and polycycloalkanes such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane. In particular, groups obtained by removing one or more hydrogen atoms from cyclohexane and adamantane (which may further have substituents) are preferred.

[0191] Furthermore, the above R 16b and R 17b When the aliphatic cyclic group formed by has substituents on its cyclic skeleton, examples of such substituents include polar groups such as hydroxyl groups, carboxyl groups, cyano groups, and oxygen atoms (=O), as well as linear or branched alkyl groups having 1 to 4 carbon atoms. Among the polar groups, oxygen atoms (=O) are particularly preferred.

[0192] The above Y bThe group is an aliphatic cyclic group or an alkyl group, and examples include groups obtained by removing one or more hydrogen atoms from polycycloalkanes such as monocycloalkanes, bicycloalkanes, tricycloalkanes, and tetracycloalkanes. Specifically, examples include groups obtained by removing one or more hydrogen atoms from monocycloalkanes such as cyclopentane, cyclohexane, cycloheptane, and cyclooctane, and polycycloalkanes such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane. In particular, a group obtained by removing one or more hydrogen atoms from adamantane (which may further have substituents) is preferred.

[0193] Furthermore, the above Y b When the aliphatic cyclic group has substituents on its cyclic skeleton, examples of such substituents include polar groups such as hydroxyl groups, carboxyl groups, cyano groups, and oxygen atoms (=O), as well as linear or branched alkyl groups having 1 to 4 carbon atoms. Among the polar groups, oxygen atoms (=O) are particularly preferred.

[0194] Also, Y b If the alkyl group is an alkyl group, it is preferably a linear or branched alkyl group having 1 to 20 carbon atoms, more preferably 6 to 15 carbon atoms. Such alkyl groups are particularly preferably alkoxyalkyl groups, and examples of such alkoxyalkyl groups include 1-methoxyethyl group, 1-ethoxyethyl group, 1-n-propoxyethyl group, 1-isopropoxyethyl group, 1-n-butoxyethyl group, 1-isobutoxyethyl group, 1-tert-butoxyethyl group, 1-methoxypropyl group, 1-ethoxypropyl group, 1-methoxy-1-methylethyl group, and 1-ethoxy-1-methylethyl group.

[0195] Preferred specific examples of the constituent units represented by the above formula (b5) include those represented by the following formulas (b5-1) to (b5-33).

[0196] [ka]

[0197] In the above formulas (b5-1) to (b5-33), R 24b represents a hydrogen atom or a methyl group.

[0198] Preferred specific examples of the constituent units represented by the above formula (b6) include those represented by the following formulas (b6-1) to (b6-26).

[0199] [ka]

[0200] In the above equations (b6-1) to (b6-26), R 24b represents a hydrogen atom or a methyl group.

[0201] Preferred specific examples of the constituent units represented by the above formula (b7) include those represented by the following formulas (b7-1) to (b7-15).

[0202] [ka]

[0203] In the above formulas (b7-1) to (b7-15), R 24b represents a hydrogen atom or a methyl group.

[0204] Among the constituent units represented by equations (b5) to (b7) described above, the constituent unit represented by equation (b6) is preferred because it is easy to synthesize and relatively easy to achieve high sensitivity. Furthermore, among the constituent units represented by equation (b6), Y b A constituent unit in which R is an alkyl group is preferred. 19b and R 20b A preferred structural unit is one or both of which are alkyl groups.

[0205] Furthermore, it is preferable that the acrylic resin (B3) is a resin comprising a copolymer containing structural units derived from polymerizable compounds having ether bonds, along with the structural units represented by the above formulas (b5) to (b7).

[0206] Examples of polymerizable compounds having the above-mentioned ether linkage include radical polymerizable compounds such as (meth)acrylic acid derivatives having both ether and ester links. Specific examples include 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, methoxytriethylene glycol (meth)acrylate, 3-methoxybutyl (meth)acrylate, ethyl carbitol (meth)acrylate, phenoxypolyethylene glycol (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, methoxypolypropylene glycol (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, and (2-methyl-2-ethyl-1,3-dioxolan-4-yl)methyl (meth)acrylate. Furthermore, the polymerizable compounds having the above-mentioned ether linkage are preferably 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, and methoxytriethylene glycol (meth)acrylate. These polymerizable compounds may be used individually or in combination of two or more.

[0207] Furthermore, the acrylic resin (B3) may contain structural units derived from other polymerizable compounds in order to appropriately control its physical and chemical properties. Examples of such polymerizable compounds include known radical polymerizable compounds and anionic polymerizable compounds.

[0208] Examples of such polymerizable compounds include monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid; dicarboxylic acids such as maleic acid, fumaric acid, and itaconic acid; methacrylic acid derivatives having carboxyl groups and ester bonds, such as 2-methacryloyloxyethyl succinic acid, 2-methacryloyloxyethyl maleic acid, 2-methacryloyloxyethyl phthalic acid, and 2-methacryloyloxyethyl hexahydrophthalic acid; alkyl esters of (meth)acrylate such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, and cyclohexyl (meth)acrylate; and hydroxyalkyl esters of (meth)acrylate such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate. Examples include sters; aryl (meth)acrylates such as phenyl(meth)acrylate and benzyl(meth)acrylate; dicarboxylic acid diesters such as diethyl maleate and dibutyl fumarate; vinyl group-containing aromatic compounds such as styrene, α-methylstyrene, chlorostyrene, chloromethylstyrene, vinyltoluene, hydroxystyrene, α-methylhydroxystyrene, and α-ethylhydroxystyrene; vinyl group-containing aliphatic compounds such as vinyl acetate; conjugated diolefins such as butadiene and isoprene; polymerizable compounds containing nitrile groups such as acrylonitrile and methacrylonitrile; chlorine-containing polymerizable compounds such as vinyl chloride and vinylidene chloride; polymerizable compounds containing amide bonds such as acrylamide and methacrylamide; and so on.

[0209] As described above, the acrylic resin (B3) may contain constituent units derived from polymerizable compounds having a carboxyl group, such as the monocarboxylic acids and dicarboxylic acids mentioned above. The ratio of constituent units derived from polymerizable compounds having a carboxyl group in the acrylic resin (B3) is preferably 1% by mass or more and 20% by mass or less, and more preferably 5% by mass or more and 15% by mass or less.

[0210] Furthermore, polymerizable compounds include (meth)acrylic acid esters having acid-nondissociable aliphatic polycyclic groups, vinyl group-containing aromatic compounds, and the like. Among the acid-nondissociable aliphatic polycyclic groups, tricyclodecanyl, adamantyl, tetracyclododecanyl, isobornyl, and norbornyl groups are particularly preferred due to their industrial availability. These aliphatic polycyclic groups may have linear or branched alkyl groups with 1 to 5 carbon atoms as substituents.

[0211] Examples of (meth)acrylic acid esters having an acid-nondissociable aliphatic polycyclic group include those with the structures shown in the following formulas (b8-1) to (b8-5).

[0212] [ka]

[0213] In the above equations (b8-1) to (b8-5), R 25b represents a hydrogen atom or a methyl group.

[0214] When the acrylic resin (B3) contains a constituent unit (b-3) that includes a -SO2--containing cyclic group or a lactone-containing cyclic group, the content of the constituent unit (b-3) in the acrylic resin (B3) is preferably 5% by mass or more, more preferably 10% by mass or more, particularly preferably 10% by mass or more 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 an amount of the constituent unit (b-3) within the above range, it is easy to achieve both good developability and good pattern shape.

[0215] Furthermore, the acrylic resin (B3) preferably contains 5% by mass or more of the constituent units represented by the formulas (b5) to (b7) described above, more preferably 10% by mass or more, and particularly preferably 10% by mass or more and 50% by mass or less.

[0216] The acrylic resin (B3) preferably contains structural units derived from the polymerizable compound having the ether linkage described above. The content of structural units derived from the polymerizable compound having the ether linkage in the acrylic resin (B3) is preferably 1% by mass or more and 50% by mass or less, and more preferably 5% by mass or more and 40% by mass or less.

[0217] The acrylic resin (B3) preferably contains constituent units derived from (meth)acrylic acid esters having the above-mentioned acid-nondissociable aliphatic polycyclic groups. The content of constituent units derived from (meth)acrylic acid esters having the acid-nondissociable aliphatic polycyclic groups in the acrylic resin (B3) is preferably 0% by mass or more and 50% by mass or less, and more preferably 5% by mass or more and 30% by mass or less.

[0218] The polystyrene-equivalent mass-average molecular weight of resin (B) described above is preferably 10,000 to 600,000, more preferably 20,000 to 400,000, and even more preferably 30,000 to 300,000. By having such a mass-average molecular weight, sufficient strength of the photosensitive layer can be maintained without reducing the peelability from the substrate, and furthermore, blistering of the profile and the occurrence of cracks during plating can be prevented.

[0219] Furthermore, the degree of dispersion of resin (B) is preferably 1.05 or higher. Here, the degree of dispersion is the value obtained by dividing the mass-average molecular weight by the number-average molecular weight. By achieving such a degree of dispersion, it is possible to avoid problems such as the desired stress resistance to plating and the tendency of the metal wiring obtained by the plating process to swell.

[0220] The content of resin (B) is preferably 5% by mass or more and 99% by mass or less, relative to the total solid content of the photosensitive composition.

[0221] <Alkali-soluble resin (D)> The photosensitive composition may further contain an alkali-soluble resin (D) to improve alkali solubility. Here, an alkali-soluble resin is defined as a resin that dissolves at a thickness of 0.01 μm or more when a 1 μm thick resin film is formed on a substrate using a 20% by mass resin solution (solvent: propylene glycol monomethyl ether acetate) and immersed in a 2.38% by mass TMAH (tetramethylammonium hydroxide) aqueous solution for 1 minute, and does not fall under the aforementioned resin (B) component (typically, it refers to a resin whose alkali solubility does not substantially change even with the action of an acid). 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).

[0222] [Novolac resin (D1)] Novolac resins can be obtained, for example, by addition-condensation of aromatic compounds having phenolic hydroxyl groups (hereinafter simply referred to as "phenols") and aldehydes under acid catalyst conditions.

[0223] Examples of the above-mentioned phenols include phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, o-butylphenol, m-butylphenol, p-butylphenol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol, 2,3,5-trimethylphenol, 3,4,5-trimethylphenol, p-phenylphenol, resorcinol, hydroquinone, hydroquinone monomethyl ether, pyrogallol, phloroglycinol, hydroxydiphenyl, bisphenol A, salicylic acid, gallic acid, gallic acid ester, α-naphthol, β-naphthol, and the like. Examples of the above-mentioned aldehydes include formaldehyde, furfural, benzaldehyde, nitrobenzaldehyde, and acetaldehyde. The catalyst used in addition-condensation reactions is not particularly limited, but for example, acid catalysts such as hydrochloric acid, nitric acid, sulfuric acid, formic acid, oxalic acid, and acetic acid are used.

[0224] Furthermore, the flexibility of the novolac resin can be further improved by using o-cresol, substituting hydrogen atoms of hydroxyl groups in the resin with other substituents, or using bulky aldehydes.

[0225] The mass-average molecular weight of the novolac resin (D1) is not particularly limited as long as it does not hinder the objectives of the present invention, but it is preferably 1,000 or more and 50,000 or less.

[0226] [Polyhydroxystyrene resin (D2)] Examples of hydroxystyrene compounds that constitute polyhydroxystyrene resin (D2) include p-hydroxystyrene, α-methylhydroxystyrene, and α-ethylhydroxystyrene. Furthermore, the polyhydroxystyrene resin (D2) is preferably a copolymer with a styrene resin. Examples of styrene-based compounds that constitute such a styrene resin include styrene, chlorostyrene, chloromethylstyrene, vinyltoluene, and α-methylstyrene.

[0227] The mass-average molecular weight of the polyhydroxystyrene resin (D2) is not particularly limited as long as it does not hinder the objectives of the present invention, but it is preferably 1,000 or more and 50,000 or less.

[0228] [Acrylic resin (D3)] The acrylic resin (D3) preferably contains structural units derived from polymerizable compounds having ether bonds and structural units derived from polymerizable compounds having carboxyl groups.

[0229] Examples of polymerizable compounds having the above-mentioned ether linkage include (meth)acrylic acid derivatives having ether and ester links, such as 2-methoxyethyl (meth)acrylate, methoxytriethylene glycol (meth)acrylate, 3-methoxybutyl (meth)acrylate, ethyl carbitol (meth)acrylate, phenoxypolyethylene glycol (meth)acrylate, methoxypolypropylene glycol (meth)acrylate, and tetrahydrofurfuryl (meth)acrylate. Preferably, the polymerizable compounds having the above-mentioned ether linkage are 2-methoxyethyl acrylate and methoxytriethylene glycol acrylate. These polymerizable compounds may be used individually or in combination of two or more.

[0230] Examples of polymerizable compounds having the carboxyl group include monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid; dicarboxylic acids such as maleic acid, fumaric acid, and itaconic acid; and compounds having a carboxyl group and an ester bond, such as 2-methacryloyloxyethyl succinic acid, 2-methacryloyloxyethyl maleic acid, 2-methacryloyloxyethyl phthalic acid, and 2-methacryloyloxyethyl hexahydrophthalic acid. The polymerizable compounds having the carboxyl group are preferably acrylic acid and methacrylic acid. These polymerizable compounds may be used individually or in combination of two or more.

[0231] The mass-average molecular weight of the acrylic resin (D3) is not particularly limited as long as it does not hinder the objectives of the present invention, but it is preferably 50,000 or more and 800,000 or less.

[0232] The content of alkali-soluble resin (D) is preferably 0 to 80 parts by mass, and more preferably 5 to 70 parts by mass, when the total solid content of the photosensitive composition is 100 parts by mass.

[0233] <Sulfur-containing compounds (E)> The photosensitive composition preferably contains a sulfur-containing compound (E). The sulfur-containing compound (E) is, for example, a compound containing a sulfur atom capable of coordinating with a metal. In the case of a compound capable of producing two or more tautomers, if at least one tautomer contains a sulfur atom capable of coordinating with the metal constituting the surface of a metal substrate, then the compound is considered a sulfur-containing compound.

[0234] Preferred sulfur-containing compounds (E) include, for example, compounds containing a mercapto group (-SH), a thiocarboxyl group (-CO-SH), a dithiocarboxyl group (-CS-SH), or a thiocarbonyl group (-CS-). It is preferable for the sulfur-containing compound to have a mercapto group because it readily coordinates with metals and has excellent fitting suppression effects.

[0235] A preferred example of a sulfur-containing compound having a mercapto group is the compound represented by the following formula (e1). [ka] (In the formula, R e1 and R e2 Each independently represents a hydrogen atom or an alkyl group, R e3 R represents a single bond or an alkylene group. e4 (where 'u' indicates an aliphatic group with a u valence that may contain atoms other than carbon, and 'u' is an integer between 2 and 4.)

[0236] R e1 and R e2 If the alkyl group is an alkyl group, it may be linear or branched, but it is preferable that it be linear. e1 and R e2 When is an alkyl group, the number of carbon atoms in the alkyl group is not particularly limited as long as it does not hinder the objective of the present invention. The number of carbon atoms in the alkyl group is preferably 1 or more and 4 or less, particularly preferably 1 or 2, and most preferably 1. e1 and R e2In terms of combinations, it is preferable that one is a hydrogen atom and the other is an alkyl group, and it is particularly preferable that one is a hydrogen atom and the other is a methyl group.

[0237] R e3 If the alkylene group is an alkylene group, the alkylene group may be linear or branched, but it is preferable that it be linear. e3 When is an alkylene group, the number of carbon atoms in the alkylene group is not particularly limited as long as it does not hinder the objectives 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.

[0238] R e4 R is an aliphatic group with a valency of 2 to 4, which may contain atoms other than carbon. e4 Other atoms that may be included include nitrogen, oxygen, sulfur, fluorine, chlorine, bromine, and iodine atoms. e4 The structure of the aliphatic group may be linear, branched, cyclic, or a combination of these structures.

[0239] Among the compounds represented by formula (e1), the compound represented by the following formula (e2) is more preferred. [ka] (In formula (e2), R e4 And u are equivalent to equation (e1).

[0240] Among the compounds represented by the above formula (e2), the following compounds are preferred. [ka]

[0241] Compounds represented by the following formulas (e3-L1) to (e3-L7) are also preferred examples of sulfur-containing compounds having a mercapto group. [ka] (In equations (e3-L1) to (e3-L7), R', s'', A'', and r are the same as those in equations (b-L1) to (b-L7) described above for acrylic resin (B3).)

[0242] The following compounds are suitable examples of mercapto compounds represented by the above formulas (e3-L1) to (e3-L7). [ka]

[0243] Compounds represented by the following formulas (e3-1) to (e3-4) are also preferred examples of sulfur-containing compounds having a mercapto group. [ka] (The definitions of the abbreviations in formulas (e3-1) to (e3-4) are as previously described for acrylic resin (B3) and for formulas (3-1) to (3-4).)

[0244] The following compounds are suitable examples of mercapto compounds represented by the above formulas (e3-1) to (e3-4).

[0245] [ka]

[0246] Furthermore, a suitable example of a compound having a mercapto group is the compound represented by the following formula (e4). [ka] (In equation (e4), R e5is a group selected from the group consisting of a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an alkylthio group having 1 to 4 carbon atoms, a hydroxyalkyl group having 1 to 4 carbon atoms, a mercaptoalkyl group having 1 to 4 carbon atoms, a halogenated alkyl group having 1 to 4 carbon atoms, and a halogen atom, where n1 is an integer between 0 and 3, n0 is an integer between 0 and 3, and when n1 is 2 or 3, R e5 They may be the same or different.

[0247] R e5 Specific examples of alkyl groups that may have a hydroxyl group with 1 to 4 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and tert-butyl groups. Among these alkyl groups, methyl, hydroxymethyl, and ethyl groups are preferred.

[0248] R e5 Specific examples of cases where the alkoxy group has 1 to 4 carbon atoms include methoxy, ethoxy, n-propyloxy, isopropyloxy, n-butyloxy, isobutyloxy, sec-butyloxy, and tert-butyloxy groups. Among these alkoxy groups, methoxy and ethoxy groups are preferred, with methoxy groups being more preferred.

[0249] R e5 Specific examples of alkylthio groups having 1 to 4 carbon atoms include methylthio group, ethylthio group, n-propylthio group, isopropylthio group, n-butylthio group, isobutylthio group, sec-butylthio group, and tert-butylthio group. Among these alkylthio groups, methylthio group and ethylthio group are preferred, with methylthio group being more preferred.

[0250] R e5Specific examples of hydroxyalkyl groups having 1 to 4 carbon atoms include hydroxymethyl, 2-hydroxyethyl, 1-hydroxyethyl, 3-hydroxy-n-propyl, and 4-hydroxy-n-butyl groups. Among these hydroxyalkyl groups, hydroxymethyl, 2-hydroxyethyl, and 1-hydroxyethyl groups are preferred, with hydroxymethyl being more preferred.

[0251] R e5 Specific examples of mercaptoalkyl groups having 1 to 4 carbon atoms include mercaptomethyl, 2-mercaptoethyl, 1-mercaptoethyl, 3-mercapto-n-propyl, and 4-mercapto-n-butyl groups. Among these mercaptoalkyl groups, mercaptomethyl, 2-mercaptoethyl, and 1-mercaptoethyl groups are preferred, with mercaptomethyl being more preferred.

[0252] R e5 When is a halogenated alkyl group having 1 to 4 carbon atoms, examples of halogen atoms included in the halogenated alkyl group include fluorine, chlorine, bromine, iodine, etc. e5Specific examples of halogenated alkyl groups having 1 to 4 carbon atoms include chloromethyl, bromomethyl, iodomethyl, fluoromethyl, dichloromethyl, dibromomethyl, difluoromethyl, trichloromethyl, tribromomethyl, trifluoromethyl, 2-chloroethyl, 2-bromoethyl, 2-fluoroethyl, 1,2-dichloroethyl, 2,2-difluoroethyl, 1-chloro-2-fluoroethyl, 3-chloro-n-propyl, 3-bromo-n-propyl, 3-fluoro-n-propyl, and 4-chloro-n-butyl. Among these halogenated alkyl groups, chloromethyl, bromomethyl, iodomethyl, fluoromethyl, dichloromethyl, dibromomethyl, difluoromethyl, trichloromethyl, tribromomethyl, and trifluoromethyl are preferred, and chloromethyl, dichloromethyl, trichloromethyl, and trifluoromethyl are more preferred.

[0253] R e5 Specific examples of halogen atoms include fluorine, chlorine, bromine, or iodine.

[0254] In equation (e4), n1 is an integer between 0 and 3, and 1 is more preferred. If n1 is 2 or 3, multiple R e5 They may be the same or different.

[0255] In the compound represented by formula (e4), R on the benzene ring e5 The substitution position is not particularly limited. e5 The substitution position is -(CH2) n0 -The bond site is preferably in the meta or para position relative to the SH bond.

[0256] As for compounds represented by formula (e4), R e5 Preferably, the compound has at least one group selected from the group consisting of alkyl groups, hydroxyalkyl groups, and mercaptoalkyl groups, R e5A compound having one group selected from the group consisting of alkyl groups, hydroxyalkyl groups, and mercaptoalkyl groups is more preferred. A compound represented by formula (e4) is R e5 If it has one group selected from the group consisting of alkyl groups, hydroxyalkyl groups, and mercaptoalkyl groups, the substitution position of the alkyl group, hydroxyalkyl group, or mercaptoalkyl group on the benzene ring is -(CH2) n0 -The bond is preferably in the meta or para position relative to the SH bond, and more preferably in the para position.

[0257] In formula (e4), n0 is an integer between 0 and 3, inclusive. It is preferable that n0 be 0 or 1, and more preferably 0, because of the ease of compound preparation and availability.

[0258] Specific examples of compounds represented by formula (e4) include p-mercaptophenol, p-thiocresol, m-thiocresol, 4-(methylthio)benzenethiol, 4-methoxybenzenethiol, 3-methoxybenzenethiol, 4-ethoxybenzenethiol, 4-isopropyloxybenzenethiol, 4-tert-butoxybenzenethiol, 3,4-dimethoxybenzenethiol, 3,4,5-trimethoxybenzenethiol, 4-ethylbenzenethiol, 4-isopropylbenzenethiol, 4-n-butylbenzenethiol, 4 -tert-butylbenzenethiol, 3-ethylbenzenethiol, 3-isopropylbenzenethiol, 3-n-butylbenzenethiol, 3-tert-butylbenzenethiol, 3,5-dimethylbenzenethiol, 3,4-dimethylbenzenethiol, 3-tert-butyl-4-methylbenzenethiol, 3-tert-4-methylbenzenethiol, 3-tert-butyl-5-methylbenzenethiol, 4-tert-butyl-3-methylbenzenethiol, 4-mercaptobenzyl alcohol, 3-mercaptobenzyl alcohol L, 4-(mercaptomethyl)phenol, 3-(mercaptomethyl)phenol, 1,4-di(mercaptomethyl)phenol, 1,3-di(mercaptomethyl)phenol, 4-fluorobenzenethiol, 3-fluorobenzenethiol, 4-chlorobenzenethiol, 3-chlorobenzenethiol, 4-bromobenzenethiol, 4-iodobenzenethiol, 3-bromobenzenethiol, 3,4-dichlorobenzenethiol, 3,5-dichlorobenzenethiol, 3,4-difluorobenzenethiol, 3,5-difluorobenzene Examples include thiols, 4-mercaptocatechol, 2,6-di-tert-butyl-4-mercaptophenol, 3,5-di-tert-butyl-4-methoxybenzenethiol, 4-bromo-3-methylbenzenethiol, 4-(trifluoromethyl)benzenethiol, 3-(trifluoromethyl)benzenethiol, 3,5-bis(trifluoromethyl)benzenethiol, 4-methylthiobenzenethiol, 4-ethylthiobenzenethiol, 4-n-butylthiobenzenethiol, and 4-tert-butylthiobenzenethiol.

[0259] Furthermore, sulfur-containing compounds having a mercapto group include compounds containing nitrogen-containing aromatic heterocycles substituted with a mercapto group, and tautomers of compounds containing nitrogen-containing aromatic heterocycles substituted with a mercapto group. Suitable specific 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, cinnoline, phthalazine, quinazoline, quinoxaline, and 1,8-naphthyridine.

[0260] Suitable examples of nitrogen-containing heterocyclic compounds suitable as sulfur-containing compounds, and tautomers of nitrogen-containing heterocyclic compounds, include the following compounds. [ka]

[0261] If the photosensitive composition contains a sulfur-containing compound (E), the amount used is preferably 0.01 parts by mass or more and 5 parts by mass or less, more preferably 0.02 parts by mass or more and 3 parts by mass or less, and particularly preferably 0.05 parts by mass or more and 2 parts by mass or less, based on 100 parts by mass of the total mass of the resin (B) and alkali-soluble resin (D).

[0262] <Acid diffusion control agent (F)> The photosensitive composition may contain an acid diffusion control agent (F). Examples of the acid diffusion control agent (F) include nitrogen-containing compounds (F1), and optionally, an organic carboxylic acid, or a phosphorus oxoacid or derivative thereof (F2) may be included.

[0263] [Nitrogen-containing compounds (F1)] Examples of nitrogen-containing compounds (F1) include trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, tri-n-pentylamine, trybenzylamine, diethanolamine, triethanolamine, n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, ethylenediamine, N,N,N',N'-tetramethylethylenediamine, tetramethylenediamine, hexamethylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 4,4'-diaminobenzophenone, 4,4'-diaminodiphenylamine, formamide, N-methylformamide, N,N- Examples include dimethylformamide, acetamide, N-methylacetamide, N,N-dimethylacetamide, propionamide, benzamide, pyrrolidone, N-methylpyrrolidone, methylurea, 1,1-dimethylurea, 1,3-dimethylurea, 1,1,3,3-tetramethylurea, 1,3-diphenylurea, imidazole, benzimidazole, 4-methylimidazole, 8-oxyquinoline, acridine, purine, pyrrolidine, piperidine, 2,4,6-tri(2-pyridyl)-S-triazine, morpholine, 4-methylmorpholine, piperazine, 1,4-dimethylpiperazine, 1,4-diazabicyclo[2.2.2]octane, and pyridine. These may be used individually or in combination of two or more.

[0264] In addition, commercially available hindered amine compounds such as ADEKA LA-52, ADEKA LA-57, ADEKA LA-63P, ADEKA LA-68, ADEKA LA-72, ADEKA LA-77Y, ADEKA LA-77G, ADEKA LA-81, ADEKA LA-82, and ADEKA LA-87 (all manufactured by ADEKA Corporation), as well as 4-hydroxy-1,2,2,6,6-pentamethylpiperidine derivatives, and pyridines in which the 2,6-position is substituted with substituents such as hydrocarbon groups, such as 2,6-diphenylpyridine and 2,6-di-tert-butylpyridine, can also be used as nitrogen-containing compounds (F1).

[0265] The nitrogen-containing compound (F1) is typically used in an amount of 0 to 5 parts by mass, and is particularly preferably used in an amount of 0 to 3 parts by mass, relative to 100 parts by mass of the total mass of the resin (B) and the alkali-soluble resin (D) described below.

[0266] [Organic carboxylic acids, or phosphorus oxoacids or their derivatives (F2)] Among organic carboxylic acids, or phosphorus oxoacids or their derivatives (F2), suitable organic carboxylic acids include malonic acid, citric acid, malic acid, succinic acid, benzoic acid, salicylic acid, and others, with salicylic acid being particularly preferred.

[0267] Examples of phosphorus oxoacids or derivatives thereof include phosphoric acid, di-n-butyl phosphate, diphenyl phosphate, and other phosphoric acid derivatives and their esters; phosphonic acid and its ester derivatives such as phosphonic acid, dimethyl phosphonate, di-n-butyl phosphonate, phenylphosphonic acid, diphenyl phosphonate, and dibenzyl phosphonate; and phosphinic acid and its ester derivatives such as phosphinic acid and phenylphosphinic acid. Among these, phosphonic acid is particularly preferred. These may be used individually or in combination of two or more.

[0268] The organic carboxylic acid, or phosphorus oxoacid or derivative thereof (F2), is usually used in an amount of 0 to 5 parts by mass, and is particularly preferably used in an amount of 0 to 3 parts by mass, based on 100 parts by mass of the total mass of the above resin (B) and the alkali-soluble resin (D) described below.

[0269] Furthermore, in order to stabilize the compound by forming a salt, it is preferable to use an amount of organic carboxylic acid, or phosphorus oxoacid or its derivative (F2) equivalent to that of the nitrogen-containing compound (F1).

[0270] <Organic solvent (S)> The photosensitive composition may contain an organic solvent (S). Various organic solvents that have been conventionally added to various photosensitive compositions can be used as the organic solvent (S).

[0271] Specific examples of organic solvents (S) include ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl isoamyl ketone, and 2-heptanone; glycols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,3-butylene glycol, and hexylene glycol; polyols such as glycerin; polyacetates of polyols such as glycerin triacetate (triacetin); monools such as benzyl alcohol and terpineol; and ethylene glycol. Glycol monoacetates such as ethylene glycol monoacetate, diethylene glycol monoacetate, triethylene glycol monoacetate, propylene glycol monoacetate, dipropylene glycol monoacetate, tripropylene glycol monoacetate, and 1,3-butylene glycol monoacetate; ethylene glycol diacetate, diethylene glycol diacetate, triethylene glycol diacetate, propylene glycol diacetate, dipropylene glycol diacetate, tripropylene glycol diacetate, and 1,Diacetates of glycols such as 3-butylene glycol diacetate; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monophenyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monophenyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monopropyl ether, triethylene glycol monobutyl ether, triethylene glycol monophenyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether , propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol monophenyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monophenyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, tripropylene glycol monopropyl ether, tripropylene glycol monobutyl ether, tripropylene glycol monophenyl ether, 1,3-butylene glycol monomethyl ether, 1,3-butylene glycol monoethyl ether, 1,3-butylene glycol monopropyl ether, 1,3-butylene glycol monobutyl ether, and 1,Monoethers of glycols such as 3-butylene glycol monophenyl ether; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monophenyl ether acetate, triethylene glycol monomethyl ether acetate, triethylene glycol monoethyl ether acetate, triethylene glycol monopropyl ether acetate, triethylene glycol monobutyl ether acetate, triethylene glycol monophenyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene 1,3-Butylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, propylene glycol monophenyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol monopropyl ether acetate, dipropylene glycol monobutyl ether acetate, dipropylene glycol monophenyl ether acetate, tripropylene glycol monomethyl ether acetate, tripropylene glycol monoethyl ether acetate, tripropylene glycol monopropyl ether acetate, tripropylene glycol monobutyl ether acetate, tripropylene glycol monophenyl ether acetate, 1,3-Butylene glycol monomethyl ether acetate (3-methoxybutyl acetate), 1,3-Butylene glycol monoethyl ether acetate, 1,3-Butylene glycol monopropyl ether acetate, 1,3-Butylene glycol monobutyl ether acetate, 1,Monoether acetates of glycols such as 3-butylene glycol monophenyl ether acetate, 3-methyl-3-methoxybutyl acetate, 3-ethyl-3-methoxybutyl acetate, 2-methoxypentyl acetate, 3-methoxypentyl acetate, 4-methoxypentyl acetate, 2-methyl-3-methoxypentyl acetate, 3-methyl-3-methoxypentyl acetate, 3-methyl-4-methoxypentyl acetate, and 4-methyl-4-methoxypentyl acetate; ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether, ethylene glycol dibutyl ether, ethylene glycol diphenyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, diethylene glycol diphenyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, tri Ethylene glycol dipropyl ether, triethylene glycol dibutyl ether, triethylene glycol diphenyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether, propylene glycol dibutyl ether, propylene glycol diphenyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol dipropyl ether, dipropylene glycol dibutyl ether, dipropylene glycol diphenyl ether, tripropylene glycol dimethyl ether, tripropylene glycol diethyl ether, tripropylene glycol dipropyl ether, tripropylene glycol dibutyl ether, tripropylene glycol diphenyl ether, 1,3-butylene glycol dimethyl ether, 1,3-butylene glycol diethyl ether, 1,3-butylene glycol dipropyl ether, 1,3-butylene glycol dibutyl ether, and 1,Examples include diethers of glycols such as 3-butylene glycol diphenyl ether; ethers such as dioxane and dihexyl ether; esters such as ethyl formate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, benzyl acetate, ethyl benzoate, methyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl pyruvate, ethyl ethoxyacetate, methyl methoxypropionate, ethyl ethoxypropionate, methyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, methyl 2-hydroxy-3-methylbutanoate, diethyl maleate, cyclohexanol acetate, gamma-butyrolactone, etc. These may be used individually or in combination of two or more.

[0272] The content of the organic solvent (S) is not particularly limited as long as it does not hinder the objective of the present invention. When the photosensitive composition is used in thick film applications such as when the thickness of the photosensitive layer obtained by a spin coating method is 5 μm or more, it is preferable to use the organic solvent (S) in a range such that the solid content concentration of the photosensitive composition is 20% by mass or more and 70% by mass or less.

[0273] <Other ingredients> The photosensitive composition may or may not contain a Lewis acid compound. Including a Lewis acid compound in the photosensitive composition makes it easier to obtain a highly sensitive photosensitive composition.

[0274] Here, a Lewis acid compound is defined as "a compound that acts as an electron pair acceptor, possessing an empty orbital capable of accepting at least one electron pair." Lewis acid compounds are not particularly limited as long as they meet the above definition and are recognized as Lewis acid compounds by those skilled in the art. Preferably, Lewis acid compounds are those that do not fall under the category of Brønsted acids (protic acids). Specific examples of Lewis acid compounds include boron fluoride, ether complexes of boron fluoride (e.g., BF3·Et2O, BF3·Me2O, BF3·THF, etc., where Et is an ethyl group, Me is a methyl group, and THF is tetrahydrofuran), organoboron compounds (e.g., tri-n-octyl borate, tri-n-butyl borate, triphenyl borate, and triphenylboron, etc.), titanium chloride, aluminum chloride, aluminum bromide, and gallium chloride. Examples include um, gallium bromide, indium chloride, thallium trifluoroacetate, tin chloride, zinc chloride, zinc bromide, zinc iodide, zinc trifluoromethanesulfonate, zinc acetate, zinc nitrate, zinc tetrafluoroborate, manganese chloride, manganese bromide, nickel chloride, nickel bromide, nickel cyanide, nickel acetylacetonate, cadmium chloride, cadmium bromide, stannous chloride, stannous bromide, stannous sulfate, and stannous tartrate.

[0275] When the photosensitive composition contains a Lewis acid compound, the Lewis acid compound is preferably used in an amount of 0.01 parts by mass or more and 5 parts by mass or less, and more preferably in an amount of 0.01 parts by mass or more and 3 parts by mass or less, based on 100 parts by mass of the total mass of the resin (B) and the alkali-soluble resin (D).

[0276] Furthermore, the photosensitive composition may contain polyvinyl resin to improve its plasticity. Specific examples of polyvinyl resin include polyvinyl chloride, polystyrene, polyhydroxystyrene, polyvinyl acetate, polyvinyl benzoic acid, polyvinyl methyl ether, polyvinyl ethyl ether, polyvinyl alcohol, polyvinylpyrrolidone, polyvinylphenol, and copolymers thereof. Polyvinyl methyl ether is preferred as the polyvinyl resin due to its low glass transition temperature.

[0277] Furthermore, the photosensitive composition may contain an adhesive aid to improve the adhesion between the patterned resist film, such as a mold formed using the photosensitive composition, and the substrate.

[0278] Furthermore, the photosensitive composition may contain surfactants to improve its applicability, defoaming properties, leveling properties, etc. For example, fluorine-based surfactants and silicone-based surfactants are preferably used as surfactants. Specific examples of fluorinated surfactants include, but are not limited to, commercially available fluorinated surfactants such as BM-1000, BM-1100 (both manufactured by BM Chemie), Megafac F142D, Megafac F172, Megafac F173, Megafac F183 (all manufactured by Dainippon Ink and Chemicals, Inc.), Florard FC-135, Florard FC-170C, Florard FC-430, Florard FC-431 (all manufactured by Sumitomo 3M), Surflon S-112, Surflon S-113, Surflon S-131, Surflon S-141, Surflon S-145 (all manufactured by Asahi Glass Co., Ltd.), SH-28PA, SH-190, SH-193, SZ-6032, and SF-8428 (all manufactured by Toray Silicone Co., Ltd.). As silicone-based surfactants, unmodified silicone-based surfactants, polyether-modified silicone-based surfactants, polyester-modified silicone-based surfactants, alkyl-modified silicone-based surfactants, aralkyl-modified silicone-based surfactants, and reactive silicone-based surfactants can be preferably used. As the silicone-based surfactant, commercially available silicone-based surfactants can be used. Specific examples of commercially available silicone-based surfactants include Paintad M (manufactured by Toray Dow Corning), Topica K1000, Topica K2000, Topica K5000 (all manufactured by Takachiho Sangyo Co., Ltd.), XL-121 (polyether-modified silicone-based surfactant, manufactured by Clariant Co., Ltd.), and BYK-310 (polyester-modified silicone-based surfactant, manufactured by Bic Chemie Co., Ltd.).

[0279] Furthermore, the photosensitive composition may further contain an acid or an acid anhydride to fine-tune its solubility in the developer.

[0280] Specific examples of acids and acid anhydrides include monocarboxylic acids such as acetic acid, propionic acid, n-butyric acid, isobutyric acid, n-valeric acid, isovaleric acid, benzoic acid, and cinnamic acid; hydroxymonocarboxylic acids such as lactic acid, 2-hydroxybutyric acid, 3-hydroxybutyric acid, salicylic acid, m-hydroxybenzoic acid, p-hydroxybenzoic acid, 2-hydroxycinnamic acid, 3-hydroxycinnamic acid, 4-hydroxycinnamic acid, 5-hydroxyisophthalic acid, and syringic acid; oxalic acid, succinic acid, glutaric acid, adipic acid, maleic acid, itaconic acid, hexahydrophthalic acid, phthalic acid, isophthalic acid, terephthalic acid, 1,2-cyclohexanedicarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid, butanetetracarboxylic acid, trimellitic acid Examples include polycarboxylic acids such as triacidic acid, pyromellitic acid, cyclopentanetetracarboxylic acid, butanetetracarboxylic acid, and 1,2,5,8-naphthalenetetracarboxylic acid; and acid anhydrides such as itaconic anhydride, succinic anhydride, citraconic anhydride, dodecenylsuccinic anhydride, tricarbanylic anhydride, maleic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hymicic anhydride, 1,2,3,4-butanetetracarboxylic anhydride, cyclopentanetetracarboxylic dianhydride, phthalic anhydride, pyromellitic anhydride, trimellitic anhydride, benzophenonetetracarboxylic anhydride, ethylene glycol bis-trimellitate anhydride, and glycerin tris-trimellitate anhydride.

[0281] Furthermore, the photosensitive composition may further contain a sensitizer to improve sensitivity. Furthermore, the photosensitive composition may further contain dyes or pigments.

[0282] The photosensitive composition is prepared by mixing and stirring the above components in a conventional manner. Apparatus that can be used for mixing and stirring the above components includes dissolvers, homogenizers, and three-roll mills. After uniformly mixing the above components, the resulting mixture may be further filtered using a mesh, membrane filter, or the like.

[0283] The photosensitive layer 12a is laminated on a substrate having a metal surface, for example, as follows: A liquid photosensitive composition is applied to a substrate having a metal surface, and the solvent is removed by heating to form a photosensitive layer 12a of the desired thickness. The thickness of the photosensitive layer 12a is not particularly limited as long as a patterned resist film that serves as the template 12 can be formed with the desired thickness. The thickness of the photosensitive layer 12a is not particularly limited, but is preferably 0.5 μm or more, more preferably 0.5 μm to 300 μm, particularly preferably 1 μm to 150 μm, and most preferably 3 μm to 100 μm.

[0284] Methods for coating the photosensitive composition onto the substrate include spin coating, slit coating, roll coating, screen printing, and applicator coating. Pre-baking is preferred for the photosensitive layer 12a. The pre-baking conditions vary depending on the type and proportion of each component in the photosensitive composition, the coating thickness, etc., but are usually between 70°C and 200°C, preferably between 80°C and 150°C, for about 2 minutes to 120 minutes.

[0285] [Synthesis process] In the exposure process, the photosensitive layer 12a formed in the lamination process is exposed by selectively irradiating it with active light or radiation. The exposed photosensitive layer 12a is patterned in the development process described later. Therefore, position-selective exposure is performed on the photosensitive layer 12a so that the areas where metal wiring (plated structures) are to be formed are removed by development. Specifically, for example, the photosensitive layer 12a is selectively irradiated (exposed) with active light or radiation, such as ultraviolet or visible light with a wavelength of 300 nm to 500 nm, for example, g-rays (wavelength 436 nm), h-rays (wavelength 405 nm), or i-rays (wavelength 365 nm), through a mask of a predetermined pattern.

[0286] As radiation sources, low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, argon gas lasers, etc., can be used. Radiation includes microwaves, infrared rays, visible light, ultraviolet rays, X-rays, gamma rays, electron beams, proton beams, neutron beams, and ion beams. The radiation dose varies depending on the composition of the photosensitive composition and the thickness of the photosensitive layer 12a, but for example, 100 J / m 2 More than 10000J / m 2 The following applies. Furthermore, radiation includes light rays that activate an acid generator (A) to produce acid.

[0287] After exposure, the photosensitive layer 12a is heated using a known method to promote the diffusion of the acid, thereby changing the solubility (alkaline solubility) of the photosensitive layer 12a in the exposed portion of the photosensitive layer 12a in the developer.

[0288] [Development process] In the developing process, the photosensitive layer 12a after the exposure process is developed to form a mold 12 for forming metal wiring by plating (Figure 1(c)). The exposed photosensitive layer 12a is developed, and unwanted portions are dissolved and removed to form a mold 12 for forming metal wiring (plated objects) by plating, which is a predetermined patterned resist film. In this process, an alkaline aqueous solution is preferably used as the developer.

[0289] As a developer, aqueous solutions of alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide (tetramethylammonium hydroxide), tetraethylammonium hydroxide, pyrrole, piperidine, 1,8-diazabicyclo[5,4,0]-7-undecene, and 1,5-diazabicyclo[4,3,0]-5-nonane can be used. Alternatively, aqueous solutions of the above alkalis to which appropriate amounts of water-soluble organic solvents such as methanol and ethanol or surfactants can be added can also be used as a developer.

[0290] The development time varies depending on the composition of the photosensitive composition and the thickness of the photosensitive layer, but it is usually between 1 minute and 30 minutes. Any development method is acceptable, such as the liquid-filling method, dipping method, paddle method, or spray development method.

[0291] After development, if necessary, rinse with running water for 30 to 90 seconds and dry using an air gun or oven. In this way, a substrate with a template can be manufactured, which has a patterned resist film that serves as a template 12 for forming metal wiring (plated structures) on the metal surface (metal layer 10) of the substrate 11 having a metal surface.

[0292] The thickness of the mold 12 formed is not particularly limited. The thickness of the mold 12 (the thickness of the hottest part of the mold 12) is preferably 0.5 μm or more, more preferably 0.5 μm to 300 μm, even more preferably 0.5 μm to 200 μm, and particularly preferably 0.5 μm to 150 μm. The upper limit of the thickness may be, for example, 100 μm or less. The lower limit of the thickness may be, for example, 1 μm or more, or 3 μm or more.

[0293] [Plating process] In the plating process, the substrate 11 on which the mold 12 is formed is plated to form the metal wiring 13 (Figure 1(d)). In Figures 1 and 2, the metal species constituting the metal layer 10 and the metal species constituting the metal wiring 13 are the same metal, so the metal layer 10 and the metal wiring 13 are shown as a single layer. However, the metal species constituting the metal layer 10 and the metal species constituting the metal wiring 13 may be different.

[0294] Metal wiring 13 can be formed as a plated object by embedding a conductor such as metal in the non-resist portion (the portion removed by the developer) of the mold 12 in the substrate 11 on which the mold 12 is formed, by plating. The plating method is not particularly limited, and various conventionally known methods can be used. Solder plating, copper plating, gold plating, and nickel plating solutions are particularly preferred as plating solutions.

[0295] The mold 12 is removed after plating using a stripping solution or the like, according to a conventional method. Examples of stripping solutions include organic solvents such as acetone. After removing the mold 12, isolated metal wiring 13 is formed by removing the metal layer 10 on the surface of the substrate 11 in areas where metal wiring 13 has not been formed (Figure 1(e)). The removal of the metal layer 10 can be carried out using a liquid capable of dissolving the metal layer 10, such as an aqueous solution of ferric chloride.

[0296] In this case, when manufacturing metal wiring 13 by plating, it is sometimes preferable to perform an ashing treatment on the metal surface exposed in the non-resist portion of the patterned resist film that forms the template 12 before the plating process. Specifically, this refers to the case where metal wiring 13 is formed using a mold 12 formed using a photosensitive composition containing a sulfur-containing compound (E). In this case, the adhesion of the metal wiring 13 to the metal surface (metal layer 10) may be impaired. This problem is particularly noticeable when using the sulfur-containing compound (E) represented by formula (e1) or the sulfur-containing compound (E) represented by formula (e4). However, when the above ashing treatment is performed, it is easier to form metal wiring 13 that adheres well to the metal surface (metal layer 10), even when using a mold 12 formed with a photosensitive composition containing a sulfur-containing compound (E). Furthermore, when a compound containing a nitrogen-containing aromatic heterocycle substituted with a mercapto group is used as the sulfur-containing compound (E), the above-mentioned problems regarding the adhesion of the plated object are almost nonexistent or only mild. Therefore, when a compound containing a nitrogen-containing aromatic heterocycle substituted with a mercapto group is used as the sulfur-containing compound (E), it is easy to form metal wiring 13 with good adhesion to the metal surface without performing an ashing treatment.

[0297] The ashing process is not particularly limited as long as it does not cause damage to the mold 12 for forming the metal wiring 13 to such an extent that it becomes impossible to form the metal wiring 13 of the desired shape. A preferred ashing method is one that uses oxygen plasma. In order to ash the metal surface (metal layer 10) on the substrate 11 using oxygen plasma, an oxygen plasma can be generated using a known oxygen plasma generator, and the oxygen plasma can be irradiated onto the metal surface (metal layer 10) on the substrate 11.

[0298] The gas used to generate the oxygen plasma can be a mixture of various gases conventionally used in plasma processing with oxygen, as long as it does not hinder the objectives of the present invention. Examples of such gases include nitrogen gas, hydrogen gas, and CF4 gas. The ashing conditions using oxygen plasma are not particularly limited as long as they do not hinder the objectives of the present invention, but the processing time is, for example, in the range of 10 seconds to 20 minutes, preferably in the range of 20 seconds to 18 minutes, and more preferably in the range of 30 seconds to 15 minutes. By setting the oxygen plasma processing time within the above range, it becomes easier to improve the adhesion of the metal wiring 13 without causing any change in the shape of the mold 12.

[0299] [Insulator coating process] In the insulating film coating process, the metal wiring 13 is coated with insulating film 21 (Figure 2(a)). This results in a metal wiring substrate on which the metal wiring 13 and insulating film 21 are provided in that order on the substrate 11. In Figure 2(a), the entire surface of the substrate 11 having the metal wiring 13 is covered with an insulating film 21, but the insulating film 21 may be a patterned film. For example, the insulating film 21 may cover only the metal wiring 13 without covering the exposed substrate 11, or it may cover only a part of the metal wiring 13.

[0300] Examples of materials for the insulating film 21 include polyimide and polyamide. If the insulating film 21 is made of polyimide, for example, a composition containing a polyimide precursor (polyimide precursor solution) can be applied to a substrate 11 having metal wiring 13 to form a polyimide precursor film, and then the polyimide precursor can be cured (imidized) by heating, thereby coating the metal wiring 13 with an insulating film 21 made of polyimide.

[0301] Examples of polyimide precursors include polymers obtained by polymerizing any tetracarboxylic dianhydride with a diamine, polymers in which a portion of the polymer is imidized, and polymers in which some or all of the carboxyl groups of these polymers are esterified. Examples of polyimide precursors include polyimide precursors having a structural unit represented by the following formula (1). Note that the above-mentioned "polymers in which some or all of the carboxyl groups of these polymers are esterified" are represented by formula (1), and R A1 , and R A2 The polymer has constituent units in which some or all of the organic groups have 1 to 30 carbon atoms. Examples of such organic groups include unsaturated groups. Examples of unsaturated groups include chain-like aliphatic hydrocarbon groups having an ethylenically unsaturated double bond, and (meth)acryloyl group-containing groups. [ka] (In formula (1), X A1This is a tetravalent organic group having 4 to 40 carbon atoms. Y A1 This is an organic group having 4 to 40 carbon atoms. R A1 , and R A2 Each is independently a hydrogen atom or an organic group having 1 to 30 carbon atoms, and R A1 , and R A2 The aforementioned organic group is bonded to the oxygen atom in the ester bond via a CO bond.

[0302] The amounts of tetracarboxylic dianhydride and diamine used are not particularly limited, but it is preferable to use 0.50 moles to 1.50 moles of diamine per mole of tetracarboxylic dianhydride, more preferably 0.60 moles to 1.30 moles, and particularly preferably 0.70 to 1.20 moles.

[0303] Tetracarboxylic acid dianhydrides can be appropriately selected from tetracarboxylic acid dianhydrides that have been conventionally used as polyimide precursors or raw materials for polyimide synthesis. Examples of tetracarboxylic acid dianhydrides include compounds represented by the following formula (2). [ka] (In formula (2), X A1 (This refers to a tetravalent organic group with 4 to 40 carbon atoms.)

[0304] The tetracarboxylic dianhydride may be an aromatic tetracarboxylic dianhydride or an aliphatic tetracarboxylic dianhydride, but from the viewpoint of the heat resistance of the resulting polyimide film, it is preferable to use an aromatic tetracarboxylic dianhydride. The tetracarboxylic dianhydride may be used alone or in combination of two or more types.

[0305] Suitable specific examples of aromatic tetracarboxylic dianhydrides include 4,4'-oxydiphthalic anhydride, pyromellitic dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, bis(2,3-dicarboxyphenyl)methane dianhydride, bis(3,4-dicarboxyphenyl)methane dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 2,2, 6,6-biphenyltetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)-1,1,1,3,3,3-hexafluoropropane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)-1,1,1,3,3,3-hexafluoropropane dianhydride, 3,3',4,4'-ben Zophenone tetracarboxylic dianhydride, bis(3,4-dicarboxyphenyl) ether dianhydride, bis(2,3-dicarboxyphenyl) ether dianhydride, 2,2',3,3'-benzophenone tetracarboxylic dianhydride, 4,4-(p-phenylenedioxy)diphthalic acid dianhydride, 4,4-(m-phenylenedioxy)diphthalic acid dianhydride, 1,2,5,6-naphthalene tetracarbone dianhydride, 1,4,5,8-naphthalene tetracarbone Examples of dianhydrides include rubonic acid dianhydride, 2,3,6,7-naphthalenetetracarboxylic acid dianhydride, 1,2,3,4-benzenetetracarboxylic acid dianhydride, 3,4,9,10-perylenetetracarboxylic acid dianhydride, 2,3,6,7-anthracenetetracarboxylic acid dianhydride, 1,2,7,8-phenanthrenetetracarboxylic acid dianhydride, 9,9-bisphthalic anhydride fluorene, and 3,3',4,4'-diphenylsulfonetetracarboxylic acid dianhydride. Examples of aliphatic tetracarboxylic acid dianhydrides include ethylenetetracarboxylic acid dianhydride, butanetetracarboxylic acid dianhydride, cyclopentanetetracarboxylic acid dianhydride, cyclohexanetetracarboxylic acid dianhydride, 1,2,4,5-cyclohexanetetracarboxylic acid dianhydride, and 1,2,3,4-cyclohexanetetracarboxylic acid dianhydride.Among these, 3,3',4,4'-biphenyltetracarboxylic dianhydride and pyromellitic dianhydride are preferred due to their price, availability, etc. Furthermore, these tetracarboxylic dianhydrides can be used individually or in combination of two or more types.

[0306] The diamine can be appropriately selected from diamines that have been conventionally used as polyimide precursors or raw materials for polyimide synthesis. Examples of diamines include compounds represented by the following formula (3). H2N-Y A1 -NH2···(3) (In formula (3), Y A1 (This represents a divalent organic group with 4 to 40 carbon atoms.)

[0307] The diamine may be an aromatic diamine or an aliphatic diamine, but an aromatic diamine is preferred from the viewpoint of the heat resistance of the resulting polyimide film. These diamines may be used individually or in combination of two or more.

[0308] Examples of aromatic diamines include diamino compounds in which one or two to ten phenyl groups are bonded. Specifically, these include phenylenediamine and its derivatives, diaminobiphenyl compounds and their derivatives, diaminodiphenyl compounds and their derivatives, diaminotriphenyl compounds and their derivatives, diaminonaphthalene and its derivatives, aminophenylaminoindan and its derivatives, diaminotetraphenyl compounds and their derivatives, diaminohexaphenyl compounds and their derivatives, and cardo-type full orangeamine derivatives.

[0309] Phenylenediamines include m-phenylenediamine and p-phenylenediamine, while phenylenediamine derivatives include diamines to which alkyl groups such as methyl and ethyl groups are attached, such as 2,4-diaminotoluene and 2,4-triphenylenediamine.

[0310] In diaminobiphenyl compounds, two aminophenyl groups are bonded together. Examples include 4,4'-diaminobiphenyl and 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl.

[0311] Diaminodiphenyl compounds are compounds in which two aminophenyl groups are linked together via other groups. The linkages include ether bonds, sulfonyl bonds, thioether bonds, alkylene or its derivative groups, imino bonds, azo bonds, phosphine oxide bonds, amide bonds, and ureylene bonds. The number of carbon atoms in the alkylene bond is approximately 1 to 6. Alkylene derivative groups are alkylene groups substituted with one or more halogen atoms.

[0312] Examples of diaminodiphenyl compounds include 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl ketone, 3,4'-diaminodiphenyl ketone, 2,2-bis(p-aminophenyl)propane, 2,2'-bis(p-aminophenyl)hexafluoropropane, 4-methyl-2,4-bis(p-aminophenyl)-1-pentene, and 4-methyl-2,4-bis(p-aminophenyl Examples include (nyl)-2-pentene, iminodianiline, 4-methyl-2,4-bis(p-aminophenyl)pentane, bis(p-aminophenyl)phosphine oxide, 4,4'-diaminoazobenzene, 4,4'-diaminodiphenylurea, 4,4'-diaminodiphenylamide, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, and 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane.

[0313] Among these, p-phenylenediamine, m-phenylenediamine, 2,4-diaminotoluene, and 4,4'-diaminodiphenyl ether are preferred due to their price, availability, etc.

[0314] Diaminotriphenyl compounds are compounds in which two aminophenyl groups and one phenylene group are bonded together via other groups. The other groups are selected to be the same as those used in diaminodiphenyl compounds. Examples of diaminotriphenyl compounds include 1,3-bis(m-aminophenoxy)benzene, 1,3-bis(p-aminophenoxy)benzene, and 1,4-bis(p-aminophenoxy)benzene.

[0315] Examples of diaminonaphthalenes include 1,5-diaminonaphthalene and 2,6-diaminonaphthalene.

[0316] An example of aminophenylaminoindanes is 5 or 6-amino-1-(p-aminophenyl)-1,3,3-trimethylindanes.

[0317] Examples of diaminotetraphenyl compounds include 4,4'-bis(p-aminophenoxy)biphenyl, 2,2'-bis[p-(p'-aminophenoxy)phenyl]propane, 2,2'-bis[p-(p'-aminophenoxy)biphenyl]propane, and 2,2'-bis[p-(m-aminophenoxy)phenyl]benzophenone.

[0318] Examples of cardo-type fluororangeamine derivatives include 9,9-bisanilinefluorene.

[0319] The number of carbon atoms in aliphatic diamines is preferably between 2 and 15. Specific examples of aliphatic diamines include pentamethylenediamine, hexamethylenediamine, and heptamethylenediamine.

[0320] Furthermore, these diamines may be compounds in which the hydrogen atoms are substituted with at least one substituent selected from the group consisting of halogen atoms, methyl groups, methoxy groups, cyano groups, phenyl groups, etc.

[0321] There are no particular restrictions on the means used to produce the polyimide precursor; for example, known methods such as reacting an acid and a diamine component in a solvent can be used.

[0322] The reaction between tetracarboxylic dianhydride and diamine is usually carried out in a solvent. The solvent used in the reaction between tetracarboxylic dianhydride and diamine is not particularly limited as long as it can dissolve the tetracarboxylic dianhydride and diamine and does not react with them. One solvent may be used alone, or two or more solvents may be used in combination.

[0323] Examples of solvents used in the reaction between tetracarboxylic dianhydrides and diamines include nitrogen-containing polar solvents such as N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-diethylacetamide, N,N-dimethylformamide, N,N-diethylformamide, N-methylcaprolactam, and N,N,N',N'-tetramethylurea; lactone-based polar solvents such as β-propiolactone, γ-butyrolactone, γ-valerolactone, δ-valerolactone, γ-caprolactone, and ε-caprolactone; dimethyl sulfoxide; acetonitrile; fatty acid esters such as ethyl lactate and butyl lactate; ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, dioxane, tetrahydrofuran, methyl cellulose acetate, and ethyl cellulose acetate; and phenolic solvents such as cresols and xylene-based mixed solvents. These solvents may be used individually or in combination of two or more. There are no particular restrictions on the amount of solvent used, but it is desirable that the content of the resulting polyimide precursor be 5 to 50% by mass.

[0324] Among these solvents, nitrogen-containing polar solvents such as N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-diethylacetamide, N,N-dimethylformamide, N,N-diethylformamide, N-methylcaprolactam, and N,N,N',N'-tetramethylurea are preferred due to their solubility of the resulting polyimide precursor.

[0325] The polymerization temperature is generally between -10°C and 120°C, preferably between 5°C and 30°C. The polymerization time varies depending on the composition of the raw materials used, but is usually between 3 hours and 24 hours.

[0326] If the polyimide precursor is a polyimide precursor that is partially imidized, it can be produced, for example, by reacting a diamine with a tetracarboxylic dianhydride, then imidizing it by heating or other means to produce a polymer having imide units, and then reacting this polymer with a diamine and a tetracarboxylic dianhydride. Alternatively, a polyimide precursor that is partially imidized can also be produced by reacting a diamine with a tetracarboxylic dianhydride, and then imidizing it by heating or other means.

[0327] When the polyimide precursor is a polymer obtained by polymerizing a tetracarboxylic dianhydride and a diamine, or a polymer in which part of this polymer is imidized, some or all of the carboxyl groups of the polymer are esterified (for example, when the polyimide precursor is represented by formula (1) and R A1 , and R A2 If the constituent unit has some or all of its components being organic groups, a polyimide precursor can be produced by reacting some or all of the dicarboxylic acid anhydride groups in the tetracarboxylic dianhydride represented by formula (2) with alcohols to open the ring, and then condensing the resulting compound with a diamine according to a conventional method. In this case, the tetracarboxylic dianhydride represented by formula (2) may be condensed with a diamine, along with a compound obtained by reacting some or all of the dicarboxylic anhydride groups of the tetracarboxylic dianhydride represented by formula (2) with alcohols to open the ring.

[0328] The alcohols reacted with the tetracarboxylic dianhydride represented by formula (2) may be unsaturated alcohols having an ethylenically unsaturated double bond, or saturated alcohols.

[0329] Specific examples of unsaturated alcohols include allyl alcohol; butenols such as buta-3-en-1-yl alcohol and buta-2-en-1-yl alcohol; pentenols such as penta-4-en-1-yl alcohol, penta-3-en-1-yl alcohol and penta-2-en-1-yl alcohol; hexenols such as hexa-5-en-1-yl alcohol, hexa-4-en-1-yl alcohol, hexa-3-en-1-yl alcohol and hexa-2-en-1-yl alcohol; and hepta-6-en-1-yl alcohol. Heptenols such as hepta-5-en-1-yl alcohol, hepta-4-en-1-yl alcohol, hepta-3-en-1-yl alcohol, and hepta-2-en-1-yl alcohol; octenols such as octa-7-en-1-yl alcohol, octa-6-en-1-yl alcohol, octa-5-en-1-yl alcohol, octa-4-en-1-yl alcohol, octa-3-en-1-yl alcohol, and octa-2-en-1-yl alcohol; nona-8-en-1-yl alcohol, nona-7-en Nonenols such as nona-1-yl alcohol, nona-6-en-1-yl alcohol, nona-5-en-1-yl alcohol, nona-4-en-1-yl alcohol, nona-3-en-1-yl alcohol, and nona-2-en-1-yl alcohol; deca-9-en-1-yl alcohol, deca-8-en-1-yl alcohol, deca-7-en-1-yl alcohol, deca-6-en-1-yl alcohol, deca-5-en-1-yl alcohol, deca-4-en-1-yl alcohol, deca-3-en-1-yl alcohol, and4-en-1-yl alcohol, deca-3-en-1-yl alcohol, and deca-2-en-1-yl alcohol; Decenols such as car-2-en-1-yl alcohol; undecenols such as undeca-10-en-1-yl alcohol; dodecenols such as dodeca-11-en-1-yl alcohol; tridecenols such as trideca-12-en-1-yl alcohol; tetradecenols such as tetradeca-13-en-1-yl alcohol; pentadecenols such as pentadeca-14-en-1-yl alcohol; hexadecenols such as hexadeca-15-en-1-yl alcohol; heptadecenols such as heptadeca-16-en-1-yl alcohol;Examples include octadecenols such as octadeca-17-en-1-yl alcohol and octadeca-9-en-1-yl alcohol (oleyl alcohol); nonadecenols such as nonadeca-18-en-1-yl alcohol; eicosenols such as eicosan-19-en-1-yl alcohol; and octadienols such as octadeca-9,12-dien-1-yl alcohol (linoleyl alcohol).

[0330] Other specific examples of unsaturated alcohols include mono(meth)acrylates of diols such as 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 3-hydroxypropan-2-yl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 5-hydroxypentyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 2-(2-hydroxyethoxy)ethyl (meth)acrylate, and 1-(2-(meth)acryloyloxyethyl)2-(2-hydroxypropyl) phthalate; hydroxyalkyl group-substituted (meth)acrylamides such as N-(2-hydroxyethyl)(meth)acrylamide; and hydroxyl group-containing ketones such as (hydroxymethyl) vinyl ketone and (2-hydroxyethyl) vinyl ketone.

[0331] Furthermore, the following compounds are also preferred as unsaturated alcohols. [ka]

[0332] Specific examples of saturated alcohols include alkane monools such as methanol, ethanol, n-propanol, isopropanol, n-butanol, n-pentanol, and n-hexanol; phenols or naphthols such as phenol, p-cresol, m-cresol, o-cresol, α-naphthol, and β-naphthol; and monoethers of glycols such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, 1,3-propanediol monomethyl ether, 1,3-propanediol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, dipropylene glycol monomethyl ether, and dipropylene glycol monoethyl ether.

[0333] The polyimide precursor may be used alone or in combination of two or more types.

[0334] The heating conditions for curing (imidizing) the polyimide precursor are not particularly limited, as long as the polyimide precursor does not decompose and the imidization proceeds well. The heating temperature is preferably between 180°C and 400°C, and more preferably between 200°C and 350°C. The heating time depends on the heating temperature, but is preferably between 1 hour and 24 hours, and more preferably between 2 hours and 12 hours.

[0335] If the insulating film 21 is a patterned film, for example, after coating a substrate 11 having metal wiring 13 with the insulating film 21, a photosensitive layer can be formed on the insulating film 21 using a photosensitive composition such as the above-mentioned photosensitive composition, and then exposure and development can be performed to form a desired pattern shape, thereby forming a patterned insulating film 21.

[0336] [Metal wiring formation process on insulating film] In the insulating film metal wiring formation process, after the insulating film coating process, metal wiring 24 is further formed on the insulating film 21.

[0337] In the process of forming metal wiring on an insulating film, for example, a metal layer 22 is first formed on the surface of the insulating film 21 by sputtering or the like (Figure 2(b)). The metal species constituting the metal layer 22 may be the same as the metal species constituting the metal surface of the metal layer 10, etc., as described above.

[0338] After forming a metal layer 22 on the surface of the insulating film 21, a photosensitive layer 23a made of a photosensitive composition such as the above-mentioned photosensitive composition is laminated on the metal layer 22 (Figure 2(c)). One method for laminating the photosensitive layer 23a onto the metal layer 22 is the same as the method described above in the [lamination process], in which the photosensitive layer 12a is laminated onto a substrate having a metal surface (metal layer 10).

[0339] Next, the photosensitive layer 23a is exposed by selectively irradiating it with active light or radiation. A method for exposing the photosensitive layer 23a by positionally irradiating it with active light or radiation is the same as the method described above in the [exposure step], in which the photosensitive layer 12a is exposed by positionally irradiating it with active light or radiation. After exposure, the photosensitive layer 23a is heated using a known method to promote the diffusion of the acid, thereby changing the solubility of the photosensitive layer 23a in the developer in the exposed portion of the photosensitive layer 23a.

[0340] Next, the photosensitive layer 23a after exposure is developed to form a mold 23 for forming the metal wiring 24 by plating (Figure 2(d)). A method for developing the photosensitive layer 23a after exposure to form a mold 23 for forming metal wiring 24 by plating is the same as the method described above in the [development step], in which the photosensitive layer 12a after exposure is developed to form a mold 12 for forming metal wiring 13 by plating.

[0341] Next, the substrate 11 on which the mold 23 is formed is plated to form the metal wiring 24 (Figure 2(e)). A method for forming metal wiring 24 by plating the substrate 11 on which the mold 23 is formed is the same as the method for forming metal wiring 13 by plating the substrate 11 on which the mold 12 is formed in the [plating process] described above. In Figure 2, the metal type constituting the metal layer 22 and the metal type constituting the metal wiring 24 are the same metal, so the metal layer 22 and the metal wiring 24 are shown as one layer, but the metal types constituting the metal layer 22 and the metal types constituting the metal wiring 24 may be different.

[0342] The mold 23 is removed after plating using a stripping solution or the like, according to a conventional method. Examples of stripping solutions include organic solvents such as acetone. Furthermore, after removing the mold 23, isolated metal wiring 24 is formed by removing the metal layer 22 in the areas where metal wiring 24 has not been formed (Figure 2(f)). The removal of the metal layer 22 can be carried out using a liquid capable of dissolving the metal layer 10, such as an aqueous solution of ferric chloride. Furthermore, similar to the [plating process] described above, when manufacturing the metal wiring 24 by plating, an ashing process may be performed on the exposed metal surface (metal layer 22) in the non-resist portion of the patterned resist film that forms the template 23 before the plating process.

[0343] By the manufacturing method described above, a metal wiring substrate is obtained, which is a laminated substrate in which metal wiring 13, insulating film 21, and metal wiring 24 are arranged on the substrate 11 in that order. As described above, metal wiring substrates offer superior long-term reliability because oxidation of the metal wiring 13 (metal wiring between the substrate 11 and the insulating film 21) is suppressed. In Figure 2, a metal wiring substrate having rewiring including the insulating film 21 and metal wiring 24 is described, but the metal wiring 24 does not have to be provided. For example, a metal member other than the metal wiring 24, such as a UBM, may be provided instead of the metal wiring 24. Alternatively, an insulating film may be formed on top of the metal wiring 24, and metal wiring may be provided on top of that insulating film.

[0344] As described above, the present inventors provide the following [1] to [8]. [1] A lamination step of laminating a photosensitive layer made of a chemically amplified photosensitive composition onto a substrate having a metal surface, The photosensitive layer is exposed by positionally irradiating it with active light or radiation, A developing step involves developing the photosensitive layer after the exposure step to form a mold for forming metal wiring by plating, A plating step is performed on the substrate on which the mold is formed to form metal wiring. A method for manufacturing a metal wiring substrate, comprising an insulating film coating step of covering the metal wiring with an insulating film, The chemically amplified photosensitive composition comprises an acid generator (A) that generates acid upon irradiation with active light or radiation, The acid generator (A) is F-SO2-N - -SO2-F, PF6 - A method for manufacturing a metal wiring substrate, comprising an acid generator that generates an acid containing at least one anion selected from the group consisting of an anion represented by the following formula (ai) and an anion represented by the following formula (aii). [ka] (In formula (ai), R a01 is a halogen atom or alkyl group, n01 is an integer between 0 and 5, If n01 is an integer between 2 and 5, multiple R a01 These may be the same or different. [ka] (In formula (aii), R a02 , R a03 , R a04 , and R a05 These are, independently, aromatic hydrocarbon groups that may have substituents. [2] The acid generator (A) is F-SO2-N - -SO2-F, PF6 -A method for manufacturing a metal wiring substrate according to [1], comprising an acid generator that generates an acid containing at least one anion selected from the group consisting of the anion represented by formula (ai) and the anion represented by formula (aii). [3] The method for manufacturing a metal wiring substrate according to [1] or [2], wherein the metal wiring is copper wiring. [4] A method for manufacturing a metal wiring substrate according to any one of [1] to [3], wherein the chemically amplified photosensitive composition is of positive type. [5] The method for manufacturing a metal wiring substrate according to [4], wherein the chemically amplified photosensitive composition comprises a resin (B) whose solubility in alkali increases by the action of an acid. [6] The method for manufacturing a metal wiring substrate according to [4] or [5], wherein the chemically amplified photosensitive composition comprises an alkali-soluble resin (D). [7] The method for manufacturing a metal wiring substrate according to [6], 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). [8] A method for manufacturing a metal wiring substrate according to any one of [1] to [7], wherein the chemically amplified photosensitive composition comprises a sulfur-containing compound (E). [Examples]

[0345] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[0346] In the examples and comparative examples, P1 to P8 and FP1 to FP3 were used as the acid generator (A) listed below. [ka]

[0347] [ka]

[0348] In the examples and comparative examples, the following resins A1 and A2 (acrylic resin (B3)) and H1 (styrene-based resin (B2)) were used as resins whose solubility in alkali increases due to the action of acid (resin (B)). In the structural formulas below, the number in the lower right of the parentheses in each constituent unit represents the content (mass%) of the constituent unit in the resin. Resins A1 and A2 have a weight-average molecular weight (Mw) of 40,000 and a dispersion degree (Mw / Mn) of 2.8. Resin H1 has a weight-average molecular weight (Mw) of 10,000 and a dispersion degree (Mw / Mn) of 2.0.

[0349] [ka]

[0350] [ka]

[0351] In the examples and comparative examples, the following resin N1 was used as the alkali-soluble resin (D). N1 (novolac resin (D1)) has a weight-average molecular weight Mw of 6500 and a dispersion degree (Mw / Mn) of 5.0. [ka]

[0352] In the examples and comparative examples, T1 was used as the sulfur-containing compound (E) as shown below. [ka]

[0353] In the examples and comparative examples, the following Q1 was used as the acid diffusion control agent (F). Q1: Transesterification reaction product of 1,2,3,4-butanetetracarboxylic acid tetramethyl ester, 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.

[0354] In the examples and comparative examples, the following S1 was used as the organic solvent (S). S1: A mixed solvent of 3-methoxybutyl acetate (MA) and propylene glycol monomethyl ether acetate (PGMEA) (MA / PGMEA = 6 / 4 (volume ratio))

[0355] [Examples 1-9 and Comparative Examples 1-4] <Manufacturing of chemically amplified photosensitive compositions> A chemically amplified photosensitive composition for use in Examples 1-9 and Comparative Examples 1-4 was obtained by dissolving the resin (B) and alkali-soluble resin (D) of the type and mass parts listed in Table 1, the acid generator (A) of the type and mass parts listed in Table 1, 0.05 mass parts of Q1 (acid diffusion control agent (F)), T1 (sulfur-containing compound (E)), 0.05 mass parts of surfactant (BYK310, manufactured by Bic Chemie), and 0.05 mass parts of tri-n-octyl borate in S1 (organic solvent (S)) to a solid content concentration of 38% by mass.

[0356] <Manufacturing of metal wiring boards (copper wiring boards)> A metal wiring board (copper wiring board) was formed using the manufacturing method shown in Figures 1 and 2. Specifically, first, copper was sputtered onto an 8-inch diameter silicon wafer (substrate 11) to form a 2000 Å copper film (metal layer 10). A chemically amplified photosensitive composition was applied to a silicon wafer on which a copper film had been formed using a spin coater to form a coating film with a thickness of 10 μm. The coating film was then pre-baked at 135°C for 300 seconds to obtain a photosensitive layer 12a. The photosensitive layer 12a was pattern-exposed using a line-and-space pattern mask with a line width of 2 μm and a space width of 2 μm, and an exposure apparatus FPA-5510iV (manufactured by Canon Inc.) (NA 0.18), at an exposure dose 1.2 times the minimum exposure dose required to form a pattern of a predetermined size, using the i-line (wavelength: 365 nm). Next, the substrate 11 was placed on a hot plate and subjected to post-exposure heating (PEB) at 95°C for 180 seconds. Then, a 2.38 wt% aqueous solution of tetramethylammonium hydroxide (TMAH) (developer, NMD-3, manufactured by Tokyo Ohka Kogyo Co., Ltd.) was dropped onto the exposed photosensitive layer 12a, and the process of letting it stand at 23°C for 30 seconds was repeated three times. After that, the resist pattern surface was washed with running water and then nitrogen-blown to obtain a resist pattern that would serve as the template 12 for plating. Next, plasma ashing was performed on the copper surface exposed in the non-resist portion of the resist pattern (template 12) using oxygen gas (O2). The plasma ashing was carried out under the following conditions: processing time: 60 seconds, processing temperature: 25°C, plasma generator output: 300W. Next, using the resist pattern as a template, copper sulfate plating solution was used, with a solution temperature of 25°C and a cathode current density of 5 ASD (A / dm²). 2 Plating was performed under the following conditions until the plating height reached 5 μm. Next, after removing the resist pattern (template 12) with acetone, the copper film (metal layer 10) on the wafer surface where plating had not been formed was removed using an aqueous ferric chloride solution to obtain a substrate on which the first copper wiring (metal wiring 13) was formed.

[0357] A polyimide precursor solution was applied to the substrate on which the first copper wiring was formed to create a polyimide precursor film with a thickness of 10 μm. This film was then heated in a nitrogen atmosphere at 230°C for 2 hours to form a polyimide film (insulating film 21). The polyimide precursor solution used was obtained by the method described below. 0.0645 moles of 4,4'-oxydiphthalic anhydride were dissolved in 40.0 g of N-methyl-2-pyrrolidone (NMP). To the resulting solution, 0.135 moles of hydroxyethyl methacrylate and 0.135 moles of pyridine were added. The resulting solution was stirred at room temperature for 12 hours to obtain a dicarboxylic acid, which is a reaction product of tetracarboxylic dianhydride (4,4'-oxydiphthalic anhydride) and alcohol (hydroxyethyl methacrylate). The resulting solution containing the dicarboxylic acid was cooled to 0°C. To the cooled solution, a condensing agent solution containing 0.142 moles of dicyclohexylcarbodiimide dissolved in 8.5 g of NMP and a solution containing 0.0645 moles of 4,4'-diaminodiphenyl ether dissolved in 35.0 g of NMP were added dropwise. After the dropwise addition was complete, the resulting reaction mixture was stirred at 30°C for 6 hours to condense the dicarboxylic acid and the diamine (4,4'-diaminodiphenyl ether). After the reaction was complete, 15.0 g of methanol was added to the reaction solution. After removing the precipitated by-products by filtration, the filtrate containing the polyimide resin precursor was added dropwise to a large amount of aqueous isopropyl alcohol. After addition, the polyimide resin precursor precipitated in the aqueous solution in isopropyl alcohol was recovered by filtration. The recovered precipitate was washed three times with isopropyl alcohol. The precipitate after washing was dried under reduced pressure, and the resulting polyimide precursor powder was dissolved in an organic solvent: gamma-butyrolactone to obtain a polyimide precursor solution with a solid content of 30% by mass.

[0358] Next, copper was sputtered onto the polyimide film (insulating film 21) to form a 2000 Å copper film (metal layer 22). A chemically amplified photosensitive composition was applied to the formed copper film (metal layer 22) using a spin coater to form a coating film with a thickness of 10 μm. Next, the coating film was pre-baked at 135°C for 300 seconds to obtain a photosensitive layer 23a. The photosensitive layer 23a was pattern-exposed using a line and space pattern mask with a line width of 2 μm and a space width of 2 μm, and an exposure apparatus FPA-5510iV (manufactured by Canon Inc.) (NA 0.18) at an exposure dose 1.2 times the minimum exposure dose required to form a pattern of a predetermined size, using the i-line (wavelength: 365 nm). Next, the substrate 11 was placed on a hot plate and post-exposure baking (PEB) was performed at 95°C for 180 seconds. Then, an operation of dropping a 2.38 wt% aqueous solution of tetramethylammonium hydroxide (TMAH) (developer, NMD-3, manufactured by Tokyo Ohka Kogyo Co., Ltd.) onto the exposed photosensitive layer 23a and then leaving it standing at 23°C for 30 seconds was repeated three times. Then, after washing the resist pattern surface with running water, nitrogen blowing was performed to obtain a resist pattern (mold 23). Next, plasma ashing using oxygen gas (O2) was performed on the surface made of copper exposed in the non-resist portion of the resist pattern (mold 23). The plasma ashing was performed under the conditions of a treatment time of 60 seconds, a treatment temperature of 25°C, and a plasma generator output of 300W. Next, using the resist pattern as a mold and a copper sulfate plating solution, plating was performed at a liquid temperature of 25°C and a cathode current density of 5 ASD (A / dm 2 ) until the plating height reached 5 μm. Next, after removing the resist pattern (mold 23) with acetone, the copper film (metal layer 22) on the surface of the polyimide film where no plating was formed was removed using an aqueous solution of ferric chloride, thereby obtaining a metal wiring substrate in which the first copper wiring (metal wiring 13), the polyimide film (insulating film 21), and the second copper wiring (metal wiring 24) were provided in this order.

[0359] 〔Evaluation〕 For the obtained metal wiring substrate, the following HAST evaluation and HST evaluation were performed. The results are shown in Table 1.

[0360] <HAST (High Accelerated Stress Test) evaluation> High-speed accelerated life test<​​​​​​×: The thickness of the oxide film (copper oxide film) on the surface of the first copper wiring exceeds 100 nm.

[0361] <HST (High Temperature Storage Test) Evaluation> The metal wiring substrate was exposed to an environment of 175 °C and an absolute humidity not exceeding 20 g / m 3 for 100 hours, and then the cross-section was observed with a scanning electron microscope and evaluated according to the following criteria. ◎: The thickness of the oxide film (copper oxide film) on the surface of the first copper wiring is 50 nm or less. ○: The thickness of the oxide film (copper oxide film) on the surface of the first copper wiring exceeds 50 nm and is 100 nm or less. ×: The thickness of the oxide film (copper oxide film) on the surface of the first copper wiring exceeds 100 nm.

[0362]

Table 1

[0363] According to Table 1, in the method for manufacturing a metal wiring substrate having the above-described lamination step, exposure step, development step, plating step, and insulating film coating step, it can be seen that by using a chemically amplified photosensitive composition containing an acid generator that generates an acid containing F-SO2-N - -SO2-F, PF6 - , an anion represented by formula (ai), or an anion represented by formula (aii), oxidation of the metal wiring between the substrate and the insulating film under high temperature and high humidity environments can be suppressed.

Explanation of Reference Numerals

[0364] 10 Metal layer 11 Substrate 12a Photosensitive layer 12 Mold 13 Metal wiring 21 Insulating film 22 Metal layer 23a Photosensitive layer 23 Mold 24 Metal wiring

Claims

1. A lamination process in which a photosensitive layer made of a chemically amplified photosensitive composition is laminated on a substrate having a metal surface, The photosensitive layer is exposed by positionally irradiating it with active light or radiation, A developing step involves developing the photosensitive layer after the exposure step to form a mold for forming metal wiring by plating, A plating step is performed on the substrate on which the mold is formed to form metal wiring. A method for manufacturing a metal wiring substrate, comprising an insulating film coating step of covering the metal wiring with an insulating film, The chemically amplified photosensitive composition includes an acid generator (A) that generates acid upon irradiation with active light or radiation, The acid generator (A) is F-SO ２ -N － -SO ２ - F, PF ６ － A method for manufacturing a metal wiring substrate, comprising an acid generator that generates an acid containing at least one anion selected from the group consisting of an anion represented by the following formula (ai) and an anion represented by the following formula (aii). 【Chemistry 1】 (In formula (ai), R ａ０１ is a halogen atom or alkyl group, n01 is an integer between 0 and 5, If n01 is an integer between 2 and 5, multiple R ａ０１ These may be the same or different. 【Chemistry 2】 (In formula (aii), R ａ０２ , R ａ０３ , R ａ０４ , and R ａ０５ are each independently an aromatic hydrocarbon group which may have a substituent.)

2. The acid generator (A) is F-SO ２ -N － -SO ２ - F, PF ６ － A method for manufacturing a metal wiring substrate according to claim 1, comprising an acid generator that generates an acid containing at least one anion selected from the group consisting of the anion represented by formula (ai) and the anion represented by formula (aii).

3. The method for manufacturing a metal wiring substrate according to claim 1, wherein the metal wiring is copper wiring.

4. A method for manufacturing a metal wiring substrate according to any one of claims 1 to 3, wherein the chemically amplified photosensitive composition is of the positive type.

5. The method for manufacturing a metal wiring substrate according to claim 4, wherein the chemically amplified photosensitive composition includes a resin (B) whose solubility in alkali increases by the action of an acid.

6. The method for manufacturing a metal wiring substrate according to claim 4, wherein the chemically amplified photosensitive composition comprises an alkali-soluble resin (D).

7. The method for manufacturing a metal wiring substrate according to claim 6, 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).

8. The method for manufacturing a metal wiring substrate according to claim 1, wherein the chemically amplified photosensitive composition contains a sulfur-containing compound (E).

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